Current Situation of Emerging Technologies For Upgrading of Heavy Oils
Current Situation of Emerging Technologies For Upgrading of Heavy Oils
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
a r t i c l e i n f o a b s t r a c t
Article history: With the increased production of heavy and extra-heavy crude oils, and the need to add them into the reg-
Received 17 January 2013 ular diet to refineries, there has been much interest for developing new technologies for upgrading those
Received in revised form 22 April 2013 heavy materials. Traditional commercially available carbon rejection and hydrogen addition routes are
Accepted 27 May 2013
still applicable for this purpose, however they have shown some limitations when the oil is heavier, which
Available online 4 July 2013
directly impact in the economy of the technology. Various emerging technologies have been reported in
the literature, mainly in patents, which have been developed and tested at different scale and with a wide
Keywords:
variety of heavy petroleum. The most important emerging technologies for upgrading of heavy crude oils
Heavy oil
Upgrading
are reviewed and discussed. Particular emphasis is put in a comparison with the available information.
Emerging technologies It is recognized that all the technologies have great opportunity to be applied commercially depending
on the support that they receive by the petroleum companies.
© 2013 Elsevier B.V. All rights reserved.
A number of technologies have been developed over the years Carbon rejection is one of the first types of conversion pro-
for heavy crude and residue oil upgrading, which include pro- cesses applied in the oil industry, and has been used since
cesses that are based on carbon rejection, hydrogen addition and 1913 for different fuels and heavy hydrocarbons heated under
combination of both routes [1,2], most of them with proven com- pressure. This group of technologies includes processes such as
mercial experience. Fig. 1 summarizes the distribution of these visbreaking, thermal cracking, and coking. Foster Wheeler and
technologies and their processing capacity. Carbon rejection pro- Universal Oil Products made an agreement to combine their tech-
cesses represent 56.6% of the total worldwide processing capacity nical experiences, developing over 50 visco-reduction plants. Shell
mainly due to its relative low investment. and ABB-Lummus have developed and commercialized a drum
There are also other technologies at different level of develop- type application namely Reaction Chamber (Soaker), with over 80
ment or close to commercialization or even already used, that have projects based on this process [3,4]. Fluid coking and Flexicoking
been abandoned as uncompetitive during the years of cheap crude are developments of Exxon Mobil Research & Engineering (EMRE).
oil. The combined capacity of Fluid coking and Flexicoking amounts
The changing prices of crude oils as well as the increasing pro- 241,000 and 426,000 bbl/day, respectively. Delayed Coking a
duction of heavy and extra-heavy crude oils have motivated more mature technology is offered by Foster Wheeler SYDEC (Selective
research and development aiming at upgrading of such heavy mate- Yield Delayed Coking) with over 25 revamps designed in the last
rials. The new approaches are named emerging technologies. This 10 years, and over 20 new units designed in the last 5 years [5].
group of technologies is reviewed in this work and their advantages,
disadvantages and current situation are highlighted. 2.2. Hydrogen addition
2. Typical technologies for upgrading of heavy oils Traditional upgraders reduce carbon-to-hydrogen ratio by
adding hydrogen obtained from natural gas. Hydrogen addition
Standard technologies developed for heavy crude and residue technologies are classified depending on the type of reactor
oil upgrading include processes that are based on carbon rejection, used, e.g. fixed-bed, moving-bed, ebullated-bed and slurry-bed
hydrogen addition and combination of these two routes. processes.
Axens technology utilizing its Hyvahl process (Permutable
Reactor System), has reached an important commercialization
∗ Corresponding author. Tel.: +52 55 9175 6619; fax: +52 55 9175 8429. level. Chevron Lummus Global (CLG) licenses On-stream Catalyst
E-mail addresses: [email protected], [email protected] Replacement technology (OCR) for processing high-metal feeds and
(L.C. Castañeda), [email protected] (J.A.D. Muñoz), [email protected] (J. Ancheyta). the revamp alternative, an Upflow reactor (UFR). Shell developed
0920-5861/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2013.05.016
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 249
Nomenclature
PSA Pressure Swing Adsorption
AB Athabasca bitumen RFCC Residue Fluid Catalytic Cracking
ADC Accelerated decontamination RIPI Research Institute of Petroleum Industry
AERI Alberta Energy Research Institute RTP Rapid Thermal Processing
AMEC AMEC Group Ltd. RVP Reid Vapor Pressure
BA BA Energy Inc. RVTI Company Rival Technologies Inc.
