School of Chemical Engineering - 20. Caso Estudio Acrilonitrilo PDF
School of Chemical Engineering - 20. Caso Estudio Acrilonitrilo PDF
School of Chemical Engineering - 20. Caso Estudio Acrilonitrilo PDF
By
Ames, IA
2005
Dissertation Approved:
Dr. RobWhiteley
Dr. AJ Johannes
ii
DEDICATION
This dissertation is dedicated to my lovely parents Mr. and Mrs. Olasupo Shadiya for
Also to my brother and sister, Akinola Shadiya and Feyisola Shadiya for always lifting
Lastly this thesis would not have been completed without the constant motivation,
prayers and encouragement from my cherished friend and fiancé, Tolulope Oluwadairo.
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ACKNOWLEDGMENTS
First and foremost, I will like to thank God for seeing me through the years I
worked on this degree. I express deepest gratitude to my advisor Dr. Karen High for all
her mentorship, advice and the financial support she provided while working on my
doctorate degree. I would like to thank my committee members Dr. A.J Johannes, Dr.
Rob Whiteley and Dr. DeeAnn Sanders for their guidance while completing this research.
I would like to thank the Yarborough Distinguished Graduate Fellowship and the
Department of Chemical Engineering for the Funding I received towards completing this
degree. Lastly, I would like to thank Modupe Oluwadiya, Obianuju Udezue, Subuola
Sofolahan, and Kanyinsola Keleko for their support and taking time to read and edit
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TABLE OF CONTENTS
Chapter Page
1. INTRODUCTION .............................................................................................................. 1
2. PROCESS DESIGN FRAMEWORK............................................................................... 11
2.1 PROCESS DESIGN SYNTHESIS ................................................................................... 11
2.1.1 Select the Process Type – Batch vs. Continuous ................................................... 12
2.1.2 Design the input-output structure ........................................................................... 13
2.1.3 Define Recycle Structure ....................................................................................... 13
2.1.4 Define Separation Scheme ..................................................................................... 14
2.1.5 Define Energy Recovery System ........................................................................... 14
2.2 TOOLS AVAILABLE FOR DESIGNING CHEMICAL PROCESSES ......................... 15
2.2.1 Features of a Process Simulator ............................................................................. 16
2.2.2 Classifications of Chemical Process Simulators .................................................... 17
2.3 PROCESS DESIGN ISSUES AND OPTIMIZATION .................................................... 19
2.3.1 Process Design Issues ............................................................................................ 20
2.3.2 Optimization .......................................................................................................... 23
2.4 SUMMARY ...................................................................................................................... 32
3. ECONOMIC, ENVIRONMENTAL AND HEALTH AND SAFETY EVALUATION
TOOLS.............................................................................................................................. 33
3.1 INTRODUCTION ............................................................................................................ 33
3.2 ECONOMIC EVALUATION TOOLS ............................................................................ 33
3.2.1 Capital Cost Estimator (CAPCOST)...................................................................... 35
3.2.2 Profitability Analysis Spreadsheet ......................................................................... 35
3.2.3 HYSYS Spreadsheet .............................................................................................. 36
3.2.4 Aspen Process Economic Analyzer ....................................................................... 36
3.2.5 Design Option Ranking Tool (DORT)................................................................... 37
3.2.6 Summary of Economic Assessment Tools............................................................. 37
3.3 ENVIRONMENTAL EVALUATION TOOLS ............................................................... 39
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3.3.1 Environmental Concerns ........................................................................................ 39
3.3.2 Environment Impact Assessment Tools ................................................................. 50
3.4 SAFETY AND HEALTH EVALUATION TOOLS ........................................................ 57
3.4.1 Health and Safety Concerns ................................................................................... 57
3.4.2 Health Risk Assessment ......................................................................................... 63
3.4.3 Health and Safety Screening Tools ........................................................................ 66
3.5 SUMMARY ...................................................................................................................... 74
4. SUSTAINABILITY METRICS AND INDICATORS..................................................... 75
4.1 INTRODUCTION ............................................................................................................ 75
4.2 SURVEY OF SUSTAINABILITY METRICS AND INDICATORS ............................. 77
4.2.1 Sustainability Metrics ............................................................................................ 77
4.2.2 Sustainability Indicators......................................................................................... 79
4.3 PROPOSED SUSTAINABILITY METRICS AND INDICATOR SYSTEMS .............. 81
4.3.1 Sustainability Process Index .................................................................................. 81
4.3.2 Inherent Process Safety Index ................................................................................ 83
4.3.3 Sustainability Indicators......................................................................................... 83
4.3.4 AIChE/ CWRT Sustainability Metrics .................................................................. 84
4.3.5 Dow Jones Sustainability Index (DJSI) ................................................................. 84
4.3.6 BASF Socio-Eco-efficiency Metrics ..................................................................... 85
4.3.7 Green Metrics......................................................................................................... 85
4.3.8 IChemE Sustainability Metrics .............................................................................. 86
4.3.9 Indicator of Sustainable Production ....................................................................... 86
4.3.10 Global Environmental Risk Assessment (GERA) Index ....................................... 87
4.3.11 BRIDGES Sustainability Metrics .......................................................................... 87
4.3.12 Three Dimensional Sustainability Metrics ............................................................. 88
4.3.13 Sustainability Indices ............................................................................................. 88
4.3.14 AIChE Sustainability Index ................................................................................... 89
4.4 SUMMARY ............................................................................................................... 89
5. IMPLEMENTING METHODOLOGY FOR DESIGNING PROCESSES FOR
SUSTAINABILITY DURING EARLY STAGES OF DESIGN ..................................... 93
5.1 INTRODUCTION ............................................................................................................ 93
5.2 SIMULATION OF THE BASE CASE PROCESS MODEL ........................................... 95
5.3 ASSESSMENT OF THE PROCESS USING THE SUSTAINABILITY EVALUATOR
96
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5.3.1 Economic Impact in the SUSTAINABILITY EVALUATOR .............................. 98
5.3.2 Environmental Burden in the SUSTAINABILITY EVALUATOR .................... 100
5.3.3 Social Concerns in the SUSTAINABILITY EVALUATOR .............................. 110
5.3.4 Overall Sustainability Impact in the Sustainability Evaluator ............................. 122
5.4 SENSITIVITY ANALYSIS ........................................................................................... 128
5.5 PROCESS OPTIMIZATION.......................................................................................... 129
5.6 SUSTAINABILITY RE-EVALUATION ...................................................................... 130
5.7 SUMMARY .................................................................................................................... 131
6. DEMONSTRATION OF THE PROPOSED METHODOLOGY .................................. 133
6.1 VALIDATION CASE STUDY: METHYL CHLORIDE PROCESS ............................ 134
6.1.1 Brief Description of the Methyl Chloride Process ............................................... 135
6.1.2 Sustainability Assessment of the Methyl Chloride Process ................................. 139
6.1.3 Validation of the Results Obtained from the SUSTAINABILITY EVALUATOR
using the Waste Reduction Algorithm ................................................................................. 148
6.2 CASE STUDY: DIMETHYL ETHER PRODUCTION PROCESSES ......................... 151
6.2.1 Brief Description of the DME Production Process .............................................. 151
6.2.2 Sustainability Evaluation of the DME Production Process.................................. 157
6.2.3 Selection of the More Sustainable DME Production Process .............................. 163
6.3 CASE STUDY: ACRYLONITRILE PRODUCTION PROCESS ................................. 165
6.3.1 Acrylonitrile Base Case Process Modeling .......................................................... 168
6.3.2 Sustainability Assessment of the Acrylonitrile Base Case .................................. 170
6.3.3 Acrylonitrile Base Case Sensitivity Analysis ...................................................... 177
6.3.4 Optimization of the Base Case Acrylonitrile ....................................................... 185
6.3.5 Sustainability Assessment of the Optimized Acrylonitrile Process ..................... 187
6.3.6 Summary .............................................................................................................. 193
6.4 CASE STUDY: ALLYL CHLORIDE PROCESS ......................................................... 194
6.4.1 Allyl Chloride Base Case Process Modeling ....................................................... 197
6.4.2 Sustainability Assessment of the Base Case Allyl Chloride Process ................... 199
6.4.3 Allyl Chloride Base Case Sensitivity Analysis .................................................... 205
6.4.4 Optimization of the Allyl Chloride Process ......................................................... 209
6.4.5 Sustainability Assessment of the Optimized Allyl Chloride Processes ............... 210
6.4.6 Selection of the Sustainable Allyl Chloride Process ............................................ 217
7. CONCLUSIONS AND FUTURE WORK ..................................................................... 218
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7.1 CONCLUSIONS ............................................................................................................. 218
7.2 FUTURE WORK ............................................................................................................ 226
8. REFERENCES ............................................................................................................... 231
9. APPENDIX A: SUSTAINABITY EVALUATOR USER MANUAL ........................... 252
10. APPENDIX B: INPUT FILE FOR THE FOLLOWING CASE STUDIES: METHYL
CHLORIDE, DIMETHYL ETHER, ACRYLONITRILE AND ALLYL CHLORIDE . 268
11. APPENDIX C: PROCESS FLOW DIAGRAM, STREAM SUMMARY TABLE,
EQUIPMENT SPECIFICATION FOR THE FOLLOWING CASE STUDIES: METHYL
CHLORIDE, DIMETHYL ETHER, ACRYLONITRILE AND ALLYL CHLORIDE . 323
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LIST OF TABLES
Table Page
ix
Table 5.28: Impact Weights Sensitivity Analysis ........................................................................ 128
Table 6.1: Physical Properties of Methyl Chloride ...................................................................... 134
Table 6.2: Methyl Chloride Process Kinetic Data ....................................................................... 137
Table 6.3: Methyl Chloride Process Key Input Variables ........................................................... 139
Table 6.4: Summary of Economic data for the Methyl Chloride Process ................................... 140
Table 6.5: Economic Assessment Results for the Methyl Chloride Process from the
SUSTAINABILITY EVALUATOR ........................................................................................... 141
Table 6.6: Chemicals in the Methyl Chloride Process Contributing to each Environmental Impact
Category ....................................................................................................................................... 143
Table 6.7: Results of Resource Usage Metric Evaluation for the Methyl Chloride Process ....... 144
Table 6.8: Health Impact Assessment Results from the SUSTAINABILITY EVALUATOR for
the Methyl Chloride Process ........................................................................................................ 145
Table 6.9: Safety Assessment Results from the SUSTAINABILITY EVALUATOR for the
Methyl Chloride Process .............................................................................................................. 147
Table 6.10: Summary of Impact Assessment Results from the SUSTAINABILITY
EVALUATOR for the Methyl Chloride Process ......................................................................... 148
Table 6.11: Chemicals in the Methyl Chloride Process Contributing to each Environmental
Impact Category ........................................................................................................................... 150
Table 6.12: Physical Properties of Dimethyl Ether...................................................................... 152
Table 6.13: Summary of Economic data for the Dimethyl Ether Process ................................... 158
Table 6.14: Comparison of Economic Metrics for the two DME options ................................... 158
Table 6.15: Summary of Chemicals Contributing to Environmental Impact for the Two DME
Options ......................................................................................................................................... 160
Table 6.16: Summary of Resource Usage Metrics Results from the SUSTAINABILITY
EVALUATOR for the two DME Options ................................................................................... 161
Table 6.17: Summary of Chemicals Contributing to Health Risks for the Two DME Options .. 162
Table 6.18: Results of Safety Metrics from the SUSTAINABILITY EVALUATOR for the two
DME Options ............................................................................................................................... 163
Table 6.19: Overall Sustainability Impact from the SUSTAINABILITY EVALUATOR for the
two DME Options ........................................................................................................................ 163
Table 6.20: Summary of Impact Assessment Results from the SUSTAINABILITY
EVALUATOR for the two DME Options ................................................................................... 164
Table 6.21: Physical Properties of Acrylonitrile .......................................................................... 166
Table 6.22: Acrylonitrile Process Kinetic Data ........................................................................... 169
Table 6.23: Summary of Economic Data for the Acrylonitrile Process ...................................... 171
Table 6.24: Economic Assessment Results for the Base Case Acrylonitrile Process from the
SUSTAINABILITY EVALUATOR ........................................................................................... 172
Table 6.25: Results of Environmental Impact Assessment for the Base Acrylonitrile Process ... 173
Table 6.26: Results of Resource Usage Evaluation for the Base Case Acrylonitrile Process ..... 174
Table 6.27: Results of Health Impact Assessment for the Base Case Acrylonitrile Process ....... 175
Table 6.28: Safety Assessment Results from the SUSTAINABILITY EVALUATOR for the Base
Case Acrylonitrile Process ........................................................................................................... 176
Table 6.29: Results of Top 19 cases for Sensitivity Analysis of Varying Feed Ratio ................. 178
Table 6.30: Variables used in the Optimization of the Acrylonitrile Process .............................. 186
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Table 6.31: Key Differences between the Base and Optimized Acrylonitrile Processes ............ 187
Table 6.32: Comparison of Economic Metrics for the Base and Optimized Acrylonitrile Processes
..................................................................................................................................................... 188
Table 6.33: Percent Reduction of the Environmental Impact of the Acrylonitrile Optimized Case
relative to the Base Case .............................................................................................................. 190
Table 6.34: Resource Usage Metrics Results for the Base and Optimized Acrylonitrile Cases .. 191
Table 6.35: Percent Reduction of the Health Impact of the Acrylonitrile Optimized Case relative
to the Base Case ........................................................................................................................... 192
Table 6.36: Summary of Results of Safety Metrics for the Base and Optimized Acrylonitrile
Processes ...................................................................................................................................... 193
Table 6.37: Physical Properties of Allyl Chloride ....................................................................... 195
Table 6.38: Allyl Chloride Process Kinetic Data ......................................................................... 199
Table 6.39: Economic Data for the Allyl Chloride Process ......................................................... 200
Table 6.40: Economic Assessment Results for the Base Case Allyl Chloride Process from the
SUSTAINABILITY EVALUATOR ........................................................................................... 201
Table 6.41: Results of Environmental Impact for the Base Case Allyl Chloride Processes ........ 202
Table 6.42: Results of Resource Usage Evaluation for the Base Case Allyl Chloride Process ... 202
Table 6.43: Results of Health Impact Assessment for the Base Case Allyl Chloride Process .... 203
Table 6.44: Safety Assessment Results from the SUSTAINABILITY EVALUATOR for the Base
Case Allyl Chloride Process ........................................................................................................ 204
Table 6.45: Comparison of Calculated Parameters for the Adiabatic PFR Case and the Isothermal
PFR Case...................................................................................................................................... 208
Table 6.46: Variables Used in the Optimization of the Allyl Chloride Process .......................... 210
Table 6.47: Key Differences between the Base Case and the Optimized Cases .......................... 211
Table 6.48: Comparison of Economic Impact Results for the Base, Optimized Adiabatic and
Isothermal Allyl Chloride Processes ............................................................................................ 211
Table 6.49: Environmental Impact Results for Base and Optimized Allyl Chloride Processes .. 213
Table 6.50: Summary of Resource Usage Metrics Results for the Allyl Chloride Base and
Optimized Cases .......................................................................................................................... 214
Table 6.51: Comparison of Health Impact Assessment Results from the SUSTAINABILITY
EVALUATOR Allyl Chloride Processes .................................................................................... 215
Table 7.1: Summary of Proposed Methodology .......................................................................... 220
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LIST OF FIGURES
Figure Page
xii
Figure 6.10 : Summary of Economic Results for the two DME Production Options from the
SUSTAINABILITY EVALUATOR ........................................................................................... 159
Figure 6.11: Results of Environmental Impacts Assessment from the SUSTAINABILITY
EVALUATOR ............................................................................................................................. 160
Figure 6.12: Results of Health Impacts Assessment from the SUSTAINABILITY EVALUATOR
for the two DME Options ............................................................................................................ 161
Figure 6.13: Proposed Methodology for Addressing Sustainability Concerns of the Acrylonitrile
Process ......................................................................................................................................... 167
Figure 6.14: Block Flow Diagram for the Base Case Acrylonitrile Process................................ 168
Figure 6.15: Breakdown of Annual Operating Costs for the Base Case Acrylonitrile ................ 172
Figure 6.16: Effect of Plug Flow Reactor Temperature on Conversion ...................................... 180
Figure 6.17: Effect of Plug flow Reactor Pressure on Conversion .............................................. 180
Figure 6.18: Effect of Plug Flow Reactor Length on Conversion ............................................... 181
Figure 6.19: Effect of Varying Plug Flow Reactor Diameter on Conversion .............................. 181
Figure 6.20: Effect of Varying Feed Stage on Water Removal and Acrylonitrile Recovery....... 182
Figure 6.21: Effect of Absorber Reflux Ratio on Condenser and Re-boiler Duty ....................... 183
Figure 6.22: Block Flow Diagram of the Reconfigured Acrylonitrile Process ............................ 185
Figure 6.23: Comparison of Economic Assessment of the Base Case and Optimized Acrylonitrile
Process ......................................................................................................................................... 189
Figure 6.24: Comparison of Environmental Impacts Assessment for the Optimized and Base Case
Acrylonitrile Process .................................................................................................................... 190
Figure 6.25: Comparison of Health Impacts Assessment the Base and Optimized Acrylonitrile
Process ......................................................................................................................................... 192
Figure 6.26: Proposed Methodology for Addressing Sustainability Concerns of the Allyl Chloride
Process ......................................................................................................................................... 196
Figure 6.27: Block Flow Diagram of the Allyl Chloride Process ................................................ 197
Figure 6.28: Breakdown of Annual Operating Costs for the Base Case Allyl Chloride Process 201
Figure 6.29: Effect of Feed Ratio on the Allyl Chloride Process ................................................ 206
Figure 6.30: Effect of Reactor Temperature on the Allyl Chloride Process ................................ 207
Figure 6.31: Effect of Varying Residence Time on the Allyl Chloride Process .......................... 207
Figure 6.32: Block Flow Diagram of the Reconfigured Allyl Chloride Process ......................... 209
Figure 6.33: Comparison of Economic Assessment of the and Base and Optimized Allyl Chloride
Processes ...................................................................................................................................... 212
Figure 6.34: Comparison of Environmental Impacts Assessment for the Optimized and Base
Cases Allyl Chloride Process ....................................................................................................... 213
Figure 6.35: Comparison of Health Impacts Assessment the Base and Optimized Allyl Chloride
Processes ...................................................................................................................................... 216
Figure 7.1: Proposed Methodology for Addressing Sustainability Concerns During Early Stages
of Design ...................................................................................................................................... 219
Figure 7.2: Proposed Improved Optimization Framework .......................................................... 228
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CHAPTER I
INTRODUCTION
The world we live in today is not the same as it was in the 20th Century.
health risks are some of the issues facing us in the 21st century. Most of these issues, and
the associated concerns, are caused by man’s desire for industrialization. To avoid the
extinction of mankind and to maintain a sustainable planet, some of these issues must be
The awareness of the need to protect the environment did not occur overnight.
Several 20th century scientists have promoted the need for protecting our planet. In 1949,
Aldo Leopold published a book titled ―A Sand Country Almanac‖ to express the
movement in the United States, published a book titled ―Silent Spring‖ (Carson, 1962).
1
As the world became aware of the ecological issues, several groups such as
―Greenpeace‖ (1969) and ―Friends of the Earth‖ (1971) were established to ensure
Protection Agency (1970), United Kingdom Environmental Agency (1898) and the
(2010) have been established by the governments of these countries to ensure protection of
land, air and water resources. Also, world summits such as United Nations Conference on
the Human Environment (1972) and United Nations World Commission on Environment and
Development (1983) were created to discuss uprising environmental issues affecting the
global community. Despite the long history of environmental awareness and governmental
regulations, our planet is still threatened, and something must be done about it.
As we approached the 21st century, it became clear that environmental concerns were
not the only issues affecting the global community; a new term called ―sustainability‖ was
coined. Sustainability can be defined as ―economic well being linked to health of the
environment and the success of the world citizens‖ (Schwarz et al., 2002). Another
―development that meets the needs of the present without compromising the ability of future
(Darton, 2003). As shown in the Venn diagram (Figure 1.1), it can be concluded that a
process that is designed for only economic and environmental concerns is classified as
2
viable; a process that is designed for only environmental and social concerns is classified as
bearable and a process that is designed for economic and social concerns is equitable. Thus,
Economic
Viable Equitable
Sustainable
There has been an increased awareness towards sustainability development in the last
few years. Major key players including industry, academia, the United States Government
and the United Nations are all concerned with the sustainability challenge. Per United
Nations Environmental Programme’s GEO-2002, some of the concerns driving the need for
Around half of the world’s water supply systems such as rivers can be
3
The ozone layer is depleting steadily as a result of chlorofluorocarbon
emissions.
There is an increase concentration of CO2 (25% higher than 150 years ago)
Around 80 countries, which account for 40% of humanity, have limited access
the global chemical industry in the summit, the chemical industry has laid a solid platform
for moving towards becoming a sustainable sector. However, some issues still have to be
(ICCA, 2002).
90% of the energy needs of the world because of high dependence on oil and other petroleum
including optimizing product refining processes is vital for sustainability for the next few
decades to come. For several years, environmental agencies have struggled to regulate the
environmental impacts resulting from oil exploration & production and petroleum refining.
This proved to be very difficult for the oil and gas refining sector. Determining ways to
the challenges surrounding conservation of world petroleum resources in the long term.
4
The launching of a new product in industry involves a series of step by step events.
These include chemical discovery, product development, process development and full scale
production. In this work, the concentration is on the process development stage (Sugiyama,
2007). In process development stage, a sequence of events must be carried out. These are
market research, product specification, early stages and later stages of process design as well
as product registration. The focus of this research is on the early stages of process design as
Market Research
Product Specification
Chemical Discovery
Process Chemistries
Early Stages of Process
Product Development Design
Conceptual Design
Process Development
Piloting
Start Up
incorporated into early stages of process design?‖ The answer to this question is not as easy
as it seems. Process design has always had difficulties as engineers deal with lots of details,
while at the same time taking into consideration profits, regulations and even community
5
relationships. Early process design was carried out by hand until computer-aid design (CAD)
tools appeared. Today, small single-functional programs have been replaced by professional
scientific models and massive databases, has significantly facilitated the engineer’s ability to
accurately mimic the system’s physical condition and carry out sophisticated designs. Yet
when engineers are confronted with sustainability, it is not clear which tools they should use.
This leads to one of the most critical driving forces of this study: process designers need a
sustainability issues.
Although researchers have put forth efforts towards quantifying some sustainability
concerns, there are several limitations in existing methods. One of the important drawbacks
is that existing methods could be complicated, time consuming and not address the three
decision making scenarios because of several concerns as shown in Table 1.1. This makes it
Thus, the main objective of this work is to introduce a methodology for designing
sustainable chemical and petroleum processes during early stages of design. This
framework. This approach ensures that the most sustainable process is designed while taking
into account profitability, environmental impacts and health and safety issues. This project
seeks to examine processes that use non-renewable resources, identify ways to conserve
these resources and develop a methodology for optimizing processes for sustainability. This
6
prevent waste than to treat or clean up waste after it has been created and Design for Energy
environmental and economic impacts and should be minimized (Anastas and Warner, 2000).
Table 1.1: Sustainability Concerns (de Haes et al., 1999; Fiksel et al., 1999; IChemE Metrics,
2002; Azapagic et al., 2004)
Economic concerns Environmental concerns Social concerns
Micro-Economic Energy Use Health and Safety
Capital Costs Water Use Illness & Disease Reduction*
Operating Costs Water Discharge Accident & Injury Reduction*
Profitability Solid Waste Peace of Mind*
Decommissioning Costs Abiotic Reserve Depletion Quality of Life*
Macro-Economic Costs Global Warming Complaints*
Value- added Ozone Depletion Employment opportunities*
Taxes paid on investment Acidification External stakeholders*
(e.g. pollution prevention, Eutrophication Community benefits*
health and safety, Eco-toxicity Work force capability*
decommissioning and ethical Public reporting*
investments Organizational learning
Environmental Liability Remuneration*
Management attention to HR*
*Not addressed in this research
The proposed framework explores the possibility of using the sequential process
simulator, ASPEN PLUS (version 22) to simulate processes and calculate mass and energy
balances. As part of the methodology, an Excel based tool titled the ―SUSTAINABILITY
EVALUATOR‖ has been developed for this research to address the three dimensions of
shown in Table 1.2 are presented in the next few chapters. This dissertation was written for
audience without a process design background. In this chapter, process issues that need to be
7
tackled when designing or modifying processes are presented. Chapter 3 provides
chapter discusses economic, environmental and health and safety concerns as well as tools
available for addressing these issues. Because several tools are available to handle certain
aspects of sustainability, this chapter reviews some of these tools and presents applicability
and drawbacks of existing tools used in the evaluation of process economics, environmental
environmental and social concerns are introduced, and the limitations and contributions
of each work are presented. Chapter 5 introduces the proposed framework. The
the previous four chapters into a novel systematic technique that addressed sustainability
concerns in chemical process design as shown in Figure 1.3. Lastly in Chapter 6, the
8
applicability of the proposed methodology and tool are demonstrated on the following
four industrial processes that have been simulated on ASPEN PLUS (version 22):
Dimethyl Ether
Acrylonitrile
Allyl Chloride
Methyl Chloride
Figure 1.3: Proposed Methodology for Addressing Sustainability Concerns During Early
Stages of Design
9
This research will contribute to sustainability development in chemical processes
as benefits such as reduced pollution, resource usage minimization and more economic
products will be thoroughly explored. The application of this research extends well
10
CHAPTER II
concepts. What tools are available for designing chemical processes? Also, what issues
are engineers faced with when designing or modifying existing chemical processes?
(retrofits), and or exploring new technology. The design process could be very
quite unique; there is never a single solution towards attaining a specific goal. As an
example, consider a process engineer that is tasked with creating a new manufacturing
process for dimethyl ether production (500,000 metric tons per year). The engineer is
already aware that dimethyl ether can be synthesized by the dehydration of methanol as
11
The first step is to develop a base case process flowsheet. Process flowsheet
synthesis is one of the important goals of chemical process design (Diwekar et al., 1992).
The best approach to solving this problem is to use the Douglas five step hierarchical
approach for process synthesis (Taal et al., 2003). This hierarchical approach consists of
The following sections show the implementation of the Douglas hierarchical approach on
According to Biegler, Grossman and Westerberg (1997), there are several factors
that influence whether a production process should be batch or continuous. One of these
factors is time. If there is an urgent demand for the product, and there is a competitive
market advantage, then a batch process could be selected. Another factor is quantity of
product. If the quantity of product needed is low such that a small amount is required a
few times a year, then a batch process could be selected. Another factor is limited
information. If the information required to design the process is limited, then the batch
process is the favorable option. Finally if the product is not profitable, then a batch
12
process is usually selected. For the dimethyl ether production process, reasons above are
place to create the product. When products are formed, there is never 100 percent
conversion of raw materials. Thus, separators will be needed to separate the un-reacted
raw material from the product. Figure 2.1 shows the input-output structure for this
process.
Methanol
Methanol
DME
Water DME
Methanol
Reactor Separator
Water
At this step, the recycle structure for the process is defined. Many processes have
un-reacted raw materials and by-products, and thus it is important to recycle the un-
reacted raw material for economic reasons. In the dimethyl ether example, there is some
un-reacted methanol which is recycled and sent back to the reactor, as shown in Figure
2.2.
13
Methanol
Methanol DME
Methanol DME
Reactor Water Separator
Water
This step involves the design and placements of separation units. Designers
The key thing is that the designer must determine the order of the separation columns and
their operating conditions. For the dimethyl ether process, the separation scheme
sequence is shown in Figure 2.3. Dimethyl ether is separated first because it has a lower
For any manufacturing process, energy usage for utilities and day to day operation
is one of the most expensive aspects. Therefore, investigating ways to conserve, integrate
and optimize the energy consumption is vital for economic reasons. This aspect of the
14
solutions the designer could generate in solving this problem. Such solutions will be
discussed in later sections of this dissertation. Once a process flowsheet has been
developed, the next stage of process design is to calculate the mass and energy balances
for the process of interest. The next section discusses the tools available for achieving
this objective.
]
2.2 TOOLS AVAILABLE FOR DESIGNING CHEMICAL PROCESSES
When a designer was faced with devising a new chemical process, six decades
ago, it took months or even years to design the process flowsheet for a particular process
(Motard et al., 1975). This was due to the complicated mass and energy balance
calculations that were needed to be hand-calculated for the process. It was not until the
late 50’s that a new tool called the chemical process simulator was developed to solve
Chemical process simulators are software tools developed to mimic the behavior
of an actual process plant. Chemical process simulators are best known for designing,
15
optimizing, testing and integrating new or retrofit processes (Casavant and Côté, 2004).
solve mass and energy balance for a processing unit (Motard et al., 1975). The process
simulator can be used to locate process malfunctions and predict process performance
(Seider et al., 2008). If the material stream is entered, the process simulator is able to
predict the process conditions for the waste, product sand by product streams. The
process simulator is also able to calculate information for equipment sizing and
and energy balances can now be calculated in a matter of days or hours. Today, most
chemical process simulators offer a graphical user interface where users can see the
objects being selected for the simulation and later run it. Over the years, several process
have been developed for the chemical industry. The proceeding sections discuss the
Process simulators have the same generic structure and have six main features
(Turton et al., 2009). The first feature, the component database, is where the constants
that are needed for calculating thermodynamic models are located. Another feature is the
thermodynamic model solver, which contains thermodynamic models that can predict
phase behavior. Additionally, the flowsheet builder is a graphic user interface, where the
designer is able to keep track of selected process equipment and flow streams. The unit
16
operation block solver is the fourth feature that has computational blocks for mass and
energy balance calculations and other design calculations. The data output generator is
the section where the results of the simulation run are provided. Lastly the flowsheet
solver shows the sequence of how the calculations in the simulation were completed and
The following are the three basic types of solution algorithm chemical process
characterizing process equipment are grouped and solved sequentially, starting from the
first to the last. In this approach, the output from one piece of equipment becomes the
input for the next, thus, this simulator requires detailed degree of freedom analysis before
it converges. One key assumption held by this type of simulator is that ―variables and the
process stream variables associated with streams entering the flow sheet are completely
defined and are not treated as unknowns (Stephenson and Shewchuk, 1986).
easy to visualize, very robust, even when complex process flow diagrams are simulated,
17
and it is able to reach rigorous convergence (Sloan, 2006; Baudet et al., 2008). Another
optimization problems. Due to the key assumptions held by this type of simulator, a
setback with this type of simulator is that it only runs in the forward direction, thus
limiting its application in complex design and optimization problems. Another limitation
to this type of simulation is that it does not perform at optimum standards when there are
several recycle streams (Britt et al., 1997). Popular examples of this type of simulator
ASPEN PLUS, a FORTRAN coded simulator, has been selected for simulating
Massachusetts Institute of Technology (Kotoupas et al., 2007). It can be linked with other
tools for external analysis. As this software is readily available at Oklahoma State
process are solved simultaneously using matrix techniques. In this approach, because all
unknowns are solved simultaneously, inputs can be changed anytime (Sloan, 2006). This
time is required to set-up all equations representing the process (Turton et al., 2009).
Therefore, because variables are not specified, the equation solving simulator is an
18
excellent option for a complex optimization problem. Examples of this simulator
solving and sequential modular approaches. In this approach all simulation modules are
solved simultaneously by a single routine. Thus, good initial guesses need to be provided
to ensure simulation accuracy (Kulikov et al., 2005). This approach is able to address the
limitations of the other types of simulators. Several researchers (Mahalec, Kluzik and
Evans (1979), Patterson and Rozsa (1980), Fagley and Carnahan (1983), Byrne and
Bogle (2000) have done extensive work on developing simultaneous modular simulators.
Once a process has been simulated, an engineer must still investigate ways to
improve performance. The next section discusses some of the concerns engineers must
This section covers the issues designers are faced with when designing chemical
processes. Optimization applications are introduced as well as how they are used to
19
2.3.1 Process Design Issues
Every designer must ensure that any newly proposed project is making a profit.
Economics has been the number one driving force for building any process, thus trying to
ensure that the process is running optimally can really ensure optimum returns. Chemical
improvement involves evaluating the process flowsheet and ensuring that the process is
completing studies that involve varying different types of equipment, varying operating
Some of the questions a designer might ponder upon during the process
Should one consider a batch reactor, plug flow reactor or continuous stirred
Until recently, it was the job of a process designer to ensure that all process
conditions were optimized to meet economic goals only. With the advancement of strict
met both environmental standards and economic goals. For a long time, most
20
considered at later stages of design even as late as the operation stage. In essence, waste
was generated and treated from air, water, and land sources. One problem with this type
of plan is that it is very unlikely that there will be significant environmental protection
(Chen and Shonnard, 2004). With rising concerns about limited resources, wastes must
activities that have caused drastic consequences leading to air, water and soil pollution
must be prevented. One thing to keep in mind is that environmental regulation fines are
high, the ability to directly reduce unnecessary resource consumption and waste treatment
Safety is another aspect an engineer must consider when creating a new process.
Most chemical processing plants deal with hazardous chemicals and are operated at high
temperatures and pressures. Thus, the health and wellbeing of employees and
incorporated into design. Exposure to chemicals, fire and explosion are the major safety
concerns in industry because such events lead to drastic health hazards. Exposure to
breathing in chemicals during leaks and adsorption through the skin by accidental spills.
Drastic health hazards from industrial tragedy are a social issue of concern because they
can result in shortened life expectancy and even instant death. For example, the Bhopal
industrial catastrophe, which occurred in 1984, involved the release of methyl isocyanate
gas and other toxins at a Union Carbide plant is one of the largest disasters in the history
of the chemical industry. Over 10,500 people died from this incident, and over 50,000
21
people suffered from various illnesses such as visual impairment, respiratory problems
It is evident that industry still has a long way to go in terms of reducing workplace
fatalities. In 2008, exposure to harmful substances or environment and fire and explosion
accounts for about 12% of deaths in the private industry (United States Bureau of Labor
Statistics, 2008). Although workplace fatalities has reduced over the years, as shown in
Figure 2.4, the numbers are still at an alarming high and must be reduced at all costs.
Therefore, it is important for designers to also incorporate safety into chemical process
design.
7000 6632
6331 6275 6202 6238
6217
6055 6054
5920 5915
6000 5764 5734 5840 5657
5534 5575
5071
Number of Fatal Injury
5000
4000
3000
2000
1000
Year
Figure 2.4: Work Place Fatalities from 1992- 2008 (U.S Bureau of Labor Statistics,
2008)
health and safety concerns into chemical process design is optimization. Optimization
22
provides several opportunities to prevent safety losses, reduce environmental impact
while maximizing economics. This could be via reducing energy costs and wastes, while
operating at safer operating conditions. These objectives can be conflicting and must be
handled using an appropriate technique. The next section provides an overview of the
various optimization methodologies that have been incorporated into chemical process
design.
2.3.2 Optimization
processes for conflicting objectives is optimization. When economics was the major
engineering (Storti et al., 1993; Storti et al., 1995; Dunnebier and Klatt, 1999; Karlsson et
al., 1999; Wu et al., 1999). As discussed earlier, other concerns such as environmental
impact and social concerns must be accounted for by using a technique called
optimization problem because a wide range of concerns, as shown in Table 1.1, must be
addressed. Designing and incorporating all the concerns tends to be difficult because of
23
which economic, environmental and social objectives are formulated is the ideal way to
generating methods and preference based methods, as shown in Figure 2.6 (Miettinen,
optimization technique where one or more solutions are created without the assistance of
the decision maker to input preferences before the optimization problem can be solved.
techniques, and a posterior methods using pareto optimization techniques are the three
prioritized and preferences articulation by the decision-maker are not required (Marler
and Arora, 2004; Rangaiah, 2008). Examples of this method include global criterion
methods and neutral compromise solution. For more information about this approach, the
article by Marler and Arora (2004) can be consulted. One application of Preference
method was in the work by Krokida and Kiranoudis (2000) who applied this approach in
the minimization of product color and unit cost for a fluidized bed reactor.
has been used to address multiobjective optimization. This involves combining multiple
objectives into a single scalar objective by using weight factors. Scalarization can be
24
classified into weighing and epsilon-constraint methods (Rangaiah, 2008). According to
Kim and de Weck (2004), the traditional way to tackle the solutions to vector
optimization problems is to use the weighted-sums method which solves ―the optimal
solution is solved one by one by systematically changing the weights among the objective
functions.‖ The method however gives poor results near the convex region. Kim and de
Weck (2004) proposed the adaptive weighted-sums which give optimum solutions near
the non- convex solution area. This new proposed method focused on ―unexplored
regions by changing the weights adaptively rather than by using a priori weight selections
Generating Perference
Methods Methods
A-posterior Method
No Preference A-posterior Methods
Multiobjectve A Prior Methods Inteactive Methods
Methods (scalerization)
approach
Epsilon constrained method was first introduced by Haimes, Ladson and Wismer
(1971) but other researchers such as Chankong and Haimes (1983), Ehrgott and Ruzika,
(2008) and Berube, Gendreau and Potvin (2009) have also studied this approach. This
method involves a process where one objective is minimized and the other objectives are
converted to inequality constraints (Ehrgott and Ruzika, 2008). One group of researchers
who has used the epsilon constrained approach is Hugo et al. (2004), who maximized net
present value, minimized environmental impact and carcinogenic plant emissions for the
25
supply chain of the vinyl chloride monomer and ethylene glycol. Also Hoffmann,
Hungerbuhler and McRae (2001; 2004) maximized economic benefit and minimized
environmental impact using the epsilon constraint approach for the hydrogen cyanide
production process. One limitation of the epsilon method is that it is inefficient and
limitations. Scalarization can result in the loss of some optimum solutions because
weighting factors are assigned randomly (Haimes, 1977; Chankong and Haimes, 1983;
Bhaskar et al., 2000; Zhou et al., 2000). To address this limitation, multiobjective
optimization problems are solved using a vector function approach where each objective
techniques (Marler and Arora, 2004). In this approach, many Pareto optimum solutions
are presented and the decision-maker selects the optimum solution based on his/her
time since the decision maker only selects one solution. Two examples of this approach
Non-dominated sorting genetic which mimics the process of natural selection and
Information about this approach can be consulted from papers by Srinivas and
Kalyanmoy (1994), Kalyanmoy, Samir et al.(2000) and Al Jadaan, Rajamani and Rao,
(2008). This approach is better than traditional optimization methods because objective
functions are used directly. This approach has been applied to a semibatch reactive
26
crystallization process in which the weight mean size is maximized and the coefficient of
variation is minimized in order to find the optimum feed addition profile (Sarkar et al.,
2007). Multiobjective simulated annealing is a process where the search method for
solving the optimization problem is an imitation of the cooling of molten metal. This
approach follows the Boltzmann probability distribution function and is a useful method
for finding optimum solutions for cooling procedures (Bhaskar et al., 2000).
Methods. A Prior Methods is an approach that requires the decision maker to specify
advantageous because it is efficient since one Pareto optimum solution will be provided
based on the decision-makers preference. Critics of this approach believe that this
approach can be difficult to utilize if the decision maker has no knowledge of the
optimum values for the problem (Rangaiah, 2008). Two examples of this approach are
according to importance and solved in sequence. The limitation of this method is that it
does not satisfy the Kuhn–Tucker optimality conditions1 (Karush, 1939; Marler and
Arora, 2004). Meadowcroft, Stephanopoulos and Brosilow (1992) used the lexicographic
1
For more information on the Kuhn–Tucker optimality conditions, the thesis by (Karush, 1939) can be
consulted.
27
defined as a process where a solution is generated by minimizing the deviation of the
weighted average of the objective function by using goals set by the decision-maker.
Although this approach allows multiple objectives, limitations of this approach are that it
locates inferior solutions and it is difficult to homogenize values. Goal programming has
been implemented in waste management for process plants (Chakraborty and Linninger,
2002a; Chakraborty and Linninger, 2002b). In this research, costs and environmental
Interactive Methods require continuous interface with the decision maker. This
approach eases the complexity of problems with several objectives since only a few
Pareto optimal solutions are presented due to the decision-maker specifying preferences.
Therefore this method requires time and high cognitive load from the decision maker and
hence might not be realistic approach. Interactive methods have been applied to the
optimization of a paper mill recovery system where mass flow rate of steam, heat
exchanger area and cooling/heating needs are minimized (Hakanen et al., 2006). Also
this method was used to minimize solvent consumption, and maximize product purity and
methodology for the design of more economical and environmental friendly processes
28
developing process models, establishing and implementing pollution prevention
techniques (Dantus and High, 1996). To address the uncertainty involved in addressing
implemented (Dantus and High, 1999). The capability to reduce pollution generated in a
chemical process was achieved. Also, an economic based model for waste minimization
and energy reduction in the chemical industry was developed (Dantus and High, 1996).
impact and profitability was analyzed (Gollapalli et al., 1999; Gollapalli et al., 2000).
social concerns. In this work, he thoroughly explored the sustainability concept and
processes (Jin and High, 2004a). In addition, a generic evolutionary algorithm for
searching for the global optimal sustainability solution over a set of different process
29
alternatives was proposed. With this algorithm, engineers are able to select the most
select the most optimum sustainable process that minimizes material and energy
method can handle intricate scenarios one level at a time by using the results of a
previous level, making the process easier to unravel. The process of hierarchy must be
for sustainability, the ultimate solution is not a unique one, rather there are several
For example, a certain alternative for a process may be the most economical, but not
necessarily meet environmental, health and safety standards. Another alternative may be
evolutionary optimization technique has the ability to give results in multiple solutions as
single objective optimization method and give results in a one point solution (Zitzler and
designers developing industrial processes are able to meet the key objective, which is
economic benefit while having the flexibility to modify their processes for environmental
30
In the research of Singh and Lou (2006), an economic index to be maximized and
production process, where profit was maximized and environmental impact was
minimized (Sun and Lou, 2008). A Monte Carlo analysis optimization framework was
system using economic, energy, environmental and sustainable costs as constraints while
them for maximum net present value and minimum environmental impact.
Environmental impact for the chemical supply chain was assessed by using a life cycle
assessment tool, Eco-indicator 99 (Gonzalo and Grossmann, 2009). In this approach, net
present value was maximized while environmental impacts were all converted to
constraints using the epsilon approach. Also, uncertainty has also been addressed in the
inventory used for the life cycle assessment of the chemical supply chain.
as well as social qualitative indicators was proposed to design processes for sustainability
(Othman et al., 2010). To address economic concerns, calculation of net present value
and discounted cash flow was the suggested approach. The waste reduction algorithm
indicators were used to tackle social concerns. For each suggested metric or indicator,
31
weights were assigned based on relative importance of the issue at hand. A four step
inventory analysis of process, sustainability assessment and decision making based on the
2.4 SUMMARY
This chapter presented the issues engineers face when developing a new process
as well as the tools available to address these concerns. The chapter also discusses the
concerns that must be addressed during process design, and optimization techniques that
could be used to address these issues. There are several tools available for mimicking
complexes processes, but in this research, ASPEN PLUS, a FORTRAN coded simulator,
has been selected for simulating chemical processes. This sequential chemical process
simulator has been chosen because it is readily available at Oklahoma State University.
In addition to providing the results of mass and energy balances; it could be used to attain
the following: complete steady and dynamic mode calculations, size equipment and
provide economic analysis results, perform sensitivity analysis and optimization. It can
also be linked with other tools for external analysis. ASPEN PLUS will be used to
simulate and optimize chemical processes that will be retrofitted for sustainability
32
CHAPTER III
3.1 INTRODUCTION
and safety assessment tools that are currently used for evaluating the impact of chemical
processes on the environment and society. The features and applicability of the tools are
illogical to embark on a project that does not assure profit. Therefore, it is necessary to
evaluate the manufacturing costs and product revenue of any process to determine
viability. The cost of manufacturing is determined by capital, labor, utility and raw
material costs. Depending on the information available, the economic analysis can be
determined by using methods such as payback period, rate of return on investment and
33
Payback period, as shown in Equation 3.1, is defined as the time frame a project
must achieve break even, i.e. pay back all expense embarked on the project. Rate of
return (ROI) on investment is the ratio of the net income to the capital investment, as
shown in Equation 3.2. Net Present Value (NPV) for a project is a sum of all the positive
cash flows subtracted from the initial investment over a time period at a particular interest
rate. In the past, economic analysis of processing plants was done by hand; this could
become cumbersome for process plants with several pieces of equipment, sometimes
leading to inaccurate results. Capital cost is the bulk of the estimation that is required for
Cost of Investment
Pay Back Period = Cash flow per period (3.1)
Net Income
ROI = Cost of Investment (3.2)
feasibility studies and assessments. Thus the next section discusses the following reliable
tools for profit estimation: Capital Cost Estimator (CAPCOST), Aspen Process Economic
34
Analyzer, HYSYS Spreadsheet, Profitability Analysis and The Design Option Ranking
Tool.
Guthrie (1974) and Ulrich (1984) have been implemented into the tool. CAPCOST is a
Microsoft Excel / Visual Basic computer program that can be used for estimating the
capital and operating costs for a chemical process. One advantage of CAPCOST is that it
an inbuilt Monte Carlo Simulation. CAPCOST has served as a useful capital cost
estimator for researchers, professors and students (Abedi, 2007; Ferrandona et al., 2008;
Visual Basic computer program that can evaluate the economics of a chemical process.
The types of analysis that can be completed include rate of return on investment, net
present value and investors’ rate of return. The spreadsheet is unique in that it is able to
complete a sensitivity analysis on variable costs. The profitability analysis software has
also been used by researchers, professors and students (Murthy et al., 2006; Abuschinow
et al., 2009).
35
3.2.3 HYSYS Spreadsheet
simulator. This tool has many modeling applications such as optimization, simple
calculations such as pressure drop calculations and economic calculations (Prasad, 2009).
In this tool, users can input equations for sizing and capital costs evaluations into the
simulator, and hence results of the economic calculations are updated automatically when
flowsheet variables are changed. This option has not been widely used in assessing
however one researcher used this tool to assess the economics of four biodiesel
The Aspen Process Economic Analyze, formally known as the Aspen Icarus
al., 1999). The software is a sophisticated tool that is able to collect process data from
process simulators such as ASPEN PLUS, CHEMCAD, HYSYS, HYSIM, DESIGN II,
WinGEMS and PROII (Taal et al., 2003). This economic analyzer is able to use process
data to accomplish the following: size process equipment, provide results of capital,
The tool is able to estimate profitability analysis for various process options. As
this software has an expert system analysis, most of the inputs are obtained from
imported data from a process simulator. The software maps selected equipment, sizes it
36
and provides the capital and operating costs. The Aspen Icarus Economic Analyzer is a
widely accepted assessment tool that has been used by industry and academia (Adams
and Seider, 2005; Smejkal et al., 2005; Cornelissen et al., 2006; Giorgio et al., 2006;
Ordorica-Garcia et al., 2006; Ringer et al., 2006; Fan and Lynd, 2007; Persson et al.,
(Toth, 1995). This tool is unique in that it is able to incorporate stochastic and multi-
criteria decision analysis (Toth, 1995). The tool is able to calculate equipment costs,
operating costs, income and other expenses as well as perform a full economic analysis
by providing economic results such as payback period, net present value, and fixed
capital investment. The DORT software was used by a few researchers at Michigan
Technological University (Toth and Barna, 1996; Chen and Shonnard, 2004). For
example, the DORT software has been integrated into the Simultaneous Comparison of
Five different economic assessment tools were presented in this section. All
assessment tools can evaluate capital costs, with the exception of the Profitability
project economics, in order to use the tool, the engineer will need to calculate capital
37
costs by hand or incorporate one of the other capital cost estimating software such as
parameters vary with different conditions. It is also able to determine the net present
value for a chemical process when economic parameters are specified. However, one
there are changes in process conditions, the user will manually have to update the input
The limitation of the HYSYS spreadsheet is that even though it can estimate
capital costs, all equations for capital costs have to be inputted manually into the tool.
This could be very cumbersome and time consuming. However, the pros to using the
software is that once the equations have been incorporated, the tool will automatically
estimate capital cost with any change in process conditions because it is linked to the
that it does not evaluate full blown economic analysis such as net present value.
The DORT Tool and Aspen Process Economic Analyzer are advantageous
because they can link to process simulators and import mass and energy balance data for
capital cost estimation making it very convenient for the process engineer. These
software tool are also able to complete full blown economic analysis involves estimating
net present value and discounted flash flow. However, one limitation of the DORT
software and Aspen Process Economic Analyzer is that, unlike CAPCOST, they do not
38
Because the ASPEN process simulator will be used for simulating processes in
this research, the Aspen Process Economic Analyzer has been selected as the tool for the
economic assessments.
introduced and the tools available for addressing these impacts are discussed.
Environmental issues have been a major topic of discussion since the early
1960’s. Activities leading to a more comfortable lifestyle have led to pollution of air,
water and land. Air pollutants such as particulate matter, lead, sulfur dioxide, carbon
monoxide and nitrogen oxide are prone to causing respiratory diseases such as asthma,
bronchitis and emphysema, and even mortality in infants and aging adults (Hersh, 2005).
Pollution of water threatens and affects access to clean portable water and affects the
To protect human life and the environment, the Clean Air Act and Clean Water
Act were established by the United States Congress. Although amended in 1990, the
Clean Air Act, established in 1970, includes standards set and regulated by the EPA to
ensure the reduction of certain harmful air pollutants (United States Environmental
Protection Agency, 1990). This act certifies that industrial facilities, car manufacturers
and refineries are designing products or processes that meet regulated standards. The
Clean Air Act ensures pollutants are emitted at a regulated standard. In 1977, the Clean
39
Water Act, was established to guarantee water quality standards are met by eliminating
the release of toxic materials into water sources (United States Environmental Protection
Agency, 1977).
onion diagram (Figure 3.1) proposed by Smith and Linnhoff (1988), in the chemical
industry, pollution arises from process equipment and utilities. There is never a 100
percent conversion of raw materials into products. By-products and intermediates are
formed, raw materials and not completely converted to products and utilities are not used
efficiently, which all contribute to waste generation. Even when separators are in place,
some products and raw material might not be recovered completely and hence, contribute
to waste generation.
Reactor
Utilities
Figure 3.1 :Onion Diagram Showing Wastes from the Chemical Processing Industry
(Smith and Linnhoff, 1988)
If pollution issues are not handled appropriately, it could lead to expensive fines
and even law suits. Hence, pollution prevention and mitigation strategies have become
an integral aspect of the design process. Several methodologies exist for handling
40
pollution issues. These include end of the pipe design and source reduction tools,
End of pipe treatment involves using methodologies that separate and treat waste
and polluted steams. This treatment effort began as early as the early 70’s, and there are
so many researchers who have introduced approaches that have benefited the process
industry. Notable approaches include mass exchange network (Miguel and Vasilios,
1992), heat induced separation network (El-Halwagi et al., 1995), energy induced
separation network (Dunn et al., 1999) and membrane separation network where
pollutants are removed from waste streams by using separation equipment (El-Halwagi,
1992). These ends of the pipe treatment options can cost millions of dollars, and source
Source reduction technology can include introducing new reaction pathways that
create the product in an environmentally friendly way, using more benign reactants and
solvents, implementing heat integration techniques to reduce energy usage and emissions,
recycling waste water and un-used reactants, converting pollutants into useful products
and implementing heat and energy induced waste minimization methodologies. Even
environmental regulations are being met and economic liability is kept at a minimum.
41
Environmental impact assessments accomplish the following: allow the
requirements are met, reduce health risks as well as reduce ecological damage. Several
environmental concerns are discussed in literature and in this dissertation. The next
Global warming, defined as the change in weather over a long period of time, is
exist, carbon dioxide (CO2) is the major contributor to global warming. CO2 is emitted
from various sectors such as the residential, commercial, industrial, transportation and
electricity generation as shown in Figure 3.2. As shown in the graph, in 2008, the
transportation sector accounted for 33%, industrial sector accounted for 27%, the
commercial sector accounted for 19% and the residential sector accounted for 23% of the
CO2 emissions. CO2 in the atmosphere has increased by 35% since 1850 (United States
CO2 emissions has caused tremendous environmental and health concerns. There
has been an increased awareness towards global climate change in the last few years.
Major key players including industry, academia, the United States Government and the
United Nations are all concerned with global climate change. The effect of global
climate change have been noticed around the world with rapid rising temperatures
leading to the melting of ice in the arctic region, heavier rainfall leading to floods in
42
certain regions of the world, increased hurricane frequency, droughts, decreased
biodiversity and threats to human health due to rapid spread of diseases from warmer
temperatures (Gardiner, 2004). Health issues linked to global warming include deaths
warmer temperature.
2000
1500
1000
500
has become necessary to determine ways to reduce greenhouse gas emissions. On the
personal level, individuals can reduce their footprint by reducing energy consumption,
using energy saving bulbs, replacing filters in air conditioners, using energy efficient
appliances and reducing fossil fuel consumptions by carpooling, using fuel efficient cars
and using public transportation. On the industrial level, companies can determine ways
to reduce greenhouse gas emissions by designing processes that minimize wastes and
emissions. On the academic level, research can be done to improve carbon capture
43
techniques as well as development of more efficient energy and fuel appliances. On the
governmental level, incentive based policies such as implementing a carbon tax i.e.
taxing companies who emit certain levels of CO2 and carbon trade and cap, a process
were companies are allowed to trade and buy emission limits from each other are also
3.3.1.2 Acidification
generation and other industrial activities can result in the deposition of acidic causing
chemicals that reduce alkalinity and increase acidity of the environment including land
and water to pH levels below 5 (Doney et al., 2007). Acidic chemicals such as sulfuric
acid (H2SO4) and nitric acid (HNO3) can be deposited dry or wet. Wet deposition
commonly known as acid rain, fog or mist, is damaging to the ecosystem, resulting in
stunted plant growth, building material decay, poor health of organisms and even
affects different organisms as shown in Figure 3.3. Some of the health problems of
such as on smoke stacks and exhaust pipes. Scrubbers can be used to eliminate sulfur
oxide emissions from power plant stacks. Natural gas can also be used instead of coal for
running power plants because it contains fewer pollutants. To reduce pollution from
44
exhaust pipes, efficient working catalytic converters should continue to be used in cars.
Using alternative energy such as nuclear, wind, batteries and fuel cell is one other vital
Mayfly
Snail
CrayFish
Clams
Slamanders
Frogs
Perch
Bass
Trout
0 1 2 3 4 5 6 7
pH
3.3.1.3 Eutrophication
unwanted nutrients include: agricultural and husbandry activities such as fertilizer usage;
industrial activity due to emission of nitrates and phosphates; sewage from towns and soil
erosions. The eutrophication cycle shown in Figure 3.4, illustrates that the outcome of
phytoplankton that will compete for nutrients with submerged aquatic vegetation.
every 24 hours (Wright, 2007). Once nutrients become scare, survival becomes difficult
45
and the end result is accumulation of dead phytoplankton which leads to bacteria growth.
Bacteria growth leads to depletion of oxygen which affects the health of larger aquatic
organisms sometimes leading to suffocation and death. Contaminated water sources due
humans because water quality becomes poor and even toxic, limiting the access to clean
portable water. Turbid and cloggy water conditions, also halts life events such as
Growth of
Bacteria
•Nutrient •Depletion of
Enrichment •Accumulation dissolved
of deritus oxygeen
into water sources, improving waste water treatment methodologies, banning the use of
manure and soil conservation practices in order to reduce erosion (Conley et al., 2009).
Also treatment options include applying herbicides to lakes and ponds, implementing
phytoplankton growth and drawing down dammed lakes to kill aquatic plants.
46
3.3.1.4 Photochemical Smog Formation
when pollutants such as nitrogen oxide and volatile organic carbon react with sunlight to
form a haze like appearance in the atmosphere. Sources of nitrogen oxide include
emissions from industrial plants; coal fired power plants, exhaust pipes of vehicles.
pesticides, and biogenic sources. At certain weather conditions i.e. when advection and
*R = Hydrocarbon.
ozone and peroxyacetyl nitrate) curb photosynthesis and hence reduce plant growth.
Health effects associated with photochemical fog formation include respiratory and
cardiovascular issues, eye irritation, coughing, wheezing and increased cancer risk
smog, efficient catalytic converters and lower combustion temperature should be used
because it reduces the formation of nitrogen. Alternative fossil fuels such as liquefied
47
petroleum and compressed natural gas reduce the emission of volatile organic compounds
short amount of time and these include, water, animals, insects, reptiles, plants, trees,
water, grass, solar and wind energy. Fossil fuels, oil, coal; copper, diamonds, natural gas,
iron ore, minerals, gold, silver, platinum and rocks are examples of non-renewable
resources i.e. resources that take millions of years to regenerate if used up.
Environmentalists are most concerned with non-renewable resource depletion. This type
reserves in a sustainable manner where we are building and improving upon technology.
This could include using alternative energy to reduce the burden of fossil fuels, replanting
trees, eliminating wastes and reducing our energy footprint by using sustainable options
gradually diminished. Chlorofluorocarbons (CFCs) are the major chemicals that cause
ozone depletion. CFCs are found in refrigerants used in air conditioners and heat pumps.
They are also found in plastic foam production, electronic industry for computer parts
48
and pressurizing agents in aerosol cans (Wright, 2007). The breakdown of ozone is
depicted in the Equations 3.8-3.10 below. CFC reacts with sunlight and breaks down into
chlorine and a smaller CFC molecule. Chlorine reacts with ozone to form oxygen
molecule and chlorine oxide. This is the reaction that depletes the ozone layer. A third
reaction takes place where two molecules of chlorine oxide combine to form chlorine and
more oxygen.
Table 3.2: Ozone Depletion Causing Chemicals Phase Out Dates (Site, 1997)
Chemicals Phase out date
Developed Country Developing Country
Halons 1994 2010
CFCs, chloroform 1996 2010
Carbon tetrachloride 1996 2015
Methyl bromide –
Freeze 1995 2002
Phase-out 2010
HCFCs –
90% cut 2016
Phase out 2030 2040
The depletion of the ozone layer is an issue of concern because it protects us from
harmful ultraviolet rays. Ultraviolet rays damage proteins and DNA molecules of all
organisms and could lead to complications such as sun burn and skin cancer in humans,
poor development in aquatic organisms such as fish, shrimp, crab, amphibians and other
depletion by phasing out ozone depleting substances as shown in Table 3.3. Table 3.3
shows fazing schedule for certain ozone depleting chemicals for developed and
49
developing countries. Regulating emitted ozone causing chemicals and ensuring that
refrigerants and extinguishers are recycled appropriately are some of the other ways to
The previous section presents a range of environmental concerns that are caused
by manmade activities. The key question is how exactly can scientists evaluate the
environmental impact processes and products? So much research has been done to
addresses these environmental issues. Pioneers in the process industry have considered
pinch analysis (Ferrandona et al., 2008; Seay and Eden, 2008), waste minimization
optimization approach (Dantus and High, 1999) and environmental impact assessment
tools to tackle these concerns. It is clear that in order to address environment concerns;
all feasible mitigation options must be considered. However it is important to have tools
impact assessment tools exist and the features and applications of the following
assessment tool are discussed below: Tool for the Reduction and Assessment of Chemical
Environmental Fate and Risk Assessment Tool (EFRAT) and Minimizing Environmental
Impact (MEI).
3.3.2.1 Tool for the Reduction and Assessment of Chemical and Other Environmental
Impacts
The Tool for the Reduction and Assessment of Chemical and Other
50
associated with using the product of interest. This software is one of the many Life Cycle
Assessment (LCA) tool available. LCA can be defined as an incorporated study of the
Keeping track of the material, energy, wastes and toxic emission from the product
or process.
The TRACI software serves as a decision making tool where options can be
compared and the product with the least environmental impact can be considered. The
tool was developed for product evaluation during the design stage (Bare et al., 2002). In
TRACI, the user has the ability of selecting any of the following type of LCA (Umited
Cradle to Grave: Defined as a LCA approach that includes all stages from raw
Cradle to entry gate: Type of assessment that looks at upstream supplier and
Entry gate to exit gate: An assessment of the environmental impact when the
51
The TRACI software can be divided into four major categories: inventory of
Global warming
TRACI has been used be several researchers (Wu et al., 1999; Kim and Dale,
2005; Morris, 2005; Bare et al., 2006; Güereca et al., 2007; Singh et al., 2007; Thorneloe
et al., 2007; Kim and Dale, 2008; Morris and Bagby, 2008; Zhou and Schoenung, 2009).
It has been incorporated into the Environmental Knowledge and Assessment Tool
(EKAT), a screening tool for environmental and health impacts (Boguski et al., 2007).
Although TRACI has been used by researchers it is has some limitations. One limitation
software. Also TRACI can only be used as a screening tool because risk estimates are
not provided in this tool (Bare, 2002). Lastly uncertainty and variability assessments
52
environment impact of chemicals found in industrial processes (Chen and Shonnard,
2004; Seay and Eden, 2008). The WAR uses an index based approach to characterize
potential pollution reductions using report files from a process simulator such as ASPEN
PLUS or CHEMCAD. The tool measures the environmental impact of emission of mass
and energy for any simulated process (Cabezas et al., 1999). In the WAR, nine impact
depletion, and photochemical oxidant formation, three human toxicity effects from air,
water, and soil, and ecotoxicity effects on aquatic and terrestrial environments.
The WAR algorithm has been used my many researchers to evaluate the
environmental impact of several processes (Mallick et al., 1996; Young and Cabezas,
1999; Cardona et al., 2004; Eliceche et al., 2007; Li et al., 2007; Carvalho et al., 2008;
Quintero et al., 2008; Monteiro et al., 2009). Although the WAR algorithm has been
widely used, Fermeglia, Longo and Toma (2007) suggest that the WAR algorithm is
limited because it only has toxicology data for 1700 chemicals and some chemicals might
not be covered in the software. Also, the WAR algorithm is not a full LCA and it only
focuses on the manufacturing step while incorporating the impact of energy consumption
The Environmental Fate and Risk Assessment Tool (EFRAT) was developed by
Shonnard and Hiew (2000) is a ―gate to gate‖ assessment. The tool is able to evaluate the
air emission estimation, environmental fate and transport, and relative risk assessment.
53
In order to complete these calculations, process simulator data such as number and sizes
piece of equipment, utility type and consumption and production rate are supplied to the
EFRAT software. With this information, an overall environment index can be calculated
for a process. The results of the EFRAT tool can be used for decision making, i.e.
The limitation of the EFRAT software is that it is a partial LCA since it is a gate
to gate assessment. Despite the limitations, EFRAT has been used by several researchers
developing other environmental tools (Chen et al., 2001a; Chen et al., 2001b; Chen et al.,
provide assessment resources for environmental, health and safety risks associated with
material and systems used in creating products. The tool is able to provide emissions
and safety compliance issues from chemicals, toxic chemical air concentrations, conduct
environmental impact assessment using indexes found in TRACI. The tool also has links
to other external databases such as toxicology and hazardous chemicals. Because this a
fairly new tool it has not been used by many researchers. One researcher incorporated
the screening tool found in the EKAT tool into another tool called the online emergency
54
preparation and green engineering (EPGE) tool in order to identify green solvents
impacts in batch and continuous chemical processes. The tool has an embedded LCA
with an optimization framework that accounts for economic concerns as well (Stefanis
and Pistikopoulos, 1997). The issues addressed by the software include the
environmental risks associated with process wastes, leaks and fugitive emissions.
Several researchers have used this tool to evaluate environmental impact (Stefanis et al.,
Srinivasan (2002) for qualitative waste minimization assessment. This tool provides a
systematic procedure for identifying ways to reduce emissions, solid waste generation
and utility wastes so that non experts in the area of waste minimization are able to
complete the assessment. The tool is able to classify process steams such as raw
materials, solvents, cooling, heating agents, and products as valuable, material impurities
and waste byproducts as worthless. The tool is able to use imported mass and energy
balance data from the HYSYS Process simulator to complete the waste minimization
55
3.3.2.7 Summary of Environmental Impact Assessment Tools
summarizes the key features and differences between the environmental impact
assessments tools discussed earlier. The ENVOP Expert system is not compared in Table
3.3, because it is quite different from the other tools. Unlike the other tools, it used for
deducing waste minimization strategies and not for environmental impact assessment.
The ENVOP Expert system can be linked to data from a process simulator to determine
As for the other five environmental impact assessment tools, the WAR and EFRAT
are advantageous because they have the ability to get input from a process simulator used
in completing the the environmental impact assessment. One pro of TRACI, MEIM and
EKAT is that it takes into account the entire life cycle stages for environmental impact.
One advantage of EFRAT and EKAT is that they all have the capability of conducting air
emission modeling. In all, these tools could be quite complicated and might not be
appropriate for early stages of process design. Therefore an appropriate tool is developed
56
3.4 SAFETY AND HEALTH EVALUATION TOOLS
In this section, safety and health issues relating to industrial activity are
introduced and the tools available for addressing these impacts are discussed.
This year, we approach the 26th anniversary of the Bhopal tragedy, the largest
industrial accident to date. This catastrophe, caused by the release of methyl isocyanate
gas from a Union Carbide plant, led to 10,500 deaths, long term environmental issues and
liabilities (Wright, 2007). Months after the incident, management in Union Carbide
probably completed a safety review, investigating what could have been done differently
to avoid the tragedy. The era of waiting for an incident to occur and then implementing
other preventive measures is long gone and is no longer acceptable to society. For
example, after the Fixborough, England cyclohexane release that killed 28 and injured 99
people due to the collapse of a pipe leading to the escape of 35 tons of cyclohexane, it
was determined that calculations were not completed to determine if the pipes could
The key issue is that these incidents could have been prevented. Some notables
approaches to preventing safety incident include using less hazardous materials, using
devices such as safety valves, emergency shutdown procedures and ensuring operating
procedures are incident and injury free. Every new and existing manufacturing facility
must now complete a health and safety assessment to predict and prevent an unsafe
following: mechanical crushings, dropped objects, corrosive burns, acute poisoning due
57
to toxic chemical exposure, asphyxiation, fire and explosion. Whenever there is a
catastrophic event, the cost is drastic. Companies could lose millions of dollars from an
unexpected shut down; millions of dollars in fines imposed by the government will have
to be paid back for the damage inflicted on the environments and millions of dollars
might have to be paid to employees to compensate them for chronic health effects and
even incapacitation.
One cannot over emphasize the importance of completing safety risk assessments
during the early stages of process design as it has the potential of preventing dreadful
incidents. Companies are now required to conduct safety analysis that addresses the
following concerns: hazard that can occur, probability of the hazard to occur and impact
of the hazard (Arendt and Lorenzo, 2000). The assessment must also consider the risks
of long and short term exposure to chemical substances to employees and the public
living in close proximity to the chemical facility. The subsequent sections discuss the
different types of chemical processing plant accidents and tools available for predicting
events that can result in financial and personal loss. In processing plants, accidents can
58
such as vacuum problems, blocked out let valve, cooling water failure can
lead to an incident.
When any or the combination of the events mentioned above occurs, several of
the following incidents can occur at the right conditions: fires, explosion and toxic
3.4.1.2 Fires
Fires occur when oxygen reacts with a fuel at the proper temperature in the
presence of heat and mixing. The potential for a substance to cause fire is determined by
its flammability limit, flash point temperature, burning velocity, ignition energy and auto
ignition temperature (Flynn and Theodore, 2002). For most fires to occur there must be
an ignition source. Figure 3.7 shows the typical ignition sources for industrial fires,
Theodore, 2002). As shown in the figure, electrical accidents is the major ignition source
accounting for 23% of industrial fires while chemical action, lightening, static electricity
According to the National Fire Protection Association, fire can be classified into
59
Class A Fires: These are fires that result from the burning of solid materials e.g.
wood, paper, cloth, trash etc. This type of fire can be extinguished by water
Class B Fires: These are fires that occur as a result of a vapor-air mixture over
flammable liquid e.g. gasoline, diesel etc. This type of fire can be stopped by
25%
20%
15%
10%
5%
0%
Figure 3.7: Ignition Sources of Industrial Fires (Flynn and Theodore, 2002)
Class C Fires: These are fires that result from electrical equipment failure and can
vaporizing liquid.
Class D Fires: These are fires that occur in combustible metals e.g. magnesium
and aluminum etc. This type of fire can be quenched by using graphite based
extinguishers.
60
To prevent industrial fires, spills should be cleaned up immediately, leaks should
be sealed off as soon as possible and equipment that tends to overheat should be insulated
disposed accordingly and not stored on site. Once the fire occurs, it is important to
identify the class of fire in order to quench it with the correct material.
3.4.1.3 Explosions
which results in extremely high temperature and gas release. Accidental explosion
include condensed phase, combustion, pressure vessel and vapor cloud explosions (Flynn
and Theodore, 2002). The tendency for a substance to cause an explosion is determined
by its explosion limit. The explosion limit is the range of concentration that explosion
can occur. The range is bounded by the upper explosion limit (UEL) and the lower
explosion limit (LEL). Plant explosions are mainly caused by equipment failures, or
incorrect operational procedure. For example when two incompatible chemicals are
reacted, an explosion can occur. Vessel rupturing due to pressure build up in a gaseous
exothermic reactor can lead to an explosion. Inappropriate vessel material for certain
toxic substance at extreme high temperatures can also lead to an explosion. Explosions
chemical exposure can cause significant threats to human life sometimes leading to death.
61
Planned exposure of chemicals is usually controlled by an exposure limit. Some
chemicals are not toxic at certain concentration. The toxicity of most chemicals is
evaluated by its toxic limit value. There are three different toxic level limits that are used
in industry:
Toxic Limit Value- Time Weighted Average: The toxic limit value- time
weighted average also known as the permissible exposure limit, is defined as the
hour period.
Toxic Limit Value- Short Term Exposure Limit: According to the American
term exposure limit is the concentration of toxic chemical that a person can be
Hazardous chemicals which may exist in the three different states of matter are
ignitable, reactive, corrosive, radioactive and infectious. Hazardous spills include the
explosives, reactive metals, salts, acids and wastes. Uncontrolled hazardous chemical
spills pose serious threats to human life, natural water, land environment and the
ecosystem. An example of one of the most significant hazardous spill is the Exxon 1989
Valdez Oil Spill. The ExxonMobil 1989 Valdez Oil spill involved the accidental release
62
of 250,000 barrels of crude oil into the Prince William Sound, Alaska ocean basin. Some
of the negative impacts of this incident include the death of 375,000 sea birds, marine
Most recently, in April 2010, the largest marine oil spill occurred when one of
BP’s offshore facilities exploded in the Gulf of Mexico as a result of a failed emergency
blow out preventer. The effect of this incident has been devastating, leading to 11 death
and 17 injuries (Brown, 2010; Welch and Joyne, 2010). Also for several months, more
than 80,000 barrels of oil per day was gushing into the gulf, resulting in serious damage
to marine life, wildlife, fishing and tourism (Mcquaid, 2010). It is evident that toxic
to prevent, contain and clean these spills up by using sound sustainable engineering
practice.
Health risk assessment measure the probability for a particular chemical at the
correct dose to cause an adverse effect on human health. There are four steps that are
conducted in a health risk assessments and these include hazard identification, dose-
produces, transport or stores the particular hazardous chemical(s), plant design, amount
particular chemical(s) will increase the likelihood for adverse health effect such as
cancer, birth effects etc. to occur is completed in this step (Flynn and Theodore, 2002).
63
There are many published methods for hazard identification and these include toxicology,
epidemiology, molecular and structural analysis, material safety and data sheet, fate of
source for information on health risk regulatory data. In this database of 540 chemicals,
oral reference doses2, and inhalation reference concentrations3 for non –carcinogen risk
effects and oral slope factors4 and oral5 and inhalation6 unit risks for carcinogenic effects
are available (United States Environmental Protection Agency). This information can be
be exposed to a particular toxic chemical and for how long. In exposure assessments, the
2
The maximum acceptable oral dose of a toxic chemical
3
The maximum acceptable dose of a toxic chemical that can be inhaled
4
Upper bound value used in calculating cancer risks
5
Upper bound value used in calculating life time cancer risks from oral exposure
6
Upper bound value used in calculating life time cancer risks from inhalation exposure
64
Population Exposed: The people who are exposed to a particular toxic substance.
The health risk characterization step involves the estimation of the perceived
health and ecosystem risks from a chemical exposure. Non-cancer risks for one
The non-cancer risks for several substances can be evaluated by calculating a hazard
Low and high cancer risk as shown in Equation 3.13 and 3.14 respectively, are a
measure of the probability that if one is exposed to a carcinogen, that person will be
diagnosed with cancer. To evaluate the cancer risk for a mixture of substances, the risk is
There are 5 risks levels that are used to qualitatively identify adverse health
effects in hazard characterization and they are listed below (Flynn and Theodore, 2002):
65
Risk Level 1: No adverse health effect
Risk Level 4: There is a possibility that chemical will cause adverse health
hazards
Risk assessment on an annual or life time basis can also be expressed quantitatively as
shown in Table 3.4. In this table, assessments that have a level 1 characterization are
Several decades ago, risks were managed in the chemical industry by adding layer
of protection between the hazard, people and environment leading to the reduction in the
probability of the accident and or the magnitude of the impact. To determine the correct
and adequate layer of protection that must be incorporated into design, health and safety
risk assessment must be completed. One approach that has been used to assess the safety
and health risk in a process is to complete a Hazard and Operability (HAZOP) Study.
66
A HAZOP analysis is a procedure that is completed for existing and new facilities
and it involves identifying all the hazards and operability issues in a chemical process. In
the HAZOP study, the safety impact of all the different equipment found in a process,
specifically looking at the potential hazards when the process deviates from design
detailed engineering design must be completed and process and instrumentation diagrams
must be readily available. Although HAZOP analysis has been extensively used in the
chemical process industry, it has some limitations. It is time consuming, as only one
accident scenario can be looked at a time. It cannot be used during conceptual stages of
Other simpler tools and approaches that can be used at earlier stages of design that
are less time consuming and more straight forward have been developed. This section
focuses on screening tools for evaluating various aspects of process health and safety.
The following are the tools discussed: Dow Fire and Explosion Index, Dow Exposure
Index, Mond Fire, Explosion and Toxicity Index, Simulation of Chemical Industrial
Accidents Software Package, Mortality Index, Hazard Identification and Ranking, IFAL
Index, MAXCRED, Safety Weighted Hazard Index and Inherent Safety Index.
The Dow Fire and Explosion Index was developed to quantify the potential
damage from fire and explosion hazards in chemical processing plants that handle 1000Ib
or more of flammable, combustive and reactive toxic chemicals (Kavitha, 2003). The
index is applicable at the design stage when equipment have been configured and sized.
67
The Dow Fire and Explosion index involves a step by step analysis as depicted in the
The Dow Fire and Explosion Index have been used by many researchers to
incorporate safety into chemical process design. It has been implemented into an
optimization framework where technical, economic and safety considerations are being
met for process design at the conceptual stage (Suardin et al., 2007). A modified version
of this index which involves including credit for loss control measures has been
demonstrated on an ammonia synthesis reactor (Gupta et al., 2003). The index has also
been used as tool to classify hazards for the manufacture of epichlorohydrin (Khan and
Abbasi, 1997). To assess the risk of fire and explosion for operations taking place in the
Microbiology Laboratory at the University of Reno Nevada, the Dow Fire and Explosion
The limitations of the Dow Fire and explosion are that it only addresses fire and
explosion safety concerns but it does not address toxicological data. To address this
limitation, Dow Chemical Exposure Index (Dow Chemical Company, 1994) was
developed to be incorporated with the Dow Fire and Explosion Index. The Dow
Chemical Exposure Index was proposed to measure toxicity risks by using the physical
and chemical properties of the material, equipment process information and operating
conditions.
68
3.4.3.2 Mond Fire, Explosion and Toxicity Index
The Mond Index developed at the Mond division of the Imperial Chemical
Industries, is used to systematically access the risks of fire, explosion and toxic release in
a chemical process (Lewis, 1979; Tyler et al., 1994). The Mond Index is an expansion of
the Dow Explosion Index, but other hazard factor such as inventory of material, and a
layout hazard and toxicity factors have been incorporated. There are six indices that have
been proposed by the Mond group and these include: fire load index, unit toxicity index,
major toxicity incident index, explosion index and aerial explosion index.
The Mond index differs from the Dow fire and explosion index in that it can
evaluate safety impact of wider ranges of chemicals such as explosive properties and
toxicity assessments. The Mond Index also incorporates hazards credits for processes
with safety control devices (Khan and Abbasi, 1998). The Mond index like the Dow Fire
and Explosion index can be used when plant equipment configuration have been
was developed to evaluate the possible risk of accidents in chemical processes (El
Harbawi et al., 2008). This graphical based tool is able to perform hazard analysis that
determines risks and damage associated with accidental releases, fires and explosions.
This newly developed software is a useful tool for risk assessment because it can be used
69
3.4.3.4 Mortality Index
The Mortality Index was suggested by Marshall (1977) evaluates the fatality of
lethal chemical substances. The mortality index is shown in Equation 3.15 below.
hazards from pool fires, vapor fires, uncondensed cloud explosions, condensed cloud
with a computer (Singh and Munday, 1979; Munday et al., 1980). This index was
proposed by the United Kingdom Insurance Technical Bureau, to access hazards for each
and Abbasi to evaluate the risk of fire, explosion and toxic release. This methodology
consists of two indices: the fire and explosion damage index and the toxicity damage
index. To determine the fire and explosion damage index, a five step procedure has been
suggested by Khan and Abbasi (1998). This methodology has been demonstrated on the
sulfolane production process and the safety risk was determined. To validate this
methodology, results of other indices such as the Dow Fire and Explosion Index, IFAL
Index and the Mond Fire and Explosion Index have been compared to the HIRA
methodology. The results of the comparison show that HIRA is more sensitive and
70
accurate compared to other methods (Khan and Abbasi, 1998). However, it has some
limitations.
One drawback of HIRA is that it does not tell if existing control systems are
sufficient or need modifications. It also does not incorporate an emergency response plan
such as toxic release control and firefighting equipment into the calculation (Khan et al.,
2001). A new tool to improve some of the limitation of HIRA was proposed and this was
called the Safety Weighted Hazard Index (sWeHI). The Safety Weighted Hazard Index
was developed by Khan et al. (2001) to accurately and precisely address safety concerns
in chemical industry while integrating credits for safety measures that are already in
place.
software developed by Khan and Abbasi (1999) to simulate accident and damage
potential in order to evaluate safety risk of processes in the chemical industry. A number
of different risk assessment models for fire, explosion, toxic release and dispersion have
Two different accident scenarios namely boiling liquid / vapor cloud explosion followed
by flash fire and confined vapor cloud explosion have been modeled for the British
Petroleum Texas City Refinery incident. This was developed to show that hazard
assessment can prevent safety incidents and provide adequate emergency response (Khan
71
and Amyotte, 2007). MAXCRED was also used for damage prediction for an oxidation
The Inherent Safety Index was proposed by Heikkila (1999) to evaluate process
safety. There are two categories of safety indexes presented by this researcher and they
are chemical and process safety index. The summation of these two indices yields the
Inherent Safety Index. The chemical index describes how raw materials, products, by-
products, and intermediates interactions affect safety of a process. The index evaluates
the risk from chemicals with high heats of reaction, flammability, explosiveness, toxicity,
corrosiveness, and chemical interactions. While the process safety index depicts how
equipment configuration and operating conditions can impact the safety of a process.
The index measures the risks from high temperatures, pressures and the type of
equipment present in a process and chemical inventory. This Inherent Safety index has
several applications such as route selection, flow sheet development, and selection of best
The limitation of this safety index is that it does not model safety risks resulting
from deviations in operating conditions. In spite of its limitation, the Inherent safety
Index has been used by other researchers. It was integrated into an expert system called
iSafe for ranking safety of process flow sheet structure (Palaniappan et al., 2002). It was
used to select the safest production route from 10 different options for acetic acid
(Palaniappan et al., 2004). This index was used to access the safety of simulated
chemical and mechanical heat pump systems and the safest option was selected based on
the inherent safety index (Ajah et al., 2008). This inherent safety methodology has been
72
incorporated into the SUSTAINABILITY EVALUATOR and will be discussed in details
in section 5.
This section presents two categories of tools for evaluating safety in the chemical
industry and the key features are summarize in Table 3.5. The first category is the
accidental consequence analysis tools which include SCIASP and MAXCRED. The two
tools are intelligent systems that can evaluate accident consequence analysis for a
chemical processing plant. The second category of tool are indices such as the Dow Fire
and Explosion Index, Dow Exposure Index, Mond Fire, Explosion and Toxicity Index,
Mortality, HIRA, IFAL Index, sWeHI and Inherent Safety Index which measure several
aspects of safety such as fire, explosion and toxic exposure risks to humans. These
indices are not automated and require manual computation by plugging equations into a
spreadsheet or a calculator.
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3.5 SUMMARY
This chapter presents economic, environmental and health and safety concerns
facing the chemical industry. All of these issues discussed are important and it is very
critical that they are addressed and incorporated into early stages of process design using
user friendly approaches. The tools that are available for evaluating economic,
environmental and social concerns for the process industry were presented in this chapter.
A summary of the tool discussed are presented in Figure 3.9. The key issue with these
tools is that many of them are complicated and only address limited aspect of
sustainability. It would be useful to have one tool that can evaluate and incorporate all
dimensions of sustainability into process design. The next chapter introduces metrics that
address the three sustainability concerns. The applications of this metrics to process
Environmental Tools
LCA Tools, TRACI, WAR,
MEI, ENVOP
Social Tools
Economic Tools SCIASP, MAXCRED, Dow
CAPCOST, Aspen Process Fire and Explosion
Economic Analyzerr, HYSYS Index,Mond Index, Mortality
spreadsheet , Profitability Index, HIRA,IFAL
Analysis Spreadsheet , DORT Index,Safety Weighted Hazard
Index , Inherent Safety Index
Tools
available for
Evaluating
Sustainability
Concerns
74
CHAPTER IV
4.1 INTRODUCTION
The issues driving sustainability as shown in Figure 4.1 can be classified into the
financial risks, safety and supply chain pressure (Bakshi, 2000; Beloff, 2009).
Stakeholder
Demands
• Greener Products
• Community
Contributions
Safety
• Ethical business
• Health and practice Regulatory
Safety risks for Environment
society
• Air Emission
• Health and
• Water Pollution
safety risks for
employees
Sustainability
Visible Impacts
• Resource Financial
Constraints Markets
• Climate Change • Economic Risks
• Social disparity Supply Chain
Pressure
• Sustainability
Requirements
• Market for green
products and
Services
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To summarize these issues, society would like to have environmentally friendly
processes and products using as little resources as possible while considering health and
safety risks. In order to determine if our processes or products are sustainability, we must
says, ―only what gets measured gets managed,‖ we must , therefore, have a set of guiding
concerns and transform them into quantitative and or qualitative measures that are useful
for making vital decisions (Beloff et al., 2005). Although metrics and indicators are often
progress towards increased sustainability (Alberta Round Table on the Environment and
the Economy, 1993). Tanzil and Beloff (2006) noted that an indicator defines a
quite different from performance goals, which companies have measured for years. Jin
chemical changes.
76
Treating a process or situation as related to the ecosystem as opposed to handling
view of a system or process, they are termed a sustainability index or indices (Mayer,
2008). Several researchers have suggested several metrics, indicators and indices to
measure progress. The next section discusses the merits and limitations of the work
According to Tanzil and Beloff (2006), sustainability metrics and indicators can
considerations link environmental concerns such as resource usage, health and safety
concerns that can impact the society. Eco-efficiency, address the use of limited resources
measures for a certain process. Below are few characteristics suggested by (Atlee and
Kirchain, 2006):
77
Predictive and consistent
Unbiased
Economic Growth
Socio-Economic Eco-efficiency
Environmental
Social Progress Socio-
environmental Stewardship
concerns into process design. The use of sustainability metrics is a good technique to
could be calculated. For example, decision makers can select between several
metric. Without going through complicated optimization routines, metrics can be used as
78
Sustainability metrics are expressed in ratios. For environmental and economical
metrics, the numerator is usually the impact such as resource consumption or pollutant
emission while the denominator is usually an impact such as physical or financial. Social
such as ―benefit as percentage of payroll expense (%), working hours lost as percent of
total hours worked, lost time accident frequency (number per million hours worked) and
number of complaint per unit value added (Beloff et al., 2005).‖ A majority of the metric
and index systems focus on environmental and economic impacts and do not quantify
social concerns. Social concern is an import dimension that must not be left out.
indicators must be relevant to the user and the community, be understandable by its
intended user, must address long term impact and show linkages between the three
the society or community being observed. They measure economic improvements that
can be tracked over a long period of time. Examples of economic indicators include the
following: net job growth, employment diversity, number of jobs with benefits, work
required to support basic needs, ―percent of tourism dollars that come from recreational
uses and number of new businesses that are more environmentally friendly, number of
agriculture e.g. number of acres used for organic farming‖ (Anderson et al., 2001).
79
Environmental indicators measure positive environmental progress of the society
following:
Measure of improved water quality over time (pH, dissolved oxygen, etc.)
Number of vehicle miles traveled and the ecological impact of the emissions
Social indicators measure issues that relate to the health, safety and well-being of
the society or community being observed. They target social concerns and address
societal benefits over a period of time. Examples of social indicators include the
warming
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Indicators, like metrics, are useful in measuring sustainability progress.
knowledgeable on the subject matter. It can also be used to educate the community on
measured quantitatively, individuals can stay focused and motivated because they are
Several indicators and metrics have been proposed by researchers over the years.