CAT CAT process SAGD steam assisted gravity drainage
CCR Conradson carbon SCO Synthetic crude oil
CCU Catalytic Crude Upgrading SDA Solvent deasphalting
CDP Commercial Demo Plant SYDEC Selective Yield Delayed Coking
CE3 Canadian Environmental Equipment and Engineer- T Temperature
ing TaBoRR Tank Bottoms Recovery and Remediation
CIMAV Centro de Investigación en Materiales Avanzados TDG-1 Terre de Grace
CLB Cold Lake Bottoms TRU TRU process
CLG Chevron Lummus Global UAOD Ultrasound assisted oxidative desulfurization
CP Cracking Process UFR Upflow reactor
CPBB Chinese Paraffinic Bottoms Blend UOP Universal Oil Products
CPJ Conversion Pierre Jorgensen USP Ultra selective pyrolysis
DAO Deasphalted oil USPTO United States Patent and Trademark Office
DBT Dibenzothiophene VCG Value Creation Technology
DBTO Dibenzothiophene sulfone VCI Value Creation INC
DC Delayed Coking VGO Vacuum gas oil
DRV Distillate Recovery Unit VR Vacuum residue
EMRE Exxon Mobil Research & Engineering VTB Vacuum tower bottoms
EST Eni Slurry Technology WHB Waste heat boiler
FCC Fluid Catalytic Cracking WRI Western Research Institute
FGDSU Flue Gas Desulphurization Unit WRITE Western Research Institute Thermal Enhancement
GCC Gulf Cooperation Council P Pressure drop
GHG Green House Gases
GHU Genoil Hydroconversion Upgrader
HCAT Hydrocracking technology the HYCON process (Bunker Reactor System) which uses conven-
HCU Heavy Crude Upgrader tional fixed-bed reactors and a system for continuous catalyst
HDC Hydrocracking replacement [6,7].
HDCCR Conradson Carbon Residue Reduction In the ebullating-bed processes, the H-Oil process of Axens/IFP
HDM Hydrodemetallization and the LC-Fining process of Chevron Lummus Global, similar in
HDN Hydrodenitrogenation concept but different in some mechanical details, offer a final prod-
HDS Hydrodesulfurization uct containing around 25% of non-converted residual [8,9].
HDT Hydrotreating The slurry phase reactor processes employ disposable catalysts
HGO Prototype heavy oil upgrader whose development aimed at decreasing the cost of the catalyst
HOG Heavy oil upgrader inventory, i.e., cost of the fresh hydroprocessing catalysts and that
HOUP Heavy Oil Upgrade Project of the spent catalysts. A number of processes employing a dispos-
HP High pressure able catalyst are in a developmental stage and others are in a near
HRH Heavy Residue Hydroconversion commercial stage [10].
HTGI Headwaters Technology Innovations Group
HTL Heavy to light 2.3. Combined technologies
HVGO Heavy vacuum gas oil
HYCON Hydroconversion process The main advantages of the integrated process schemes are
HYT Haiyitong Inc. in terms of product yields, quality of products, elimination
IBA Ion Beam Applications of low-value by-products, and reduction of impurities. Various
IFP Institut Français du Pétrole integrations of upgrading processes are reported in the liter-
IGCC Integrated Gasification Combined Cycle ature, which include deasphalting, gasification, delayed coking,
IMP Instituto Mexicano del Petróleo RFCC, ebullating-bed reactor, slurry phase reactor and fixed-bed
LP Low pressure hydrotreating [11].