The limitation with some of these metric systems is that they only cover a certain
dimension of sustainability and not all three dimensions. A summary of the key
presented in the next sections and in Table 4.1. The table highlights the concerns
index to evaluate process and product ecological footprint. This index takes into account
the process area while evaluating the impact of renewable resource consumption,
emission and waste production. The sustainable process index has been used as a
(Hertwich et al., 1997). A low value of the index indicates that a process is competitively
81
sustainable. An Excel based tool, SPIonExcel that uses this index to calculate the
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The limitation of this tool is that it only evaluates environmental concern, leaving out the
This index system is based on the work suggested by (Heikkila, 1999). This
index system addresses the chemical and process risk of a chemical plant (Tugnoli et al.,
process. The efficacy of this index system was demonstrated on an acetic acid
production process where the safety risks were identified. The limitation of this metric
system is that it only addresses safety concerns in a chemical processes, leaving out other
sustainability issues.
Afgan, Carvalho and Hovanov (2000) developed an indicator system in 2000 that
assesses the sustainable energy usage in a process by taking into account resource,
environment, economic and social criteria. The resource indicator consists of four
metrics namely; fuel resources, stainless steel resource, copper resource and aluminum
nitrogen oxide, sulfur dioxide and waste production. Economic indicator proposed
includes system efficiency, capital investment, and gross national product. Social
indicators recommended include new job creation, standard of living and community
benefit. Although this indicator system addresses the three dimension of sustainability, it
83
has limited applications as it has been tailored towards accessing the impact of energy
systems.
water intensity, energy intensity, toxic release, solid waste and pollutant emission. One
limitation of this metric system is that it only addresses one dimension of sustainability,
leaving out the other two dimensions. Also, the system categorizes environmental impact
of pollution into one metric versus breaking it down into individual concerns such as
issues such as human right issues, illegal corporate activities, discriminatory work place
incidents and workplace safety. The assessment criteria for this index system include the
environmental performance and eco-design of products and services; and social factors
such as employee benefits resolution, occupational health and safety and non-
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performance and establish risk for stakeholders. The limitation of this metric system is
that most of the indices are qualitative measures and are not applicable to early stages of
design.
products and process developed at the company (Saling et al., 2002). These metrics
include: raw materials consumption, energy consumption, land use, air and water
emissions, solid waste, and potential toxicity. Later on, a set of social metrics were also
SEEBALANCE is a life cycle assessment (LCA) tool that evaluates the impact of
performance (Saling et al., 2005). The social metrics developed by this group evaluates
the effect of products or processes on the wellbeing of employees, future generation, and
SEEBALANCE is one of the few tools that address social metrics, it requires extensive
data and information making it limited for early stages of design. In addition, the social
metrics presented, pose difficulty in terms of correlation with process design parameters.
This metric system was suggested by Constable, Curzons and Cunningham (2002)
include effective mass yield, E-factor, atom economy, mass productivity, mass intensity,
reaction mass efficiency and carbon efficiency, energy, ecotoxicity and human health
85
metrics. The metric suggested was used to compare the environmental impacts of various
solvents. This would aid manufactures in creating greener solvents. This metric system
is limited as it only evaluates resource usage impact and does not incorporate other
sustainability issues.
environmental and social concerns of an operating unit (IChemE Metrics, 2002). Some
of the examples of the economic metrics suggested include profit, project investment etc.
Environmental metrics include resource usage, emissions, effluents and wastes. Social
metrics include workplace benefit package, health and safety at work, number of
complaints concerning process facility and products etc. The limitation of this metric
system is that for the social metrics presented, it is difficult to correlate them with process
design parameters.
A set of indicators were proposed by Krajnc and Glavič (2003) to assess the
indicator system include: resource usage, product quality, environment impact, economic
viability and societal benefit. This group combined the indicators and metrics suggested
by several researchers (FEM and FEA, 1997; AIChE Center for Waste Reduction
Technologies (CWRT), 2000; Azapagic and Perdan, 2000; Veleva and Ellenbecker,
86
sustainability indicators into economic, environmental and social indicators. Economic
Social indicators measure production ethics and societal progress such as income
distribution. Although some of the metrics suggested by this researcher are useful, too
many metrics were suggested and not all of them are applicable to early stages of design.
This index system was proposed by Achour et al. (2005) and it accesses the
environmental and safety risk associated with a process by evaluating the contributions of
process streams and units. Indices such as toxicity index, flammability index, reactivity
index etc. were assigned different numerical values from 0-4 based on the national fire
hazard codes. An index value of 0 means no risk and a value of 4 means high risk. This
group defined an environmental risk index for components present in the inlet and outlet
stream of a process. This index system is limited because economic concerns have not
been incorporated into the index system. In addition, environmental impacts of emissions
Tanzil and Beloff (2006) suggested this metric in 2002 and it assesses how
impacts can be measured in a production process. The metrics are categorized into socio-
include benefits as percentage of payroll expense (%), employee turnover (%). promotion
87
rate (%) and lost-time accident frequency. Socio-environmental metrics include number
of citing for toxic industrial emissions and amount of waste released to natural habitats.
Eco-efficiency metrics include material intensity, water intensity, energy intensity, toxic
release, solid waste and pollutant emission. One limitation of this metric is that it
categorizes environmental impact of pollution into one metric versus breaking it down
include material intensity, energy intensity, potential chemical risk, and potential
environmental impact. The suggested three dimension metrics can be used to compare
the sustainability of processes with alterative production methods. The metrics have been
used to compare the sustainability of chlorine production process using three different
alternatives; namely mercury cells, diaphragm cells, and membrane cells. The three
dimension framework has also been used to compare the sustainability of two
presented for environmental impact as well as health risks, safety issues were not
addressed.
Tungnoli, Santarelli and Cozzani (2008b) proposed this indicator system and it
addresses the three major concerns of sustainability during early stages of design. For
social concern, inherent safety index and an occupational index were proposed. To
88
address economic concerns, calculation of the net present value was suggested. For
environmental concerns, the impact of air, water and soil emission as well as resource
consumption was evaluated. The indicator system is used for comparing alternatives
while analyzing the environmental, economic and social impact of each alternative. This
metric system is limited in that not all apply to early stages of design.
has been used to evaluate the sustainability performance of 11 companies namely; Air
Products, Akzo Nobel, Ashland, BASF, Celanese, Dow, DuPont, Eastman, Lyondell,
Praxair and Rohm & Hass. This system is limited as most of the suggested indices are
qualitative measures and are not applicable to early stages of process design.
4.4 SUMMARY
Although they are useful in tracking progress, not all of them are applicable to early
stages of process design. Table 4.2 summarizes the applications of the metric, indicator
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Table 4.2: Summary of the Metric, Indicator and Index Systems Introduced in this
Chapter
System Applications Missing Aspects
Sustainable Process Index Applicable to detailed Although environmental
(Krotscheck and process design impacts are considered, reaction
Narodoslawsky, 1996) efficiency has not been
incorporated. Not applicable to
early stages of design. Also
social concerns have not been
addressed in this index system.
Inherent Process Safety Index Applicable for Only addresses safety concerns
(Heikkila, 1999) assessing the safety and the other dimensions of
of a chemical process sustainability are not addressed.
at all stages of design
90
IChemE Sustainability Useful in assessing For the social metrics presented,
Metrics (IChemE Metrics, the sustainability of it is difficult to correlate them
2002) production processes with process design parameters.
Indicators of sustainable Useful in assessing Although some of the metrics
production (Krajnc and the sustainability of are useful for early stages of
Glavič, 2003) an operating unit design, too many metrics were
suggested and not all of them
are applicable to early stages of
design.
Global Environmental Risk Useful in addressing Economic concerns and
Assessment (GERA) Index health and safety environmental impact of
(Achour et al., 2005) risks of an operating emissions has not been
unit and stream incorporated in this system.
BRIDGES to Sustainability Applicable for Only addresses one dimension
Metrics (Tanzil and Beloff, comparing of sustainability. Metric
2006) environmental impact categorizes environmental
of chemical processes impact of pollution into one
metric versus breaking it down
into individual concerns such as
global warming, acidification.
Three Dimensional Useful in evaluating Although two metrics have been
Sustainability Metrics the sustainability of presented for environmental
(Martins et al., 2007) an industrial process impact and health and safety
risk, the direct correlation
between operating conditions,
chemical process risk and
environmental impact was not
addressed.
Sustainability Indices Useful in evaluating Not all metrics are applicable to
(Tugnoli et al., 2008b) the sustainability of early stages of design.
chemical process
alternatives
AIChE Sustainability Index Applicable for Most of the indices are
("AIChE Sustainability Index: comparing different qualitative measures and are not
Strategic Commitment to companies’ applicable to early stages of
Sustainability," 2008) performance design.
The ability to measure sustainability using indicators or metrics are important because it
91
technical alternatives e.g. different raw materials and process improvement options and
or business alternatives, for example, different supplier and acquisition options. It can
also be used to track performance over time as well as compare facilities or business units
One thing to point out from this study is that it is complex to quantitatively
evaluate social sustainability. This is because it is difficult to transform social issues into
a scientific vision. As the focus of this research is addressing social, economic and
researchers in this chapter and the ideas from chapters 2-4 have been incorporated into a
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CHAPTER V
The first four chapters discussed environmental, economic and social tools that
are available for estimating project economics, environmental impacts, health and safety
concerns. The previous chapter also introduced sustainability metrics which can be used
to address these concerns. This chapter focuses on a methodology that was developed for
this PhD work which incorporates sustainability concerns into early stages of design.
The framework involves the use of a newly developed novel screening tool, the
5.1 INTRODUCTION
activities that can be executed at all stages of design. Like end of pipe waste treatment
methodologies, waiting until the last stage of process design to incorporate sustainability
93
concerns is not economical and resource efficient. Thus, sustainability ideas must be
transformed at early stages of design in order to curb the source of concerns. When
designing products and processes, engineers must look at the bigger picture, i.e. the
economy and environment, instead of merely focusing on the process plant and the
economic benefits to the corporation (Bakshi and Fiksel, 2003). In order to design
Figure 5.1: Proposed Methodology for Addressing Sustainability Concerns During Early
Stages of Design
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This methodology includes the following: base case process modeling,
process optimization based on result of sensitivity analysis, and impact assessment of the
The base case model is simulated using information from literature. For this work,
the base case was simulated using ASPEN PLUS version 22. This version of ASPEN has
a component database which is where the constants that are needed for calculating
thermodynamic models are located. Also, it has a solver which contains thermodynamic
models that can predict phase behavior. The simulator has a graphic user interface where
the designer is able to keep track of selected process equipment and flow streams. There
is also a unit operation block solver that has computational blocks for mass and energy
balance calculations and other design calculations. The simulator has a data output
generator where the result of the simulation run is provided. Lastly it has a flow sheet
solver that shows the sequence of how the calculations in the simulation were completed
For ASPEN PLUS to calculate mass and energy balances for any selected
process, the following are the basic inputs into the simulator:
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Operating conditions such as temperature, pressure etc.
The ASPEN process simulator has been chosen because it is readily available at
Oklahoma State University and in addition to providing the results of mass and energy
balances; it is useful for equipment sizing, economic estimates, sensitivity analysis and
optimization. ASPEN PLUS will be used to simulate and optimize chemical processes
for evaluating processes for sustainability. This tool uses selected metrics and indices
SUSTAINABILITY EVALUATOR is a Microsoft Excel based tool that uses mass and
energy flows as inputs to evaluate the sustainability of a process. Some of the concerns
that are addressed by this tool include the following as shown in Figure 5.2:
etc.
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Health and Safety Impact: Health and safety risks such as risk of exposure,
The ultimate goal in every industrial process is to maximize profits; thus a process
evaluate the sustainability of a process and or compare process alternatives to select the
most sustainable process. The inputs into this tool as shown in Figure 5.3 are mass flow
rates, raw material and product costs, and capital costs from ASPEN PLUS. The outputs
of this tool are the selected sustainability metrics as shown in Figure 5.3.
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The SUSTAINABILITY EVALUATOR, an impact assessment tool is quite novel
as there is no other tool that is able to address the three dimensions of sustainability in
this fashion. The user manual for the SUSTAINABILITY EVALUATOR is provided in
APPENDIX A of this dissertation. The following section describes the metrics that
address economic, environmental, health and safety concerns that have been incorporated
The economic benefit for any process is very important because a project that is
not profitable is not sustainable. There are several methods that are available for
Seider et al. (2008) and Turton et al (2009) and in Chapter 3. In this work a set of
economic metrics that can be used in evaluating the cost effectiveness of a process is
listed below:
1. Product Revenue: This is a measure of the revenue that is generated from the
manufactured product and by-products. The higher the product revenue, the more
2. Raw Material Costs: This is defined as costs of the raw materials used in
3. Waste Treatment Costs: This is defined as the expenses associated with treating
particular product.
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Sustainability Evaluator
Economic Index Environmental Index Social Index
Raw Material Costs Global Warming Mass Productivity Flammability Index Immune System Damage*
Annualized Capital Costs Ozone Depletion Reaction Mass Efficiency Toxic Exposure Index Skeletal System Damage*
Waste Treatment Costs Smog Energy Intensity Explosisivity Index Developmental Damage*
Reproductive System
Material Vallue added Ecotoxicity to Aquatic Life Water Intensity Temperature Index
Damage*
Respiratory System
Profit Eutrophication Pressure Index
Damage*
Cardiovascular System
Aquatic Oxygen Demand Corrosivity Index
Damage*
Endocrine System
Equipment Safety Index
Damage*
Safety Level of Process
Liver Damage*
Structure
Kidney Damage*
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5. Material Value Added: This is defined as the difference between the product revenue
6. Annualized Capital Costs: This is the conversion of the capital costs to an annual
i(1+i)n
CRF (5.1)
(1+i)n-1
Where
Once the economics of a process has been evaluated, the next step is to determine
the environmental impact. The environmental impact can be evaluated by using metrics
(Constable et al., 2002) and Bridges to Sustainability (Tanzil and Beloff, 2006). The
following nine impact categories listed below are suggested: global warming,
resource usage.
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5.3.2.1 Global Warming
This is defined as the increase in the temperature of the earth surface due to
activities such as industrial and transportation emissions. Several chemicals cause global
warming but carbon dioxide emissions is the major cause. Thus, other substances that
lead to global warming are converted to carbon dioxide equivalent by using potency
Table 5.1: Potency Factors for Chemicals that Cause Global Warming (IChemE Metrics,
2002)
Substances Potency Factor
Carbon dioxide 1
Carbon monoxide 3
Carbon tetrachloride 1400
Chlorodifluoromethane, R22 1700
Chloroform 4
Chloropentafluoroethane, R115 9300
Dichlorodifluoromethane, R12 8500
Dichlorotetrafluoroethane, R114 9300
Difluoroethane 140
Hexafluoroethane 9200
Methane 21
Methylene chloride 9
Nitrogen oxides (NOx) 40
Nitrous oxide 310
Pentafluoroethane, R125 2800
Perfluoromethane 6500
Tetrafluoroethane 1300
Trichloroethane (1,1,1) 110
Trichlorofluoromethane, R11 4000
Trichlorotrifluoroethane, R113 5000
Trifluoroethane, R143a 3800
Trifluoromethane, R23 11700
Volatile organic compounds 11
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5.3.2.2 Stratospheric Ozone Depletion
The ozone layer is very important in protecting the earth from ultraviolet rays.
Depletion of this layer can result in skin cancer in humans. Examples of chemicals
leading to ozone depletion are trichlorofluoromethane and carbon trichloride etc. For this
equivalent by multiplying the mass flow rates of emitted wastes with the potency factors
Table 5.2: Potency Factors for Chemicals that Cause Stratospheric Ozone Depletion
(IChemE Metrics, 2002)
Substances Potency Factor
Carbon dioxide 1
Carbon monoxide 3
Carbon tetrachloride 1400
Chlorodifluoromethane, R22 1700
Chloroform 4
Chloropentafluoroethane, R115 9300
Dichlorodifluoromethane, R12 8500
Dichlorotetrafluoroethane, R114 9300
Difluoroethane 140
Hexafluoroethane 9200
Methane 21
Methylene chloride 9
Nitrogen oxides (NOx) 40
Nitrous oxide 310
Pentafluoroethane, R125 2800
Perfluoromethane 6500
Tetrafluoroethane 1300
Trichloroethane (1,1,1) 110
Trichlorofluoromethane, R11 4000
Trichlorotrifluoroethane, R113 5000
Trifluoroethane, R143a 3800
Trifluoromethane, R23 11700
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5.3.2.3 Photochemical (Smog) Formation
This is a reaction that occurs when photochemical smog causing chemicals such
appearance at the right temperature and sunlight (IChemE Metrics, 2002). For this
metric, substances that cause photochemical smog formation are converted to ethylene
equivalent. Potency factors for chemicals that cause the formation of photochemical
Table 5.3: Potency Factors for Chemicals that Result in the Formation of Photochemical
Smog (IChemE Metrics, 2002)
Substances Potency Factor
1,1-Dichloroethylene 0.232
1,2,3-Trimethylbenzene 1.245
1,2,4- Trimethylbenzene 1.324
1,3,5- Trimethylbenzene 1.299
1-Butene 1.130
1-Pentene 1.040
2,2-Dimethylbutane 0.321
2,3-Dimethylbutane 0.943
2-Butene 0.990
2-Methylbut-1-ene 0.830
2-Methylbut-2-ene 0.770
2-Methylheptane 0.694
2-Methylhexane 0.719
2-Methylnonane 0.657
2-Methyloctane 0.706
2-Methylpentane 0.778
2-Pentene 0.950
3,5-Diethyltoluene 1.195
3,5-Dimethylethylbenzene 1.242
3-Methylbut-1-ene 1.180
3-Methylhexane 0.730
3-Methylpentane 0.661
Acetaldehyde 0.650
Acetic acid 0.156
Acetone 0.182
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Acetylene 0.280
Benzaldehyde -0.056
Benzene 0.334
Butyl glycol 0.629
Butylene 0.703
Butyraldehyde 0.770
Carbon monoxide 0.027
cis 1,2- Dichloroethylene 0.172
Cyclohexane 0.595
Cyclohexanol 0.622
Cyclohexanone 0.529
Diacetone alcohol 0.617
Dimethyl ether 0.263
Ethane 0.140
Ethyl acetate 0.328
Ethyl alcohol 0.446
Ethylbenzene 0.808
Ethylene 1.000
Formaldehyde 0.554
Formic acid 0.003
i-Butane 0.426
i-Butanol 0.591
i-Butyraldehyde 0.855
i-Pentane 0.599
i-Propanol 0.216
i-Propyl acetate 0.291
i-Propylbenzene 0.744
Isoprene 1.180
Methane 0.034
Methyl acetate 0.046
Methyl alcohol 0.205
Methyl chloride 0.035
Methyl cyclohexane 0.732
Methyl- i -butylketone 0.843
Methyl- t -butyl ether 0.268
Methyl chloroform 0.002
Methylene chloride 0.031
Methylethylketone 0.511
m-Ethyltoluene 0.985
m-Xylene 0.080
n-Butane 0.600
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n-Butanol 0.628
n-Butyl acetate 0.511
n-Decane 0.680
n-Dodecane 0.577
n-heptane 0.770
n-Hexane 0.648
Nitric oxide 0.427
Nitrogen dioxide 0.028
n-Nonane 0.693
n-Octane 0.682
n-Pentane 0.624
n-Propyl acetate 0.481
n-Propylbenzene 0.713
n-Undecane 0.616
o- Xylene 0.831
o-Ethyltoluene 0.846
p- Xylene 0.948
p-Ethyltoluene 0.935
Propane 0.411
Propionaldehyde 0.755
Propionic acid 0.035
Propylene 1.080
Propylene glycol methyl ether 0.518
s-Butanol 0.468
s-Butyl acetate 0.452
Styrene 0.077
Sulphur dioxide 0.048
t-Butanol 0.191
Tetrachloroethylene 0.035
Toluene 0.774
trans 1,2- Dichloroethylene 0.101
Trichloroethylene 0.075
Valeraldehyde 0.887
Vinyl chloride 0.272
presence of pollutants in water sources. For this metric, all substances that are toxic to
aquatic life are converted to copper equivalent using the factors are shown in Table 5.4.
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Table 5.4: Potency Factors for Chemicals that Cause Eutrophication (IChemE Metrics,
2002)
Substances Potency Factor
1,2-Dichloroethane (EDC) 0.50
Ammonia 0.24
Arsenic 0.20
Benzene 0.17
Cadmium 2.00
Carbon tetrachloride 0.42
Chloride 0.50
Chlorobenzene 1.00
Chloroform 0.42
Chromium 0.33
Copper 1.00
Cyanide 1.00
Formaldehyde 1.00
Hexachlorobenzene 166.67
Hexachlorobutadiene 50.00
Iron 0.005
Lead 0.20
Manganese 0.10
Mercury 16.67
Methylene chloride 0.50
Nickel 0.17
Nitrobenzene 0.25
Nitrophenol 0.50
Tetrachloroethylene (PER) 0.50
Toluene 0.13
Trichloroethylene (TRI) 0.50
Vanadium 0.05
Xylenes 0.17
Zinc 0.13
to the presence of pollutants in water sources. For this metric, all substances that cause
an increase in aquatic oxygen demand are converted to oxygen equivalent. The potency
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Table 5.5: Potency Factors for Chemicals that Cause Aquatic Oxygen Demand (IChemE
Metrics, 2002)
Substances Potency Factor
Acetic acid 1.07
Acetone 2.09
Ammonium nitrate in solution 0.80
Ammonium sulphate in solution 1.00
Chlorotrifluoroethane 0.54
1,2 – Dichloroethane (EDC) 0.81
Ethylene 1.00
Ethylene glycol 1.29
Ferrous ion 0.14
Methanol 1.50
Methyl methacrylate 1.50
Methylene Chloride 0.47
Phenol 2.38
Vinyl chloride 1.28
This metric measures the acid increase in the environment when chemicals such
as ammonia, sulfuric acid, hydrochloric acid, hydrogen fluoride, nitrogen dioxide and
sulfur dioxide are emitted into the atmosphere (IChemE Metrics, 2002; da Costa and
Pagan, 2006). To calculate this metric, the mass flow rate of the substance is multiplied
by a potency factor for each substance. The potency factor converts, the chemicals to
sulfur dioxide equivalent. Potency factors for acidic chemicals are presented in Table
5.6.
Table 5.6: Potency Factors for Chemicals that Cause Atmospheric Acidification (IChemE
Metrics, 2002)
Substances Potency Factor
Ammonia, NH3 1.88
Sulfuric acid mist, H2SO4 0.65
Hydrochloric acid, HCL 0.88
Hydrogen fluoride, HF 1.60
Nitrogen dioxide, NO2 0.70
Sulfur dioxide, SO2 1.00
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5.3.2.7 Aquatic Acidification
This metric measures the acid increase in water sources when chemicals such as
acetic acid, hydrochloric acid and hydrogen fluoride etc. are discharged (IChemE
Metrics, 2002). To calculate this metric, the mass flow rate of the substance is multiplied
by a potency factor for each substance as shown in Table 5.7. The potency factor
Table 5.7:Potency Factors for Chemicals that Cause Aquatic Acidification (IChemE
Metrics, 2002)
Substances Potency Factor
Acetic acid 0.020
Hydrochloric acid, HCL 0.027
Hydrogen fluoride, HF 0.050
Sulfuric acid 0.020
5.3.2.8 Eutrophication
This metric is defined as the addition of unwanted nutrients into water sources
which leads to the increase in plant growth. For this metric, all substances that cause
Table 5.8: Potency Factors for Chemicals that Cause Eutrophication (IChemE Metrics,
2002)
Substances Potency Factor
Ammonia 0.33
COD 0.02
Nitrogen 0.42
Nitrogen dioxide, NO2 0.20
Nitrogen oxide, NO 0.13
NOx 0.13
Phosphorus 3.06
PO4 (III-) 1.00
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5.3.2.9 Resources usage
energy and water usage as well as reaction efficiency. For more information on these
metrics, papers by Constable, Curzons and Cunningham (2002) and Tanzil and Beloff
(2006) can be consulted. The sub-metrics under this category include, E-factor, mass
productivity, reaction mass efficiency, energy intensity and water consumption. The
calculations for these metrics are shown in Equation 5.3-5.8 (Constable et al., 2002;
Total Waste
E-Factor = (5. 3)
Kg of Product
Mass of Product
Reaction Mass Efficiency = (5. 4)
Mass of Reactants
1
Mass Productivity = X 100 (5. 5)
Mass Intensity
Energy Consumed
Energy Intensity = (5. 7)
Mass of Product
Water Consumed
Water Intensity = (5. 8)
Mass of Product
process is as follows:
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energy intensity and water intensity; the chemical process is more
environmentally friendly.
Also, the higher the value of the following metrics: reaction mass efficiency
Social concerns affect society as a whole. These concerns could be how the
creation of a new product could create potential job opportunities, societal income as well
as process health and safety risks. Or what are the risks involved in manufacturing
social metrics exist, however for the scope of the proposed research, health and safety
metrics were selected. Health and safety has been an area of concern in industry for
several years and researchers have put forth efforts towards quantifying it (Heikkila,
available. In this work, we focus on evaluating process safety risk by implementing the
index developed by Heikkila (1999) and health risk by using data from the International
Agency for Research on Cancer (2009) and Score Card (2005). In this section, two
Health Risks
The following process safety metrics are discussed below: heat of main and side
reaction index, flammability index, explosivity index, corrosive index, toxic exposure
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index, temperature index, pressure index, equipment process safety index and process
This metric as shown in Equation 5.9, measures the amount of heat that is
released during a chemical reaction. Reactions that generate high quantities of heat could
be potentially dangerous due to the potential release of dangerous gases. Many processes
have multiple reactions, thus this metric can be used to evaluate both main and side
reactions. This metric is calculated by Equation 5.9 below (Heikkila, 1999; Jensen et al.,
2003). To interpret the results obtained from this equation, index scores as shown in
Table 5.9 have been provided. The index score ranges from 0-8 with 8 being the worse
This metric measures the potential for chemicals to burn with air in the event that
there is a chemical leak. The flammability index is based on the flash point temperature.
In general, the lower the flash points temperature, the more flammable the chemical is.
In this work, flash point temperature for chemicals have been obtained from ―Chemical
Process Safety‖ (Crowl and Louvar, 1989). The index score for this metric is shown in
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Table 5.10. The index score ranges from 0-8 with 8 being the worse safety scenario as
The metric measures the potential for a gas to form an explosive mixture with air.
The explosivity index is calculated by subtracting the upper explosive limit (UEL) from
the lower explosive limit (LEL) of chemicals. Substances with a large explosive limit
difference tend to be more explosive. UEL and LEL for explosive chemicals have been
obtained from Crowl and Louvar (1989), material data safety sheets and Dow Fire &
1994). The index score for this metric is shown in Table 5.11. The index score ranges
from 0-8 with 8 being the worse safety scenario as suggested by the author of this
dissertation.
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5.3.3.1.4 Corrosive Index
This index measures the possibility for chemicals such as acids, acid anhydrides
and bases to corrode plant equipment. The corrosion of plant equipment can be a
dangerous situation leading to toxic exposure due to leakages, explosions and fires.
designing plant equipment to avoid corrosion issues. The corrosive index is based on the
material used for construction as shown in Table 5.12. As suggested by the author of this
dissertation, the index score ranges from 0-4 with 4 being the worse safety scenario.
This is a measure of the potential risk in a process due to the temperature range in
the process. Temperature is a very important parameter because high and cryogenic
issues. The index score according to the temperature range can be found in Table 5.13.
As suggested by the author of this dissertation, the index score ranges from 0-8 with 8 set
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5.3.3.1.6 Pressure Index
This is a measure of the potential risk in a process due to the pressure range in the
process. Pressure is a very important parameter because high pressure conditions affect
leakage rates and vessel strength (Heikkila, 1999). The index score according to the
pressure range can be found in Table 5.14. As suggested by the author of this
dissertation, the index score ranges from 0-8 with 8 set as the worse safety scenario.
This index measures the risk associated with your process based on equipment
found in a process. For example, plants that have furnaces and fire heaters have a higher
equipment process safety index than plants that have simpler equipment such as storage
vessels. The index score according to process equipment can be found in Table 5.15. As
suggested by the author of this dissertation, the index score ranges from 0-8 with 8 set as
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5.3.3.1.8 Process Safety Structure Index
standard, engineering practice and related incidents. The index score for process safety
structure can be found in Table 5.16. As suggested by the author of this dissertation, the
index score ranges from 0-10 with 10 set as the worse safety scenario.
This is a measure of the health risk associated with a certain chemical and it is
determined by its threshold limit value (TLV). Substances with a lower TLV tend to be
more harmful compared to substances with a higher TLV. TLVs can be obtained from
the American Conference of Governmental Industrial Hygienists (2009). The index score
for this metric is shown in Table 5.17. As suggested by the author of this dissertation, the
index score ranges from 0-65 with 65 being the worse safety scenario.
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5.3.3.1.10 Summary of Safety Metrics
summing each of the ten metrics shown in Table 5.18. A chemical process with a process
safety index of 100 has the maximum process safety risk and is an extremely unsafe
process.
The following health metrics are discussed below: carcinogenic health risk,
developmental health risk, reproductive health risk, cardiovascular health risk, endocrine
system health risk, liver damage health risk, immune system damage health risk, kidney
damage health risk, skeletal system damage health risk, neurological damage health risk
This index measures the carcinogenic risk of a process based on the chemicals
present in the process. Carcinogenic chemicals can be classified into four major
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categories namely, carcinogenic to humans, probably carcinogenic to humans, possibly
carcinogenic to humans, carcinogenic to animals but not humans and probably not
carcinogenic to humans (International Agency for Research on Cancer). For this metric,
an index score ranging from 0 to 1 were selected by the author as shown in Table 5.19.
For each known carcinogen, the index value is multiplied by the amount being emitted to
This index measures the risks posed to a developing child when a pregnant
woman is exposed to toxic chemicals. Developmental problems that can arise include
deficit and even brain damage. For this research, lists of known and suspected
developmental toxicants were obtained from Score Card. For this work, suspected and
known developmental toxicants were selected by the author and assigned an index value
of 0.6 and 1 respectively. These index values were chosen because a value of 0.6 and 1
have been assigned for suspected and known carcinogens, respectively. Therefore
because these metric will be compared against each other it was better to use similar
index values. For each known toxicant, the index value is multiplied by the amount
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5.3.3.2.3 Reproductive Health Risk
This index measures the risks posed to the reproductive system of an adult when
they are exposed to reproductive toxicants. Reproductive system problems that can arise
include abnormal sexual behavior, decreases in fertility, loss of the fetus during
pregnancy. For this research, a list of known and suspected reproductive toxicants was
obtained from Score Card. For this work, suspected and known reproductive toxicants
were selected and assigned an index value of 0.6 and 1 respectively by the author. For
each known toxicant, the index value is multiplied by the amount being emitted to
This index measures the risks posed to the circulatory system of an adult after
ischemia. For this research, a list of suspected reproductive toxicants was obtained from
Score Card and was assigned an index value of 0.6 by the author. For each known
toxicant, the index value is multiplied by the amount being emitted to calculate this
metric.
This index measures the risks posed to the endocrine system of an adult after
exposure to endocrine toxicants. Endocrine system problems that can arise include
For this research, a list of suspected endocrine toxicants was obtained from Score Card
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and was assigned an index value of 0.6 by the author. For each known toxicant, the index
This index measures the risks posed to the gastrointestinal tract, liver, or gall
bladder of an adult after exposure to toxicants. For this research, a list of suspected
toxicants was obtained from Score Card and was assigned an index value of 0.6 by the
author. For each known toxicant, the index value is multiplied by the amount being
This index measures the risks posed to the immune system after exposure to
immunotoxicants. When the immune system has been compromised, there will be an
increased rate of infectious diseases and cancer. For this research, a list of suspected
immunotoxicants was obtained from Score Card and was assigned an index value of 0.6
by the author. For each known toxicant, the index value is multiplied by the amount
This index measures the risks posed to the kidney, ureter and bladder after toxic
exposure. For this research, a list of suspected toxicants was obtained from Score Card
and was assigned an index value of 0.6 by the author. For each known toxicant, the index
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5.3.3.2.9 Skeletal System Damage Health Risk
This index measures the risks posed to the bones, muscles and joint after toxic
exposure. Skeletal system damage induced by toxicants includes arthritis, fluorosis and
osteomalacia. For this research, a list of suspected toxicants was obtained from Score
Card and was assigned an index value of 0.6 by the author. For each known toxicant, the
index value is multiplied by the amount being emitted to calculate this metric.
This index measures the risks posed to the nervous system after toxic exposure.
brain damage and loss of coordination. For this research, a list of suspected toxicants
was obtained from Score Card and was assigned an index value of 0.6 by the author. For
each known toxicant, the index value is multiplied by the amount being emitted to
This index measures the risks posed to nasal passages, pharynx, trachea, bronchi,
and lungs of an adult when they are exposed to toxicants. Respiratory system damage
irritations, emphysema, and cancer. For this research, a list of suspected toxicants was
obtained from Score Card and was assigned an index value of 0.6 by the author. For each
known toxicant, the index value is multiplied by the amount being emitted to calculate
this metric.
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5.3.3.2.12 Skin or Sensory Organ Damage Health Risk
This index measures the risks posed to the skin or sensory organ after toxic
exposure. Damage to the sensory organ leads to hearing loses, sense of smell, eye
irritations etc. For this research, a list of suspected toxicants was obtained from Score
Card and was assigned an index value 0.6 by the author. For each known toxicant, the
index value is multiplied by the amount being emitted to calculate this metric.
Twelve health metrics were introduced in this section. The index ranges for the
metrics are presented in Table 5.20. To determine the health impact associated with a
manufacturing process emitting waste, the mass flow rate of the substance being emitted
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5.3.4 Overall Sustainability Impact in the Sustainability Evaluator
objective optimization problem. In this research, the three major sustainability concerns
are weighted and summed up into a single objective resulting in an equation called the
impact (SUI) was developed by the author based on the economic, environmental and
Where
EI = Economic Impact
ENVI = Environmental Impact
SCI = Social Impact
To determine the overall SUI, weights were assigned to the calculated economic,
using weights has been a conventional approach used by several researchers because it is
instead of multiple Pareto solutions (Jin et al., 2001; Yaochu et al., 2001).
A weight of 0.20 was assigned to the economic impact while social and
environmental impacts were assigned a higher value of 0.4 because when environmental
and social risks occur, the overall risks are costly. The objective here was to derive an
impact value ranging from 0-1, where processes with overall impact values close to 0 are
more sustainable compared with processes with values close to 1. Hence the lower the
overall sustainability impact, the more sustainable the process is. Economic,
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environmental and social metrics were normalized using a ranking system procedure
An overall economic impact (EI) was developed based on calculating the profit
relative to investment (PRI) as shown in Equation 5.11. The profit relative to investment
was the selected metric as this is an important criterion used in making investment
decisions. Based on the calculated PRI value, an impact score ranging from 0-1 is
Profit
PRI (Expenses) *100 (5.11)
As shown in the table, when the calculated PRI is greater than 25% an impact
score of 0 is assigned. As the calculated PRI decreases, an impact score is assigned based
resource usage and environmental burden metrics and using Equation 5.12.
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A value of 0.25 was assigned to resource usage impact because this metric measures one
burdens were assigned 0.75, as this metric measure eight other ecological concerns. The
resource usage impact (RUI) was first normalized from 0-1 where each of the individual
metric are assigned weights as shown in Table 5.22. The goal here was to ensure that the
sum for the worst case scenario would equal 1. As this impact has five sub metrics, each
individual concern under resource usage were ranked from 0-0.20 based on the calculated
metric as shown in Tables 5.22 and 5.23. Calculated values for mass productivity and
reaction mass efficiency were assigned impact values based on Table 5.22, while E-
factor, energy intensity and water usage, were assigned values based on Table 5.23.
Table 5.22: Resource Usage Metric Impact Value for Metrics Expressed in
percentages
Resource Usage metric (%) Score
0 0.20
20 0.10
40 0.07
60 0.05
80 0.04
100 0.00
Table 5.23: Resource Usage Metric Impact Value for metrics expressed in
Kilogram
Resource Usage Metrics (kg) Score
0 0.00
0.5 0.03
1 0.04
5 0.05
10 0.07
50 0.10
200 0.20
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Next each environmental burden such as global warming, stratospheric ozone
aquatic acidification, eco-toxicity to aquatic life and eutrophication was assigned a value
ranging from 0 to 0.125 based on the calculated equivalent value as shown in Table 5.24.
The goal here was to ensure that the sum for the worst case scenario would equal 1 as this
An impact value of 0 was assigned if that particular metric was not an issue of
concern i.e. the calculated impact value is 0 Tones/year equivalent. While it was
assigned a value of 0.125 if its calculated impact value was greater than 100,000
Tonnes/year equivalent. For the worst case scenario, where all environmental burdens
are an issue of concern and the calculated equivalent impact value is greater than 100,000
An overall social impact (SI) was developed based on normalizing the safety
impact (SAI) and health impact (HEI) using Equation 5.13. Weights of 0.5 were selected
for both indices because they are of equal importance. An overall safety impact (SAI)
was developed using the calculated process safety index value. Based on the calculated
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process safety index, an impact score ranging from 0-1 is assigned as shown in Table
5.25. A process that is assigned an impact of 1 has the highest possible safety risk.
For the health impact, the carcinogenic risk was assigned a value ranging from 0 -
0.25 as shown in Table 5.26. The other eleven other health concerns such as
developmental health risk, reproductive health risk, cardiovascular health risk, endocrine
system health risk, liver damage health risk, immune system damage health risk, kidney
damage health risk, skeletal system damage health risk, neurological damage health risk
and respiratory system health risk have been assigned a weight of 0-0.068 so that for the
worst case scenario, where all health burdens are an issue of concern and the calculated
equivalent impact value is greater than 100,000 Tonnes/year, the health impact (HEI) is
1.
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A larger weight was assigned to carcinogenic risk as cancer is the most severe
health concern. For carcinogen risk, weights were assigned based on Table 5.26, while
all other health impacts, were assigned weights s based on Table 5.27. The overall sum
of each assigned health impact value for the worst case scenario is 1.
As stated before, a weight of 0.20 was assigned to the economic impact while
social and environmental impacts were assigned a higher value of 0.4. To determine if
changing the weights for each impact category would affect the overall result, a
sensitivity analysis was done on the ally chloride case study (see Chapter 6). In this case
study, there are three processes that are evaluated and are compared. These are the base,
adiabatic PFR and isothermal PFR cases. The analysis showing the calculated overall
sustainability impact for the three cases, when the impact weights are varied, are
presented in Table 5.28. As shown in the table, regardless of what weights are selected,
the Adiabatic PFR always has the lowest overall sustainability impact value and the base
case always had the highest overall sustainability impact value. However, the calculated
overall sustainability impact value changed. For this case study, since the impact values
were not competing, the selection of weights did not change the overall outcome. Further
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Table 5.28: Impact Weights Sensitivity Analysis
Economic Environmental Social Base Adiabatic Isothermal
Case Weight Weight Weight Case* PFR+ PFR
1 0.1 0.1 0.8 0.50 0.35 0.35
2 0.1 0.5 0.4 0.37 0.20 0.23
3 0.2 0.4 0.4 0.45 0.20 0.22
4 0.2 0.5 0.3 0.42 0.16 0.19
5 0.2 0.7 0.1 0.35 0.09 0.13
6 0.3 0.1 0.6 0.59 0.26 0.27
7 0.33 0.33 0.33 0.53 0.16 0.18
8 0.4 0.1 0.5 0.64 0.22 0.22
9 0.4 0.4 0.2 0.54 0.11 0.13
10 0.5 0.2 0.3 0.65 0.14 0.15
11 0.6 0.1 0.3 0.73 0.13 0.14
12 0.6 0.3 0.1 0.67 0.06 0.08
13 0.7 0.1 0.2 0.78 0.09 0.10
14 0.7 0.2 0.1 0.75 0.06 0.07
*Adiabatic PFR case always has the lowest impact value
+ Base case always has the highest impact value
are independent and dependent variables. Dependent variables are variables that are
being evaluated when independent variables are fluctuated. As the goal of this research
is to determine the most sustainable process option, the dependent variables in this work
will be the sustainability metrics that were discussed in the previous section, while the
independent variables are the parameters that are being investigated such as operating
conditions, mass flow rate, reactor temperature and pressure, number of stages in
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The sensitivity analysis was carried out using ASPEN PLUS. ASPEN PLUS has
affected the overall sustainability of a process. Once the sensitivity analysis has been
conducted and important variables have been selected, the next step is to reconfigure the
process. Process reconfiguration is not process specific and can include a wide range of
synthesis
production of by products
Once the process has been reconfigured, the next step is to optimize the process. The
results of the sensitivity analysis will provide reasonable estimates for constraints used in
After the sensitivity analysis has been completed, the next step is to optimize the
process for maximum profit while minimizing wastes and incorporating constraints that
have been selected based on the results of the sensitivity analysis. The process
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optimization was carried out in ASPEN PLUS. ASPEN PLUS has an optimization block
that is available for finding optimum conditions in a process. In this research, profit as
defined by Equation 5.2 is maximized and the mass flow rates of the streams that are
Reducing wastes will lessen environmental impact and health risks. Also finding the
optimum operating conditions will also improve safety risks. The optimization of this
impact of the process. The case studies in the next sections will show the objective
After process optimization, the newly optimum process is re-evaluated using the
impact, the user can accept the optimized process. However, it is important to note that,
the first optimization run might give the optimum sustainable solution. Constraints and
parameters might need to be tweaked in order to ensure that the process is as economic,
environment friendly and socially acceptable as it could be. Once the process changes
have been implemented, the optimization step is repeated and the process is evaluated
improvement, the designer can accept the optimized process otherwise the user will need
to keep re-optimizing the process until they are satisfied with the final solution.
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5.7 SUMMARY
In this chapter, a novel methodology proposed for this research was presented. A
impact assessment methodology is novel for two reasons. The first is that economic,
environmental and impact assessments can be evaluated by one tool making it easier for
Secondly the incorporation of social metrics, i.e. health and safety metrics is quite new as
many researchers don’t incorporate all three dimensions into process design. Also, an
overall sustainability impact was developed. This sustainability impact value provides a
health and safety metrics have been programmed into the tool. A framework which is
useful in identifying and improving sustainability concerns in early stages of design was
conditions.
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Sustainability re-evaluation of the process to ensure it is more sustainable than
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CHAPTER VI
The previous chapter presented the methodology for this research. This
first demonstrated by showing how it can be used to evaluate processes for sustainability.
EVALUATOR can be used to select the most sustainable process option when comparing
two processing alternatives. The dimethyl ether (DME) production process is used to
achieve this step. Once the tool was validated, the overall methodology proposed in
Chapter 5 and Figure 5.1 is later tested with two additional production processes namely:
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6.1 VALIDATION CASE STUDY: METHYL CHLORIDE PROCESS
colorless, extremely flammable and toxic gas. This slightly sweet gas has the physical
used as a chemical intermediate in the drug industry and in the manufacture of methyl
cellulose ether. It is used to synthesize silicone polymers which are used for
agent for several organic chemicals. It also sometimes used as a local anesthetic and as
an herbicide. It was also once used as a refrigerant but was banned due to its toxic
nature. Although the chemical was once synthesized by the reaction of sodium chloride
with methanol in the presence of sulfuric acid, the two major commercial approaches
the impact assessment tool because of the tremendous toxic waste streams present in this
process. These waste steams pose a threat to the environment and human health. Human
exposure to methyl chloride has occurred via contamination of water via hazardous waste
134
sites and occupational exposure. For example, a DuPont methyl chloride leak occurred
recently and affected the health of workers at the exposed facility (Ward, 2010).
Environmental Protection Agency, as one on the top toxic chemicals The health threat of
this chemical poses a serious issue as methyl chloride is a probable carcinogen and is also
linked to other health problems such as nervous system damage and kidney damage etc.
Handling waste streams in the methyl chloride process is a challenge that must be
evaluate the economic, environmental and social impacts of the methyl chloride process.
The information compiled from literature is simulated in ASPEN PLUS version 22 using
thermodynamic package. The block flow diagram for the process is shown in Figure 6.1.
The methyl chloride production process can be divided into three sections namely
thermal chlorination of methane, drying columns and methyl chloride separation. In the
thermal chlorination step, methane (CH4) and chlorine (Cl2) at 14.7 psia and 77oF are sent
to a Mixer (M-601), which combines the two streams into one stream. The mixture is
heated by E-601 to 572oF. Next it is sent to a continuous stirrer reactor (R-601) where
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Figure 6.1: Methyl Chloride Block Flow Diagram
Key design consideration must be incorporated when designing this reactor. The
first is that for the reactions to take place efficiently, methane and chlorine must be
heated above 572oF (Dantus, 1999; Holbrook, 2000). Also the reactor must be operated
at a range of 662 to1022oF in order to control the high heat of reaction (Deforest, 1979;
Dantus, 1999). Also one of the reactants, methane, must not have impurities of more
than 100 ppm to prevent the formation of other by-products such as vinyl chloride,
vinylidene chloride, methyl chloroform etc. (Johnson et al., 1959; Dantus, 1999).
chloride and hydrochloric acid are synthesized in the reactor as shown in Equation 6.1,
several side reactions take place resulting in the following by products: methylene
Equation 6.2-6.4. The rate constants for the kinetics for the reactions taking place in the
reactor are presented in Table 6.2 and the power law expression is shown in Equation 6.5.
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CH3 Cl2 + Cl2 CHCl3 + HCl (6.3)
CHCl3 + Cl2 CCl4 + HCl (6.4)
Table 6.2: Methyl Chloride Process Kinetic Data (Scipioni and Rapisardi, 1961; Dantus,
1999)7
Reaction Number Activation Energy, Ei Pre Exponential Factor
KJ/(kg mol) ( )
1 82000 2.56 X 108
2 71100 6.28 X 107
3 82000 2.56 X 108
4 87200 2.93 X 108
Where
V = Rate of reaction
A = Pre- exponential factor
T = Temperature
a = Temperature exponent
Ea = Activation energy
R = Universal Gas Constant
Cn = Concentration
b = Concentration exponent
After the reaction process, the reactor effluent is cooled to 100oF by cooler (E-
602). Next the separation of methyl chloride from byproducts and the un-reacted raw
materials occurs. First a water stream at 90oF and 14.7 psia is sent along with the cooled
effluent to an absorber (T-601). The water aids the removal of hydrogen chloride and
chlorine gas. The dissociation reactions are presented in the Equations 6.6-6.9 below.
7
Data obtained from Dantus (1999) based on information reported by Scipioni and Rapisardi (1961)
137
To prevent corrosion of equipment and the hydrolysis and decomposition of
chloromethane, the distillate leaving the absorber is sent to a series of drying towers. In
the first drying tower, (T-602) sodium hydroxide is introduced at 86oF and 14.7 psia and
Next the distillate leaving the drying tower, T-602 is cooled to 100oF and 14.7 psia. This
cooled stream is sent along with a sulfuric acid stream to a drying tower, T-603, where
the following reactions shown in Equations 6.12 and 6.13 take place. Excess water is
removed as the bottoms of the drying column, T-603. The distillate from, T-603 is sent
This cooled stream is sent to a flash column, T-604 at 115oF. This is where the
separation steps take place. The bottom of the flash column is sent to three distillation
columns, T-605, T-606 and T-607. In T-605, the separated bottom is sent to T-606 where
methyl chloride is separated as the overhead product. The bottoms of T-606 is sent to T-
607 where carbon tetrachloride and is separated as the overhead product and the bottoms
is considered wastes. The overhead of T-605 is sent to another flash column, T-608. In
this flash column, methyl chloride is also separated as the bottoms while the overhead
column is combined along with the overhead of flash column T-604 and sent to a mixer.
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The mixture which is mostly methane is then sent to a splitter which splits the
mixed stream into a purge stream and another stream is sent to a compressor C-602. The
compressor, C-602 compresses this methane stream at 45 psia. This compressed stream
is later cooled to 77oF before being recycled back to the first mixer, M-301 completing
the process cycle. The key input variables for this process adapted from (Dantus, 1999)
are summarized in Table 6.3. The schematic for this process, the equipment specification
and stream summary tables are presented in Figure C.1, Table C.1 and Table C.2 in
APPENDIX C.
Table 6.3: Methyl Chloride Process Key Input Variables (AIChE, 1966; Dantus, 1999)
Variable Value
Feed Ratio 0.3
Reactor Type Isothermal, CSTR
Reaction Temperature 977 oF
Reactor Effluent, cooling temperature 77 oF
Condenser Temperature -58 oF
Condenser Outlet Pressure 114.7 psia
The economic, environmental and social impacts of the base case methyl chloride
process are calculated using the SUSTAINABILITY EVALUATOR. The data used in
completing the economic evaluations are presented in Table 6.4. The annual production
The ASPEN Economic Evaluation uses imported data from ASPEN PLUS and estimates
capital and operating costs. The capital and operating costs values obtained from the
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ASPEN Economic Evaluator, the mass flow rates of the raw material and product stream
and the economic data shown in Table 6.4 are inputted into the SUSTAINABILITY
EVALUATOR.
Table 6.4: Summary of Economic data for the Methyl Chloride Process
Item Cost ($)
Chlorine Costs $0.21/kg (Reed Business Information Limited, 2010b)
Methane $0.21/kg (Dantus, 1999)8
Process Water $0.00067/kg (Turton et al., 2009)
Sulfuric Acid $0.081/kg (Reed Business Information Limited, 2010b)
Sodium Hydroxide $0.441/kg (Reed Business Information Limited, 2010b)
Methyl Chloride $0.82/kg (Reed Business Information Limited, 2010b)
Methylene Chloride $1.2/kg (Reed Business Information Limited, 2010b)
Chloroform $1.014/kg (Reed Business Information Limited, 2010b)
Carbon Tetrachloride $1.03 (Dantus, 1999)9
Hydrogen Chloride $0.09 (Reed Business Information Limited, 2010b)
Waste Treatment Costs $0.2/kg (Turton et al., 2009)
Capital Recovery Factor 0.1175
The result of this assessment is shown in Table 6.5. As shown in the table, the
estimated annual revenue generated from selling methyl chloride and it’s by product is
around $50.4 million. The annual expenses for this production process were estimated to
be around $66.3 million. The breakdown of the expenses is shown in Figure 6.2. As
shown in Figure 6.2, the raw material costs accounts for 91% of the annual operating
expenses of the methyl chloride process. Operating cost, which is about5% of the
Several waste streams are present in the methyl chloride process, and must hence be
treated.
8
Cost obtained from Dantus (1999) and inflated to 2009 prices
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The waste treatment cost as shown in Figure 6.2 is around $1.5 million and this is
about 2% of the costs. The capital costs for this process is around $9 million but the
purpose of calculating profit, the costs were annualized using the capital recovery factor
shown in Table 6.4. The annualized capital cost is about 2% of the expenses incurred in
Table 6.5: Economic Assessment Results for the Methyl Chloride Process from the
SUSTAINABILITY EVALUATOR
Economic Parameters Base Case (MM)
Revenue $50.4
Operating Costs $3.0
Waste Treatment Costs $1.5
Raw Material Costs $60.7
Capital Costs $9.9
Material Value Added -$10.3
Profit -$19.2
Annualized
Capital Cost, Operating Costs,
$1,168,067.5, $6,220,000.00,
2% 9%
Waste Treatment
Costs,
$1,462,000.00,
2%
Raw Material
Costs,
$60,719,521.70,
87%
Operating Costs Waste Treatment Costs Raw Material Costs Annualized Capital Cost
Figure 6.2: Breakdown of Annual Operating Costs for the Methyl Chloride Process from
the SUSTAINABILITY EVALUATOR
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As shown in Table 6.5, this is not profitable as the process is running at a loss.
The reason for this is that the selling price for the raw material is at least $10 million
more than the products. The negative profit is probably because the simulated process is
based on a 1966 case study and perhaps process improvements have been made over the
years leading to a more profitable process. Another reason could be that methyl chloride
is used to synthesize other chemicals such as silicone. Perhaps those other final products
are more profitable and hence could offset the negative intermediate profit.
Once the economics of the methyl chloride process were calculated, the next step
involved entering the mass flow rates of the waste streams into the SUSTAINABILITY
EVALUATOR. The result of the environment assessment is presented in Table 6.6 and
Figure 6.3. As shown in table and figure, the methyl chloride process, poses a serious
Due to the tremendous waste streams the potential environmental burden includes
to aquatic life and eutrophication. The chemicals contributing to each impact category is
also presented in Table 6.6. Efforts should be made to reduce the waste streams
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Figure 6.3: Environmental Impact Assessment for the Methyl Chloride Process
Table 6.6: Chemicals in the Methyl Chloride Process Contributing to each Environmental
Impact Category
Impact Category Impact Assessment Chemicals Present
Value (Tonnes/year)
2.3E+05 Hydrochloric Acid and
Atmospheric Acidification Sulfuric Acid
2.0E+06 Methane, Methylene Chloride
Chloroform, Carbon
Tetrachloride and Methyl
Global Warming Chloride
Stratospheric Ozone Depletion 1.4E+06 Carbon Tetrachloride
Photochemical Smog 1.2E+02 Methylene Chloride and
Formation Methyl Chloride
7.0E+03 Hydrochloric Acid and
Aquatic Acidification Sulfuric Acid
Aquatic Oxygen Demand 1.1E+03 Methylene Chloride
3.2E+03 Methylene Chloride
Chloroform, Carbon
Ecotoxicity to Aquatic Life Tetrachloride and Chloride
Eutrophication 3.0E+02 Nitrogen
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The resource usage efficiency for this process is also evaluated and the results are
presented in Table 6.7. As shown in the table, the results of the evaluation show that the
methyl chloride production process is not a very resource friendly process. This is
because the methyl chloride process is not a single reaction process, several side reactions
take place and many unwanted products which are considered wastes are created. The
values of the energy intensity, mass productivity, and reaction efficiency are all very low.
While the values of the E-Factor, water intensity, and material intensity are all high.
Investigating ways to reduce the waste streams and improve reaction efficiency would be
Table 6.7: Results of Resource Usage Metric Evaluation for the Methyl Chloride Process
Environmental Impact Value Units
E-Factor 16.7 Kg/Kg
Mass Productivity 5 %
Reaction Mass Efficiency 28 %
Energy Intensity 0.00062 KW/Kg
Water Intensity 4.6 Kg/Kg
After the environmental impact assessment, the next step was to complete a health
and safety impact evaluation using the SUSTAINABILITY EVALUATOR. For the
health assessment, the mass flow rate of each specific component found in the waste
and Figure 6.4, the methyl chloride process poses a serious health risk in all categories.
Methyl chloride and hydrochloric acid are considered group 3 carcinogens. Apart from
cancer risks, other health threats are eminent; these are shown in Table 6.10. In this
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table, the chemical contributing to each health impact category is presented. Due to the
tremendous health risk, it is therefore vital to ensure that the wastes from this process are
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Figure 6.4: Health Impact Assessment for the Methyl Chloride Process
For the safety assessment, the operating conditions, chemicals and equipment
present in the process, are selected in the input section of the software. Also, the mass
enthalpy is entered to estimate the heat of reaction index. The result of the safety
assessment is presented in Table 6.9. The overall total inherent safety index for this
process was around 64. The maximum overall safety index i.e. the worst case scenario
Toxic exposure risks are eminent because the following toxic chemicals are
present in the process: methylene chloride, methyl chloride, chloroform, chlorine, carbon
tetrachloride and sulfuric acid. Another eminent risk is fire due to flammable chemicals
such as methane, methyl chloride and methylene chloride. There are also risks of
corrosion since there are strong acids present in the process. The process is also
146
construction to address this issue. Risk of explosion is present in this process because of
methyl chloride and methylene chloride. These risks must not be ignored, it is important
Table 6.9: Safety Assessment Results from the SUSTAINABILITY EVALUATOR for
the Methyl Chloride Process
Safety Assessment Results Maximum
Heat of main reaction index 2 8
Heat of side reaction index 0 8
Flammability index 8 8
Explosiveness index 6 8
Toxic Exposure Index 24 30
Corrosiveness index 4 4
Temperature index 6 8
Pressure index 2 8
Equipment safety index 4 8
Safety Level of Process Structure index 8 10
Total Inherent Safety index 64 100
The methyl chloride process presented in this case study is not a sustainable process.
As shown in Table 6.10, it is not profitable and hence it has a high economic impact of 1.
There are several waste streams leading to several environmental burdens, therefore it has
a high environmental impact of 0.54. The safety index for the process is around 64 and
there are several health concerns, thus the social impact of 0.59. This process is very
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Table 6.10: Summary of Impact Assessment Results from the SUSTAINABILITY
EVALUATOR for the Methyl Chloride Process
Summary of Results Methyl Chloride
Profit $-19.2 (Not profitable)
Economic Impact 1
Global warming, atmospheric acidification, eutrophication,
ecotoxicity to aquatic life, aquatic acidification
photochemical smog formation and
Environmental Concerns aquatic oxygen demand
Environmental Impact 0.54
Safety Index 64
Carcinogenic risk, developmental damage, reproductive
system damage, circulatory system damage
skeletal system damage, endocrine system damage, liver
damage, immune system damage, kidney damage, skeletal
system damage, nervous system damage, respiratory system
Health Concerns damage and sensory system damage
Social Impact 0.59
Overall Sustainability
Impact 0.65
be validated because the capital and operating costs were obtained from ASPEN PLUS
Economic Analyzer (see chapter 3). ASPEN PLUS Economic Analyzer is a widely used
tool used in industry and academia, for evaluating the economics of chemical processes.
The ASPEN PLUS Economic Analyzer is robust, efficient and reliable and hence the
EVALUATOR are validated with the Waste Reduction Algorithm (WAR). The WAR
(see chapter 3) is a publicly available screening tool used to evaluate the potential
environment impact and health impact of emission of mass and energy for any simulated
148
process. It is able to evaluate and compare the environmental impact of two or more
processes. The impacts categories in the waste reduction algorithm include: acid rain
potential (AP), aquatic toxicity potential (ATP), global warming potential (GWP), human
(PCOP) and terrestrial toxicity potential (TTP). The software provides the potential
For this research, this software is used to validate the environmental portions of
the SUSTAINABILITY EVALUATOR. The objective was to check if the WAR would
developed for this research. Only atmospheric acidification, global warming, ecotoxicity
to aquatic Life, stratospheric ozone depletion and photochemical smog formation was
selected for this validation because these were the only metrics that were similar to
evaluate the environmental impact of the methyl chloride process. To evaluate the
impact, the software reads a user specified report file from ASPEN PLUS and the user
also inputs the energy usage. The results generated from the WAR and the
As shown in the Figure 6.5 and Table 6.11, the major concerns for the methyl
chloride process are aquatic toxicity potential, global warming potential, photochemical
oxidation potential, stratospheric ozone depletion and aquatic acidification. Note that the
WAR provides environmental impact results in kg /hr. This unit was converted to
149
These results compare well and show similar trends with the environmental impact
results provided by the SUSTAINABILITY EVALUATOR. The two tools do not have
the same impact assessment values because a different weight and methodology was used
Figure 6.5: Environmental Impact Evaluation from the Waste Reduction Algorithm
150
The safety portion of the software is mostly valid as the methodology was
obtained from a reliable PhD dissertation (Heikkila, 1999). The only portion of the tool
that was not validated was the health impacts. This is because there are no other health
impact assessment tools to compare results in this manner. Now that the
impact assessment tool, the next step of this research was to test the overall methodology
options. This was demonstrated using the Dimethyl Ether (DME) process case study. In
this case study, there are two chemistries available for producing DME. These are via
dehydration of methanol and via natural gas. The objective is to use the
results obtained from steps 1 and 2 of the proposed methodology as shown in Figure 5.1
DME is a colorless gas that is used as a propellant and as a fuel additive for diesel
151
when it is combusted, it produces minimum amounts of nitrogen oxides, carbon
monoxide and it is sulfur free. It is highly flammable but considered nontoxic. The
Recently, because of its clean burning nature, several scholars have proposed
DME as an alternative fuel for diesel engines, petrol engines and gas turbines (Horstman
et al., 2005; Semelsberger et al., 2006; Arcoumanis et al., 2008; Savadkouhi et al., 2010).
It could be used as fuel for transportation, power generation, cooking heating etc. (Ogawa
et al., 2004). In China and Japan, DME is already being considered as a fuel because of
the abundance of coal (Ogawa et al., 2004; Han et al., 2009). DME can be produced by
two chemistry pathways namely: DME production via dehydration of methanol and DME
DME and water as shown in Equation 6.14 below (Turton et al., 2009). The block
diagram and the schematic of the process are shown in Figure 6.6 and Figure 6.7
respectively.
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This process is simulated in ASPEN PLUS version 22 using the Universal Functional
was selected because it predicts the properties of non-ideal mixtures well and it was
recommended in literature (Jonasson et al., 1995; Kleiber, 1995). The input file for this
Methanol (Stream 1) with 99.5% purity at 25oC and 1 bar is fed as a liquid stream
and pumped by P-201 at 25 bars and combined with another methanol recycle stream
(Stream 13) as shown in Figure 6.7. The combined steams are sent to two heat exchanger
E-201 and E-202 where it is heated to 154oC and 220oC respectively before being sent to
a reactor. The exothermic reaction taking place is the reactor (R-201) results in 80%
conversion of methanol to DME. The products exiting the reactor steam are heated to
364 oC. This exiting stream is cooled down by two coolers E-203 and E-204 to a
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13
DME
10
T-201
11
9
Methanol P-201
E-201 E-202
2
1 12
3
4
T-202
R-201
15 Waste
E-203
6
7 8 16
14
E-204
This throttled steam is sent to the first distillation column (T-101) where the
product DME (stream 10) is separated from the other components. Next the other
components (stream 11) are sent to another distillation column (T-102) where methanol
(stream 13) and water (Stream 15) are separated. Waste Stream 15 is further cooled to
50oC by cooler E-205. The ASPEN PLUS schematic for this process is show in Figure
6.8. The stream summary and equipment specification tables for this process are
154
6.2.1.2 DME Production via Natural Gas
The second option, DME production via natural gas is simulated in ASPEN PLUS
version 22 using UNIFAC, the same thermodynamic package as the previous option.
The block flow diagram and schematic for this process are shown in Figure 6.8 and
Figure 6.9 respectively. The input file for the simulated process is available in
Carbon Monoxide
Hydrogen
Methanol Wastes
Compressor Reactor Separator
Methanol
Carbon Monoxide Carbon Monoxide
Hydrogen Hydrogen
Natural Gas
Methanol
Water Reactor
Steam Reactor Separator
DME
Water
DME
Wastes
Distillation
Column
Wastes
In the steam reforming step, methane (stream 1) with 87.5% purity at 35oC and 1
atm is heated by E-301 to 800oC (stream 2) as shown in Figure 6.9. Water (stream 3) at
35oC and 1atm is also heated by E-302 to 800oC (stream 4). Stream 2 and 4 are fed into
reactor (R-301) where natural gas is reacted with steam over nickel or magnesium oxide
155
CH H 2 O CO 3H 2
4
(6.15)
methane
synthesis gas is cooled to 35oC by E-303 and then sent to a separator to remove excess
water (stream 7). The separated synthesis gas (Stream 8) is sent to a compressor where
the pressure is increased from atmospheric pressure to 40 atm (stream 9). Next, this
stream is sent to a cooler to cool the stream from 644 oC to 240 oC before being sent to
with the aid of carbon dioxide on alumina support as shown in Equation 6.16.
CO 2H 2 CH 3 OH (6.16)
methanol
The reaction results in a 75.5% conversion of carbon monoxide to methanol. Next the
synthesized stream (stream 11) is compressed shortly before being sent to separator (T-
302) where methanol is separated from the syngas mixture. The syngas (stream 14) is
heated from 20 oC to 240 oC shortly before it is sent to the last reactor. Lastly, the
mixture is compressed to a lower pressure and sent to distillation column (T-303). The
mixture (stream 17) is also separated into two streams, a waste stream (Stream 18) and a
DME stream (Stream 19). The schematic of this process is show in Figure 6.9. The
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equipment specification table and stream summary table for this process are presented in
E-304 R-302
P-301
10
Water E-302
9 11
3
8
R-301
4
Methane
T -301
12
2
1
Waste
T -302
5 6
13
E-303
7 Waste Water
E-301
T -304 DME
14
20
19 E-305
T -303 R-303
15
21
M-301 Waste
22
18
16
17
differ by reaction pathways. The two DME processes have been simulated on ASPEN
PLUS version 22 using data from literature (Horstman et al., 2005; Turton et al., 2009).
In this work, the sustainability of the two DME processes are evaluated and compared.
The two DME base cases were simulated on ASPEN PLUS and set to a
production rate of 129.70 kmol/hr and a purity of 99%. The two cases were evaluated for
157
economics, environmental and social concerns. The data used for the economic
evaluation is summarized in Table 6.13. The capital and utility costs are evaluated using
ASPEN PLUS and the results are inputted into the SUSTAINABILITY EVALUATOR.
The raw material and product sale price and the flow rates are imputed as well. The tool
outputs the capital costs, annualized capital costs, material value added and profit as
Table 6.13: Summary of Economic data for the Dimethyl Ether Process
Item Cost ($)
Methanol $0.294/kg (Turton et al., 2009)
Industrial Natural Gas $ 0.21/kg (Dantus, 1999)9
Electricity $0.0717/kilowatt-hour (Energy Information
Administration : Official Energy Statistics
from the U.S. Government, 2009)
DME $1.17/kg (Turton et al., 2009)
Process Water $0.00067/kg (Turton et al., 2009)
Waste Treatment $0.036/kg (Turton et al., 2009)
Capital Recovery Factor 0.1175
Table 6.14: Comparison of Economic Metrics for the two DME options
Economic Parameters DME Via Methanol DME Via Natural Gas
(Option 1) (MM) (Option 2) (MM)
Revenue $61.2 $61.2
Operating Costs $5.4 $10.0
Waste Treatment Costs $0.76 $3.4
Raw Material Costs $21.6 $13.6
Capital Costs $4.7 $12.0
Annualized Capital Cost $0.55 $1.4
Material Value Added $39.7 $47.7
Profit $32.9 $32.8
The capital recovery factor used for the annualized capital cost is based on 20
years and a 10% interest rate. The results of the economic evaluation for the two DME
9
Prices obtained from (Dantus, 1999) but inflated to 2009 costs
158
production options are compared in Figure 6.6 and Table 6.14. The cylinder in the chart
represents option 1 and the box represents Option 2. As shown in the figure both options
are economical with profits of $30 million. However, DME via natural gas has higher
Figure 6.10 : Summary of Economic Results for the two DME Production Options from
the SUSTAINABILITY EVALUATOR
The environmental impacts of the two cases are evaluated based on assessing the
waste streams for potential land or water impact. The inputs of this evaluation include:
mass flow rate of each component in the waste stream. The software supplies the
potency factor for each substance and converts it to the right impact unit. The results of
comparing the environmental burden of the two processes have been depicted on the bar
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Table 6.15: Summary of Chemicals Contributing to Environmental Impact for the Two
DME Options
Environmental Environmental Environmental DME Via DME Via
Impact Impact DME Impact DME Via Methanol Natural Gas
Via Methanol Natural Gas
(Tonnes/year) (Tonnes/year)
Global Warming 2.8E+03 2.8E+05 CH3OH, CH4,CO,
DME CH3OH &
C2H6, C3H8,
Photochemical 5.2E+01 3.0E+03 DAME CO,C2H6,
Smog C3H8 & CH4
Aquatic Oxygen 3.7E+02 1.3E+04 CH3OH CH3OH
Demand
As shown in Figure 6.11, for both cases, because the waste streams don’t have
ozone depletion, aquatic acidification, ecotoxicity to aquatic life and eutrophication, the
environmental impacts are not depicted on the bar graph. The only environmental
concerns for producing DME for both cases are aquatic oxygen demand. Table 6.16
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shows a summary of the chemicals contributing to global warming, photochemical smog
and aquatic oxygen demand. The efficiency of the reactions used in DME formation and
resource usage was also evaluated. The inputs of this evaluation include the following:
mass flow rate of product, reactant and waste streams, energy and water consumed by the
process. Table 6.16 shows a comparison of the results for each of the different cases.
Table 6.16: Summary of Resource Usage Metrics Results from the SUSTAINABILITY
EVALUATOR for the two DME Options
DME Via DME Via Natural
Outputs Methanol Gas Units
E-Factor 0.4 1.8 Kg/kg
Mass Productivity 71 35 %
Reaction Mass Efficiency 71 35 %
Energy Intensity/ Fossil Fuel Usage 0.0002 0.002 KW/Kg
Water Intensity 0.0 1.6 Kg/Kg
161
Social concerns are also evaluated for the two processes. Social impact can be
categorized into health impact and safety risk. The result of the health impact assessment
is depicted in Figure 6.12 and Table 6.17. As shown in the figure, for both options, the
major health risks from potential chemical exposure include developmental damage,
respiratory system damage, nervous system damage and liver damage. DME production
via natural gas has an additional health risk which is reproductive system damage. The
Table 6.17: Summary of Chemicals Contributing to Health Risks for the Two DME
Options
Health Impact Health Impact Health Impact DME Via DME Via
DME Via DME Via Methanol Natural Gas
Methanol Natural Gas
(Tonnes/year) (Tonnes/year)
Developmental 1.5E+05 2.8E+07 CH3OH CH3OH, CO
Damage
Reproductive N/A 1.4E+04 None CO
Damage
Respiratory 1.5E+02 2.4E+04 CH3OH CH3OH,
System Damage CO,C2H6, CH4,
C3H8
Liver Damage 1.5E+02 5.0E+03 CH3OH CH3OH
Nervous System 1.5E+02 6.3E+03 CH3OH CH3OH
Damage
The results of the safety metrics for the two cases are presented in Table 6.18.
The safety assessments of the two processes are compared in Table 6.18. As shown in
the table, DME via methanol has a process safety index of 44 while DME via natural gas
impact from the SUSTAINABILITY EVALUATOR are presented in Table 6.19. The
162
impact for all categories has been scaled from 0 to 1. The smaller the impact value, the
Table 6.18: Results of Safety Metrics from the SUSTAINABILITY EVALUATOR for
the two DME Options
DME Via DME Via
Outputs for Process Safety Evaluation Methanol Natural Gas
Heat of main reaction index 0 2
Heat of side reaction index 0 4
Flammability index 8 8
Explosiveness index 4 6
Toxic exposure index 12 16
Corrosiveness index 4 4
Temperature index 6 8
Pressure index 2 6
Equipment safety index 4 8
Inputs for safety level of process structure index 4 4
Total inherent safety index 44 66
The selection of the most sustainable DME production process is based on the
result obtained from the SUSTAINABLE EVALUATOR. In this section, the results of
each of the sustainable category are discussed and are summarized in Table 6.20. As
shown in Table 6.20, the profits for the cases are similar with a value of $33 million.
However, DME production via natural gas has a higher capital and operating costs
163
compared to the first option. For both cases, an economic impact of 0, was obtained,
process compared to DME via natural gas as presented in Figure 6.11. DME via
methanol option is more environmental friendly because intermediate products are not
produced and the process also has a methanol recycle stream reducing the amount of
wastes from this option. Also as shown in the results presented in Table 6.16, DME
production via methanol is more efficient in all categories compared to DME production
via natural gas. DME via methanol dehydration is more environmental friendly because
164
it had a lower environmental impact value of 0.09 compared to option 2 which have a
value of 0.24.
In terms of social concerns, as shown in Figure 6.12, DME production via natural
gas (option 2) has a higher health risk from the following impact categories:
developmental damage, respiratory system damage, and liver damage compared to DME
production via methanol. The results for safety risk evaluation as shown in Table 6.18,
illustrates that DME production via methanol has a process safety index of 44 and is thus
a safer process compared to DME production via natural gas which has a process safety
index of 66. DME production via natural gas has a higher process safety index value due
to the more exothermic reactions taking place in the process, more toxic chemicals,
higher process temperature and the presence of compressors and high hazard reactors.
DME via methanol dehydration is more socially acceptable because it had a lower social
DME via methanol dehydration also had a lower overall sustainable impact value
of 0.11 compared to option 2 which had a value of 0.24. Based on the results presented
earlier and overall sustainable impact obtained from the SUSTAINABLE EVALUATOR,
it can be concluded that the production of DME production via methanol dehydration is
friendly and socially acceptable compared to the DME production via natural gas.
Acrylonitrile is a colorless liquid with a slightly sharp, irritating odor. Its physical
properties are shown in Table 6.21. The chemical is a monomer used in the synthesis of
165
polymers in the chemical industry. These polymers are utilized in the manufacturing of
plastics, acrylic fibers, rubber and nylons. It is also used as an intermediate in the
in the United States (Kanuri, 2000; Fechter et al., 2004). Although the chemical can be
America Sohio Process. The Sohio process involves a catalytic gas phase oxidation
toxic waste streams and byproducts such acetonitrile, acrolein, carbon monoxide and
hydrogen cyanide.
the proposed methodology because of the tremendous toxic waste streams present in this
process. These waste steams pose a threat to the environment and human health. Human
exposure to acrylonitrile has occurred via contamination of water via hazardous waste
sites and occupational exposure. This chemical is listed in the toxic release inventory
compiled by the Environmental Protection Agency, as one on the top toxic chemicals
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• ACRYLONITRILE BASE CASE PROCESS MODELING
Step 1 •Collection of input data from literature
•Simulate process on a process simulator e.g. Aspen Plus
Also, this chemical polymerizes easily and can become a severe fire and
explosion hazard if exposed to light (Reed Business Information Limited). The health
threat of this chemical poses a serious issue as acrylonitrile is a suspected carcinogen and
is also linked to other health problems such as nervous system damage, kidney damage
etc. Handling the waste streams in this process is a challenge that must be handled in a
6.13 is applied towards handling the sustainability concerns of the acrylonitrile process.
167
6.3.1 Acrylonitrile Base Case Process Modeling
1996; de Haes et al., 1999; Kanuri, 2000). The information compiled from literature is
simulated in ASPEN PLUS version 22 using the Electrolyte Non-Random Two Liquid
diagram and the schematic for this process are shown in Figure 6.14 and Figure C.2
Figure 6.14: Block Flow Diagram for the Base Case Acrylonitrile Process
The production process can be divided into two sections namely propane
propane and oxygen at 14 psia and 80oF are fed to a mixer (M-301), which combines the
three streams into one stream. The mixture is sent to R-301, a plug flow reactor (PFR).
The PFR is operated at 852 oF and 28.9 psia. Propylene and ammonia are reacted with
shown in Equation 6.18 in this reactor, several side reactions take place resulting in other
168
by products (acetonitrile, arolein, carbon dioxide, carbon monoxide and hydrogen
cyanide) as shown in Equations 6.19-6.23. The kinetics or the reactions taking place in
the reactor is presented in Table 6.22 and the rate constant are presented in Equation
6.24-6.29.
After the reaction process, a sulfuric acid stream at 80 oF and 14.7 psia is
introduced and sent along with the reacted mixture to another mixer (M-302). Next the
separation of acrylonitrile from byproducts and the un-reacted raw materials occurs. First
the mixture is sent to a neutralizer (R-302), where ammonia reacts with sulfuric acid and
169
ammonium sulfate is produced as shown in Equation 6.30. This reaction aids in the
removal of un-reacted ammonia. Next the steam exiting the neutralizer is sent to a
separator (T-301) where the ammonium sulfate and sulfuric acid are separated from the
Ammonium Sulphate
2NH3 + H 2SO 4 NH4 2 SO 4 (6.30)
The un-separated distillate stream is cooled via a cooler (E-301) to 40oF and 20
psia and a water stream operating at 161 oF and are sent to an absorber (T-302) , where
carbon monoxide, propylene and oxygen are separated as the distillate stream and
aqueous solution of acrylonitrile, acetonitrile and hydrocyanic acid are present in the
bottoms of the distillation column. The bottoms stream is heated by heat exchanger E-
202 to 173 oF and 15 psia. The heated stream is sent to a stripper (T-303) where excess
water is removed from the nitrile mixture. The nitrile mixture is cooled to 126 oF and
14.7 psia by heat exchanger E-303. The heated stream is sent to two distillation columns
(T-304 and T-305) where waste hydrocyanic acid and acrolein are removed. Finally in
the last column (T-306), acrylonitrile is separated from acetonitrile. The schematic for
this process, the equipment specification and stream summary tables are presented in
The economic, environmental and social impact of the base case acrylonitrile
completing the economic evaluations are presented in Table 6.23. The annual production
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Table 6.23: Summary of Economic Data for the Acrylonitrile Process
Item Cost ($)
Ammonia $0.38/kg (Reed Business Information Limited, 2010b)
Propylene $0.981/kg (Turton R. et al., 2009)
Oxygen $0.11/kg (Remediation & Natural Attenuation Services Inc.,
2010)
Sulfuric Acid $0.081/kg (Reed Business Information Limited, 2010b)
Process Water $0.00067/kg (Turton et al., 2009)
Acrylonitrile $2.6/ kg (Reed Business Information Limited, 2010a)
Acetonitrile $2.5/ kg (Reed Business Information Limited, 2010b)
Waste Treatment Costs $0.12/kg (Turton et al., 2009)
Low Pressure Steam $14.05/GJ (Turton et al., 2009)
o
Cooling Water: 30 C $0.354/ GJ (Turton et al., 2009)
Capital Recovery Factor 0.1175
The ASPEN Economic Evaluation uses imported data from ASPEN PLUS and estimates
capital and operating costs. The capital and operating costs values obtained from the
ASPEN Economic Evaluator, the mass flow rates of the raw material and product stream
and the economic data shown in Table 6.23 are inputted into the SUSTAINABILITY
EVALUATOR.
The result of this assessment is shown in Table 6.24. As shown in the table, the
estimated annual revenue generated from selling the acrylonitrile is around $23.9 million.
The annual expenses for this production process were estimated to be around $18.3
million. The breakdown of the expenses is shown in Figure 6.15. As shown in Figure
6.15, the raw material costs accounts for 78% of the annual operating expenses of the
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Table 6.24: Economic Assessment Results for the Base Case Acrylonitrile Process from
the SUSTAINABILITY EVALUATOR
Economic Parameters Base Case (MM)
Revenue $23.9
Operating Costs $2.1
Waste Treatment Costs $1.9
Raw Material Costs $18.3
Capital Costs $9.2
Material Value Added $5.6
Profit $0.43
Raw Material
Costs,
$18,288,257.20,
78%
Operating Costs Waste Treatment Costs Raw Material Costs Annualized Capital Cost
Figure 6.15: Breakdown of Annual Operating Costs for the Base Case Acrylonitrile
Several waste streams are present in the acrylonitrile production process, and
must hence be treated. The waste treatment cost as shown in Figure 6.15 is around $1.9
million and this is about 8% of the costs. The capital costs for this process is around $9
million but the purpose of calculating profit, the costs were annualized using the capital
recovery factor shown in Table 6.24. The annualized capital cost is about 5% of the
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profitable process in which the estimated annual profit was calculated to be around $0.43
million.
Once the economics of the acrylonitrile process had been calculated, the next step
involved entering the mass flow rates of the waste streams into the SUSTAINABILITY
shown in Table 6.25, the acrylonitrile production process, poses a serious threat to the
environment.
Table 6.25: Results of Environmental Impact Assessment for the Base Acrylonitrile
Process
Impact Category Impact Assessment Chemicals Present
Value (Tonnes/year)
Atmospheric Acidification 15.5 Ammonia and Sulfuric Acid
Global Warming 11280.5 Carbon dioxide, Carbon
Monoxide, Acrolein, Propylene,
Acrylonitrile and Acetonitrile
Stratospheric Ozone Depletion 0.0 N/A
Photochemical Smog 291.5 Carbon Monoxide & Propylene
Aquatic Oxygen Demand 0.1 Ammonium Sulphate
Ecotoxcity to Aquatic Life 979.7 Ammonia
Eutrophication 1.4 Ammonia
eutrophication. The chemicals contributing to each impact category are also presented in
Table 6.25. Efforts should be made to reduce the waste streams associated with this
production process.
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The resource usage efficiency for this manufacturing process is also evaluated and
the results are presented in Table 6.26. As shown in the table, the results of the
evaluation show that the base case acrylonitrile process is not resource friendly. This is
because the formation of acrylonitrile is not a single reaction process. Several side
reactions take place and many unwanted products which are considered wastes are
created. The values of the, mass productivity, and reaction mass efficiency are all very
low, while the values of the E-Factor, water intensity, and energy intensity are all high.
Investigating ways to reduce the waste streams and improve reaction efficiency would be
Table 6.26: Results of Resource Usage Evaluation for the Base Case Acrylonitrile
Process
Environmental Impact Value Units
E-Factor 1.8 Kg/Kg
Mass Productivity 19 %
Reaction Mass Efficiency 25 %
Energy Intensity 0.0021 KW/Kg
Water Intensity 0.5 Kg/Kg
After the environmental impact assessment, the next step was to complete a health
and safety impact evaluation using the SUSTAINABILITY EVALUATOR. For the
health and safety assessment, the mass flow rates of each specific component found in the
Table 6.27, the acrylonitrile process poses a serious health risk in all categories.
Apart from cancer risks, other health threats are eminent; these are shown in Table 6.27.
In this table, the chemical contributing to each health impact category is presented. Due
174
to the tremendous health risk, it is therefore vital to ensure that the wastes from this
process are handled appropriately and explosions and spills are kept at a minimum.
Table 6.27: Results of Health Impact Assessment for the Base Case Acrylonitrile Process
Impact Category Impact Value Chemicals Present
(Tonnes/year)
Carcinogenic Risk 2.06E+02 Acrolein & Acrylonitrile
Immune System Damage 2.1E+02 Acrylonitrile
Skeletal System Damage 1.2E+02 Sulfuric Acid
Developmental Damage Acrolein, Acetonitrile,
Acrylonitrile, Ammonia, Carbon
4.0E+03 Dioxide &Carbon Monoxide
Reproductive System Damage Acetonitrile, Acrolein,
Acrylonitrile, Ammonia, Carbon
Dioxide, Carbon Monoxide &
4.3E+03 Hydrogen Cyanide
Kidney Damage 2.1E+02 Acrylonitrile
Respiratory System Damage Acetonitrile, Acrolein,
Acrylonitrile, Ammonia, Carbon
Dioxide, Carbon Monoxide,
Hydrogen Cyanide, propylene,
Sulfuric acid & Ammonium
9.9E+03 Sulphate
Cardiovascular System Damage Acetonitrile, Acrolein,
Acrylonitrile, Ammonia, Carbon
2.4E+03 Monoxide & Hydrogen Cyanide
Endocrine System Damage 1.0E+03 Acrylonitrile
Liver Damage Acetonitrile, Acrolein,
Acrylonitrile, Ammonia, Hydrogen
Cyanide, Propylene, Sulfuric acid
4.6E+03 & Ammonium Sulphate
Nervous System Damage Acetonitrile, Acrolein,
Acrylonitrile, Ammonia, Carbon
Dioxide, Carbon Monoxide,
Hydrogen Cyanide & Ammonium
7.6E+03 Sulphate
Sensory System Damage Acrolein, Acrylonitrile &
1.2E+03 Ammonia,
For the safety assessment, the operating conditions, chemicals present and
equipment present are selected in the input section of the software. Also, the mass
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enthalpy is entered to estimate the heat of reaction index. The result of the safety
assessment is presented in Table 6.28. The overall total inherent safety index for this
process was around 70. The maximum overall safety index i.e. the worst case scenario
for any process is 100. As shown in the table, the obvious safety concerns are
flammability, toxic exposure risks and heat of main reaction which are at their maximum
index value. Flammable risks are present due to presence of the following chemicals;
Table 6.28: Safety Assessment Results from the SUSTAINABILITY EVALUATOR for
the Base Case Acrylonitrile Process
Safety Assessment Results Maximum
Heat of main reaction index 4 8
Heat of side reaction index 4 8
Flammability index 8 8
Explosiveness index 6 8
Toxic Exposure Index 24 30
Corrosiveness index 4 4
Temperature index 6 8
Pressure index 2 8
Equipment safety index 4 8
Safety Level of Process Structure index 8 10
Total Inherent Safety index 70 100
Toxic exposure risks are eminent because the following toxic chemicals that are
carbon monoxide, hydrogen cyanide and sulfur dioxide. Other eminent risks are heat of
side reaction, temperature, and explosive index. The risk level of these index are due to
the nature of the reaction taking place in the reactors, the operating temperature in the
process and the explosive chemicals present in the process. These risks must not be
176
ignored, it is important to investigate ways to ensure safety is not compromised in this
process.