LVGO Light Vacumm Gas Oil
MIB Maya–Isthmus blend 3. Emerging technologies
NCUT National Center for Upgrading Technology
NRC National Research Council Since the light crude reservoirs are getting scarce and because
NRL National Refinery Limited the current processes in refineries are not totally adequate to pro-
OCR On-Stream Catalyst Replacement cess heavy and extra-heavy crude oils a new group of technologies
P Pressure has emerged as a promising solution of the problem. These tech-
PDVSA Petroleos de Venezuela Sociedad Anonima nologies are focused on the upgrading of the properties of those
PEMEX Petroleos Mexicanos crudes, i.e. increase of API gravity and reduction of viscosity and
PONA Paraffin, Olefin, Naphthenic, Aromatic impurities content such as sulfur, nitrogen and metals, either to
transportation purposes or to feed to refineries.
250 L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273
Table 1
Emerging technologies for heavy, extra-heavy crude oil processing.
HCAT Process (Headwaters Reported as a breakthrough process to convert low quality feedstock (high asphalt and metals). Conversion up to 95% and
Heavy Oil) higher reactor throughput. Uses a molecule sized catalyst (slurry phase reactor) and offers several significant advantages over
supported catalysts based processes
HTL (Heavy-to-Light) Process Short contact time thermal conversion process (rapid thermal processing) that operates at moderate temperature and
(Ivanhoe Energy) atmospheric pressure. Unique thermal cracking technology that solves some of the disadvantages of delayed coking, fluid
coking, and visbreaking processes
GHU Process (Genoil Inc.) Multiple fixed-bed reactor system. Feedstocks ranging from 6.5 to 17.5 ◦ API. Only tested with feeds that have relatively low
Technology Inc. metals content
Viscositor Process for upgrading of heavy oil at the oil field; based on the atomization of oil with steam and further collision with heated
process-Ellycrack-Wescorp sand in a high-velocity chamber to “crack” the oil where any catalyst is not required. Low severity makes this process
technically feasible
IMP Process (Mexican Institute Low or moderate pressure technology for upgrading of heavy oils and residua. Catalysts with improved stability and proper
of Petroleum) selection of reactors and feedstock preparation to work under moderate conversion regime that allow for working with low
sediment formation
NexGen-Ultrasound process System for upgrading heavy oil employing ultrasonic waves to break long hydrocarbon chains and simultaneously adds H2
generated from purified water to the molecules. It uses ultrasonic waves to create cavitation bubbles within the working fluid,
in this case, oil
HRH (heavy residue Catalytic hydrocracking process, which targets conversion of heavy and extra-heavy crude to valuable crude. This technology
hydroconversion) can be used for two main purposes: Hydroconversion in refining and Hydroconversion in wellhead
CCU (catalytic crude Based on traditional FCC principles processing only enough of the crude to create sufficient accumulation to produce a synthetic
upgrading) crude meeting pipeline specifications. High coke yield, opportunity to produce large quantities of steam and electrical power
Sonocracking, SulphCo, Inc., Ultrasound technology to desulfurize and hydrogenate heavy crude oil. The transfer of hydrogen from water to the numerous
petroleum streams leads to the conversion of crude oil
Eni Process Process enables an almost complete conversion of the feedstock (>95%) and guarantees an excellent level of upgrading of the
products. Flexible in treating different types of heavy feedstocks, such as VR, heavy and extra-heavy crudes and bitumen from
oil sands
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 251
shows the HCAT process which converts low quality feedstock such 2010/0294701 A1, methods for hydrocracking a heavy feedstock
as heavy oil, residue and oil sands bitumen into synthetic crude using an in situ colloidal or molecular catalyst and recycling the
oil. The process uses a molecule sized catalyst, chemically gener- colloidal or molecular catalyst. Since 2008, the United States Patent
ated within the reactor system through a conditioning process, to and Trademark Office (USPTO) has given the HCAT trademark serial
achieve high conversion of oil. HCAT significantly improves the con- number of 77,042,411 to Headwaters Incorporated, South Jordan,
version of heavy oil as well as reduces sediment formation [17,18]. UT 84095.
HCAT technology offers several advantages over processes using
supported catalysts such as non-deactivating molecular catalyst,
3.1.3. Current situation
constant product quality, feedstock flexibility, flexible conver-
Recently HTIG has announced that Neste Oil Corporation’s
sion (up to 95%), higher reactor throughput, simple, two-phase
Porvoo Refinery at South Jordan, Utah, is the first refinery to
gas–liquid reactor.
commercially implement Headwater’s HCAT heavy oil upgrading
technology. During 2011 Neste Oil and HTI completed a 40-day
3.1.1. History commercial test at the Porvoo refinery. Since more than 500,000
The (HCAT/HC)3 process was initially developed by Alberta barrels of heavy oil are processed in their upgraders every day, at
Research Council and designed to upgrade indigenous heavy crude least 200,000 BPD of additional capacity would be added by 2014
oils or bitumens. Now the process is called HCAT and licensed by [20].
Headwaters. In this process the catalyst is homogeneously dis-
persed as a colloid with particles similar in size to that of asphaltene
molecules, whereby high conversion of the asphaltenes can be 3.1.4. Results
achieved. Catalysts used in the process are oil-soluble, such as iron Different feedstocks have been tested with this technology.
pentacarbonyl or molybdenum 2-ethyl hexanoate with excellent Table 2 shows the typical results for a reactor temperature between
anti-coking performance. Conversion ranged from 60% to 98% when 430 and 450 ◦ C, reactor pressure of 2000 psig, and the hydrogen
the Cold Lake bitumen was treated in a pilot unit [10]. treat rate was 5000 standard cubic feet per barrel of heavy oil.
These solid catalysts, typically a combination of two or more
transition metals on an alumina support base, are limited by their
3.2. HTL-heavy oil upgrading
physical structure as to the amount of heavy oil they can process
and the quality of the product slate that can be produced [19].
Ivanhoe Energy has developed and patented the Heavy-to-Light
(HTL) upgrading process. HTL is a heavy oil upgrading process that
3.1.2. Patents converts heavy, viscous crude oil to lighter, transportable and more
Patent No. US 7,578,928 B2 (August 2009), hydroprocessing valuable synthetic oil. HTL operates at a significantly smaller scale
method and system for upgrading heavy oil using a col- and at a fraction of the per-barrel costs as compared with conven-
loidal or molecular catalyst. Patent Application Publication US tional technologies [21].
252 L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273
Table 2
Results of the test (conversion).
Feedstock
Properties
Temperature cut 565 ◦ C+ 538 ◦ C+
API gravity 8.5 0.4 1.5
Sulfur, wt% 5.02 6.22 4.7
Nitrogen, wt% 0.66
Nickel, ppm 79 176
Vanadium, ppm 209 416
C7 Asphaltenes, wt% 12.6
CCR, wt% 12.8 26.9
◦
975 F + resid conversion, % 94 94 63 95
Asphaltene (C5 Ins.) conversion, % 95 93 67 96
Sulfur conversion, % 78 78 56 92
AB: Athabasca bitumen, CLB: Cold Lake Bottoms, MIB: Maya/Isthmus Blend, CPBB: Chinese Paraffinic Bottoms Blend.
Run A: 220 h, stopped when P in the second reactor increased significantly. A post-run inspection showed significantly fouling on the screen of the reactor liquid recycle
cup.
Run B: 400 h, little change in reactor P. The screen at the reactor liquid recycle cup with minimal fouling.
The HTL processing plant can be located upstream, at or near the 3.2.3. Current situation
well-head, fully integrated with field operations. Alternatively, it Ivanhoe Energy has completed HTL technology development,
can be located midstream, upgrading heavy crude oil from onshore scale-up and testing operations, and is now working with AMEC,
and offshore resources and exporting upgraded product to refiner- its main engineering contractor, in the design and engineering of
ies that have limited coking capacity. full-scale HTL facilities for identified heavy oil projects. Ivanhoe
The HTL process uses a circulating transport bed of hot sand to Energy is currently focused on projects in Canada, Latin America
heat the heavy feedstock, such as vacuum tower bottoms (VTB) and and the Middle East. The HTL process is economic at feed capacities
convert them to lighter products. The high yield and high quality as low as 10,000–30,000 barrels per day, and the typical Class 4 cost
configuration can be applicable to heavy oil or bitumen upgrading, estimate for the HTL plant ranges from USD $12,000 to $20,000 per
where upgraded products are quenched at the exit of the reactor installed barrel of capacity [22,23].