After evaluating the sustainability of the base case, it was apparent that it was
necessary to optimize the process for economic, environmental, health and safety risk
improvements. But before the optimization step, it was essential to identify parameters
that affect the selected metrics. In order to identify these parameters, a sensitivity
analysis was completed for the acrylonitrile base case. The sensitivity analysis was
carried out using ASPEN PLUS. The parameters that were considered were operating
conditions, variation of inlet flow-rates and equipment configuration. The above mention
parameters are varied and the effect on the following was studied: acrylonitrile mass flow
rate, propylene conversion, total waste produced, material value added (revenue-raw-
The key raw materials involved in the manufacture of acrylonitrile are propylene,
ammonia and oxygen. Literature data recommends using the following feed ratio range
Since this was a range, it was therefore important to investigate how varying the feed
ratio affected revenue, material value added, and raw material costs. The inlet feed flow
Annual
Material
Ammonia Oxygen Propylene Total Annual Raw Annual Value Oxygen Propylene
Flow rate Flow rate Flow rate Waste materials Revenue Added /Propylene /Ammonia
Case (Ibmol/hr) (Ibmol/hr) (Ibmol/hr) (Ibmol/hr) Cost ($MM) ($MM) ($MM) feed ratio feed ratio
Base
Case 85 129 85 10885 16.4 19.6 3.2 1.5 1
1 70 140 95 9390 17.2 27.2 9.98 1.47 1.36
2 75 140 95 9559 17.4 27.2 9.79 1.47 1.27
3 70 135 90 9135 16.4 26.0 9.60 1.50 1.29
4 70 135 95 9269 17.2 26.8 9.57 1.42 1.36
5 60 130 75 8439 13.8 23.3 9.55 1.73 1.25
6 65 130 75 8650 13.9 23.4 9.46 1.73 1.15
7 75 135 90 9440 16.6 26.0 9.39 1.50 1.20
8 65 130 80 8789 14.7 24.1 9.38 1.63 1.23
9 75 135 95 9574 17.4 26.8 9.36 1.42 1.27
10 65 140 85 9356 15.6 24.9 9.35 1.65 1.31
11 60 130 80 8593 14.6 23.9 9.32 1.63 1.33
12 80 140 100 11887 18.4 27.6 9.20 1.40 1.25
13 60 125 70 8182 12.9 22.1 9.18 1.79 1.17
14 75 135 100 9719 18.3 27.4 9.17 1.35 1.33
15 80 135 90 9785 16.8 26.0 9.17 1.50 1.13
16 70 130 80 9139 14.9 24.1 9.17 1.63 1.14
17 80 135 95 9919 17.7 26.8 9.14 1.42 1.19
18 70 140 100 9590 18.1 27.1 9.09 1.40 1.43
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Ammonia: 60 -120 lbmole/hr
Oxygen:60-180 lbmole/hr
The total number of runs for this analysis was 1378 runs and the results of the 19 best
scenarios are presented in Table 6.29. These runs were selected because they had the
highest material value added value. The best case scenario, case 1 has a material added
value of $9.98M.
propylene conversion and acrylonitrile production. The higher the conversion, the lower
waste produced and the higher the acrylonitrile production value would be. According to
literature, typical reactor temperature range for the acrylonitrile process ranges from 600-
1111 oF (Kanuri, 2000). Therefore, the reactor temperature was varied at that range as
increases as well as acrylonitrile formation. However, after 860oF, the increase in both
parameters comes to a halt, there by resulting in the conclusion that the optimum
propylene conversion. According to literature, typical reactor pressure range for the
acrylonitrile production process ranges from 5 -45 psia (Venkataraman, 1996; Kanuri,
2000). Therefore, the reactor pressure was varied at that range as shown in Figure 6.17.
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As the reactor pressure is varied, it can be concluded that conversion of propylene to
80
70
60
50
Conversion (%)
40
30
20
10
0
600 700 800 900 1000 1100 1200
Temperature (oF)
180
6.3.3.4 Effect of Varying Plug Flow Reactor Length and Diameter on Conversion
The reactor length is varied from 10-30ft as shown in Figure 6.18. At first,
conversion increases from 52-74% the length is varied from 0 -18ft but after 12ft, the
conversion remains constant even when the length is increased. The reactor diameter is
also varied from 0.5-3ft. As shown in Figure 6.19, as reactor diameter is increased
80
75
70
65
Conversion (%)
60
55
50
45
40
35
30
0 5 10 15 20 25 30 35
Reactor Length (ft)
80
70
60
50
Conversion (%)
40
30
20
10
0
0 0.5 1 1.5 2 2.5 3 3.5
Reactor Diameter (Ft)
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6.3.3.5 Effect of Varying Stripper Feed Tray (T- 303)
The objective of the stripper is to remove water from the by-products while
ensuring that there is almost complete recovery of acrylonitrile. The feed stage was
noticed to impact this objective. The stripper has 30 stages, thus in order to determine the
optimum feed stage, it is varied from 2-30. As shown in Figure 6.20, the ideal feed stage
was found to be feed stage of 10 with a water removal flowrate of 317 lbmole/hr and
320 120
100
315
Water Removal (Ibmole/hr)
60
305
Water Removal Acrylonitrile Recovery
40
300
20
295 0
0 5 10 15 20 25 30
Feed Stage
Figure 6.20: Effect of Varying Feed Stage on Water Removal and Acrylonitrile Recovery
The absorber separates the gases from the liquid products. The absorber reflux
was noticed that it not have an effect on acrylonitrile recovery but it did have an effect on
the condenser and re-boiler duty as shown in Figure 6.21. The lower the reflux ratio, the
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lower the condenser and re-boiler duty. Hence the optimum re-boiler duty and condenser
Figure 6.21: Effect of Absorber Reflux Ratio on Condenser and Re-boiler Duty
The sensitivity analysis assisted in identifying parameters that affected, profit and
Feed ratio
183
The step after completing the sensitivity analysis is process reconfiguration. The
first step was to investigate if some of the waste streams could be converted to recycle
streams. The elimination of waste streams impacts economics positively because it leads
to a reduction in environmental and health impacts as well as waste treatments costs. The
acrylonitrile process was reconfigured so that waste stream 10 leaving the absorber (T-
302) was separated and then recycled. To aid this objective, two distillation columns are
incorporated into the process. The distillate stream leaving the absorber which contains
carbon dioxide, carbon monoxide, propylene and hydrogen cyanide are sent to two
distillation columns, T-307 and T-308. T-307 separates carbon monoxide and carbon
dioxide from the mixture. The bottom stream is sent to T-308 where the recovery of
propylene takes place and hydrogen cyanide is also separated. The recovered propylene
is recycled back to reactor (R-301). This distillation column (T-307) recovers some of
the un-reacted propylene. Since HCN is being recovered in T-307, one of the earlier
HCN separator columns, T-304 is eliminated. Since water is being produced in the
process, water recovered from the stripper (T-303) is recycled back to the absorber
eliminating the need for process stream 6. The modified process is presented in the block
flow diagram shown in Figure 6.22. Another important consideration was improving the
reaction efficiency. If more of the raw materials are converted to the desired product,
less waste would be generated. Once the process had been reconfigured based on the
changes described above, it is then optimized in ASPEN PLUS as discussed in the next
section.
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Figure 6.22: Block Flow Diagram of the Reconfigured Acrylonitrile Process
The key goal in this step is to maximize annual profit ($/yr) while minimizing waste
(kg/yr). Profit is defined by Equation 5.2 shown below. The waste streams as shown in
Figure C.2 (Appendix C) include stream 5, 14, 19 and 23. Thus total waste is presented
in Equation 6.3.1. Thus the optimization equations for this problem are shown below are
described in Equation 6.32-6.36. The process is optimized based on the different ranges
Total Waste= Mass Flow Rates of Stream 5+ Mass Flow Rates of Stream 14+ Mass
Flow Rates of Stream 19+ Mass Flow Rates of Stream 23 (6.31)
185
Conversion ≥ 60% (6.36)
in Figure C.3. The stream summary and the equipment specification table for the
optimized acrylonitrile process are presented in Table C, 9 and Table C.10 respectively in
APPENDIX C. After the optimization of the base case, the next step was to complete an
economic assessment using ASPEN Economic Evaluator. Also, the process is evaluated
186
economical, environmental friendly and socially acceptable compared to the base case.
Table 6.31. The first key change was the reduction in raw material flow rate. This was
possible because some of un-reacted raw material was recycled back to reactor (R-301).
Another important change was the fact that acrylonitrile production increased from 44 lb
-mole/hr to 51.6 lb-mole/hr. The optimization of the acrylonitrile process led to a waste
Table 6.31: Key Differences between the Base and Optimized Acrylonitrile Processes
Major Change Base Case Value Optimized Value
Feed Flow Rate Ammonia = 85 lbmole/hr Ammonia = 67 lbmole/hr
Oxygen = 129 lbmole/hr Oxygen = 129 lbmole/hr
Propylene = 85 lbmole/hr Propylene = 66 lbmole/hr
Sulfuric Acid 11 lbmole/hr 2.097 lbmole/hr
Number of Recycle Streams 0 2 (propylene to the reactor
and water to the absorber)
Acrylonitrile Production 44 lb-mole/hr 46.8 lb-mole/hr
Stream Elimination N/A Water Stream Elimination
Waste 1.65 E+07 lb/year 9.44 E+06 lb/year
Profit $0.4MM $ 3.5MM
Profit Relative to 2% 17%
Investment
Sustainability Impact 0.50 0.36
Once the maximum profit and minimum waste had been determined, the next step
was to evaluate and compare the sustainability of optimized and base case acrylonitrile
processes. The first step was to compare the economics of the two cases. The results of
the economic assessment are shown in Table 6.32 and Figure 6.23. As shown in Table
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6.32, although the optimized acrylonitrile process has higher operating and capital costs,
it has lower raw material and waste treatment costs compared to the base case.
Table 6.32: Comparison of Economic Metrics for the Base and Optimized Acrylonitrile
Processes
Economic Parameters Base Case Acrylonitrile Optimized
Process (Million) Acrylonitrile Process
(Million)
Revenue $23.9 $23.9
Operating Costs $2.1 $3.9
Waste Treatment Costs $1.9 $1.1
Raw Material Costs $18.3 $14.2
Capital Costs $9.2 $10.1
Material Value Added $5.6 $9.7
Profit $0.43 $3.5
The higher operating cost is due to the addition of the distillation columns and the
recycle stream. A slight increase in product led to increase in revenue compared to the
base case. Also the recycle of propylene back to the reactor and the reduction in
ammonia feed rate led to lower raw material costs. This also led to lower waste treatment
costs as less wastes were being produced. As shown in Figure 6.23 the optimized
acrylonitrile process which has an overall profit of $3.5 million is a more profitable
process compared to the base case which has a profit of $0.43 million. The profit relative
to investment for the optimized case is around 17% which is higher compared to the base
case which has a value of about 2%. Therefore the optimized case had a lower economic
impact value of 0.50 compared to the base case which had a value of 0.95.
The environmental impacts of the two cases are evaluated based on assessing the
waste streams for potential land or water impact. The results of comparing the
environmental burden of the two processes have been depicted on the bar graph shown in
Figures 6.24. As shown in Figure 6.24, the optimized acrylonitrile process has a lower
188
environmental impact in all categories compared to the base case. An analysis was
completed to investigate the percent reduction for each environmental impact category.
As shown in Table 6.33, the percent reduction is significant for all categories. This
Figure 6.23: Comparison of Economic Assessment of the Base Case and Optimized
Acrylonitrile Process
Next the efficiency of the reactions used in acrylonitrile formation and resource
usage is evaluated and compared with the base case. Table 6.34 shows a comparison of
the results of the two cases. As shown in the table, mass productivity and reaction mass
for the optimized case increased to 28%, 29% and 30% respectively. While E-factor, and
elimination of the water stream. Rather, water is generated and recycled. The only
metric that did not improve was energy usage because of the higher utility needs of the
189
optimized case. In general for all resource usage metrics except energy usage, the
optimized acrylonitrile process is more efficient compared to the base case. Also the
optimized case is more ecological efficient because it has a lower environmental impact
Figure 6.24: Comparison of Environmental Impacts Assessment for the Optimized and
Base Case Acrylonitrile Process
190
Table 6.34: Resource Usage Metrics Results for the Base and Optimized
Acrylonitrile Cases
Outputs Base Case Optimized Case Units
E-Factor 1.8 1.0 Kg/kg
Mass Productivity 19% 28 %
Reaction Mass Efficiency 25% 29 %
Energy Intensity 0.0018 0.0021 KW/Kg
Water Intensity 0.5 0.0 Kg/Kg
The health impact of the optimized acrylonitrile process is also evaluated and
compared with the base case and this is presented in Figure 6.25. From the figure, in
general the health risk for the optimized case is lower compared to the base case. An
assessment was completed to determine the percent reduction for each health impact
category. As shown in Table 6.35, the percent reduction is highest for carcinogenic
health risk (96%), immune system damage (97%), kidney damage (97%) and skeletal
The safety of the optimized acrylonitrile process was also evaluated and
compared with the base case. As shown in Table 6.36, the results of the optimized
acrylonitrile process shows that there are no changes in overall safety impact. It was
difficult to really improve safety impact values because most of the other impact values
are based on the chemicals present in the process and the operating temperature and
pressure. Changes made to the operating temperature would have affected conversion
leading to a loss in product formation. Also the process was not directly optimized for
safety, so no improvement in safety was expected. The overall social impact for the
optimized case was 0.52 compared to the base case which was 0.62.
191
Figure 6.25: Comparison of Health Impacts Assessment the Base and Optimized
Acrylonitrile Process
Table 6.35: Percent Reduction of the Health Impact of the Acrylonitrile Optimized Case
relative to the Base Case
Base Case Optimized
(Tonnes/year) Case Percent
Health Impacts (Tonnes/year) Reduction
Carcinogenic Risk 2.1E+02 7.9E+00 96%
Immune System Damage 2.1E+02 7.2E+00 97%
Skeletal System Damage 1.2E+05 4.0E+03 97%
Developmental Damage 4.0E+03 3.7E+03 8%
Reproductive System Damage 4.3E+03 3.9E+03 9%
Kidney Damage 2.1E+02 7.2E+00 97%
Respiratory System Damage 9.9E+03 5.4E+03 45%
Cardiovascular System Damage 2.4E+03 2.1E+03 13%
Endocrine System Damage 1.0E+03 9.8E+02 2%
Liver Damage 4.6E+03 1.6E+03 65%
Nervous System Damage 7.6E+03 4.5E+03 41%
Sensory System Damage 1.2E+03 9.9E+02 18%
192
Table 6.36: Summary of Results of Safety Metrics for the Base and Optimized
Acrylonitrile Processes
Outputs for Process Safety Evaluation Base case Optimized Case
Heat of main reaction index 4 4
Heat of side reaction index 4 4
Flammability Index 8 8
Explosiveness Index 6 6
Toxic Exposure Index 24 24
Corrosiveness Index 4 4
Temperature Index 6 6
Pressure Index 2 2
Equipment safety Index 4 4
Inputs for Safety Level of Process Structure Index 8 8
Total Inherent Safety Index 70 70
6.3.6 Summary
The optimized acrylonitrile process differed from the base case because the
Recycling water from the stripper (T-303) which aided in the elimination
of process stream 6.
The optimized acrylonitrile process has an economic impact of 0.75 compared to the base
case which has a value of 0.95. The optimized case has lower raw material costs and
higher revenue. Therefore the profit of the optimized case relative to investment was
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The optimized acrylonitrile process is environment friendly as wastes reduced by
43% compared to the base case. This waste reduction of the optimized case led to
improve resource usage metrics and lower environmental impacts resulting in a lower
environmental impact of 0.17 compared to 0.22. This happened as a result of the recycle
of un-reacted raw material and the elimination of process water. In terms of social
concerns, the optimized acrylonitrile case has a lower health risk compared to the base
case. There were no changes made to the process safety index. The social impact value
of the optimized case is 0.43 compared to the base case which was 0.35.
lower overall sustainability impact value of 0.31 compared to the base case which had a
value of 0.45. Based on the results obtained from the SUSTAINABLE EVALUATOR, it
the base case because it is more economical viable, environmentally friendly and socially
chloro-2 propene, is a colorless organic liquid. This compound is insoluble in water, but
miscible in other substances such as chloroform, alcohols and ethers. The physical
properties of this extremely flammable and toxic chemical are shown in Table 6.37. The
discovery of the synthesis of allyl chloride via substitutive chlorination of propylene was
194
However, allyl chloride via substitutive chlorination of propylene is the more economic
the pharmaceutical industry and in the manufacture of allyl alcohol, allylamine, allyl
most cases, allyl chloride is converted to epichlorohydrin which is used for creating
epoxy resins and glycerol. It is also used for synthesizing sodium allyl sulfonate which is
used for brightening metals for electroplating baths (Kneupper and Saathoff, 2000).
demonstrate the proposed methodology because of the tremendous toxic waste streams
present in this process that are regulated by the Environmental Protection Agency (EPA).
These waste steams pose a threat to the environment and human health. According to the
EPA, allyl chloride is considered a very volatile hazardous air pollutant that must be
chemical that must comply with the EPA’s Resource Conservation and Recovery Act
195
• ALLYL CHLORIDE BASE CASE PROCESS MODELING
Step 1 •Collection of input data from literature
•Simulate process on a process simulator e.g. Aspen Plus
Figure 6.26: Proposed Methodology for Addressing Sustainability Concerns of the Allyl
Chloride Process
Workers in allyl chloride processing plants have been exposed to the chemical via
Agency, 1986). Skin contact with allyl chloride leads to skin irritation and possibly
delayed burns. Breathing in vapors of the chemicals, results in severe, eye, noses and
throat irritations. Severe exposure to the chemical can even lead to death. There are
other long term health risks associated with exposure to allyl chloride. These include
cancer, liver and kidney damage, nervous system damage, reproductory system damage
and sensory system damage. The two other by products of ally chloride 1, 2 –
196
dichloropropane and 1, 3-dichloropropene are also volatile hazardous compounds
to handle the allyl chloride process waste streams in a sustainable manner. The
Allyl chloride is modeled based on literature (van der Helm, 1992). The
information compiled from literature is simulated in ASPEN PLUS version 22 using the
ideal gas model with Raoutls law (SYSOPQ) equation of state thermodynamic package.
The block flow diagram of this process is shown in Figure 6.27. The allyl chloride
production process can be divided into two main sections namely substitutive
heated via a heater, E-901 to 730 oF. This heated propylene stream is combined by mixer
(M-901), with chlorine (Cl2) at 14.7 psia and 80oF. Next, the heated stream is sent to an
197
adiabatic plug flow reactor (R-901) where the substitutive chlorination of propylene as
Key design consideration must be incorporated when designing this reactor. The
first is that for the reactions to take place efficiently, the reactor must be operated at a
temperature range of 570-1110 oF to ensure favorably formation of allyl chloride (van der
Helm, 1992). When the reactor is operated below 570 oF, the formation of one of the
Equation 6.38 below. Thus the reaction must be kept above 570 oF to keep allyl chloride
as the major product and 1, 2 dichloropropane as well as cis and trans 1,3
dichloropropane as the byproducts as shown in Equations 6.38 and 6.39. This reaction is
highly exothermic, thus it is recommended that these is no heat transfer across the
reactor. The rate constants for the kinetics for the reactions taking place in the reactor are
Propylene 1,2-dichloropropane
CH 2 = CH - CH 3 + Cl 2 CH 2 Cl - CHCl - CH 3 (6.38)
AllylChloride 1,3-dichloropropene
CH 2 = CH - CH 2 Cl + Cl 2 CHCl CH - CH 2Cl HCl (6.39)
After the reaction step, the purification of the product from the by product and un-
reacted raw material begin. The reactor effluent is cooled to 70oF by cooler (E-602) and
hydrochloric acid and propylene are separated as the distillate stream while allyl chloride,
overhead product of T-901 along with a water stream operating at 70oF and 14.7 psia are
198
sent to the second distillation column, T-902. Here propylene and water are separated as
the distillate and hydrochloric acid and water are separated as the bottoms stream. The
overhead product of T-902 is sent to separator, T-903 where propylene is separated as the
distillate and water as the bottoms stream. The recovered propylene is compressed to 90
Table 6.38: Allyl Chloride Process Kinetic Data (van der Helm, 1992)
Reaction Number Activation Energy, Ei Pre Exponential Factor
J/(kmol) ( )
1 7.43E+7 4.04E+7
2 7.11E+4 2.3E+3
3 1.11E+4 9.03E+10
The bottom stream of T-902 is sent to a distillation column, T-904 where water
and hydrochloric acid are separated as the overhead product and bottoms stream
respectively. The bottom stream of T-901 is sent to a distillation column, T-905 where
overhead product and bottom stream respectively. The key input variables for this
process adapted from (van der Helm, 1992). The schematic for this process, the
equipment specification and stream summary tables are presented in Figure C.4, Table
The economic, environmental and social impact of the base case allyl chloride
completing the economic evaluations are presented in Table 6.39. The annual production
199
Table 6.39: Economic Data for the Allyl Chloride Process
Item Cost ($/kg)
Allyl Chloride 1.80 (Turton et al., 2009)
Hydrochloric acid (32 Wt%) 0.095 (Turton et al., 2009)
Propylene Costs 0.98 (Turton et al., 2009)
Chlorine Costs $0.375 (Turton et al., 2009)
Process Water 0.00067 (Turton et al., 2009)
Waste Treatment Costs $0.2 (Turton et al., 2009)
1,2 Dichloropropane (97wt%) 0.12 (Young et al., 2000)10
1,3 Dichloropropane (97wt%) 0.19 (Young et al., 2000)8
Capital Recovery Factor 0.1175
6.4.2.1 Economic Impact Assessment of the Base Case Allyl Chloride Process
The capital and operating costs values obtained from the ASPEN Economic Evaluator,
the mass flow rates of the raw material and product stream and the economic data shown
in Table 6.39 are entered into the SUSTAINABILITY EVALUATOR. The result of this
assessment is shown in Table 6.40 and Figure 6.28. As shown in the table, the estimated
annual revenue generated from selling the allyl chloride process is around $41.6 million.
The annual expenses for this process are estimated to be around $39.6 million. The
As shown in Figure 6.28, the raw material costs accounts for 80% of the annual
operating expenses of the allyl chloride manufacturing process. Toxic waste streams are
present in the allyl chloride process, and must hence be treated. The waste treatment cost
as shown in Figure 6.32 is around $3.7 million and this is about 2% of the costs.
Operating cost, which is about 9% of the expenses, is the third largest expenditure
incurred in manufacturing the products. The capital costs for this process is around 6.7
million but the purpose of calculating profit, the costs were annualized using the capital
10
Price in Journal article was obtained from Chemical Market reporter. This prices were inflated to 2009
200
recovery factor shown in Table 6.40. The annualized capital cost is about 2% of the
profitable process in which the estimated annual profit was calculated to be around $1.6
million.
Table 6.40: Economic Assessment Results for the Base Case Allyl Chloride Process from
the SUSTAINABILITY EVALUATOR
Economic Parameters Base Case (MM)
Revenue $41.6
Operating Costs $3.5
Waste Treatment Costs $3.7
Raw Material Costs $31.9
Capital Costs $7.4
Material Value Added $9.6
Profit $1.6
Figure 6.28: Breakdown of Annual Operating Costs for the Base Case Allyl Chloride
Process
6.4.2.2 Environmental Impact Assessment of the Base Case Allyl Chloride Process
Once the economics of the allyl chloride process had been calculated, the next
step was to evaluate the environmental impacts. The environmental impact assessment
201
involved entering the mass flow rates of the waste streams into the SUSTAINABILITY
EVALUATOR. The result of the environment assessment is presented in Figure 6.29 and
Table 6.41. As shown in the table, the only threat posed by the allyl chloride process to
Table 6.41: Results of Environmental Impact for the Base Case Allyl Chloride Processes
Base Case
Environmental Impacts (Tonnes/year) Chemicals Present
Allyl chloride, 1,3-dichloropropene
Global Warming 2.03E5 and 1,2-dichloropropane.
Next, the resource usage efficiency for the allyl chloride process is also evaluated
and the results are presented in Table 6.42. As shown in the table, the base case allyl
chloride process is not a very resource friendly process. This is because of the several
side reactions taking place leading to two unwanted products which are considered
wastes. The values of the effective mass yield, mass productivity, and reaction efficiency
are all very low. While the values of the E-Factor, water intensity, and material intensity
are all high. Investigating ways to improve reaction efficiency would be important in
Table 6.42: Results of Resource Usage Evaluation for the Base Case Allyl Chloride
Process
Environmental Impact Value Units
E-Factor 0.9 Kg/Kg
Mass Productivity 22 %
Reaction Mass Efficiency 37 %
Energy Intensity 0.00071 KW/Kg
Water Intensity 1.8 Kg/Kg
202
6.4.2.3 Social Impact Assessment of the Base Case Allyl Chloride Process
After the environmental impact assessment, the next step was to complete a health
and safety impact analysis using the SUSTAINABILITY EVALUATOR. For the health
assessment, the mass flow rates of each specific component found in the waste stream are
entered into the SUSTAINABILITY EVALUATOR. As shown in Table 6.43, the allyl
chloride process poses a serious health risk in all categories except skeletal system
damage. Allyl chloride and 1,2-dichloropropane are considered group 2b, while 1,3-
Table 6.43: Results of Health Impact Assessment for the Base Case Allyl Chloride
Process
Impact Category Impact Value Chemicals Present
(Tonnes/year)
Carcinogenic Risk Allyl chloride, 1,2-Dichloropropane
9.5E+03 & 1,3-Dichloropropene
Immune System Damage 6.5E+06 1,3-Dichloropropene
Skeletal System Damage 0.0E+00 N/A
Developmental Damage 6.2E+01 Allyl chloride
Reproductive System Damage 1,2-Dichloropropane & 1,3-
1.1E+04 Dichloropropene
Kidney Damage 6.5E+03 1,3-Dichloropropene
Respiratory System Damage 1.1E+04 1,3-Dichloropropene
Cardiovascular System Damage Allyl chloride, 1,2-Dichloropropane
4.5E+03 & 1,3-Dichloropropene
Endocrine System Damage 4.5E+03 1,2-Dichloropropane
Liver Damage Allyl chloride, 1,2-Dichloropropane
1.1E+04 & 1,3-Dichloropropene
Nervous System Damage Allyl chloride, 1,2-Dichloropropane
1.1E+04 & 1,3-Dichloropropene
Sensory System Damage Allyl chloride, 1,2-Dichloropropane
1.1E+04 & 1,3-Dichloropropene
Apart from cancer risks, other health threats are eminent; these are shown in
Table 6.43. In this table, the chemicals contributing to each health impact category as
well as the calculated impact value is presented. Due to the tremendous health risk, it is
203
therefore vital to ensure that the wastes from this process are handled appropriately and
For the safety assessment, the operating conditions, chemicals present and
equipment present are selected in the input section of the software. Also, the mass
enthalpy is entered to estimate the heat of reaction index. The result of the safety
assessment is presented in Table 6.44. The overall total inherent safety index for this
process was 58. The maximum overall safety index i.e. the worst case scenario for any
process is around 100. As shown in the table, the first obvious safety concerns are the
flammability, toxic exposure and equipment safety index risks which are at their
maximum value.
Table 6.44: Safety Assessment Results from the SUSTAINABILITY EVALUATOR for
the Base Case Allyl Chloride Process
Safety Assessment Results Maximum
Heat of main reaction index 0 8
Heat of side reaction index 0 8
Flammability index 8 8
Explosiveness index 2 8
Toxic Exposure Index 24 30
Corrosiveness index 4 4
Temperature index 6 8
Pressure index 2 8
Equipment safety index 8 8
Safety Level of Process Structure index 4 10
Total Inherent Safety index 58 100
Flammability risks are eminent due to presence of the following chemicals; allyl
are prominent because the following toxic chemicals that are present in the process: allyl
204
equipment safety index is high because the process has a fired heater and a compressor.
Another eminent risk is temperature and corrosion risk. The allyl chloride process is
operating at high temperature and corrosive chemicals are present. Hence extra care must
be taken when designing equipment. These risks must not be ignored, it is important to
After evaluating the sustainability of the base case, it was apparent that it was
necessary to optimize the process for economic, environmental, health and safety risk
improvements. But before the optimization step, it was essential to identify parameters
that affect the selected metrics. In order to identify these parameters, a sensitivity
analysis was completed for the allyl chloride process. The sensitivity analysis was
carried out using ASPEN PLUS. According to literature, there are two key variables that
affect allyl chloride formation these are propylene to chlorine feed ratio and reactor
choice of type of reactor can affect reaction selectivity. Thus the parameters that were
considered for the sensitivity analysis were operating conditions, variation of inlet flow
rates and equipment configuration. The above mention parameters are varied and the
effects on the following were studied: allyl chloride formation and total waste produced.
6.4.3.1 Effect of Varying Inlet Flow Rates for the Base Case Allyl Chloride Process
The raw materials used in the manufacture of allyl chloride are propylene and
chlorine. As mentioned earlier, the feed ratio of the raw materials affect ally chloride
formation, thus propylene to chlorine ratio was varied from 1 to 12. It was important to
205
investigate how varying the raw material ratio affected conversion and ultimately ally
chloride formation. Propylene was varied from 133-1600 lbmole/hr while the chlorine
flow rate was kept constant at 133 lbmole/hr. As shown in Figure 6.29, as feed ratio
increases from 1-12, allyl chloride formation increases. However there is a trade off
because waste increases at first when feed ratio is varied from 1-2, but decreases when it
is varied from, 3-10 but later starts increases at a sharp rate when it is varied from 10-12
90 140
80
120
70
100
Allyl Chloride (Ibmole/hr)
50 80
40 60
30
40
20
20
10
Allyl Chloride Formation Total Waste
0 0
0 2 4 6 8 10 12 14
Feed Ratio
6.4.3.2 Effect of Varying Reactor Temperature for the Base Case Allyl Chloride Process
The effect of reaction temperature on allyl chloride formation and total waste is
also studied. As discussed earlier, the reaction must operate at temperature range of 570-
1110oF to ensure favorably formation of allyl chloride (van der Helm, 1992). Thus the
study was completed at this temperature range. As shown in Figure 6.30, when
temperature is increased from 570 -650oF, allyl chloride formation increases but after
680oF it begins to decrease. On the other hand, as the temperature is increased from 570-
700 oF, waste production reduces because less of the byproducts (1, 2 dichloropropane
206
and 1, 3 dichloropropane) are being synthesized. When temperature increases from 700
o
F- 1100, the wastes increase as more byproducts are formed.
75 60
70
55
65
50
45
45
40
40
30 35
500 600 700 800 900 1000 1100 1200
6.4.3.3 Effect of Varying Reactor Residence for the Base Case Allyl Chloride
Process
The reactor residence time was varied from 0-16s and as shown in Figure 6.31,
residence time does not have significant impact on allyl chloride formation and wastes.
67.5 41.5
67.5 41.48
Total Waste (Ibmole/hr)
Allyl Chloride (Ibmole/hr)
67.5 41.46
67.5 41.44
67.4 41.42
67.4 41.4
Allyl Chloride Formation Total Waste
67.4 41.38
0 2 4 6 8 10 12 14 16
Figure 6.31: Effect of Varying Residence Time on the Allyl Chloride Process
207
6.4.3.4 Effect of Changing Reactor Specification for the Base Case Allyl Chloride
Process
isothermal plug flow reactor is also considered for this process. Table 6.45 shows a
comparison of key differences of the exit stream of the plug flow reactor and isothermal
reactor. As shown in Table 6.45, at isothermal reactor conditions, there is slight variation
in product formation and the wastes being formed. At isothermal condition, there is 15%
conditions.
Table 6.45: Comparison of Calculated Parameters for the Adiabatic PFR Case and the
Isothermal PFR Case
Reactor Parameters Adiabatic PFR Isothermal PFR
o
Temperature ( F) 937 702.4
Hydrochloric Acid (lb mole/hr) 116.3 100.7
Propylene (lb mole/hr) 891.4 878.5
Allyl Chloride(lb mole/hr) 67.5 77.8
Total Wastes (lbmole/hr) 41.1 43.7
chloride formation and waste generation. The next procedure after completing the
sensitivity analysis is process re-configuration. In this step, two distillation columns are
placed after waste stream 10, in order to separate byproducts 1, 2 dichloropropane and 1,
3 dichloropropane.
Also the water feed stream 15 was increased to 1000 lbmole/hr. This resulted in
the addition of a separator to recover hydrochloric acid. The block flow diagram for the
re-configured process is shown in Figure 6.32 and the equipment specification table is
208
shown in Table C.13 in APPENDIX C. After this step, process optimization using
Figure 6.32: Block Flow Diagram of the Reconfigured Allyl Chloride Process
Two options are considered for the optimization for the Allyl Chloride Process.
Option 1 is the base case in which the reactor is operated at adiabatic conditions. While
in option two, the reactor is operated at isothermal conditions. The key goal in this step
is to maximize annual profit ($/yr) while minimizing waste (kg/yr). Profit as defined by
Equation 5.1 as shown below. Waste is simply the mass flow rate of stream 11. Thus the
optimization equations for this problem are shown below. The two options are optimized
209
Allyl Chloride Purity ≥ 99% (6.43)
1,2 Dichloropropane Purity ≥ 96% (6.44)
1,3 Dichloropropane Purity ≥ 96% (6.45)
Table 6.46: Variables Used in the Optimization of the Allyl Chloride Process
Variable Description Base Case Value Optimization Range
Feed Flow Rate Cl = 133 lbmole/hr Cl = 130-1000 lbmole/h
PFR Reactor Temperature 937 oF 200-1100oF
PFR Reactor Pressure 40 psia 25-50 psia
The stream summary tables of the optimized adiabatic plug flow reactor and the
optimized isothermal plug flow reactor cases are shown in Table C.14 and C.15 in
APPENDIX C respectively. After optimizing the process, the next step was to complete
an economic analysis for both options using the ASPEN PLUS Economic Evaluator.
Also, the optimized options are evaluated and compared with the base case using the
next section.
Table 6.47. The first key change was a 2% reduction in raw material flow rate of
chlorine for both optimized cases. Another important change was an increase in allyl
chloride production to 68.7 lbmole/hr and 84.2 lbmole/hr for the optimized adiabatic and
The reactor temperature reduced to 652.8 oF for the optimized adiabatic PFR
reactor case but increased to 742.3 oF for the optimized isothermal PFR case. The reactor
pressure decreased to 39.4 psia for the optimized adiabatic PFR case but increased to 47.1
psia optimized isothermal PFR. The optimization of the allyl chloride process resulted in
210
88% and 85% waste reduction for both the optimized adiabatic and isothermal PFR cases
respectively. Profit increased significantly for the both cases as shown in Table 6.47.
Table 6.47: Key Differences between the Base Case and the Optimized Cases
Major Change Base Case Optimized Optimized
(Adiabatic PFR) (Isothermal PFR)
Chlorine Feed Flow
Rate (lbmole/hr ) 133 130 149.2
Reactor Feed
Temperature (oF) 703.4 652.8 742.3
Reactor Pressure (Psia) 40.0 39.4 47.1
Ally Chloride
Production (lbmole/hr ) 67.1 68.7 84.2
Waste (lbmole/hr ) 41.5 4.8 6.0
Profit ($MM/year) 1.6 14.4 19.4
Once the maximum profit and minimum waste had been determined, the next step
was to evaluate and compare the sustainability of optimized allyl chloride processes to
the base case. The first step was to compare the economics of the three cases. As shown
in Table 6.48 and Figure 6.33, the optimized adiabatic PFR case has lower energy cost,
capital costs and raw material cost compared to the optimized isothermal case. For both
cases, there was an increase in capital and utility costs due to the addition of the one
Table 6.48: Comparison of Economic Impact Results for the Base, Optimized Adiabatic
and Isothermal Allyl Chloride Processes
Economic Parameters Base Case (MM) Optimized Optimized
Adiabatic Case Isothermal Case
(MM) (MM)
Revenue $41.6 $52.9 $64.0
Utility Costs $3.5 $4.9 $5.4
Waste Treatment Costs $3.7 $0.44 $0.54
Raw Material Costs $31.9 $31.9 $37.3
Capital Costs $7.4 $10.7 $11.3
Material Value Added $9.6 $21.0 $26.7
Profit $1.6 $14.4 $19.4
211
Figure 6.33: Comparison of Economic Assessment of the and Base and Optimized Allyl
Chloride Processes
Although both optimized cases had higher operating and capital costs, the waste
treatments costs were lower for both cases. The higher capital and operating cost is as
result of additional separation equipment to separate the by product. Both cases are more
economical compared to the base case and they have an economic impact of 0 compared
to the base case which had a value of 0.95. However, the optimized isothermal allyl
The environmental impacts of the two optimized cases are evaluated and
compared to the base case. The results of comparing the environmental burden of the
three options are depicted on the bar chart shown in Figures 6.34 and Table 6.49. As
shown in the Figure 6.34, both cases had a significant lower global warming impact
compared to the base case. An analysis was completed to investigate the percent
reduction for both cases relative to the base case. The adiabatic and isothermal PFR case
212
had 88% and 85% reduction in global warming impact respectively. Hence the adiabatic
Figure 6.34: Comparison of Environmental Impacts Assessment for the Optimized and
Base Cases Allyl Chloride Process
Table 6.49: Environmental Impact Results for Base and Optimized Allyl Chloride
Processes
Base Case Optimized Optimized
(Tonnes/year) Adiabatic PFR Isothermal PFR
Environmental Impacts Case Case
Global Warming 2.03E5 2.4E+04 2.9E+04
The efficiency of the reactions used in ally chloride formation and resource usage
for the optimized cases are evaluated and compared with the base case as shown in Table
6.50. As shown in the table, the two optimized cases have a lower E-factor value of 0.1
compared to the base case value which had a value of 0.9. This is because fewer wastes
are being produced for the optimized options. The optimized adiabatic PFR case has the
highest mass productivity value and lower water intensity because less raw materials and
process water were being used to make allyl chloride, while the isothermal PFR case had
213
a higher reaction mass efficiency as smaller amounts raw materials are being used to
Table 6.50: Summary of Resource Usage Metrics Results for the Allyl Chloride Base and
Optimized Cases
Optimized Optimized
Adiabatic Isothermal
Outputs Base Case PFR Case PFR Case Units
E-Factor 0.9 0.1 0.1 Kg/Kg
Mass Productivity 22 34 19 %
Reaction Mass Efficiency 37 38 40 %
Energy Intensity 0.00071 0.0013 0.0012 KW/Kg
Water Intensity 1.8 0.3 2.8 Kg/Kg
Note that energy intensity is higher for the two cases because of the additional
adiabatic PFR case is the more efficient process compared to the other two cases. The
overall environmental impact for the adiabatic case is 0.10 while the isothermal case is
0.12. This is a substantial improvement because this is lower than the base case which
The health impact of the optimized cases are also evaluated and compared with
the base case and this is presented in Table 6.51 and Figure 6.35. From the figure, in
general the health risks for the optimized cases are significantly lower compared to the
base case. An assessment was completed to determine the percent reduction for each
health impact category. As shown in Table 6.51, there is a substantial percent reduction
in all categories for both cases. The percent reduction was over 84% for all categories.
For both cases, developmental damage had the highest percent reduction of 100%
because allyl chloride, the chemical contributing to this health effect is not being emitted
214
The significant percent reduction is as a result of reducing wastes by a significant
amount.
215
Figure 6.35: Comparison of Health Impacts Assessment the Base and Optimized Allyl
Chloride Processes
The safety of the optimized allyl chloride processes was also evaluated and
compared with the base case. The process safety index for the base case and the
adiabatic PFR case are the same with a value of 58. While the process safety index of the
isothermal PFR case increased to 60 because of the higher reaction temperature leading
It was difficult to really improve the safety index values because this index is
based on the chemicals present in the process and the operating temperature and pressure.
Significant changes made to the operating conditions would have affected conversion
leading to a loss in product formation. Also the process was not directly optimized for
calculated and the optimized cases had a value of 0.43, while the base case had a value of
0.49.
216
6.4.6 Selection of the Sustainable Allyl Chloride Process
For this study three process options were compared. The first process was the
base case allyl chloride process, while the other two options were an optimized
modification to the base case. The two optimized cases differed from the base case in
that the byproducts were separated through a series of 2 distillation columns and a flash
separator. The optimized cases differed from each other by the type of reactor used in the
process. The adiabatic PFR case had an overall sustainable impact value of 0.21 while
the isothermal PFR case had a value of 0.22. The values calculated for the optimized
cases are significantly lower than the base case which has a value of 0.45. Thus the
optimized cases are more sustainable compared to the base case. The base case had a
profit of $1.6 million but optimization of the process led to improved economics. The
optimized isothermal PFR case is more profitable with a value of $19.4 million compared
The optimize allyl chloride processes is more environmental friendly because less
wastes. This waste reduction led to improve resource usage metrics and lower
environmental impacts. Overall the optimized adiabatic PFR case is more environmental
friendly compared to the other two options. In terms of social concerns, the optimized
PFR case has a lower health risk compared to the other two cases. Although the
isothermal PFR case is 26% more profitable, the optimized adiabatic PFR case is the
more sustainable option because it had an overall impact of 0.21 and hence it is more
217
CHAPTER VI
7.1 CONCLUSIONS
regulations, financial risks, safety and supply chain pressure have heightened our interest
industry has gained global attention. There is increasing pressure for processes to
become more environmentally friendly and socially acceptable. One way to ensure that
the needs of future generations are met and not jeopardized is to ensure that we
Addressing sustainability concerns after the fact in chemical process design is no longer
acceptable as this could result in more expensive consequences. The ideal approach is to
incorporate sustainability concerns into all stages of design to ensure environmental and
218
socially acceptable products and processes. This can be accomplished by evaluating the
sustainability of products and processes that are developed as shown in Figure 7.1.
Figure 7.1: Proposed Methodology for Addressing Sustainability Concerns During Early
Stages of Design
incorporates sustainability concerns into chemical process design during early stages.
The methodology discussed by this author as summarized in Figure 7.1 and Table 7.1
includes the following: base case process modeling, sustainability assessment of the base
219
identify process parameters that affect process sustainability, process optimization based
on the result of sensitivity analysis and impact assessment of the optimized process using
220
The major contribution to this research was the development of a novel impact
assessment tool called the SUSTAINABILITY EVALUATOR. This Excel based impact
assessment tool was developed based on seven economic metrics, thirteen environmental
metrics and twenty one social metrics. The economic, environmental and safety metrics
The novel contribution to the sustainability tool was the introduction of health
metrics and the selection of the metrics that apply to process design. Economic,
environmental and social indices based on this selected metrics were developed using a
assigning weights to the economic, environmental and social indices. These indices have
been incorporated into the impact assessment tool. This impact was normalized from 0 to
1, therefore the lower the impact value, the more sustainable the process is. The impact
Apart from the tool’s ability to identify and evaluate sustainability concerns in
chemical process, it can also be used to handle both single objective and multiobjective
optimization problems in chemical process design. For this research, the tool was used to
221
implementing scalerization‖. This involves combining this multiple objective problem
The proposed impact assessment methodology is innovative for two reasons. The
first is that economic, environmental and impact assessments can be evaluated by one
tool making it easier for engineers to see how process improvements affect the overall
sustainability of a process. Secondly the incorporation of social metrics i.e. health and
safety metrics in this way is new as researchers to date haven’t incorporated all three
dimensions into process design. Also, an overall sustainability impact was developed.