cyclone and routed to the atmospheric distillation unit where dis-
tillate and lighter material are sent to product tank and blended 3.2.4. Results
with straight-run gas oils. Atmospheric bottoms are recycled to the The properties of the HTL product compared with the original
front end of the vacuum unit to separate VGO and lighter material. heavy oil feedstock are shown in Table 3.
VTB can be recycled to extinction depending on the site specific
energy requirements. The general flow process scheme is shown in 3.3. Genoil process
Fig. 3.
The major drawbacks of HTL technology are the large size equip- Genoil Hydroconversion Upgrader (GHU) is a catalytic hydro-
ment for heat recovery, low volumetric yield of upgraded crude, low conversion technology that upgrades and increases the yields from
capacity for extra-heavy oil processing because the high dimen- heavy crude, bitumen and refinery residues. The GHU facility has
sions of the regenerator and high formation of coke, low sulfur conversion of 70–90% based on the various types of feedstocks
reduction, high formation of olefins and diolefins susceptible to (Heavy crude oil, vacuum or atmospheric residue or bitumen),
polymerization and high production of sand rich in spent heavy
metals, fine particulate and ash.
Table 3
Properties of the feedstock and product of the HTL process.
Composition, volume%
3.2.2. Patents
Naphtha, IBP–375 ◦ F 0 2.5
Patent No. US 8,105,482 B1 (January 2012). Rapid thermal Kerosene, 375–455 ◦ F 1 4.5
processing of heavy hydrocarbon feedstock. Since 08/22/2006, the Distillate, 455–650 ◦ F 12 24
USPTO has given the HTL trademark serial number of 76,647,666 VGO, 650–1000 ◦ F 35 63
Residue, 1000 ◦ F+ 52 6
to Ivanhoe Energy, Inc., Bakersfield, CA 933899279.
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 253
controlling the unconverted residue by variations in temperature The GHU can be utilized to upgrade heavy crude, bitumen and
and pressure in the process. From the integration of a distillation refinery residue streams. The processing scheme is based on a
unit after the GHU and sending the residue to a synthesis gas unit, fixed-bed reactor system with a reactor sequence. The first ves-
it is able to increase the API gravity from 24 to 34◦ . Fig. 4 shows a sels are HDM guard reactors, followed by a second main reactor
schematic of the GHU technology [24]. using HDS, or a combination of HDS and HDN beds. Genoil has
Recycle hydrogen
Make up
hydrogen
Reactor Atmospheric
tower
Feed
Fired
heater
Compressor
Syncrude
Vacuum
Reactor tower
HDM
Separator
conducted multiple pilot plant test on various sour heavy crude, Table 4
Properties of the feedstock and product of the Genoil process.
bitumen and residue oil feed stocks ranging from 6.5 to 17.5 ◦ API
gravity with the following results: desulfurization: 75–97%, deni- Bitumen feed Syncrude
trogenation: 37–53%, demetallization: 76–98%, conradson carbon API gravity 8.5 24.8
reduction: 47–87%, residue conversion: 37–88% [25]. Sulfur, wt% 5.14 0.24
Nitrogen, wt 0.27 0.14
C5 Asphaltenes, wt% 17.3 1.6
3.3.1. History C7 Asphaltenes, wt% 12.6 1.2
Starting in May 1998, Genoil (formerly CE3 Technologies Inc.: CCR, wt% 12.8 2.6
Canadian Environmental Equipment and Engineering Technologies
Composition
Inc.) researched innovative processes for the upgrading of heavy IBP–340 ◦ F 0.0 8.7
crude oils. The Genoil concept is to upgrade on-site heavy crude 340–450 ◦ F 2.0 11.5
oil to much lighter oil meeting pipeline specifications even for a 450–649 ◦ F 12.4 33.0
649–975 ◦ F 32.3 36.7
small-scale field unit of 10,000 bpd.