This sustainability index value provides a quantitative number for process designers to
The impact assessment tool has been used to evaluate the sustainability concerns
of the methyl chloride process. In this step, the results from the environmental section of
obtained from the Waste Reduction Algorithm. This algorithm is a widely accepted
screening tool used to evaluate the potential environment impact of chemicals found in a
chemical processes. The comparison proved that the two impact assessment tools
After validating the tool, an overall sustainability impact was incorporated into
developed based on assigning weights to the economic, environmental and social indices.
This aids the engineer in having a quantitative number in deciding the sustainability
222
impact of a process. The impact assessment tool is also useful in comparing processes
and selecting the best option. This has been demonstrated using the dimethyl ether
(DME), acrylonitrile and allyl chloride processes. In the DME case study, two options
with different chemistries were evaluated and the most sustainable option was selected.
In the acrylonitrile and allyl chloride processes, a sensitivity analysis was first completed
to identify parameters that affect the sustainability of the process. Once the parameters
have been identified, the processes are optimized with ASPEN PLUS. Next the
optimized cases are evaluated and compared with their base cases using the
SUSTAINABILITY EVALUATOR. The summary of the results generated for each case
manufactured via methanol or via natural gas. The tool was able to assist in selecting the
most sustainable process option. DME via methanol dehydration had a lower overall
sustainable impact value of 0.11 compared DME via natural gas which had a value of
0.24. The lower impact value was a result of the fact that DME via methanol dehydration
had a more efficient reaction process, was safer as less toxic chemicals and less
hazardous equipment were present in the process and less wastes were generated in the
process. Based on the lower overall sustainable impact obtained from the tool, DME
production via methanol dehydration is the more sustainable production option because it
223
The overall methodology presented in Figure 7.1 and Table 7.1 was first
demonstrated on the acrylonitrile process. The base case acrylonitrile process had several
waste streams leading to environmental burdens and health risks. The acrylonitrile
process was optimized to maximize profit while minimizing wastes after identifying
parameters that affected the sustainability of the process. The optimized acrylonitrile
process differed from the base case because the following changes were made to the
conditions. The profit for the base case was $0.4 million compared to the optimized
cases which had a value of $3.5 million. The improvements made to the optimized
acrylonitrile process led to a lower overall sustainability impact value of 0.31 compared
to the base case which had a value of 0.45. This impact is calculated based on the results
Thus optimized case is more sustainable compared to the base case because less
wastes are being generated from the process, the reaction is occurring more efficiently.
This aided the conversion to more products using lower quantities of raw materials. This
which resulted in a lower overall sustainability impact for the optimized processes.
the base case because it is more economical viable, environmentally friendly and socially
224
The methodology was also demonstrated on the allyl chloride process. The base
case process had a waste stream that lead to environmental burdens and health risks. The
process was optimized to maximize profit while minimizing wastes after identifying
parameters that affected the sustainability of the process. For this study three process
options were compared. The first process was the base case allyl chloride process, while
the other two options were an optimized modification to the base case. The two
optimized cases differed from the base case in that the byproducts were separated through
a series of two distillation columns and a flash separator. The optimized cases differed
from each other by the type of reactor used in the process. The adiabatic PFR case had
an overall sustainable impact of 0.21 while the isothermal PFR case had a value of 0.22.
The sustainability impact value calculated for the optimized allyl chloride cases
are significantly lower than the base case which has a value of 0.45. Thus the optimized
cases are more sustainable compared to the base case because less wastes are being
generated from the process, and the reaction is occurring more efficiently; aiding the
conversion to more products using less raw materials. Hence improved profit relative to
investment, less environmental and health impacts resulted in lower overall sustainability
The base case had a profit of $1.6 million but optimization of the process led to
improved economics. The optimized isothermal PFR allyl chloride case is more
profitable with a value of $19.4 million compared with the adiabatic case which has a
value of $14.4 million. The isothermal reactor yielded more products but generated more
wastes. Although the isothermal PFR allyl chloride case is 26% more profitable, the
optimized adiabatic PFR allyl chloride case is the more sustainable option because it has
225
a lower overall sustainability impact of 0.21 and hence it is more environmental friendly
and socially acceptable. This impact is based on the calculated economic, environmental
and social impact. The lower overall sustainability impact obtained for the optimized
economic, environmental and social concerns into early stages of chemical process
design was developed. This framework involved the use of the SUSTAINABILITY
EVALUATOR, a newly developed impact assessment tool. This impact assessment tool,
established based on metrics, has aided the engineer in identifying and evaluating
sustainability concerns during early stages of chemical process design. The tool is useful
comparing multiple processes and selecting the most sustainable option. Also it could be
used to handle single and multiple objective optimization problems. The proposed
methodology also uses ASPEN PLUS to simulate processes, calculate mass and energy
balances, complete sensitivity analysis and optimize processes for sustainability. Lastly
sustainability concerns into chemical process design, there is still room for improvement
in the approaches used in methodology. The following are the suggested research
directions to consider:
226
Link SUSTAINABILITY EVALUATOR and ASPEN PLUS: Currently the
to ASPEN PLUS. Efforts should be made towards linking the two together by
creating a dynamic data exchange link using Fortran and Visual Basic codes.
would be automatically calculated when process changes are made. For example,
process? This will save time as it will eliminate the need to manually transfer
PLUS. The approach used in this research is single objective optimization where
weights. The problem with this approach is that handling sustainability concerns
are a wide range of concerns that must be addressed. Converting the problem to a
single objective problem might not give optimum results. This was demonstrated
in the acrylonitrile and allyl chloride case studies as the safety concerns did not
directly improve when the processes were optimized. Therefore, formulating the
social objectives are formulated is the ideal way to tackle sustainability issues in
227
process design. As there were forty one different metrics in this research, the next
SUSTAINABILITY ASPEN
EVALUATOR PLUS
Improved
Optimization
Algorithm
sustainability impact was developed, more work should be done to investigate the
impact difference that would result in the conclusion that one process is more
sustainable than the other. For example, when comparing processes, is there a
difference of 0.01 and or 0.1? What should the impact difference be in order for
an engineer to conclude that one process is more sustainable than the other?
228
Improve Health Metrics: The author introduced health metrics. The reliability of
these metrics has not been validated with a similar tool. Efforts should be made
to validate the metrics or improve upon it if needed. Also the method used in
handling health concerns is limited in scope as toxicants were classified into only
two categories namely, known toxicant or possible toxicant. There are several
approaches that could be used to handle health issues in the process industry.
These include classifying health risks into chronic versus acute illness. Other
oral slope factors, oral and inhalation unit risks to classify carcinogens. Efforts
Improve Impact Assessment Tool: Additional social metrics such as land and
water impact according to plant location should be incorporated into the impact
assessment tool. Also the scope of the tool is manufacturing focus. Other
does not address scaling effect. For example, how do you compare two
production facilities that differ by production rate? More work should be done to
investigate how to address this. Lastly, the tool does not evaluate intermediate
229
streams when assessing safety risks. This is an integral safety issue that should
also be addressed.
230
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APPENDIX A: SUSTAINABILITY EVALUATOR USER MANUAL
252
SUSTAINABILITY EVALUATOR USER MANUAL
The SUSTAINABILITY EVALUATOR is an impact assessment tool developed
for evaluating the sustainability of a process. The metrics that have been used in the
sustainability evaluator are described in the ―Description of Metrics‖ section of this
manual. This tutorial presents the impact assessment of Dimethyl Ether (DME)
production via dehydration of methanol as shown in Equation 1. The schematic for this
process is shown below in Figure 1 and the block flow diagram is shown in Figure 2.
13
DME
10
T-201
11
9
Methanol P-201
E-201 E-202
2
1 12
3
4
T-202
R-201
15 Waste
E-203
6
7 8 16
14
E-204
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Figure 2: Block flow diagram of DME Production via Dehydration of Methanol
Table 1: Identified Raw Material, Product, Waste, Reactor Feed and Exit Streams
Methanol DAME Waste Reactor In Reactor Out
(Stream 1) (Stream 10) (Stream 16) (Stream 5) (Stream 6)
o
Temperature ( C) 25.00 46.45 52.33 220.00 364.00
Pressure (bar) 1.00 10.21 1.20 14.70 13.90
Total Flow (kg/year) 7.33E+07 5.23E+07 2.10E+07 9.18E+07 9.18E+07
Mass Flow ( kg/year)
Dimethyl Ether 0.00E+00 5.21E+07 4.34E+03 5.39E+05 5.27E+07
Methanol 7.29E+07 1.68E+05 2.46E+05 9.07E+07 1.81E+07
Water 3.95E+05 8.18E-05 2.08E+07 6.09E+05 2.10E+07
Mass Enthalpy (KJ/Kg) -7.49E+03 -3.94E+03 -1.57E+04 -6.02E+03 -5.97E+03
The impact assessment tool is divided into two sections namely Input and Output
section.
INPUT SECTION
In the input section, the user selects chemical and inputs mass flow rates,
molecular weight, raw material prices etc. The input section is categorized into
environmental burden, resource usage, economic impact, health and safety.
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Environmental Burden
The environmental burden section is sub divided into eight impact categories. For
each category, the chemical(s) contributing to each environmental concern is selected and
the mass flow rate in kg/yr is entered as shown in the screen shot in Figure 3. The
information on the chemicals is obtained from the waste stream. The steps for
completing the environmental impact assessment are described below.
Step 1: The first impact category is atmospheric acidification. For this category, because
the components present in the waste streams are methanol, DME and water, ―chemical
not on this list‖ is selected. This is because the above mentioned chemicals do not lead to
atmospheric acidification and therefore the mass flow rate is left blank.
Step 2: The second impact category is global warming. For this category, methanol and
DME contribute to global warming. Therefore these two chemicals are selected and the
mass flow rate in kg/yr is entered into the tool as shown in the screen shot in Figure 4.
This mass flow rates should match with waste stream values shown in Table 1.
Step 3: Repeat steps 1 and 2 for the other six categories. You should have selected
chemicals and entered mass flow rates for photochemical smog formation and aquatic
oxygen demand.
255
Figure 4: Screen Shot Demonstrating Chemicals that Contribute to Global Warming
Resource Usage
The steps for completing the resource usage assessment are described in the steps
below. After completing the steps, your screen should like Figure 5.
Step 1: Enter the total mass flow rate of the desired product shown in Table 1. The
desired product is DME and the total mass flow rate is 5.23E+07 kg/yr.
Step 2: Enter the total mass flow rate of non-benign reactant. In this case, the non-benign
reactant is methanol and the total mass flow rate is 7.33E+07kg/yr as shown in Table 1.
Step 3: Enter the total waste. In this case total waste mass flow rate 2.10E+07kg/yr as
shown in Table 1.
Step 4: Enter the molecular weight of the desired product. In this case the molecular
weight of DME is 46 kg/kmol.
Step 5: Enter the molecular weight of the reactant. In this case the molecular weight of
methanol is 32 kg/kmol.
256
Step 6: Enter total mass used in process steps. These include reactant, solvents or side
streams introduced into the process to aid separation of the product. For this process, the
total mass used in process step is 7.33E+07kg/yr as shown in Table 1.
Step 7: Enter total mass of raw material. In this case total mass flow rate of methanol is
7.33E+07kg/yr as shown in Table 1.
Step 8: Enter net energy consumed. The net energy consumed is the sum of the energy
used by the process equipment. This can be obtained directly from the process simulator.
In this case the net energy consumed is 12100KW
Economics
257
The steps for completing the economic assessment are described in the steps
below. After following the steps, your screen should like the screen shot shown in Figure
6.
Step 1: Enter the total mass flow rate of the primary product. This is obtained from Table
1 and the desired product is DME and the total mass flow rate is 5.23E+07 kg/yr. Note
that in many reactions, there might be more than one product. If this is the case, the mass
flow rates are also entered.
Step 2: Enter selling price of the primary product(s). In this case the selling price for
DME is $1.17/kg. If there are other products, their selling prices are also entered.
Step 3: Enter the total mass flow rate of the primary raw material. In this example, the
methanol mass flow rate obtained from Table 1 is 5.23E+07 kg/yr.
258
Step 4: Enter selling price of the primary raw material. In this case the selling price for
methanol is $0.294/kg. If there are other raw materials or feed streams, their selling
prices are also entered.
Step 5: Enter operating costs. The operating cost for the methyl chloride process is
obtained from ASPEN PLUS and entered. In this case the value is $3.20E+06 /yr.
Step 6: Enter capital costs. The capital cost for the methyl chloride process is obtained
from ASPEN PLUS and entered. In this case the value is $4.30E+06 /yr.
Step 7: Enter total waste. In this case total waste mass flow rate 2.10E+07kg/yr as shown
in Table 1.
Step 8: Enter waste treatment costs. The waste treatment costs for this process is
$36/1000kg.
Safety Metrics
The steps for completing the safety assessment are described in the steps below.
After following the steps described below, your screen should like the screen shot shown
in Figure 7.
Step 1: Enter the mass enthalpy of the reactants. This information is obtained from the
stream entering the reactor. As shown Table 1, the mass enthalpy value is -
6.02E+03KJ/KG.
Step 2: Enter the mass enthalpy of the product. This information is obtained from the
stream exiting the reactor. As shown Table 1, the mass enthalpy value is
5.97E+03KJ/KG.
Step 1 and 2 are repeated if there are other reactors and inputted in the side reaction
section of the SUSTAINABILITY EVALUATOR.
Step 3: Select Chemical for Flammability Index. The chemicals are selected in the drop
down menu as shown in Figure 8. For this process, only DME and methanol are
flammable, thus they are selected and the flash point temperature is supplied by the tool.
If the chemical is not found in the drop down menu, then ―chemical not on the list‖ is
selected.
Step 4: Select Chemical for Explosivity Index. The chemicals are selected in the drop
down menu. For this process, only DME and methanol are considered to be explosive,
thus they are selected and the explosive limit is supplied by the tool. If the chemical is
not found in the drop down menu, then ―chemical not on the list‖ is selected.
259
Figure 7: Screen Shot of Safety Inputs
260
Step 5: Select Chemical for Exposure Index. The chemicals are selected in the drop
down menu. For this process, only DME and methanol are considered to be chemicals
that can harm human health, thus they are selected and the toxic limit value is supplied by
the tool. If the chemical is not found in the drop down menu, then ―chemical not on the
list‖ is selected.
Step 6: Select material for Corrosion Index. Several chemicals are considered corrosive
and strong material of construction might be needed. For example strong acids such as
hydrochloric acid can corrode process equipment made from stainless steel or carbon
steel. Thus ―better material is needed‖ is selected if this is the case. For this process,
DME or methanol are not corrosive thus carbon steel is selected from the drop down
menu.
Step 7: Select inputs for Inventory Index. The range of mass flow rate of the amount of
main product being produced is selected in tones/hr. For the DME process, the inventory
range is 1-10 tonnes/hr .
Step 8: Select inputs for Temperature Index. The highest operating temperature of the
process is selected. For the DME process, the temperature range is between 300-600 oC.
Step 9: Select inputs for Pressure Index. The highest operating pressure of the process is
selected. For the DME process, the temperature range is between 0–0.5 or 5–25 bar.
261
Step 10: Select inputs for Equipment Index: The highest risk equipment present in the
process is selected. For this process, ―air coolers, reactors, high hazard pumps‖ is
selected because a reactor is present in the process.
Step 11: Inputs for Safety Level of Process Structure Index: Here the safety level is
selected and because there is no information of safety incidents relating to DME
production, ―No data or neutral‖ is selected.
Health Impact
The health impact is sub divided into eleven impact categories. For each category, the
chemical(s) contributing to each health concern is selected and the mass flow rate in
kg/yr is entered as shown in the screen shot in Figure 9. The information on the
chemicals is obtained from the waste stream. The steps for completing the health impact
assessment are described below.
Step 1: The first impact category is Neurological Damage Evaluation. For this category,
because the only components present in the waste streams that leads to this health risk is
methanol, this chemical is selected from the drop down menu and the mass flow rate is
entered as shown in Figure 9.
262
This procedure is repeated for the other 10 health impact category. If the chemical is not
on the list for any impact category, ―Chemical not on the list‖ is selected. For this
assessment you should have selected chemicals and entered inputs for the following:
developmental damage, respiratory system damage, liver damage and endocrine damage.
OUTPUT SECTION
The results of the assessments are presented in six tabs namely: Output, Economic Impact
Economic expense, Environmental Impact and Health Impact. The output tab provides
the results of all the five categories discussed earlier. The results are presented in the
screen shot shown in Figure 14. These results are graphed in the other five tabs as shown
in Figures 10-13.
Figure 10: Bar Chart Showing Results Located in the Economic Impact Section of the
Tool
263
Figure 11: Pie Chart Showing Results Located in the Economic Impact Section of the
Tool
Figure 12: Bar Chart showing Results Located in the Environmental Impact Section of
the Tool
264
Figure 12: Bar Chart Showing Results Located in the Health Impact Section of the Tool
265
Figure 14: Screen Shot Showing Results Located in the Output Section of the Tool
266
267
APPENDIX B: INPUT FILE FOR THE FOLLOWING CASE STUDIES: METHYL
CHLORIDE, DIMETHYL ETHER, ACRYLONITRILE AND ALLYL CHLORIDE
268
DIMETHYL ETHER VIA DEHYDRATION OF METHANOL INPUT FILE
DYNAMICS
DYNAMICS RESULTS=ON
SIM-OPTIONS
IN-UNITS ENG
SIM-OPTIONS OLD-DATABANK=YES
DESCRIPTION "
General Simulation with Metric Units :
C, bar, kg/hr, kmol/hr, Gcal/hr, cum/hr.
COMPONENTS
DIMET-01 C2H6O-1 /
METHA-01 CH4O /
WATER H2O
FLOWSHEET
BLOCK B1 IN=1 OUT=2
BLOCK E201 IN=3 OUT=4
BLOCK E202 IN=4 OUT=5
BLOCK B6 IN=5 OUT=6
BLOCK E-203 IN=6 OUT=7
BLOCK B8 IN=7 OUT=8
BLOCK B9 IN=8 OUT=9
BLOCK B10 IN=9 OUT=10 11
BLOCK B13 IN=11 OUT=12
BLOCK B14 IN=12 OUT=B 14
269
BLOCK B15 IN=14 OUT=15
BLOCK B2 IN=2 13 OUT=3
BLOCK B5 IN=B OUT=13 PURGE
BLOCK B3 IN=15 PURGE OUT=16
PROP-DATA NRTL-1
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='Gcal/hr' &
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=Gcal MOLE-CONC='mol/l' &
PDROP=bar
PROP-LIST NRTL
BPVAL DIMET-01 METHA-01 0.0 -18.93720000 .2951000000 0.0 &
0.0 0.0 0.0 0.0
BPVAL METHA-01 DIMET-01 0.0 653.0063000 .2951000000 0.0 &
0.0 0.0 0.0 0.0
BPVAL METHA-01 WATER -.6930000000 172.9871000 .3000000000 &
0.0 0.0 0.0 24.99000000 100.0000000
BPVAL WATER METHA-01 2.732200000 -617.2687000 .3000000000 &
0.0 0.0 0.0 24.99000000 100.0000000
PROP-DATA PRKBV-1
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='Gcal/hr' &
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=Gcal MOLE-CONC='mol/l' &
PDROP=bar
PROP-LIST PRKBV
BPVAL METHA-01 WATER -.0778000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL WATER METHA-01 -.0778000000 0.0 0.0 -273.1500000 &
726.8500000
PROP-SET IPE-1
IN-UNITS ENG
PROPNAME-LIS MASSVFRA MASSSFRA MASSFLMX VOLFLMX TEMP PRES &
MWMX MASSFLOW SUBSTREAM=ALL
PROP-SET IPE-2
IN-UNITS ENG
PROPNAME-LIS VOLFLMX MASSFLMX KMX SIGMAMX MUMX CPMX MWMX &
UNITS='kJ/kg-K' SUBSTREAM=MIXED PHASE=L
PROP-SET IPE-3
IN-UNITS ENG
270
PROPNAME-LIS VOLFLMX MASSFLMX KMX MUMX CPMX MWMX UNITS= &
'kJ/kg-K' SUBSTREAM=MIXED PHASE=V
STREAM 1
SUBSTREAM MIXED TEMP=25. PRES=1.
MOLE-FLOW METHA-01 259.7 / WATER 2.5
BLOCK B2 MIXER
BLOCK B3 MIXER
BLOCK B5 FSPLIT
FRAC 13 0.992
BLOCK B8 HEATER
PARAM TEMP=100. PRES=13.4
BLOCK B6 RSTOIC
PARAM TEMP=364. PRES=13.9
STOIC 1 MIXED METHA-01 -2. / DIMET-01 1. / WATER 1.
CONV 1 MIXED METHA-01 0.8
BLOCK B1 PUMP
271
PARAM PRES=25. EFF=0.6
BLOCK B9 VALVE
PARAM P-OUT=10.4
STREAM-PRICE
STREAM-PRICE STREAM=1 MASS-PRICE=0.0008 <$/kg>
EO-CONV-OPTI
PARAM SOLVER=DMO
CONV-OPTIONS
PARAM TEAR-METHOD=DIRECT OPT-METHOD=SQP
WEGSTEIN MAXIT=50
DIRECT MAXIT=50
SECANT MAXIT=50
BROYDEN MAXIT=50
NEWTON MAXIT=50
272
DIMETHYL ETHER VIA NATURAL GAS INPUT FILE
DYNAMICS
DYNAMICS RESULTS=ON
IN-UNITS SI FLOW='kg/hr' MASS-FLOW='kg/hr' MOLE-FLOW='kmol/hr' &
PRESSURE=atm TEMPERATURE=C DELTA-T=C PDROP=atm
SIM-OPTIONS
IN-UNITS ENG
SIM-OPTIONS OLD-DATABANK=YES
DESCRIPTION "
General Simulation with Metric Units :
C, bar, kg/hr, kmol/hr, Gcal/hr, cum/hr.
COMPONENTS
DIMET-01 C2H6O-1 /
METHA-01 CH4O /
WATER H2O /
CH4 CH4 /
OXYGE-01 O2 /
CO-2 CO2 /
CO CO /
H2 H2 /
C2H6 C2H6 /
C3H8 C3H8 /
C4H10 C4H10-1
FLOWSHEET
BLOCK E-302 IN=3 OUT=4
BLOCK E-301 IN=1 OUT=2
BLOCK R-301 IN=4 2 OUT=5
BLOCK E-303 IN=5 OUT=6
BLOCK P-301 IN=8 OUT=9
BLOCK E-304 IN=9 OUT=10
BLOCK R-302 IN=10 OUT=11
273
BLOCK B9 IN=11 OUT=12
BLOCK T-302 IN=12 OUT=13 14
BLOCK E-305 IN=14 OUT=15
BLOCK R-303 IN=15 OUT=16
BLOCK B16 IN=16 OUT=17
BLOCK T-303 IN=17 OUT=19 18
BLOCK T-301 IN=6 OUT=8 7
BLOCK B6 IN=19 OUT=20 21
BLOCK B7 IN=18 21 7 13 OUT=22
PROPERTIES NRTL
PROPERTIES NRTL-RK / PENG-ROB / SRK
PROP-DATA NRTL-1
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='Gcal/hr' &
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=Gcal MOLE-CONC='mol/l' &
PDROP=bar
PROP-LIST NRTL
BPVAL DIMET-01 METHA-01 0.0 -18.93720000 .2951000000 0.0 &
0.0 0.0 0.0 0.0
BPVAL METHA-01 DIMET-01 0.0 653.0063000 .2951000000 0.0 &
0.0 0.0 0.0 0.0
BPVAL METHA-01 WATER -.6930000000 172.9871000 .3000000000 &
0.0 0.0 0.0 24.99000000 100.0000000
BPVAL WATER METHA-01 2.732200000 -617.2687000 .3000000000 &
0.0 0.0 0.0 24.99000000 100.0000000
BPVAL METHA-01 C4H10 0.0 380.4331000 .3000000000 0.0 0.0 &
0.0 50.00000000 50.00000000
BPVAL C4H10 METHA-01 0.0 551.7243000 .3000000000 0.0 0.0 &
0.0 50.00000000 50.00000000
PROP-DATA PRKBV-1
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='Gcal/hr' &
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=Gcal MOLE-CONC='mol/l' &
PDROP=bar
PROP-LIST PRKBV
BPVAL METHA-01 WATER -.0778000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL WATER METHA-01 -.0778000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL METHA-01 CO-2 .0230000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO-2 METHA-01 .0230000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL WATER CO-2 .1200000000 0.0 0.0 -273.1500000 &
274
726.8500000
BPVAL CO-2 WATER .1200000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CH4 CO-2 .0919000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO-2 CH4 .0919000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CH4 CO .0300000000 0.0 0.0 -273.1500000 726.8500000
BPVAL CO CH4 .0300000000 0.0 0.0 -273.1500000 726.8500000
BPVAL CH4 H2 .0156000000 0.0 0.0 -273.1500000 726.8500000
BPVAL H2 CH4 .0156000000 0.0 0.0 -273.1500000 726.8500000
BPVAL CO-2 H2 -.1622000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL H2 CO-2 -.1622000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO H2 .0919000000 0.0 0.0 -273.1500000 726.8500000
BPVAL H2 CO .0919000000 0.0 0.0 -273.1500000 726.8500000
BPVAL METHA-01 C2H6 .0270000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 METHA-01 .0270000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CH4 C2H6 -2.6000000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 CH4 -2.6000000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO-2 C2H6 .1322000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 CO-2 .1322000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO C2H6 -.0226000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 CO -.0226000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL H2 C2H6 -.0667000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 H2 -.0667000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CH4 C3H8 .0140000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 CH4 .0140000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO-2 C3H8 .1241000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 CO-2 .1241000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO C3H8 .0259000000 0.0 0.0 -273.1500000 726.8500000
BPVAL C3H8 CO .0259000000 0.0 0.0 -273.1500000 726.8500000
BPVAL H2 C3H8 -.0833000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 H2 -.0833000000 0.0 0.0 -273.1500000 &
726.8500000
275
BPVAL C2H6 C3H8 1.10000000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 C2H6 1.10000000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CH4 C4H10 .0133000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 CH4 .0133000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO-2 C4H10 .1333000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 CO-2 .1333000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL H2 C4H10 -.3970000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 H2 -.3970000000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 C4H10 9.60000000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 C2H6 9.60000000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 C4H10 3.30000000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 C3H8 3.30000000E-3 0.0 0.0 -273.1500000 &
726.8500000
PROP-DATA SRKKIJ-1
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='Gcal/hr' &
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=Gcal MOLE-CONC='mol/l' &
PDROP=bar
PROP-LIST SRKKIJ
BPVAL CO-2 CO -.0154400000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CO CO-2 -.0154400000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CH4 H2 -.0244851000 0.0 0.0 -273.1500000 726.8500000
BPVAL H2 CH4 -.0244851000 0.0 0.0 -273.1500000 726.8500000
BPVAL CH4 C2H6 4.21992000E-4 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 CH4 4.21992000E-4 0.0 0.0 -273.1500000 &
726.8500000
BPVAL H2 C2H6 .0163828000 0.0 0.0 -273.1500000 726.8500000
BPVAL C2H6 H2 .0163828000 0.0 0.0 -273.1500000 726.8500000
BPVAL CH4 C3H8 .0241509000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 CH4 .0241509000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL H2 C3H8 .1014650000 0.0 0.0 -273.1500000 726.8500000
BPVAL C3H8 H2 .1014650000 0.0 0.0 -273.1500000 726.8500000
276
BPVAL C2H6 C3H8 1.69511000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 C2H6 1.69511000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL CH4 C4H10 .0226440000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 CH4 .0226440000 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C2H6 C4H10 5.32194000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 C2H6 5.32194000E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C3H8 C4H10 -2.0759400E-3 0.0 0.0 -273.1500000 &
726.8500000
BPVAL C4H10 C3H8 -2.0759400E-3 0.0 0.0 -273.1500000 &
726.8500000
PROP-SET IPE-1
IN-UNITS ENG
PROPNAME-LIS MASSVFRA MASSSFRA MASSFLMX VOLFLMX TEMP PRES &
MWMX MASSFLOW SUBSTREAM=ALL
PROP-SET IPE-2
IN-UNITS ENG
PROPNAME-LIS VOLFLMX MASSFLMX KMX SIGMAMX MUMX CPMX MWMX &
UNITS='kJ/kg-K' SUBSTREAM=MIXED PHASE=L
PROP-SET IPE-3
IN-UNITS ENG
PROPNAME-LIS VOLFLMX MASSFLMX KMX MUMX CPMX MWMX UNITS= &
'kJ/kg-K' SUBSTREAM=MIXED PHASE=V
STREAM 1
IN-UNITS MET FLOW='gm/hr' MASS-FLOW='gm/hr' TEMPERATURE=C &
DELTA-T=C
SUBSTREAM MIXED TEMP=35. PRES=1. MOLE-FLOW=425.
MASS-FRAC CH4 0.875 / C2H6 0.075 / C3H8 0.035 / C4H10 &
0.015
STREAM 3
IN-UNITS MET VOLUME-FLOW='cum/hr' ENTHALPY-FLO='Gcal/hr' &
HEAT-TRANS-C='kcal/hr-sqm-K' PRESSURE=bar TEMPERATURE=C &
VOLUME=cum DELTA-T=C HEAD=meter MOLE-DENSITY='kmol/cum' &
MASS-DENSITY='kg/cum' MOLE-ENTHALP='kcal/mol' &
MASS-ENTHALP='kcal/kg' HEAT=Gcal MOLE-CONC='mol/l' &
PDROP=bar
SUBSTREAM MIXED TEMP=35. PRES=1. <atm> MOLE-FLOW=530.
MASS-FRAC WATER 1.
BLOCK B7 MIXER
277
BLOCK B6 SEP
FRAC STREAM=20 SUBSTREAM=MIXED COMPS=DIMET-01 C2H6 C3H8 &
FRACS=0.99 0.09 0.09
278
COL-SPECS D:F=0.42 MOLE-RR=4.5
BLOCK B9 VALVE
IN-UNITS MET FLOW='gm/hr' MASS-FLOW='gm/hr' TEMPERATURE=C &
DELTA-T=C
PARAM P-OUT=20.
EO-CONV-OPTI
279
RATE-CON 1 PRE-EXP=1210000. ACT-ENERGY=80.4 <kJ/kmol>
STOIC 1 MIXED METHA-01 -2. / DIMET-01 1. / WATER 1.
REAC-ACT 1
280
ACRYLONITRILE BASE CASE INPUT FILE
DYNAMICS
DYNAMICS RESULTS=ON ;
IN-UNITS ENG
DEF-STREAMS CONVEN ALL
SIM-OPTIONS RESTART=NO OLD-DATABANK=YES
RUN-CONTROL MAX-TIME=15000 MAX-ERRORS=1000 MAX-FORT-ERR=1000
DATABANKS PURE93 / AQUEOUS / SOLIDS / INORGANIC / &
ASPENPCD
PROP-SOURCES PURE93 / AQUEOUS / SOLIDS / INORGANIC / &
ASPENPCD
COMPONENTS
NH3 H3N /
H20 H2O /
HCN CHN /
CO CO /
O2 O2 /
PROPYLEN C3H6-2 /
CO2 CO2 /
ACETO C2H3N /
ACRYLO C3H3N /
ACROLEIN C3H4O /
H2S04 H2SO4 /
AMMSUL "(NH4)2SO4"
FLOWSHEET
BLOCK M-301 IN=1A 1C 1B OUT=1
BLOCK M-302 IN=3 2 OUT=2+3
BLOCK R-302 IN=2+3 OUT=OUT
BLOCK T-301 IN=OUT OUT=4 5
BLOCK E-301 IN=4 OUT=6
BLOCK T-302 IN=6 8 OUT=10 9
BLOCK E-303 IN=9 OUT=11
BLOCK T-303 IN=11 OUT=13 12
BLOCK T-306 IN=16 OUT=18 19
BLOCK R-301 IN=1 OUT=2
BLOCK T-305 IN=15 OUT=17 16
BLOCK E-302 IN=7 OUT=8
BLOCK T-304 IN=21 OUT=14 15
BLOCK E-304 IN=14 OUT=20
BLOCK E-305 IN=13 OUT=21
281
BLOCK B2 IN=5 10 20 17 OUT=22
PROPERTIES ELECNRTL
PROPERTIES AMINES / IDEAL / NRTL / NRTL-RK / PENG-ROB /
PITZ-HG / POLYNRTL / PSRK / RK-SOAVE
USER-PROPS DRUSR2 1 2 3
PROP-DATA NRTL-1
IN-UNITS ENG
PROP-LIST NRTL
BPVAL NH3 H20 -.16424220 -1849.5450 .20 .0 .0 .0 32.0 &
392.0
BPVAL H20 NH3 -.5440720 3021.2440 .20 .0 .0 .0 32.0 &
392.0
BPVAL H20 HCN .0 909.90 .30 .0 .0 .0 50.0 230.0
BPVAL HCN H20 .0 .0 .30 .0 .0 .0 50.0 230.0
BPVAL H20 CO2 10.0640 -5882.6430 .20 .0 .0 .0 32.0 &
392.0
BPVAL CO2 H20 10.0640 -5882.6430 .20 .0 .0 .0 32.0 &
392.0
PROP-DATA PRKBV-1
IN-UNITS ENG
PROP-LIST PRKBV
BPVAL NH3 H20 -.2589000000 0.0 0.0 -459.6699923 &
1340.329993
BPVAL H20 NH3 -.2589000000 0.0 0.0 -459.6699923 &
1340.329993
BPVAL H20 CO2 .1200000000 0.0 0.0 -459.6699923 1340.329993
BPVAL CO2 H20 .1200000000 0.0 0.0 -459.6699923 1340.329993
BPVAL PROPYLEN CO2 .0933000000 0.0 0.0 -459.6699923 &
1340.329993
BPVAL CO2 PROPYLEN .0933000000 0.0 0.0 -459.6699923 &
1340.329993
STREAM 1A
SUBSTREAM MIXED TEMP=80. PRES=14.7 <psi>
MOLE-FLOW NH3 85.
STREAM 1B
SUBSTREAM MIXED TEMP=80. PRES=14.7 <psi>
MOLE-FLOW O2 129.
STREAM 1C
SUBSTREAM MIXED TEMP=80. PRES=14.7 <psi>
MOLE-FLOW PROPYLEN 85.
STREAM 3
282
SUBSTREAM MIXED TEMP=86. PRES=14.7 <psi>
MOLE-FLOW H20 0.21 / H2S04 11.
STREAM 7
SUBSTREAM MIXED TEMP=45. PRES=1. <atm>
MOLE-FLOW H20 120.
BLOCK B2 MIXER
BLOCK M-301 MIXER
PARAM PRES=14.7 <psi>
BLOCK M-302 MIXER
283
COL-CONFIG CONDENSER=TOTAL
FEEDS 11 10 ON-STAGE
PRODUCTS 12 30 L / 13 1 L
P-SPEC 1 15.
COL-SPECS D:F=0.17 MOLE-RR=7.
UTILITIES COND-UTIL=CW-RT303 REB-UTIL=LST-303
284
UTILITY CW-RT303 GENERAL
COST ENERGY-PRICE=0.354 <$/GJ>
PARAM UTILITY-TYPE=WATER PRES=1. <atm> PRES-OUT=15. &
TIN=30. <C> TOUT=93.53 CALOPT=FLASH
285
PARAM UTILITY-TYPE=STEAM PRES=5. <barg> PRES-OUT=15. &
TIN=160. <C> TOUT=70. CALOPT=FLASH
DESIGN-SPEC DS-1
DEFINE INAMM MOLE-FLOW STREAM=OUT SUBSTREAM=MIXED &
COMPONENT=AMMSUL
DEFINE OUTAMM MOLE-FLOW STREAM=5 SUBSTREAM=MIXED &
COMPONENT=AMMSUL
F RATIO = OUTAMM/INAMM
SPEC "OUTAMM/INAMM" TO "0.99"
286
TOL-SPEC "0.05"
VARY BLOCK-VAR BLOCK=T-301 VARIABLE=PRES SENTENCE=PARAM
LIMITS "0 " "70"
DESIGN-SPEC DS-2
DEFINE INH20 MOLE-FLOW STREAM=OUT SUBSTREAM=MIXED &
COMPONENT=H20
DEFINE OUTH20 MOLE-FLOW STREAM=4 SUBSTREAM=MIXED &
COMPONENT=H20
SPEC "OUTH20/INH20" TO "0.95"
TOL-SPEC "0.05"
VARY BLOCK-VAR BLOCK=T-301 VARIABLE=TEMP SENTENCE=PARAM
LIMITS "0" "600"
DESIGN-SPEC DS-3
DEFINE MOLH2 MOLE-FLOW STREAM=3 SUBSTREAM=MIXED &
COMPONENT=H2S04
DEFINE MOLNH3 MOLE-FLOW STREAM=2 SUBSTREAM=MIXED &
COMPONENT=NH3
SPEC "MOLH2" TO "MOLNH3/2"
TOL-SPEC "5"
VARY MOLE-FLOW STREAM=3 SUBSTREAM=MIXED COMPONENT=H2S04
LIMITS "2" "120"
EO-CONV-OPTI
CONV-OPTIONS
PARAM TOL=.010
WEGSTEIN MAXIT=200 QMIN=-20.0
SECANT MAXIT=60 XTOL=1E-03
ECONOMIC-REP CASH-FLOW=ANNUAL
287
RATE-CON 1 PRE-EXP=157498 ACT-ENERGY=34200
RATE-CON 2 PRE-EXP=3778 ACT-ENERGY=34200
RATE-CON 3 PRE-EXP=1.99 ACT-ENERGY=12600
RATE-CON 4 PRE-EXP=780.82 ACT-ENERGY=12600
RATE-CON 5 PRE-EXP=108308 ACT-ENERGY=35640
RATE-CON 6 PRE-EXP=8.3658 ACT-ENERGY=12600
STOIC 1 MIXED PROPYLEN -1 / NH3 -1 / O2 -1.5 / ACRYLO &
1 / H20 3
STOIC 2 MIXED PROPYLEN -1 / O2 -1 / ACROLEIN 1 / H20 &
1
STOIC 3 MIXED PROPYLEN -1 / NH3 -1 / O2 -2.25 / ACETO &
1 / CO2 .5 / CO .5 / H20 3
STOIC 4 MIXED ACROLEIN -1 / NH3 -1 / O2 -0.5 / ACRYLO &
1 / H20 2
STOIC 5 MIXED ACRYLO -1 / O2 -2 / CO 1 / CO2 1 / &
H20 1 / HCN 1
STOIC 6 MIXED ACETO -1 / O2 -1.5 / CO2 1 / HCN 1 / &
H20 1
POWLAW-EXP 1 MIXED PROPYLEN 1
POWLAW-EXP 2 MIXED PROPYLEN 1
POWLAW-EXP 3 MIXED PROPYLEN 1
POWLAW-EXP 4 MIXED ACROLEIN 1
POWLAW-EXP 5 MIXED ACRYLO 1
POWLAW-EXP 6 MIXED ACETO 1
;
;
;
;
;
288
OPTIMIZED ACRYLONITRILE INPUT FILE
DYNAMICS
DYNAMICS RESULTS=ON
IN-UNITS ENG
COMPONENTS
NH3 H3N /
H20 H2O /
HCN CHN /
CO CO /
O2 O2 /
PROPYLEN C3H6-2 /
CO2 CO2 /
ACETO C2H3N /
ACRYLO C3H3N /
ACROLEIN C3H4O /
H2S04 H2SO4 /
AMMSUL "(NH4)2SO4"
FLOWSHEET
BLOCK M-301 IN=1A 1C 1B 25 OUT=1
BLOCK M-302 IN=3 2 OUT=2+3
BLOCK R-302 IN=2+3 OUT=OUT
BLOCK T-301 IN=OUT OUT=4 5
BLOCK E-301 IN=4 OUT=6
BLOCK T-302 IN=6 19 OUT=8 9
BLOCK T-303 IN=9 OUT=12 11
BLOCK T-306 IN=15 OUT=16 17
BLOCK R-301 IN=1 OUT=2
BLOCK T-305 IN=12 OUT=14 15
BLOCK E-302 IN=11 OUT=18
BLOCK E-303 IN=24 OUT=25
BLOCK E-304 IN=21 OUT=22
BLOCK B17 IN=18 OUT=19 39
BLOCK B19 IN=5 14 20 23 OUT=42
BLOCK T-307 IN=8 OUT=20 21
BLOCK T-304 IN=22 OUT=24 23
289
PROPERTIES ELECNRTL
PROPERTIES AMINES / IDEAL / NRTL / NRTL-RK / PENG-ROB /
PITZ-HG / POLYNRTL / PSRK / RK-SOAVE
USER-PROPS DRUSR2 1 2 3
PROP-DATA NRTL-1
IN-UNITS ENG
PROP-LIST NRTL
BPVAL NH3 H20 -.16424220 -1849.5450 .20 .0 .0 .0 32.0 &
392.0
BPVAL H20 NH3 -.5440720 3021.2440 .20 .0 .0 .0 32.0 &
392.0
BPVAL H20 HCN .0 909.90 .30 .0 .0 .0 50.0 230.0
BPVAL HCN H20 .0 .0 .30 .0 .0 .0 50.0 230.0
BPVAL H20 CO2 10.0640 -5882.6430 .20 .0 .0 .0 32.0 &
392.0
BPVAL CO2 H20 10.0640 -5882.6430 .20 .0 .0 .0 32.0 &
392.0
PROP-DATA PRKBV-1
IN-UNITS ENG
PROP-LIST PRKBV
BPVAL NH3 H20 -.2589000000 0.0 0.0 -459.6699923 &
1340.329993
BPVAL H20 NH3 -.2589000000 0.0 0.0 -459.6699923 &
1340.329993
BPVAL H20 CO2 .1200000000 0.0 0.0 -459.6699923 1340.329993
BPVAL CO2 H20 .1200000000 0.0 0.0 -459.6699923 1340.329993
BPVAL PROPYLEN CO2 .0933000000 0.0 0.0 -459.6699923 &
1340.329993
BPVAL CO2 PROPYLEN .0933000000 0.0 0.0 -459.6699923 &
1340.329993
STREAM 1A
SUBSTREAM MIXED TEMP=80. PRES=15. <psi>
MOLE-FLOW NH3 67.
STREAM 1B
SUBSTREAM MIXED TEMP=80. PRES=15. <psi>
MOLE-FLOW O2 129.
STREAM 1C
SUBSTREAM MIXED TEMP=80. PRES=15. <psi>
MOLE-FLOW PROPYLEN 80.
STREAM 3
SUBSTREAM MIXED TEMP=86. PRES=14.7 <psi>
MOLE-FLOW H20 0.21 / H2S04 10.
290
BLOCK B19 MIXER
291
COL-CONFIG CONDENSER=TOTAL
FEEDS 9 10
PRODUCTS 11 30 L / 12 1 L
P-SPEC 1 14.7 <psi> / 2 14.7
COL-SPECS D:F=0.16 MOLE-RR=10.5
UTILITIES COND-UTIL=CW-RT303 REB-UTIL=LST-303
292
UTILITY CWE2 GENERAL
COST ENERGY-PRICE=0.354 <$/GJ>
PARAM UTILITY-TYPE=WATER PRES=1. <atm> PRES-OUT=20. &
TIN=30. <C> TOUT=170. CALOPT=FLASH
DESIGN-SPEC DS-1
DEFINE INAMM MOLE-FLOW STREAM=OUT SUBSTREAM=MIXED &
293
COMPONENT=AMMSUL
DEFINE OUTAMM MOLE-FLOW STREAM=5 SUBSTREAM=MIXED &
COMPONENT=AMMSUL
F RATIO = OUTAMM/INAMM
SPEC "OUTAMM/INAMM" TO "0.99"
TOL-SPEC "0.05"
VARY BLOCK-VAR BLOCK=T-301 VARIABLE=PRES SENTENCE=PARAM
LIMITS "0 " "70"
DESIGN-SPEC DS-2
DEFINE INH20 MOLE-FLOW STREAM=OUT SUBSTREAM=MIXED &
COMPONENT=H20
DEFINE OUTH20 MOLE-FLOW STREAM=4 SUBSTREAM=MIXED &
COMPONENT=H20
SPEC "OUTH20/INH20" TO "0.95"
TOL-SPEC "0.05"
VARY BLOCK-VAR BLOCK=T-301 VARIABLE=TEMP SENTENCE=PARAM
LIMITS "0" "600"
DESIGN-SPEC DS-3
DEFINE MOLH2 MOLE-FLOW STREAM=3 SUBSTREAM=MIXED &
COMPONENT=H2S04
DEFINE MOLNH3 MOLE-FLOW STREAM=2 SUBSTREAM=MIXED &
COMPONENT=NH3
SPEC "MOLH2" TO "MOLNH3/2"
TOL-SPEC "5"
VARY MOLE-FLOW STREAM=3 SUBSTREAM=MIXED COMPONENT=H2S04
LIMITS "0.5" "120"
DESIGN-SPEC DS-4
DEFINE PR2 MOLE-FLOW STREAM=1 SUBSTREAM=MIXED &
COMPONENT=PROPYLEN
SPEC "PR2" TO "85"
TOL-SPEC "0.1"
VARY MOLE-FLOW STREAM=1C SUBSTREAM=MIXED COMPONENT=PROPYLEN
LIMITS "10" "150"
EO-CONV-OPTI
PARAM SOLVER=DMO
SENSITIVITY FLOWR
DEFINE WASTE1 STREAM-VAR STREAM=42 SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE ACRYL STREAM-VAR STREAM=16 SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE NH3 STREAM-VAR STREAM=1A SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE O2 STREAM-VAR STREAM=1B SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE PROP STREAM-VAR STREAM=1C SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
294
DEFINE H20 STREAM-VAR STREAM=39 SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE H2SO4 STREAM-VAR STREAM=3 SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE MNH3 STREAM-VAR STREAM=1A SUBSTREAM=MIXED &
VARIABLE=MOLE-FLOW
DEFINE MO2 STREAM-VAR STREAM=1B SUBSTREAM=MIXED &
VARIABLE=MOLE-FLOW
DEFINE MPROP STREAM-VAR STREAM=1C SUBSTREAM=MIXED &
VARIABLE=MOLE-FLOW
DEFINE ACRYL2 MOLE-FLOW STREAM=2 SUBSTREAM=MIXED &
COMPONENT=ACRYLO
DEFINE MPROP2 MOLE-FLOW STREAM=2 SUBSTREAM=MIXED &
COMPONENT=PROPYLEN
DEFINE WATERR MOLE-FLOW STREAM=11 SUBSTREAM=MIXED &
COMPONENT=H20
DEFINE ACE MOLE-FLOW STREAM=6 SUBSTREAM=MIXED &
COMPONENT=ACRYLO
DEFINE ACE1 MOLE-FLOW STREAM=9 SUBSTREAM=MIXED &
COMPONENT=ACRYLO
DEFINE COND BLOCK-VAR BLOCK=T-302 VARIABLE=COND-DUTY &
SENTENCE=RESULTS
DEFINE REB BLOCK-VAR BLOCK=T-302 VARIABLE=REB-DUTY &
SENTENCE=RESULTS
DEFINE HCN MOLE-FLOW STREAM=14 SUBSTREAM=MIXED &
COMPONENT=HCN
DEFINE ACET MOLE-FLOW STREAM=17 SUBSTREAM=MIXED &
COMPONENT=ACETO
DEFINE Q3 BLOCK-VAR BLOCK=R-301 VARIABLE=QCALC &
SENTENCE=PARAM
DEFINE Q4 BLOCK-VAR BLOCK=T-304 VARIABLE=REB-DUTY &
SENTENCE=RESULTS
DEFINE Q5 BLOCK-VAR BLOCK=T-304 VARIABLE=COND-DUTY &
SENTENCE=RESULTS
DEFINE Q6 BLOCK-VAR BLOCK=T-307 VARIABLE=REB-DUTY &
SENTENCE=RESULTS
DEFINE Q7 BLOCK-VAR BLOCK=T-307 VARIABLE=COND-DUTY &
SENTENCE=RESULTS
F TWASTE =WASTE1
F CNH3 = 0.17
F C02 = 0.05
F CPROP = 0.44
F CH2SO4 = 0.037
F CH2O = 3.039E-5
F CACRYL = 1.18
F CACETO = 0.997
F CWASTE = 0.016364
F
F RAW = (CNH3*NH3+ CO2*O2+CPROP*PROP+CH2SO4*H2SO4)*24*365
F REV = (CACRYL*ACRYL+CH20*H20)*24*365
F MVA = REV -RAW-(CWASTE*TWASTE)
295
F
F OBYP=MO2/MPROP
F PBYN=MPROP/MNH3
F OBYN=MO2/MNH3
F
F CONV=(MPROP-MPROP2)/MPROP*100
F
F
F ACRR = (ACE/ACE1)*100
F TOT = (Q5*(8.77E-6)+Q7*(8.77E-6)+Q3*(-8.77E-6))*365*24
F TOTALQ = (( Q4* (4.31E-6)+Q6*(4.31E-6))*365*24) +TOT
TABULATE 1 "TWASTE"
TABULATE 2 "RAW"
TABULATE 3 "REV"
TABULATE 4 "MVA"
TABULATE 6 "ACRYL2"
TABULATE 7 "CONV"
TABULATE 8 "WATERR"
TABULATE 9 "ACRR"
TABULATE 10 "ACE3"
TABULATE 11 "ACET"
TABULATE 12 "HCN"
TABULATE 13 "COND"
TABULATE 14 "REB"
TABULATE 15 "TOTALQ"
VARY BLOCK-VAR BLOCK=T-306 VARIABLE=STAGE SENTENCE=FEEDS &
ID1=15
RANGE LOWER="2" UPPER="10" INCR="1"
CONV-OPTIONS
PARAM TEAR-METHOD=BROYDEN TOL=0.01
WEGSTEIN MAXIT=200 QMIN=-20.0
SECANT MAXIT=60 XTOL=1E-03
ECONOMIC-REP CASH-FLOW=ANNUAL
296
RATE-CON 5 PRE-EXP=108308 ACT-ENERGY=35640
RATE-CON 6 PRE-EXP=8.3658 ACT-ENERGY=12600
STOIC 1 MIXED PROPYLEN -1 / NH3 -1 / O2 -1.5 / ACRYLO &
1 / H20 3
STOIC 2 MIXED PROPYLEN -1 / O2 -1 / ACROLEIN 1 / H20 &
1
STOIC 3 MIXED PROPYLEN -1 / NH3 -1 / O2 -2.25 / ACETO &
1 / CO2 .5 / CO .5 / H20 3
STOIC 4 MIXED ACROLEIN -1 / NH3 -1 / O2 -0.5 / ACRYLO &
1 / H20 2
STOIC 5 MIXED ACRYLO -1 / O2 -2 / CO 1 / CO2 1 / &
H20 1 / HCN 1
STOIC 6 MIXED ACETO -1 / O2 -1.5 / CO2 1 / HCN 1 / &
H20 1
POWLAW-EXP 1 MIXED PROPYLEN 1
POWLAW-EXP 2 MIXED PROPYLEN 1
POWLAW-EXP 3 MIXED PROPYLEN 1
POWLAW-EXP 4 MIXED ACROLEIN 1
POWLAW-EXP 5 MIXED ACRYLO 1
POWLAW-EXP 6 MIXED ACETO 1
;
;
297
BASE CASE ALLYL CHLORIDE INPUT FILE
DYNAMICS
DYNAMICS RESULTS=ON
IN-UNITS ENG
SIM-OPTIONS OLD-DATABANK=YES
DESCRIPTION "
General Simulation with English Units :
F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.
COMPONENTS
H2O H2O /
HCL HCL /
PROPENE C3H6-2 /
CHLORINE CL2 /
AC C3H5CL /
12DCP C3H6CL2 /
13DCP-C C3H4CL2-D1 /
13DCP-T C3H4CL2-D2 /
H+ H+ /
CL- CL-
CHEMISTRY HCL
STOIC 1 HCL -1 / H+ 1 / CL- 1
FLOWSHEET
BLOCK E-901 IN=14 OUT=2
298
BLOCK M-902 IN=1 13 OUT=14
BLOCK M-901 IN=2 3 OUT=4
BLOCK R-901 IN=4 OUT=5
BLOCK E-902 IN=5 OUT=6
BLOCK T-901 IN=6 OUT=8 7
BLOCK T-904 IN=7 OUT=9 10
BLOCK T-902 IN=15 8 OUT=16 17
BLOCK T-903 IN=16 OUT=12 11
BLOCK C-901 IN=12 OUT=13
PROPERTIES SYSOP0
PROPERTIES ELECNRTL / UNIQ-RK / UNIQUAC
STRUCTURES
STRUCTURES 13DCP-C CL1 C2 S / C2 C3 D / C3 C4 S / &
C4 CL5 S
ESTIMATE ALL
PROP-DATA PCES-1
IN-UNITS ENG
PROP-LIST DGAQHG / DHAQHG / S25HG / OMEGHG / DHVLB / &
VB / RGYR / VLSTD
PVAL CHLORINE 2983.662941 / -10060.18917 / 28.90035349 / &
-17580.05159 / 8784.000000 / .7262124822 / &
3.2391732E-10 / .8579136616
PROP-LIST DHVLB / VB / RGYR
PVAL 13DCP-C 14431.51333 / 1.612466586 / 1.11089239E-9
PROP-DATA HENRY-1
IN-UNITS ENG
PROP-LIST HENRY
BPVAL HCL H2O -49.78140336 2186.999983 8.370700000 &
-5.3294445E-3 -3.999995968 68.00000346 0.0
BPVAL CHLORINE H2O -116.9781387 4371.515965 19.18540000 &
-4.9558834E-3 49.73000360 103.7300032 0.0
BPVAL HCL 12DCP 10.00798341 -2648.879936 0.0 0.0 &
-4.269995966 67.73000346 0.0
BPVAL PROPENE H2O 326.3806995 -28021.26578 -41.73762000 0.0 &
69.53000344 220.7300022 0.0
BPVAL PROPENE 12DCP 12.93988341 -3932.459880 0.0 0.0 &
-4.269995966 67.73000346 0.0
PROP-DATA UNIQ-1
IN-UNITS ENG
PROP-LIST UNIQ
BPVAL H2O AC -4.247000000 2292.652782 0.0 0.0 109.9400031 &
212.0000023 0.0
BPVAL AC H2O 15.46800000 -10062.08074 0.0 0.0 109.9400031 &
212.0000023 0.0
BPVAL H2O 12DCP 0.0 -539.9468957 0.0 0.0 77.00000338 &
299
77.00000338 0.0
BPVAL 12DCP H2O 0.0 -2498.536780 0.0 0.0 77.00000338 &
77.00000338 0.0
PROP-DATA VLCLK-1
IN-UNITS ENG
PROP-LIST VLCLK
BPVAL H+ CL- .5534556926 .2140997389
PROP-DATA GMELCC-1
IN-UNITS ENG
PROP-LIST GMELCC
PPVAL H2O ( H+ CL- ) 41.67400000
PPVAL ( H+ CL- ) H2O -22.15400000
PPVAL HCL ( H+ CL- ) 1.00000000E-3
PPVAL ( H+ CL- ) HCL -1.0000000E-3
PROP-DATA GMELCD-1
IN-UNITS ENG
PROP-LIST GMELCD
PPVAL H2O ( H+ CL- ) 9581.579923
PPVAL ( H+ CL- ) H2O -3967.379968
PROP-DATA GMELCE-1
IN-UNITS ENG
PROP-LIST GMELCE
PPVAL H2O ( H+ CL- ) -5.404000000
PPVAL ( H+ CL- ) H2O 5.188000000
PROP-DATA GMELCN-1
IN-UNITS ENG
PROP-LIST GMELCN
PPVAL H2O ( H+ CL- ) .0283500000
PCES-PROP-DATA
IN-UNITS ENG
GAMINF H2O 12DCP * * 68 2340 / * * 86 2310 / * * &
104 2090
PCES-PROP-DATA
IN-UNITS ENG
GAMINF H2O 13DCP-C * * 68 1360 / * * 86 1430 / * * &
104 1460
STREAM 1
SUBSTREAM MIXED TEMP=80. PRES=74.7
MOLE-FLOW PROPENE 1000.
STREAM 3
SUBSTREAM MIXED TEMP=80. PRES=74.7
MOLE-FLOW CHLORINE 133.
300
STREAM 15
SUBSTREAM MIXED TEMP=70. PRES=14.7
MOLE-FLOW H2O 500.
301
PRODUCTS 17 10 L / 16 1 V
P-SPEC 1 14.7
COL-SPECS
T-EST 1 110. / 10 68.
PROPERTIES ELECNRTL HENRY-COMPS=HENRY CHEMISTRY=HCL &
FREE-WATER=STEAM-TA SOLU-WATER=3 TRUE-COMPS=NO
302
PARAM UTILITY-TYPE=REFRIGERATIO BASIS=MASS TIN=5. <C> &
TOUT=15. <C> VFRAC=0. VFR-OUT=0. CALOPT=FLASH
COMPOSITION H2O 1.
DESIGN-SPEC FEED
DEFINE S19C3 MOLE-FLOW STREAM=14 SUBSTREAM=MIXED &
COMPONENT=PROPENE
SPEC "S19C3" TO "1000"
TOL-SPEC "0.1"
VARY MOLE-FLOW STREAM=1 SUBSTREAM=MIXED COMPONENT=PROPENE
LIMITS "50" "1000"
DESIGN-SPEC RESTM
DEFINE RESTM BLOCK-VAR BLOCK=R-901 VARIABLE=RES-TIME &
SENTENCE=PARAM
SPEC "RESTM" TO "1.11E-3"
TOL-SPEC ".0001"
VARY BLOCK-VAR BLOCK=R-901 VARIABLE=LENGTH SENTENCE=PARAM
LIMITS "1" "200"
EO-CONV-OPTI
CONV-OPTIONS
WEGSTEIN MAXIT=100
SQP MAXIT=100 MAXPASS=1000
TEAR
TEAR 13
PROPERTY-REP PCES
303
STOIC 2 MIXED PROPENE -1. / CHLORINE -1. / 12DCP 1.
STOIC 3 MIXED AC -1. / CHLORINE -1. / 13DCP-C 1. / &
HCL 1.
POWLAW-EXP 1 MIXED PROPENE 1. / MIXED CHLORINE 1.
POWLAW-EXP 2 MIXED PROPENE 1. / MIXED CHLORINE 1.
POWLAW-EXP 3 MIXED AC 1. / MIXED CHLORINE 1.
304
OPTIMIZED ADIABATIC ALLYL CHLORIDE CASE
DYNAMICS
DYNAMICS RESULTS=ON
IN-UNITS ENG
DEF-STREAMS CONVEN ALL
SIM-OPTIONS OLD-DATABANK=YES
DESCRIPTION "
General Simulation with English Units :
F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.
COMPONENTS
H2O H2O /
HCL HCL /
PROPENE C3H6-2 /
CHLORINE CL2 /
AC C3H5CL /
12DCP C3H6CL2 /
13DCP-C C3H4CL2-D1 /
13DCP-T C3H4CL2-D2 /
H+ H+ /
CL- CL-
CHEMISTRY HCL
STOIC 1 HCL -1 / H+ 1 / CL- 1
305
FLOWSHEET
BLOCK E-901 IN=14 OUT=2
BLOCK M-902 IN=1 13 OUT=14
BLOCK M-901 IN=2 3 OUT=4
BLOCK R-901 IN=4 OUT=5
BLOCK E-902 IN=5 OUT=6
BLOCK T-901 IN=6 OUT=8 7
BLOCK T-904 IN=7 OUT=9 10
BLOCK T-902 IN=15 8 OUT=16 17
BLOCK T-903 IN=16 OUT=12 11
BLOCK C-901 IN=12 OUT=13
BLOCK T-905 IN=9 OUT=18 19
BLOCK T-906 IN=19 OUT=20 21
BLOCK T-907 IN=17 OUT=22 23
BLOCK E-903 IN=10 OUT=24
BLOCK E-904 IN=20 OUT=25
BLOCK E-905 IN=23 OUT=27
BLOCK E-906 IN=22 OUT=28
BLOCK E-907 IN=21 OUT=29
PROPERTIES SYSOP0
PROPERTIES ELECNRTL / UNIQ-RK / UNIQUAC
STRUCTURES
STRUCTURES 13DCP-C CL1 C2 S / C2 C3 D / C3 C4 S / &
C4 CL5 S
ESTIMATE ALL
PROP-DATA PCES-1
IN-UNITS ENG
PROP-LIST DGAQHG / DHAQHG / S25HG / OMEGHG / DHVLB / &
VB / RGYR / VLSTD
PVAL CHLORINE 2983.662941 / -10060.18917 / 28.90035349 / &
-17580.05159 / 8784.000000 / .7262124822 / &
3.2391732E-10 / .8579136616
PROP-LIST DHVLB / VB / RGYR
PVAL 13DCP-C 14431.51333 / 1.612466586 / 1.11089239E-9
PROP-DATA HENRY-1
IN-UNITS ENG
PROP-LIST HENRY
BPVAL HCL H2O -49.78140336 2186.999983 8.370700000 &
-5.3294445E-3 -3.999995968 68.00000346 0.0
306
BPVAL CHLORINE H2O -116.9781387 4371.515965 19.18540000 &
-4.9558834E-3 49.73000360 103.7300032 0.0
BPVAL HCL 12DCP 10.00798341 -2648.879936 0.0 0.0 &
-4.269995966 67.73000346 0.0
BPVAL PROPENE H2O 326.3806995 -28021.26578 -41.73762000 0.0 &
69.53000344 220.7300022 0.0
BPVAL PROPENE 12DCP 12.93988341 -3932.459880 0.0 0.0 &
-4.269995966 67.73000346 0.0
PROP-DATA UNIQ-1
IN-UNITS ENG
PROP-LIST UNIQ
BPVAL H2O AC -4.247000000 2292.652782 0.0 0.0 109.9400031 &
212.0000023 0.0
BPVAL AC H2O 15.46800000 -10062.08074 0.0 0.0 109.9400031 &
212.0000023 0.0
BPVAL H2O 12DCP 0.0 -539.9468957 0.0 0.0 77.00000338 &
77.00000338 0.0
BPVAL 12DCP H2O 0.0 -2498.536780 0.0 0.0 77.00000338 &
77.00000338 0.0
PROP-DATA VLCLK-1
IN-UNITS ENG
PROP-LIST VLCLK
BPVAL H+ CL- .5534556926 .2140997389
PROP-DATA GMELCC-1
IN-UNITS ENG
PROP-LIST GMELCC
PPVAL H2O ( H+ CL- ) 41.67400000
PPVAL ( H+ CL- ) H2O -22.15400000
PPVAL HCL ( H+ CL- ) 1.00000000E-3
PPVAL ( H+ CL- ) HCL -1.0000000E-3
PROP-DATA GMELCD-1
IN-UNITS ENG
PROP-LIST GMELCD
PPVAL H2O ( H+ CL- ) 9581.579923
PPVAL ( H+ CL- ) H2O -3967.379968
PROP-DATA GMELCE-1
IN-UNITS ENG
PROP-LIST GMELCE
PPVAL H2O ( H+ CL- ) -5.404000000
307
PPVAL ( H+ CL- ) H2O 5.188000000
PROP-DATA GMELCN-1
IN-UNITS ENG
PROP-LIST GMELCN
PPVAL H2O ( H+ CL- ) .0283500000
PCES-PROP-DATA
IN-UNITS ENG
GAMINF H2O 12DCP * * 68 2340 / * * 86 2310 / * * &
104 2090
PCES-PROP-DATA
IN-UNITS ENG
GAMINF H2O 13DCP-C * * 68 1360 / * * 86 1430 / * * &
104 1460
STREAM 1
SUBSTREAM MIXED TEMP=80. PRES=74.7
MOLE-FLOW PROPENE 1000.
STREAM 3
SUBSTREAM MIXED TEMP=80. PRES=74.7
MOLE-FLOW CHLORINE 133.
STREAM 15
SUBSTREAM MIXED TEMP=70. PRES=14.7
MOLE-FLOW H2O 1000.
308
BLOCK E-901 HEATER
PARAM TEMP=730. PRES=74.7
PROPERTIES UNIQ-RK FREE-WATER=STEAM-TA SOLU-WATER=3 &
TRUE-COMPS=YES
UTILITY UTILITY-ID=U-1
309
VARY 1 D:F 0.001 0.999
PROPERTIES UNIQ-RK FREE-WATER=STEAM-TA SOLU-WATER=3 &
TRUE-COMPS=YES
UTILITIES COND-UTIL=U-1 REB-UTIL=U-1
310
COL-CONFIG CONDENSER=TOTAL
FEEDS 19 15
PRODUCTS 20 1 L / 21 30 L
P-SPEC 1 14.7
COL-SPECS D:F=0.01 MOLE-RR=5.
SPEC 1 MOLE-RECOV 0.9 COMPS=12DCP STREAMS=20 &
BASE-STREAMS=19
VARY 1 D:F 0.01 0.99
UTILITIES COND-UTIL=U-1 REB-UTIL=U-1
DESIGN-SPEC FEED
DEFINE S19C3 MOLE-FLOW STREAM=14 SUBSTREAM=MIXED &
COMPONENT=PROPENE
SPEC "S19C3" TO "1000"
TOL-SPEC "0.1"
VARY MOLE-FLOW STREAM=1 SUBSTREAM=MIXED COMPONENT=PROPENE
LIMITS "50" "1000"
DESIGN-SPEC RESTM
DEFINE RESTM BLOCK-VAR BLOCK=R-901 VARIABLE=RES-TIME &
SENTENCE=PARAM
SPEC "RESTM" TO "1.11E-3"
TOL-SPEC ".0001"
VARY BLOCK-VAR BLOCK=R-901 VARIABLE=LENGTH SENTENCE=PARAM
LIMITS "1" "200"
311
EO-CONV-OPTI
OPTIMIZATION MAXPROFT
DEFINE AC9 MASS-FLOW STREAM=18 SUBSTREAM=MIXED COMPONENT=AC
DEFINE HCL17 MASS-FLOW STREAM=22 SUBSTREAM=MIXED &
COMPONENT=HCL
DEFINE CL3 MASS-FLOW STREAM=3 SUBSTREAM=MIXED &
COMPONENT=CHLORINE
DEFINE PROP1 MASS-FLOW STREAM=1 SUBSTREAM=MIXED &
COMPONENT=PROPENE
DEFINE H2015 MASS-FLOW STREAM=15 SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE FDHTR BLOCK-VAR BLOCK=E-901 VARIABLE=QCALC &
SENTENCE=PARAM
DEFINE REB1 BLOCK-VAR BLOCK=T-901 VARIABLE=REB-DUTY &
SENTENCE=RESULTS
DEFINE REB2 BLOCK-VAR BLOCK=T-904 VARIABLE=REB-DUTY &
SENTENCE=RESULTS
DEFINE COMP BLOCK-VAR BLOCK=C-901 VARIABLE=BRAKE-POWER &
SENTENCE=RESULTS
DEFINE COOLER BLOCK-VAR BLOCK=E-902 VARIABLE=QCALC &
SENTENCE=PARAM
DEFINE COND1 BLOCK-VAR BLOCK=T-901 VARIABLE=COND-DUTY &
SENTENCE=RESULTS
DEFINE COND2 BLOCK-VAR BLOCK=T-904 VARIABLE=COND-DUTY &
SENTENCE=RESULTS
DEFINE WASTE STREAM-VAR STREAM=21 SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE PROFIT PARAMETER 1 PHYS-QTY=UNIT-PRICE UOM="$/lb" &
INIT-VAL=1.
F REVAC=1.80
F REVHCL=0.095
F CSTCL2=0.375
F CSTPRP= 0.981
F WASTEC=0.2
F CWATER = 6.7e-5
F REVENUE=(REVAC*AC9+REVHCL*HCL17)*24*365
F RAWCST=(CSTCL2*CL3+CSTPRP*PROP1+CWATER*H2015)*24*365
F WSTCST=(WASTEC*WASTE)*24*365
F TOTGAS=FDHTR
F LOWS =REB1+REB2
F GASCST=(TOTGAS)*(1.17E-05)*24*365
F LOWSC = LPWS*(1.48E-05)*24*365
F ELECST=0.06*COMP
312
F H20BTU=-(COND1+COND2)
F FLWH20=H20BTU*(3.7349E-07)*24*365
F H20CST=FLWH20
F PROFIT=REVENUE-RAWCST-WSTCST-UTLCST
MAXIMIZE "PROFIT"
VARY BLOCK-VAR BLOCK=E-901 VARIABLE=TEMP SENTENCE=PARAM
LIMITS "200" "1000"
VARY MOLE-FLOW STREAM=3 SUBSTREAM=MIXED COMPONENT=CHLORINE
LIMITS "130" "1000"
VARY BLOCK-VAR BLOCK=R-901 VARIABLE=PRES SENTENCE=PARAM
LIMITS "25" "50"
CONV-OPTIONS
WEGSTEIN MAXIT=100
SQP MAXIT=100 MAXPASS=1000
TEAR
TEAR 13
PROPERTY-REP PCES
313
OPTIMIZED ISOTHERMAL ALLYL CHLORIDE CASE
DYNAMICS
DYNAMICS RESULTS=ON
IN-UNITS ENG
SIM-OPTIONS OLD-DATABANK=YES
DESCRIPTION "
General Simulation with English Units :
F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.
COMPONENTS
H2O H2O /
HCL HCL /
PROPENE C3H6-2 /
CHLORINE CL2 /
AC C3H5CL /
12DCP C3H6CL2 /
13DCP-C C3H4CL2-D1 /
13DCP-T C3H4CL2-D2 /
H+ H+ /
CL- CL-
314
CHEMISTRY HCL
STOIC 1 HCL -1 / H+ 1 / CL- 1
FLOWSHEET
BLOCK E-901 IN=14 OUT=2
BLOCK M-902 IN=1 13 OUT=14
BLOCK M-901 IN=2 3 OUT=4
BLOCK R-901 IN=4 OUT=5
BLOCK E-902 IN=5 OUT=6
BLOCK T-901 IN=6 OUT=8 7
BLOCK T-904 IN=7 OUT=9 10
BLOCK T-902 IN=15 8 OUT=16 17
BLOCK T-903 IN=16 OUT=12 11
BLOCK C-901 IN=12 OUT=13
BLOCK T-905 IN=9 OUT=18 19
BLOCK T-906 IN=19 OUT=20 21
BLOCK T-907 IN=17 OUT=22 23
BLOCK E-903 IN=10 OUT=24
BLOCK E-904 IN=20 OUT=25
BLOCK E-905 IN=23 OUT=27
BLOCK E-906 IN=22 OUT=28
BLOCK E-907 IN=21 OUT=29
PROPERTIES SYSOP0
PROPERTIES ELECNRTL / UNIQ-RK / UNIQUAC
STRUCTURES
STRUCTURES 13DCP-C CL1 C2 S / C2 C3 D / C3 C4 S / &
C4 CL5 S
ESTIMATE ALL
PROP-DATA PCES-1
IN-UNITS ENG
PROP-LIST DGAQHG / DHAQHG / S25HG / OMEGHG / DHVLB / &
VB / RGYR / VLSTD
PVAL CHLORINE 2983.662941 / -10060.18917 / 28.90035349 / &
-17580.05159 / 8784.000000 / .7262124822 / &
3.2391732E-10 / .8579136616
PROP-LIST DHVLB / VB / RGYR
PVAL 13DCP-C 14431.51333 / 1.612466586 / 1.11089239E-9
PROP-DATA HENRY-1
315
IN-UNITS ENG
PROP-LIST HENRY
BPVAL HCL H2O -49.78140336 2186.999983 8.370700000 &
-5.3294445E-3 -3.999995968 68.00000346 0.0
BPVAL CHLORINE H2O -116.9781387 4371.515965 19.18540000 &
-4.9558834E-3 49.73000360 103.7300032 0.0
BPVAL HCL 12DCP 10.00798341 -2648.879936 0.0 0.0 &
-4.269995966 67.73000346 0.0
BPVAL PROPENE H2O 326.3806995 -28021.26578 -41.73762000 0.0 &
69.53000344 220.7300022 0.0
BPVAL PROPENE 12DCP 12.93988341 -3932.459880 0.0 0.0 &
-4.269995966 67.73000346 0.0
PROP-DATA UNIQ-1
IN-UNITS ENG
PROP-LIST UNIQ
BPVAL H2O AC -4.247000000 2292.652782 0.0 0.0 109.9400031 &
212.0000023 0.0
BPVAL AC H2O 15.46800000 -10062.08074 0.0 0.0 109.9400031 &
212.0000023 0.0
BPVAL H2O 12DCP 0.0 -539.9468957 0.0 0.0 77.00000338 &
77.00000338 0.0
BPVAL 12DCP H2O 0.0 -2498.536780 0.0 0.0 77.00000338 &
77.00000338 0.0
PROP-DATA VLCLK-1
IN-UNITS ENG
PROP-LIST VLCLK
BPVAL H+ CL- .5534556926 .2140997389
PROP-DATA GMELCC-1
IN-UNITS ENG
PROP-LIST GMELCC
PPVAL H2O ( H+ CL- ) 41.67400000
PPVAL ( H+ CL- ) H2O -22.15400000
PPVAL HCL ( H+ CL- ) 1.00000000E-3
PPVAL ( H+ CL- ) HCL -1.0000000E-3
PROP-DATA GMELCD-1
IN-UNITS ENG
PROP-LIST GMELCD
PPVAL H2O ( H+ CL- ) 9581.579923
PPVAL ( H+ CL- ) H2O -3967.379968
316
PROP-DATA GMELCE-1
IN-UNITS ENG
PROP-LIST GMELCE
PPVAL H2O ( H+ CL- ) -5.404000000
PPVAL ( H+ CL- ) H2O 5.188000000
PROP-DATA GMELCN-1
IN-UNITS ENG
PROP-LIST GMELCN
PPVAL H2O ( H+ CL- ) .0283500000
PCES-PROP-DATA
IN-UNITS ENG
GAMINF H2O 12DCP * * 68 2340 / * * 86 2310 / * * &
104 2090
PCES-PROP-DATA
IN-UNITS ENG
GAMINF H2O 13DCP-C * * 68 1360 / * * 86 1430 / * * &
104 1460
STREAM 1
SUBSTREAM MIXED TEMP=80. PRES=74.7
MOLE-FLOW PROPENE 1000.
STREAM 3
SUBSTREAM MIXED TEMP=80. PRES=74.7
MOLE-FLOW CHLORINE 133.
STREAM 15
SUBSTREAM MIXED TEMP=70. PRES=14.7
MOLE-FLOW H2O 1000.
317
PROPERTIES UNIQ-RK FREE-WATER=STEAM-TA SOLU-WATER=3 &
TRUE-COMPS=YES
UTILITY UTILITY-ID=U-1
318
PRODUCTS 8 1 V / 7 15 L
P-SPEC 1 20. / 15 27.
COL-SPECS D:F=0.893039 MOLE-RR=0.5
SPEC 1 MOLE-RECOV 0.9999 COMPS=AC STREAMS=7
VARY 1 D:F 0.001 0.999
PROPERTIES UNIQ-RK FREE-WATER=STEAM-TA SOLU-WATER=3 &
TRUE-COMPS=YES
UTILITIES COND-UTIL=U-1 REB-UTIL=U-1
319
UTILITIES COND-UTIL=U-1 REB-UTIL=U-1
DESIGN-SPEC FEED
DEFINE S19C3 MOLE-FLOW STREAM=14 SUBSTREAM=MIXED &
COMPONENT=PROPENE
SPEC "S19C3" TO "1000"
TOL-SPEC "0.1"
VARY MOLE-FLOW STREAM=1 SUBSTREAM=MIXED COMPONENT=PROPENE
LIMITS "50" "1000"
DESIGN-SPEC RESTM
DEFINE RESTM BLOCK-VAR BLOCK=R-901 VARIABLE=RES-TIME &
SENTENCE=PARAM
SPEC "RESTM" TO "1.11E-3"
320
TOL-SPEC ".0001"
VARY BLOCK-VAR BLOCK=R-901 VARIABLE=LENGTH SENTENCE=PARAM
LIMITS "1" "200"
EO-CONV-OPTI
OPTIMIZATION MAXPROFT
DEFINE AC9 MASS-FLOW STREAM=18 SUBSTREAM=MIXED COMPONENT=AC
DEFINE HCL17 MASS-FLOW STREAM=22 SUBSTREAM=MIXED &
COMPONENT=HCL
DEFINE CL3 MASS-FLOW STREAM=3 SUBSTREAM=MIXED &
COMPONENT=CHLORINE
DEFINE PROP1 MASS-FLOW STREAM=1 SUBSTREAM=MIXED &
COMPONENT=PROPENE
DEFINE H2015 MASS-FLOW STREAM=15 SUBSTREAM=MIXED &
COMPONENT=H2O
DEFINE FDHTR BLOCK-VAR BLOCK=E-901 VARIABLE=QCALC &
SENTENCE=PARAM
DEFINE REB1 BLOCK-VAR BLOCK=T-901 VARIABLE=REB-DUTY &
SENTENCE=RESULTS
DEFINE REB2 BLOCK-VAR BLOCK=T-904 VARIABLE=REB-DUTY &
SENTENCE=RESULTS
DEFINE COMP BLOCK-VAR BLOCK=C-901 VARIABLE=BRAKE-POWER &
SENTENCE=RESULTS
DEFINE COOLER BLOCK-VAR BLOCK=E-902 VARIABLE=QCALC &
SENTENCE=PARAM
DEFINE COND1 BLOCK-VAR BLOCK=T-901 VARIABLE=COND-DUTY &
SENTENCE=RESULTS
DEFINE COND2 BLOCK-VAR BLOCK=T-904 VARIABLE=COND-DUTY &
SENTENCE=RESULTS
DEFINE WASTE STREAM-VAR STREAM=21 SUBSTREAM=MIXED &
VARIABLE=MASS-FLOW
DEFINE PROFIT PARAMETER 1 PHYS-QTY=UNIT-PRICE UOM="$/lb" &
INIT-VAL=1.
F REVAC=1.80
F REVHCL=0.095
F CSTCL2=0.375
F CSTPRP= 0.981
F WASTEC=0.2
F CWATER = 6.7e-5
F REVENUE=(REVAC*AC9+REVHCL*HCL17)*24*365
F RAWCST=(CSTCL2*CL3+CSTPRP*PROP1+CWATER*H2015)*24*365
F WSTCST=(WASTEC*WASTE)*24*365
F TOTGAS=FDHTR
321
F LOWS =REB1+REB2
F GASCST=(TOTGAS)*(1.17E-05)*24*365
F LOWSC = LPWS*(1.48E-05)*24*365
F ELECST=0.06*COMP
F H20BTU=-(COND1+COND2)
F FLWH20=H20BTU*(3.7349E-07)*24*365
F H20CST=FLWH20
F PROFIT=REVENUE-RAWCST-WSTCST-UTLCST
MAXIMIZE "PROFIT"
VARY BLOCK-VAR BLOCK=E-901 VARIABLE=TEMP SENTENCE=PARAM
LIMITS "200" "1000"
VARY MOLE-FLOW STREAM=3 SUBSTREAM=MIXED COMPONENT=CHLORINE
LIMITS "130" "1000"
VARY BLOCK-VAR BLOCK=R-901 VARIABLE=PRES SENTENCE=PARAM
LIMITS "25" "50"
CONV-OPTIONS
WEGSTEIN MAXIT=100
SQP MAXIT=100 MAXPASS=1000
TEAR
TEAR 13
PROPERTY-REP PCES
322
APPENDIX C: PROCESS FLOW DIAGRAM, STREAM SUMMARY TABLE,
EQUIPMENT SPECIFICATION FOR THE FOLLOWING CASE STUDIES: METHYL
CHLORIDE, DIMETHYL ETHER, ACRYLONITRILE AND ALLYL CHLORIDE
323
Table C.1: Methyl Chloride Base Case Equipment Specification
Equipment Specification in Aspen
Mixer (M-601) Pressure – 14.7 psia, Phases- Vapor-liquid
Mixer (M-602) Pressure – 0 psia, Phases- Vapor-liquid
Splitter (M-603) Stream 32- Split Fraction -0.1
Heater (E-601) Temperature – 572 oF, Pressure – 14.7 psia
Reactor (R-601) Type – CSTR
Constant at specified Temperature – 977 oF
Valid Phase – Vapor Only
Reactor Volume-1600 ft3
Reaction Type- Power Law
Cooler (E-602) Temperature – 100oF, Pressure – 14.7 psia
Absorber (T-601) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-2
Condenser –None
Reboiler - None
Valid Phases : Vapor - Liquid
Feed Stage -1, and 2
Product Stage – 1– Vapor, 2- Liquid
Stage 1 Condenser Pressure – 14.7
Dryer (T-602) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-5
Condenser –None
Reboiler - None
Valid Phases : Vapor - Liquid
Feed Stage -1, and 5
Product Stage – 1– Vapor, 5- Liquid
Stage 1 Condenser Pressure – 14.7
Cooler (E-603) Temperature – 100 oF, Pressure – 14.7 psia
Dryer (T-603) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-2
Condenser –None
Reboiler - None
Valid Phases : Vapor - Liquid
Feed Stage -1, and 2
Product Stage – 1– Vapor, 2- Liquid
Stage 1 Condenser Pressure – 14.7
Multi Stage Number of Stages -2
Compressor (C-601) Compressor Model - Polytrophic using ASME method
Specification Type : Fixed discharge pressure – 115 psia
324
Feed Stream – 1
Cool specification – Stage 2 outlet temperature – 275oF
Cool specification – Stage 1 outlet temperature – 844oF
Compressor Valid Phases – Vapor Only
Cooler Valid Phase – Vapor Only
Cooler (E-604) Temperature – -58 oF, Pressure – 115 psia
Flash Column (T-604) Pressure – 115 psia, Heat Duty- 0 Btu/hr
Separator (T-605) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-12
Condenser –Partial Vapor
Reboiler - Kettle
Valid Phases : Vapor - Liquid
Distillate to Feed Ratio- 0.5, Reflux Ratio- 1.2
Feed Stage-6
Product Stage – 1– Vapor, 12- Liquid
Stage 1 Condenser Pressure – 14.7
Separator (T-606) Type – Distil,
Number of Stage-10
Condenser Type - Total
Condenser Pressure –14.7 psia
Reboiler Pressure –14.7 psia
Light key recovery- 99.9% Chloroform
Heavy Key Recovery – 0.001 – Carbon Tetrachloride
Separator (T-607) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-30
Condenser –Total
Reboiler - Kettle
Valid Phases : Vapor - Liquid
Distillate to Feed Ratio- 0.5, Reflux Ratio- 1.5
Feed Stage-10
Product Stage – 1– Vapor, 20- Liquid
Stage 1 Condenser Pressure – 14.7
Flash Column (T-604) Temperature – -100 oF, Pressure- 15 psia
Compressor (C-602) Type – Polytrophic using ASME method
Specification Type – Pressure Increase– 45 psia
Cooler (E-605) Temperature –77 oF, Pressure – 14.7 psia
325
Figure C.1: Schematic of the Methyl Chloride Base Case
326
Table C.2: Stream Summary Table of the Methyl Chloride Base Case
1 2 3 4 5 6 7 8 9 10 11
M-301 M-301 M-301 E-601 R-601 E-602 T-601 T-602 T-601 T-602
E-605 M-301 E-601 R-601 E-602 T-601 T-601
Temperature (oF) 77.00 77.00 77.00 76.80 572.00 977.00 100.00 161.40 157.30 86.00 86.00
Pressure (psia ) 14.70 14.70 14.70 14.70 14.70 14.70 14.70 14.70 14.70 14.70 14.70
Vapor Frac 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.00 0.00 0.00
Mole Flow (lbmol/hr) 323.00 323.00 780.17 1426.17 1426.17 1426.17 1426.17 1456.39 1994.78 2025.00 200.00
Mass Flow (lb/hr ) 5259.14 22902.44 13953.93 42115.52 42115.52 42115.52 42115.52 36008.05 42588.41 36480.94 7999.42
Component Mass Flow lb/hr
Methane 5078.18 0.00 11255.63 16333.81 16333.81 12632.29 12632.29 12604.05 28.25 0.00 0.00
Chlorine 0.00 22902.44 0.00 22902.44 22902.44 458.63 458.63 440.46 18.17 0.00 0.00
Methyl Chloride 0.00 0.00 1088.82 1088.82 1088.82 9292.84 9292.84 9124.04 168.80 0.00 0.00
Dichloromethane 0.00 0.00 16.48 16.48 16.48 4494.58 4494.58 4021.31 473.27 0.00 0.00
Chloroform 0.00 0.00 1.98 1.98 1.98 1606.52 1606.52 1281.26 325.26 0.00 0.00
Carbon Tetrachloride 0.00 0.00 0.16 0.16 0.16 317.89 317.89 217.21 100.68 0.00 0.00
Water 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6462.39 30018.55 36480.94 0.00
Hydrogen Chloride 0.00 0.00 0.00 0.00 0.00 11540.95 11540.95 85.84 11455.11 0.00 0.00
Nitrogen 180.97 0.00 1590.85 1771.82 1771.82 1771.82 1771.82 1771.50 0.32 0.00 0.00
Hydronium ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hydroclorous Acid 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hypochlorous Ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
hydroxide ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Chloride ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Hydroxide 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 7999.42
Sodium Ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Chloride 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Hydroxide 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sulfuric Acid 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hydrogen 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
n Sulfate ion
Sulphate Ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
327
12 13 14 15 16 17 18 19 20 21 22
E-603 T-603 C-601 T-603 E-604 M-602 T-604 T-605 T-608
T-602 T-602 E-603 T-603 T-603 C-601 T-604 E-604 T-604 T-605
300.30 307.00 100.00 204.20 346.40 90.00 275.00 -58.00 -58.00 -58.00 -23.20
o
Temperature ( F) 14.70 14.70 14.70 14.70 14.70 14.70 115.00 115.00 115.00 115.00 14.70
Pressure (psia ) 1.00 0.00 1.00 1.00 0.00 0.00 1.00 1.00 0.75 0.00 1.00
Vapor Frac 1385.74 270.64 1385.74 1084.96 1033.50 732.71 1084.96 817.56 1084.96 267.39 209.05
Mole Flow (lbmol/hr) 34322.31 9685.16 34322.31 28747.42 77438.97 71864.07 28747.42 14584.08 28747.42 14163.34 8792.23
Mass Flow (lb/hr )
Component Mass Flow lb/hr 12602.04 2.01 12602.04 12595.20 6.83 0.00 12595.20 11793.36 12595.20 801.85 801.85
Methane 0.00 440.46 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Chlorine 9105.60 18.43 9105.60 9028.95 76.66 0.00 9028.95 1049.36 9028.95 7979.59 7939.69
Methyl Chloride 3999.18 22.12 3999.18 3918.14 81.04 0.00 3918.14 18.31 3918.14 3899.83 0.00
Dichloromethane 1269.99 11.27 1269.99 1227.93 42.06 0.00 1227.93 2.20 1227.93 1225.73 0.00
Chloroform 214.35 2.86 214.35 203.12 11.23 0.00 203.12 0.18 203.12 202.94 0.00
Carbon Tetrachloride 5359.68 1102.71 5359.68 0.45 5359.24 0.00 0.45 0.00 0.45 0.45 0.00
Water 0.00 85.84 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hydrogen Chloride 1771.47 0.03 1771.47 1771.36 0.11 0.00 1771.36 1720.67 1771.36 50.69 50.69
Nitrogen 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hydronium ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hydroclorous Acid 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hypochlorous Ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
hydroxide ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Chloride ion 0.00 7999.42 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Hydroxide 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Chloride 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Hydroxide 0.00 0.00 0.00 2.27 71861.80 71864.07 2.27 0.00 2.27 2.27 0.00
Sulfuric Acid 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Hydrogen Sulfate ion 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
328
23 24 25 26 27 28 29 30 31 32 33
T-607 M-602 T-606 M-603 C-602 E-605
T-605 T-608 T-608 T-607 T-607 T-606 T-606 M-602 M-603 M-603 C-602
1.0 -100.0 99.0 145.0 141.8 171.3 -70.0 -70.0 -70.0 157.9 157.9
Temperature (oF) 15.0 15.0 14.7 14.7 14.7 14.7 15.0 15.0 15.0 60.0 60.0
Pressure (psia ) 0.0 0.0 1.0 0.0 0.0 0.0 0.0 1.0 1.0 1.0 1.0
Vapor Frac 58.3 159.8 49.3 48.2 10.1 8.8 1.4 866.9 780.2 86.7 780.2
Mole Flow (lbmol/hr) 5370.9 7871.8 920.3 4118.4 1252.5 1046.3 206.2 15504.3 13953.9 1550.4 13953.9
Mass Flow (lb/hr )
Component Mass Flow lb/hr 0.0 88.9 712.9 0.0 0.0 0.0 0.0 12506.2 11255.6 1250.6 11255.6
Methane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chlorine 39.9 7779.1 160.4 39.9 0.0 0.0 0.0 1209.8 1088.8 121.0 1088.8
Methyl Chloride 3899.7 0.0 0.0 3895.8 3.9 3.9 0.0 18.3 16.5 1.8 16.5
Dichloromethane 1225.7 0.0 0.0 182.5 1043.2 1042.1 1.0 2.2 2.0 0.2 2.0
Chloroform 202.9 0.0 0.0 0.2 202.7 0.2 202.5 0.2 0.2 0.0 0.2
Carbon Tetrachloride 0.4 0.0 0.0 0.0 0.4 0.0 0.4 0.0 0.0 0.0 0.0
Water 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Chloride 0.0 3.7 46.9 0.0 0.0 0.0 0.0 1767.6 1590.9 176.8 1590.9
Nitrogen 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydronium ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydroclorous Acid 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hypochlorous Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
hydroxide ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chloride ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Sodium Hydroxide 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Sodium Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Sodium Chloride 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Sodium Hydroxide 2.3 0.0 0.0 0.0 2.3 0.0 2.3 0.0 0.0 0.0 0.0
Sulfuric Acid 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Sulfate ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
329
Table C.3: Stream Summary Table for DME Production via Dehydration of Methanol
Stream No. 1 2 3 4 5 6 7 8 9
P-201 M-201 E-201 E-202 R-201 E-203 E-204 V-201 T-201
P-201 M-201 E-201 E-202 R-201 E-203 E-204 V-201
o
Temperature ( C ) 25.00 25.96 101.59 154.00 220.00 364.00 278.00 100.00 92.27
Pressure (bar) 1.00 25.00 7.31 15.10 14.70 13.90 13.80 13.40 10.40
Vapor Frac 0.00 0.00 0.00 1.00 1.00 1.00 1.00 0.00 0.06
Total Flow ( kg/hr) 8366.39 8366.39 10473.51 10473.51 10473.51 10473.51 10473.51 10473.51 10473.51
Component Mole Flow (kmol/hr)
Dimethyl Ether 0.00 0.00 1.33 1.33 1.33 130.45 130.45 130.45 130.45
Methanol 259.70 259.70 322.78 322.78 322.78 64.56 64.56 64.56 64.56
Water 2.50 2.50 3.85 3.85 3.85 132.97 132.97 132.97 132.97
Stream No. 10 11 12 13 14 15 16
330
Table C.4: ASPEN PLUS Equipment Specification Summary Table for DME Production
via Methanol Dehydration
Equipment Specification in Aspen
Mixer (M-201) Pressure -0 bar
Mixer (M-202) Splitter, Stream 13 and 16
Stream 16- Split fraction -0.1
Valve (V-201) Outlet Pressure -10.4 bar
Valve (V-202) Outlet Pressure -7.4 bar
Pump (P-201) Discharge Pressure- 25 bar, Pump Efficiency – 60%
Heater (E-201) Temperature – 154 oC, Pressure – 15.1 bar
Heater (E-202) Temperature – 220 oC, Pressure – 14.7 bar
Reactor (R-201) Type – Rstoic
Temperature – 364 oC, Pressure – 13.9 bar
Reaction Type- Fractional Conversion (80%) of
Methanol
Heater (E-203) Temperature – 278 oC, Pressure – 13.8 bar
Heater (E-204) Temperature –100 oC, Pressure – 13.4 bar
Columns (T-201) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-22
Condenser –Partial Vapor
Distillate Rate- 129.7 Kmol/hr, Reflux Ratio- 0.6
Feed Stage -9, Product Stage – 22 – Liquid, 1- Vapor
Pressure- 10.21 bar
Columns (T-202) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-26
Condenser –Partial Vapor
Distillate Rate- 66.3 Kmol/hr, Reflux Ratio- 1.8
Feed Stage -14, Product Stage – 26 – Liquid, 1-
Vapor
Pressure- 7.3 bar
Heater (E-204) Temperature –50 oC, Pressure – 1.2 bar
Table C.5: ASPEN PLUS Equipment Specification Summary Table for DME Production
Via Natural Gas
Equipment Specification in Aspen
o
Heater (E-301) Temperature – 800 C, Pressure – 1 atm
Heater (E-302) Temperature – 800 oC, Pressure – 1 atm
Heater (E-303) Temperature – 35 oC, Pressure – 1 atm
Heater (E-304) Temperature – 240 oC, Pressure – 40 atm
Heater (E-305) Temperature – 240 oC, Pressure – 20 atm
Mixer (M-301) Pressure – 0 atm, Valid Phases – Vapor -Liquid
Compressor (C-301) Type – Isentropic
Discharge Pressure – 40 atm
Isentropic efficiency – 80%
Reactor (R-301) Type – Rstoic
Temperature – 800oC, Pressure – 1 atm
Reaction Type- Fractional Conversion (96.6%) of Methane
Reactor (R-302) Type – Rstoic
Temperature – 240oC, Pressure – 4053 kpa
Reaction Type- Fractional Conversion (75.5%) of Carbon
Monoxide
Reactor (R-303) Type – Rstoic
Temperature – 240 oC, Pressure – 20 atm
Reaction Type- Fractional Conversion (91 %) of Methanol
Separator (T-301) Temperature – 20 oC, Pressure – 1 atm
Valid Phases- Vapor-Liquid
Separator (T-302) Temperature – 20 oC, Pressure – 20 atm
Valid Phases- Vapor-Liquid
Columns (T-303) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-45
Condenser –Partial Vapor
Distillate Rate- 129.7 Kmol/hr, Reflux Ratio- 4.5
Feed Stage -2, Product Stage – 45 – Liquid, 1- Vapor
Pressure- 8 atm
Separator (T-304) Type- Flash 3
Split fraction – DME 0.99%, Ethane -0.09 &Pentane-0.09
Valve (V-301) Outlet Pressure – 20 atm
Valve (V-302) Outlet Pressure- 8 atm
332
Table C.6: Stream Summary Table for DME Production Via Natural Gas
1 2 3 4 5 6 7 8 9 10 11
E-301 R-301 E-302 R-301 E-303 T-301 C-301 E-304 R-302 V-301
Temperature (o C ) 35.0 800.0 35.0 800.0 800.0 35.0 20.0 20.0 643.6 240.0 240.0
Pressure (atm) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 40.0 40.0 40.0
Vapor Frac 1.0 1.0 0.0 1.0 1.0 1.0 0.0 1.0 1.0 1.0 1.0
Mole Flow (kg/hr) 425.0 425.0 530.0 530.0 1726.0 1726.0 107.4 1618.6 1618.6 1618.6 1036.6
Mass Flow (kg/hr) 7316.5 7316.5 9548.1 9548.1 16864.6 16864.6 1938.7 14926.0 14926.0 14926.0 14926.0
Component Mole Flow (kmol/hr)
Dimethyl Ether 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Methanol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 9324.9
Water 0.0 0.0 9548.1 9548.1 2603.4 2603.4 1931.3 672.1 672.1 672.1 672.1
Methane 6402.0 6402.0 0.0 0.0 217.7 217.7 0.0 217.6 217.6 217.6 217.6
Carbon Monoxide 0.0 0.0 0.0 0.0 10797.7 10797.7 0.8 10796.8 10796.8 10796.8 2645.2
Hydrogen 0.0 0.0 0.0 0.0 2331.3 2331.3 0.0 2331.3 2331.3 2331.3 1158.0
Ethane 548.7 548.7 0.0 0.0 548.7 548.7 1.0 547.8 547.8 547.8 547.8
Propane 256.1 256.1 0.0 0.0 256.1 256.1 2.0 254.0 254.0 254.0 254.0
n-Butane 109.7 109.7 0.0 0.0 109.7 109.7 3.4 106.3 106.3 106.3 106.3
333
12 13 14 15 16 17 18 19 20 21 22
V-301 T-302 T-302 E-305 R-303 V-302 T-303 T-303 T-304 T-304 M-301
Temperature (o C ) 240.0 20.0 20.0 240.0 240.0 240.0 150.5 48.5 48.5 48.5 133.2
Pressure (atm) 20.0 20.0 20.0 20.0 20.0 8.0 8.0 8.0 8.0 8.0 8.0
Vapor Frac 1.0 1.0 0.0 1.0 1.0 1.0 0.0 1.0 1.0 0.9 0.1
Mole Flow (kg/hr) 1036.6 702.6 333.9 333.9 333.9 333.9 193.7 140.2 129.1 11.1 204.8
Mass Flow (kg/hr) 14926.0 4721.2 10204.7 10204.7 10204.7 10204.7 3886.1 6318.6 5942.6 376.1 4262.2
Dimethyl Ether 0.0 0.0 0.0 0.0 6019.2 6019.2 39.8 5979.4 5919.6 59.8 99.6
Methanol 9324.9 123.9 9201.1 9201.1 828.1 828.1 798.5 29.6 0.0 29.6 828.1
Water 672.1 2.3 669.8 669.8 3023.6 3023.6 3014.2 9.4 0.0 9.4 3023.6
Methane 217.6 211.4 6.2 6.2 6.2 6.2 0.0 6.2 0.0 6.2 6.2
Carbon Monoxide 2645.2 2615.0 30.2 30.2 30.2 30.2 0.0 30.2 0.0 30.2 30.2
Hydrogen 1158.0 1157.1 0.8 0.8 0.8 0.8 0.0 0.8 0.0 0.8 0.8
Ethane 547.8 432.0 115.8 115.8 115.8 115.8 0.0 115.8 10.4 105.4 105.4
Propane 254.0 115.2 138.9 138.9 138.9 138.9 0.0 138.9 12.5 126.4 126.4
n-Butane 106.3 64.4 41.9 41.9 41.9 41.9 33.6 8.3 0.0 8.3 41.9
334
Table C.7: Base Case Acrylonitrile Process Equipment Specification
Equipment Specification in Aspen
Mixer (M-301) Pressure – 0 psia, Phases- Vapor-liquid
Reactor (R-301) Type – PFR
Constant at specified Temperature – 852 oF
Mtultitube reactor
Number of Tubes = 20
Tube Length = 19 ft
Tube Diameter = 13 in
Reaction Type- Power Law
Mixer (M-302) Pressure – 0 psia, Phases- Vapor-liquid
Reactor (R-301) Type – Rstoic
Temperature – 100 oF, Pressure – 15 psia
Reaction Type- Fractional Conversion (96%) of Ammonia
Separator (T-301) Temperature – 350 oF, Pressure – 10 psia
Valid Phases- Vapor-Liquid
Cooler (E-301) Temperature – 40 oF, Pressure – 20 psia
Columns (T-302) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-15
Condenser –Partial Vapor
Bottoms to Feed Ratio- 0.85, Reflux Ratio- 4
Feed Stage -15 and 1, Product Stage – 1– Vapor, 15- Liquid
Heater (E-302) Temperature –173 oF, Pressure – 15 psi
Columns (T-303) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-30
Condenser –Total
Distillate to Feed Ratio- 0.15, Reflux Ratio- 7
Feed Stage -20
Stage 1 Condenser Pressure- 15 psia, Stage 2 Pressure-15 psia
Heater (E-303) Temperature – 126 oF, Pressure – 14.7 psia
Columns (T-304) Type –Distl
Number of Stage-15
Light Key-HCN, Recovery- 0.95
Heavy key- Acrolein, Recovery – 0.05
Condenser –Total
Condenser Pressure- 15 psia, Re-boiler Pressure 15 psia
Columns (T-305) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-12
Condenser –Total
Distillate to Feed Ratio- 0.005, Reflux Ratio- 4
335
Feed Stage -20
Stage 1 Condenser Pressure- 15 psia
Columns (T-306) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-35
Condenser –Total
Distillate to Feed Ratio- 0.96, Reflux Ratio- 4
Feed Stage -15
Stage 1 Condenser Pressure- 15 psia
336
Figure C.2: Schematic of the Acrylonitrile Process Base Case
337
Table C.8: Base Case Acrylonitrile Process Stream Summary Table
1 2 3 4 5 6 7 8 9 10
Temperature (oF) 79.70 852.00 86.00 350.00 350.00 40.00 45.00 40.00 195.50 24.60
Pressure (psia ) 14.70 14.70 14.70 23.99 23.99 20.00 14.70 20.00 20.00 15.00
Vapor Frac 1.00 347.02 11.21 324.44 12.89 324.44 120.00 120.00 377.78 66.67
Mole Flow (lbmol/hr) 330.00 9152.30 1082.66 8754.60 1480.35 8754.60 2161.83 2161.83 8512.21 2404.23
Mass Flow (lb/hr ) 9770.05
Component Mole Flow 21.77 0.00 0.87 0.00 0.87 0.00 0.00 0.78 0.09
(lbmol/hr)
Ammonia 110.00 205.60 0.21 204.32 1.50 204.32 120.00 120.00 324.19 0.13
Water 0.00 15.89 0.00 15.86 0.03 15.86 0.00 0.00 3.37 12.48
Hydrocyanic Acid 0.00 16.93 0.00 16.93 0.00 16.93 0.00 0.00 0.04 16.89
Carbon Monoxide 0.00 0.35 0.00 0.35 0.00 0.35 0.00 0.00 0.00 0.34
Oxygen 135.00 21.74 0.00 21.71 0.04 21.71 0.00 0.00 2.20 19.51
Propylene 85.00 17.37 0.00 17.36 0.01 17.36 0.00 0.00 0.14 17.22
Carbon dioxide 0.00 2.53 0.00 2.51 0.02 2.51 0.00 0.00 2.51 0.00
Acetonitrile 0.00 44.81 0.00 44.50 0.31 44.50 0.00 0.00 44.50 0.00
Acrylonitrile 0.00 0.03 0.00 0.03 0.00 0.03 0.00 0.00 0.03 0.00
Acrolein 0.00 0.00 11.00 0.02 0.53 0.02 0.00 0.00 0.02 0.00
Sulfuric Acid 0.00 0.00 0.00 0.00 10.45 0.00 0.00 0.00 0.00 0.00
Ammonium Sulphate 0.00 852.00 86.00 350.00 350.00 40.00 45.00 40.00 195.50 24.60
338
11 12 13 14 15 16 17 18 19 20
Temperature (oF) 173.00 212.80 93.60 -47.00 177.20 178.30 161.40 159.00 201.90 70.00
Pressure (psia ) 20.00 15.00 15.00 14.70 14.70 14.70 14.70 12.00 12.00 15.00
Vapor Frac 377.78 313.55 64.22 6.67 57.56 56.64 0.92 44.18 12.46 6.67
Mole Flow (lbmol/hr) 8512.21 5716.02 2796.18 223.69 2572.49 2528.71 43.78 2304.25 224.47 223.69
Mass Flow (lb/hr )
Component Mole Flow
(lbmol/hr) 0.78 0.00 0.78 0.78 0.00 0.00 0.00 0.00 0.00 0.78
Ammonia 324.19 311.54 12.64 0.00 12.64 12.64 0.00 0.18 12.46 0.00
Water 3.37 0.00 3.37 2.89 0.49 0.30 0.19 0.30 0.00 2.89
Hydrocyanic Acid 0.04 0.00 0.04 0.04 0.00 0.00 0.00 0.00 0.00 0.04
Carbon Monoxide 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Oxygen 2.20 0.00 2.20 2.20 0.00 0.00 0.00 0.00 0.00 2.20
Propylene 0.14 0.00 0.14 0.14 0.00 0.00 0.00 0.00 0.00 0.14
Carbon dioxide 2.51 0.33 2.18 0.02 2.16 2.14 0.02 2.14 0.00 0.02
Acetonitrile 44.50 1.66 42.84 0.59 42.24 41.53 0.71 41.53 0.00 0.59
Acrylonitrile 0.03 0.00 0.03 0.01 0.02 0.02 0.00 0.02 0.00 0.01
Acrolein 0.02 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sulfuric Acid 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ammonium Sulfate 173.00 212.80 93.60 -47.00 177.20 178.30 161.40 159.00 201.90 70.00
339
Figure C.3: Schematic of the Optimized Acrylonitrile Process
340
Table C.9: Optimized Acrylonitrile Process Stream Summary Table
Stream No. 1 2 3 4 5 6 7 8 9 10
Temperature (oF) 79.60 86.00 350.00 350.00 170.00 170.90 48.80 182.90 212.00 79.60
Pressure (psia ) 14.70 14.70 15.00 15.00 20.00 14.70 14.70 14.70 14.70 14.70
Vapor Frac 1.00 0.00 1.00 0.00 0.32 0.00 1.00 0.00 0.00 1.00
Mole Flow (lbmol/hr) 281.23 2.10 325.62 2.06 325.62 120.00 66.84 378.77 318.17 281.23
Mass Flow (lb/hr ) 8853.99 188.86 8793.38 249.40 8793.38 2168.84 2409.64 8553.21 5749.01 8853.99
Component Mole Flow (lbmol/hr)
Ammonia 1141.05 0.00 3.93 0.00 3.93 0.00 0.00 3.93 0.00 1141.05
Water 0.00 3.78 3700.74 2.71 3700.74 2158.16 10.31 5847.99 5723.02 0.00
Hydrocyanic Acid 3.23 0.00 431.74 0.09 431.74 0.00 323.36 108.43 0.00 3.23
Carbon Monoxide 0.00 0.00 473.39 0.00 473.39 0.00 473.32 0.08 0.00 0.00
Oxygen 4127.85 0.00 16.38 0.00 16.38 0.00 16.37 0.01 0.00 4127.85
Propylene 3574.20 0.00 915.04 0.15 915.04 0.00 818.67 96.40 0.00 3574.20
Carbon Dioxide 7.67 0.00 770.87 0.05 770.87 0.00 767.32 3.55 0.00 7.67
Acetonitrile 0.00 0.00 103.60 0.08 103.60 2.25 0.06 106.51 4.61 0.00
Acrylonitrile 0.00 0.00 2374.21 1.68 2374.21 7.33 0.24 2381.74 18.37 0.00
Acrolein 0.00 0.00 1.56 0.00 1.56 0.00 0.00 1.56 0.00 0.00
Sulfuric Acid 0.00 185.08 1.93 6.08 1.93 1.11 0.00 3.01 3.01 0.00
Ammonium Sulfate 0.00 0.00 0.00 238.57 0.00 0.00 0.00 0.00 0.00 0.00
341
Stream No. 12 13 14 15 16 17 18 19 20 21
Temperature (oF) 109.70 176.60 69.80 172.10 211.70 170.00 -34.80 -143.70 80.00 -55.60
Pressure (psia ) 14.70 14.70 14.70 14.70 14.70 20.00 14.70 14.70 15.00 14.70
Vapor Frac 0.00 0.00 1.00 0.00 0.00 0.00 0.00 1.00 1.00 0.00
Mole Flow (lbmol/hr) 60.60 53.76 6.85 46.77 6.99 318.17 31.98 34.87 31.98 19.36
Mass Flow (lb/hr ) 2804.21 2579.56 224.64 2451.85 127.71 5749.01 1152.12 1257.52 1152.12 813.28
Component Mole Flow (lbmol/hr)
Ammonia 3.93 0.00 3.93 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Water 124.97 124.97 0.00 0.23 124.74 5723.02 10.31 0.00 10.31 0.00
Hydrocyanic Acid 108.43 0.01 108.43 0.01 0.00 0.00 323.36 0.00 323.36 3.23
Carbon Monoxide 0.08 0.00 0.08 0.00 0.00 0.00 0.00 473.32 0.00 0.00
Oxygen 0.01 0.00 0.01 0.00 0.00 0.00 0.00 16.37 0.00 0.00
Propylene 96.40 0.00 96.40 0.00 0.00 0.00 810.48 8.19 810.48 802.38
Carbon Dioxide 3.55 0.00 3.55 0.00 0.00 0.00 7.67 759.65 7.67 7.67
Acetonitrile 101.90 101.70 0.20 100.22 1.48 4.61 0.06 0.00 0.06 0.00
Acrylonitrile 2363.38 2352.45 10.93 2350.96 1.49 18.37 0.24 0.00 0.24 0.00
Acrolein 1.56 0.44 1.12 0.44 0.00 0.00 0.00 0.00 0.00 0.00
Sulfuric Acid 0.00 0.00 0.00 0.00 0.00 3.01 0.00 0.00 0.00 0.00
Ammonium Sulfate 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
342
Stream No. 21 22 24
Temperature (oF)
80.00 74.00 170.90
Pressure (psia )
15.00 14.70 14.70
Vapor Frac
1.00 0.00 0.00
Mole Flow (lbmol/hr)
19.36 12.62 205.15
Mass Flow (lb/hr )
813.28 338.84 3707.87
Component Mole Flow (lbmol/hr)
Ammonia
0.00 0.00 0.00
Water
0.00 10.31 3689.60
Hydrocyanic Acid
3.23 320.12 0.00
Carbon Monoxide
0.00 0.00 0.00
Oxygen
0.00 0.00 0.00
Propylene
802.38 8.11 0.00
Carbon dioxide
7.67 0.00 0.00
Acetonitrile
0.00 0.06 3.84
Acrylonitrile
0.00 0.24 12.53
Acrolein
0.00 0.00 0.00
Sulfuric Acid
0.00 0.00 1.90
Ammonium Sulfate
0.00 0.00 0.00
343
Table C.10: Optimized Acrylonitrile Process Equipment Specification
Equipment Specification in Aspen
Mixer (M-301) Pressure – 0 psia, Phases- Vapor-liquid
Reactor (R-301) Type – PFR
Constant at specified Temperature – 852 oF
Mtultitube reactor
Number of Tubes = 13
Tube Length = 10 ft
Tube Diameter = 1.8 ft
Reaction Type- Power Law
Mixer (M-302) Pressure – 0 psia, Phases- vapor-liquid
Reactor (R-302) Type – Rstoic
Temperature – 170 oF, Pressure – 15 psia
Reaction Type- Fractional Conversion (96%) of Ammonia
Separator (T-301) Temperature – 350 oF, Pressure – 15 psia
Valid Phases- Vapor-Liquid
Cooler (E-301) Temperature – 170 oF, Pressure – 20 psia
Columns (T-302) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-15
Condenser –Partial Vapor
Bottoms to Feed Ratio- 0.85, Reflux Ratio- 2.4
Feed Stage -15, and 1, Product Stage – 1– Vapor, 15- Liquid
Heater (E-302) Temperature –170 oF, Pressure – 20 psia
Heater (E-303) Temperature –80oF, Pressure – 15 psia
Columns (T-303) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-30
Condenser –Total
Distillate to Feed Ratio- 0.16, Reflux Ratio- 10.5
Feed Stage -10
Stage 1 Condenser Pressure- 15 psia, Stage 2 Pressure-15 psia
Heater (E-304) Temperature – 80 oF, Pressure – 15 psia
Columns (T-305) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-12
Condenser – Partial vapor
Distillate to Feed Ratio- 0.113, Reflux Ratio- 10
Feed Stage -5
Stage 1 Condenser Pressure- 14.7 psia
Columns (T-306) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-35
Condenser –Total
Distillate to Feed Ratio- 0.59, Reflux Ratio- 3
Feed Stage -10
Stage 1 Condenser Pressure- 14.7 psia
Columns (T-307) Type – DSTWU, Calculation Type- Equilibrium
Number of Stage-10
Light Key Component- Carbon Dioxide
344
Recovery -99%
Heavy Key Component- Propylene
Recovery -1%
Columns (T-308) Type – DSTWU, Calculation Type- Equilibrium
Number of Stage-10
Light Key Component- Propylene
Recovery -99%
Heavy Key Component- Hydrogen Cyanide
Recovery -1%
345
Feed Stage -1, and 10
Product Stage – 1– Vapor, 10- Liquid
Stage 1 Condenser Pressure – 14.7
Separator (T-903) Type – Sep
Split- Propene -1
Column (T-904) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-10
Condenser –Partial Vapor
Re-boiler - Kettle
Valid Phases : Vapor – Liquid
Reflux Ratio-4.02
Distillate to Feed Ratio = 0.54
Feed Stage -6
Product Stage – 1– Vapor, 15- Liquid
Stage 1 Pressure – 16
Stage 2 Pressure – 25
346
Figure C.4: Schematic of the Base Case Allyl Chloride Process
347
Table C.12: Base Case Allyl Chloride Process Stream Summary Table
1 2 3 4 5 6 7 8 9 10 11
M-902 M-901 M-901 R-901 E-902 T-901 T-904 T-902 E-903 E-904 M-905
E-901 M-901 R-901 E-902 T-901 T-901 T-904 T-904 T-903
Temperature (oF) 80.0 793.6 80.0 765.8 765.0 70.0 169.9 -45.1 117.9 243.8 72.8
Pressure (Psia) 74.7 74.7 74.7 74.7 40.2 74.7 27.0 20.0 16.0 25.0 14.7
Vapor Frac 1.0 1.0 1.0 1.0 1.0 0.8 0.0 1.0 1.0 0.0 0.0
Mole Flow (lbmol/hr) 113.6 1000.0 130.0 1130.0 1108.7 1108.7 113.6 995.1 75.4 38.1 24.7
Mass Flow (lb/hr) 4779.2 42080.6 9217.7 51298.3 51298.3 51298.3 10033.7 41264.6 5772.8 4260.9 444.8
Component Flow (lb/hr)
Water 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 444.4
Hydrochloric Acid 0.0 0.0 0.0 0.0 3962.5 3962.5 0.0 3962.5 0.0 0.0 0.0
Propylene 4779.2 42080.6 0.0 42080.6 37301.5 37301.5 0.0 37301.5 0.0 0.0 0.0
Chlorine 0.0 0.0 9217.7 9217.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Allyl Chloride 0.0 0.0 0.0 0.0 5802.4 5802.4 5801.8 0.6 5772.8 29.0 0.4
1, 2 dichloropropane 0.0 0.0 0.0 0.0 2408.9 2408.9 2408.9 0.0 0.1 2408.8 0.0
Trans- 1,3 dichloropropane 0.0 0.0 0.0 0.0 1823.1 1823.1 1823.1 0.0 0.0 1823.1 0.0
Cis- 1,3 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chlorine Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
12 13 14 15 16 17 18 19 20 21
Temperature (oF) 72.8 256.1 236.4 70.0 72.2 83.5 70.0 100.0 93.1 70.0
Pressure (Psia) 14.7 90.0 74.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7
Vapor Frac 1.0 1.0 1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0
Mole Flow (lbmol/hr) 886.4 886.4 1000.0 500.0 911.1 584.0 75.4 38.1 62.8 62.8
Mass Flow (lb/hr) 37301.4 37301.4 42080.6 9007.6 37746.3 12526.0 5772.8 4260.9 4705.7 4705.7
Water 0.0 0.0 0.0 9007.6 444.4 8563.2 0.0 0.0 444.4 444.4
Hydrochloric Acid 0.0 0.0 0.0 0.0 0.0 3962.5 0.0 0.0 0.0 0.0
Propylene 37301.4 37301.4 42080.6 0.0 37301.4 0.0 0.0 0.0 0.0 0.0
Chlorine 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Allyl Chloride 0.0 0.0 0.0 0.0 0.4 0.2 5772.8 29.0 29.4 29.4
1, 2 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.1 2408.8 2408.8 2408.8
Trans- 1,3 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1823.1 1823.1 1823.1
Cis- 1,3 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chlorine Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
349
Table C.13: Optimized Allyl Chloride Process Equipment Specification
Equipment Specification in Aspen
Mixer (M-901) Pressure – 0 psia, Phases- Vapor-liquid
Mixer (M-902) Pressure – 0 psia, Phases- Vapor-liquid
Heater (E-901) Temperature – 730 oF, Pressure – 74.7 psia
Cooler (E-902) Temperature – 70oF, Pressure – 74.7 psia
Cooler (E-903) Temperature – 70oF, Pressure – 14.7 psia
Cooler (E-904) Temperature – 100oF, Pressure – 14.7 psia
Cooler (E-905) Temperature – 100oF, Pressure – 14.7 psia
Cooler (E-906) Temperature – 100oF, Pressure – 14.7 psia
Cooler (E-907) Temperature – 100oF, Pressure – 14.7 psia
Reactor (R-901) Type – Adiabatic Plug Flow Type – Isothermal Plug Flow
Length-20 Specified at Inlet Temperature
Diameter-6 Length-20
Valid Phase – Vapor Only Diameter-6
Reactor pressure -40 psia Valid Phase – Vapor Only
Reaction Type- Power Law Reactor pressure -40 psia
Reaction Type- Power Law
Compressor (C-901) Type – Polytrophic ASME Method
Discharge Pressure -90 Psia
Column (T-901) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-15
Condenser –Partial Vapor
Reboiler - Kettle
Valid Phases : Vapor - Liquid
Reflux Ratio -0.5
Distillate to Feed Ratio -0.893
Feed Stage -7
Product Stage – 1– Vapor, 15- Liquid
Stage 1 Pressure – 20, Stage 15 Pressure -27
Dryer (T-902) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-10
Condenser –None
Re-boiler - None
Valid Phases : Vapor - Liquid
Feed Stage -1, and 10
Product Stage – 1– Vapor, 10- Liquid
Stage 1 Condenser Pressure – 14.7
Separator (T-903) Type – Sep
Split- Propene -1
Column (T-904) Type – RadFac, Calculation Type- Equilibrium
Number of Stage-30
Condenser –Partial Vapor
Re-boiler - Kettle
Valid Phases : Vapor – Liquid
Reflux Ratio-7
350
Distillate to Feed Ratio = 0.54
Feed Stage -6
Product Stage – 1– Vapor, 30- Liquid
Stage 1 Pressure – 16
Stage 2 Pressure – 25
Mole Purity of 1,3 dichloropropene – 97%
Column (T-905) Type – RadFac, Calculation Type- Equilibrium
Number of Stages-30
Condenser –Total
Re-boiler - Kettle
Valid Phases : Vapor – Liquid
Reflux Ratio-5
Distillate to Feed Ratio = 0.5
Feed Stage -10
Product Stage – 30– Liquid, 1- Liquid
Stage 1 Pressure – 14.7
Mole Recovery of Allyl Chloride-99%
Column (T-906) Type – RadFac, Calculation Type- Equilibrium
Number of Stages-30
Condenser –Total
Re-boiler - Kettle
Valid Phases : Vapor – Liquid
Reflux Ratio-5
Distillate to Feed Ratio = 0.01
Feed Stage -15
Product Stage – 30– Liquid, 1- Liquid
Stage 1 Pressure – 14.7
Mole Recovery of 1,2 dichloropropane-99%
Column (T-906) Temperature -201.5 oF
Pressure -14.7 psia
351
Table C.14: Optimized Allyl Chloride Process (Adiabatic PFR) Stream Summary Table
1 2 3 4 5 6 7 8 9 10 11
M-902 M-901 M-901 R-901 E-902 T-901 T-904 T-902 T-905 E-903
Temperature (oF) 80.0 677.0 80.0 652.4 891.5 70.0 173.2 -45.1 162.0 253.8 80.7
Pressure (Psia) 74.7 74.7 74.7 74.7 39.4 74.7 27.0 20.0 16.0 25.0 14.7
Vapor Frac 1.0 1.0 1.0 1.0 1.0 0.9 0.0 1.0 1.0 0.0 0.0
Mole Flow (lbmol/hr) 110.6 1000.0 130.0 1130.0 1108.1 1108.1 110.6 997.5 93.8 16.8 32.4
Mass Flow (lb/hr) 4653.9 42080.6 9217.7 51298.3 51298.9 51298.9 9930.9 41368.1 8062.9 1868.0 584.1
Water 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 584.1
Hydrochloric Acid 0.0 0.0 0.0 0.0 3940.3 3940.3 0.0 3940.3 0.0 0.0 0.0
Propylene 4653.9 42080.6 0.0 42080.6 37427.2 37427.2 0.0 37427.2 0.0 0.0 0.0
Chlorine 0.0 0.0 9217.7 9217.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Allyl Chloride 0.0 0.0 0.0 0.0 5297.0 5297.0 5296.5 0.5 5296.5 0.0 0.0
1, 2 dichloropropane 0.0 0.0 0.0 0.0 2478.8 2478.8 2478.8 0.0 2421.7 57.0 0.0
Trans- 1,3 dichloropropane 0.0 0.0 0.0 0.0 2155.6 2155.6 2155.6 0.0 344.7 1811.0 0.0
Cis- 1,3 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chlorine Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
352
12 13 14 15 16 17 18 19 20 21 22
C-901 M-902 E-901 T-902 T-903 T-907 T-906 E-904 E-907 E-906
T-903 C-901 M-902 T-902 T-902 T-905 T-905 T-906 T-906 T-907
Temperature (oF) 80.7 264.5 244.5 70.0 80.0 90.6 113.3 204.4 202.4 213.0 201.5
Pressure (Psia) 14.7 90.0 74.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7
Vapor Frac 1.0 1.0 1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0 1.0
Mole Flow (lbmol/hr) 889.4 889.4 1000.0 1000.0 921.8 1075.7 68.9 24.9 20.1 4.8 560.5
Mass Flow (lb/hr) 37427.1 37426.7 42080.6 18015.3 38011.2 21372.1 5270.0 2792.9 2252.8 540.0 12081.3
Water 0.0 0.0 0.0 18015.3 584.1 17431.2 0.0 0.0 0.0 0.0 8160.6
Hydrochloric Acid 0.0 0.0 0.0 0.0 0.0 3940.3 0.0 0.0 0.0 0.0 3920.1
Propylene 37427.1 37426.7 42080.6 0.0 37427.1 0.2 0.0 0.0 0.0 0.0 0.2
Chlorine 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Allyl Chloride 0.0 0.0 0.0 0.0 0.0 0.5 5270.0 26.5 26.5 0.0 0.4
1, 2 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2421.7 2179.6 242.2 0.0
Trans- 1,3 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 344.7 46.8 297.9 0.0
Cis- 1,3 dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chlorine Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
353
23 24 25 27 28 29
E-905
354
Table C.15: Optimized Allyl Chloride Process (Isothermal PFR) Stream Summary Table
1 2 3 4 5 6 7 8 9 10 11
M-902 M-901 M-901 R-901 E-902 T-901 T-904 T-902 T-905 E-903
Temperature (oF) 80.0 773.4 80.0 742.3 741.6 70.0 171.5 -45.6 162.8 253.8 84.8
Pressure (Psia) 74.7 74.7 74.7 74.7 47.1 74.7 27.0 20.0 16.0 25.0 14.7
Vapor Frac 1.0 1.0 1.0 1.0 1.0 0.8 0.0 1.0 1.0 0.0 0.0
Mole Flow (lbmol/hr) 130.8 1000.0 149.2 1149.2 1121.2 1121.2 130.9 990.4 115.8 15.1 36.4
Mass Flow (lb/hr) 5504.5 42080.6 10577.7 52658.4 52658.4 52658.4 11664.0 40994.3 9990.2 1673.9 655.8
Water 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 655.8
Hydrochloric Acid 0.0 0.0 0.0 0.0 4419.8 4419.8 0.0 4419.8 0.0 0.0 0.0
Propylene 5504.5 42080.6 0.0 42080.6 36573.8 36573.8 0.0 36573.8 0.0 0.0 0.0
Chlorine 0.0 0.0 10577.7 10577.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Allyl Chloride 0.0 0.0 0.0 0.0 6473.1 6473.1 6472.4 0.6 6472.4 0.0 0.1
1, 2 Dichloropropane 0.0 0.0 0.0 0.0 3158.9 3158.9 3158.9 0.0 3107.8 51.1 0.0
Trans- 1,3 Dichloropropane 0.0 0.0 0.0 0.0 2032.7 2032.7 2032.7 0.0 409.9 1622.8 0.0
Cis- 1,3 Dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chlorine Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
355
12 13 14 15 16 17 18 19 20 21 22
C-901 M-902 E-901 T-902 T-903 T-907 T-906 E-904 E-907 E-906
T-903 C-901 M-902 T-902 T-902 T-905 T-905 T-906 T-906 T-907
Temperature (oF) 84.8 268.8 245.0 70.0 84.2 97.7 113.3 204.4 202.6 212.7 201.5
Pressure (Psia) 14.7 90.0 74.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7 14.7
Vapor Frac 1.0 1.0 1.0 0.0 1.0 0.0 0.0 0.0 0.0 0.0 1.0
Mole Flow (lbmol/hr) 869.1 869.2 1000.0 1000.0 905.5 1084.8 84.2 31.6 25.7 5.9 629.4
Mass Flow (lb/hr) 36573.7 36576.2 42080.6 18015.3 37229.5 21780.1 6440.1 3550.1 2884.5 665.6 13566.3
Water 0.0 0.0 0.0 18015.3 655.8 17359.5 0.0 0.0 0.0 0.0 9163.7
Hydrochloric Acid 0.0 0.0 0.0 0.0 0.0 4419.8 0.0 0.0 0.0 0.0 4402.0
Propylene 36573.7 36576.2 42080.6 0.0 36573.7 0.1 0.0 0.0 0.0 0.0 0.1
Chlorine 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Allyl Chloride 0.0 0.0 0.0 0.0 0.1 0.6 6440.1 32.4 32.4 0.0 0.5
1, 2 Dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 3107.8 2797.0 310.8 0.0
Trans- 1,3 Dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 409.9 55.1 354.8 0.0
Cis- 1,3 Dichloropropane 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Hydrogen Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Chlorine Ion 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
356
23 24 25 27 28 29
E-905
357
VITA
Doctor of Philosophy
Biographical:
Professional Memberships: Omega Chi Epsilon and National Organization for the
```````````````````````````````````Professional Advamcements of Black Chemists and
```````````````````````````````````Chemical Engineers
Name: Olamide Olayemi Shadiya Date of Degree: December, 2010
Scope and Method of Study: This research is focused on adopting a systematic methodology for
address sustainability concerns during early stages of engineering design. Traditionally,
engineers designed processes to achieve beneficial operations and economic goals. However,
given the need to balance the economic benefits of chemical engineering processes, safety, health
and environmental impacts, the improved focus on sustainability of production processes has
introduced more complex dimensions to consider. When it comes to addressing the three
conflicting dimensions of sustainability, there is no well-defined methodology or tool for
achieving this. A thorough review was completed to investigate the applications and limitations
of existing economic, environmental, health and safety evaluation tools. Therefore, the
methodology combines already established approaches, concepts and tools into a novel
systematic technique that addresses sustainability concerns during early stages of chemical
process design.
Findings and Conclusions: A methodology that involves the use of the SUSTAINABILITY
EVALUATOR and ASPEN PLUS was developed for evaluating processes for sustainability.
The SUSTAINABILITY EVALUATOR is a novel impact assessment tool developed for this
research. This tool applies selected metrics that address economic, environmental as well as
health and safety concerns. The SUSTAINABILITY EVALUATOR is a Microsoft Excel based
tool that uses mass and energy balance inputs from ASPEN PLUS to evaluate the sustainability of
a process. This impact assessment tool equips the process designer with a framework to design
industrial processes for sustainability. The objective is for processes designers to use the results
generated from the tool to assess and improve the sustainability of a process. The proposed
framework involved the use of ASPEN PLUS to simulate processes, calculate mass and energy
balances, complete sensitivity analysis and lastly optimize processes An overall sustainability
impact which has been incorporated into the SUSTAINABILITY EVALUATOR was developed
to quantify sustainability issues in process design. The methodology was demonstrated on two
case studies: the acrylonitrile process and the allyl chloride process. The application of the
methodology on the two case studies resulted in a more economic, environmental and socially
acceptable processes.