975 ◦ F 53.3 10.1
From May 1998 to January 1999, Genoil evaluated the TaBoRR
process (Tank Bottoms Recovery and Remediation) from the West- Process results
◦
API increase 16.3
ern Research Institute in Laramie, WY, and the CAT process, which
%HDS 95
is typically used to make diesel fuel. The evaluation of these pro- %HDN 48
cesses concluded that a major shift would be required to offer an CCR conversion, % 80
economical process for heavy oil upgrading [26]. nC7 asphaltenes conversion, % 90
Based on the TaBoRR process, which is a carbon rejection 975 ◦ F+ conversion, % 81
Norway. The verification of upgrading on this technology was done nitrogen and asphaltenes and a significant conversion of the heavier
on 2003, and the next year a demonstration testing was performed portions of the feedstock to more valuable distillates, while keep-
for PDVSA, Statoil and Wescorp Energy on a 200 bbl/day unit. In ing the formation of sediments and sludge at very low levels.
2005 the Viscositor technology was verified, the patents granted The most important characteristics of this process are relatively
and a joint venture with Wescorp Energy was signed. The National low investment and operating costs and an attractive return on
Research Council of Canada (NRC) approved a grant to Wescorp investment.
Energy in 2006. These funds were used to support an enhanced The improvements in the quality of heavy crude oils obtained by
and detailed test program of the Viscositor [29]. applying IMP’s technology include higher yields of distillates, lower
contents of sulfur, metals, asphaltenes and coke formation precur-
3.4.2. Patents sors, lower acidity, corrosivity, viscosity and deposits formation
Patent No. US 6,660,158 (December 2003). Catalytic cracking tendency. These characteristics facilitate handling, transportation
process. Patent No. US 7,892,416 B2. Low temperature ther- and refining of heavy and extra-heavy crude oils and increase their
modynamic cracking and conversion for upgrading of heavy value for the refiner.
oils. The main applications of IMP’s process are:
3.4.3. Current situation • Conversion of heavy and extra-heavy crude oils to intermediate
The short-term strategy of Ellycrack is to prepare the pilot plant crude oils of higher value
for new extensive testing, invite heavy oil producers to test their • As a first processing unit for heavy and extra-heavy crude oils in
oil on the pilot plant and assure sufficient funding to develop the a refinery.
company according to chosen business plan.
Light
fraction
Upgrader
crude
Lean
Make up amine
hydrogen
HDM
Reactor
HDS
Reactor
Rich
amine
IMP Reactors
In the application to heavy crude oils upgrading, the light frac- 3.5.2. Patents
tion and the products from the reactor system are integrated into an Patent No. US 7,651,604 B2 (January 26, 2010). Process for the
upgraded crude oil stream. In the refinery application, the reaction catalytic hydrotreatment of heavy hydrocarbons of petroleum. The
section is integrated within a conventional combined distillation invention is also protected in Mexico (No. 271,028), Russia (No.
unit. Fig. 6 shows a simplified scheme of IMP-HDT process. 2,339,680) and Singapore (No.118,896). In addition, an application
The use of a series of beds of catalysts with different formula- of this patent has been submitted to European Union, Australia,
tions allows for better selectivities in the hydrodesulfuration and Canada, Brazil, Japan and Venezuela. Patents of the catalysts have
hydrodemetallation reactions and a higher efficiency in the use of also been granted.
the catalysts, thus providing for a product with lower sulfur and
metals contents and for a lower catalyst consumption than the
conventional catalytic high-severity hydrocracking processes. The 3.5.3. Current situation
conversion of heavy molecules to lighter fractions and the relatively The IMP Process has been satisfactorily tested at semi-industrial
low selectivity to gaseous products lead to liquid products yields of level with heavy and extra-heavy crude oils. The main features
104–105% by volume. of the process have been extensively tested in the optimization
Due to the moderate operating conditions, investment costs are of the catalysts system and operating conditions as well as in the
significantly lower than those of conventional catalytic hydroc- definition of the useful life of the catalysts.
racking processes. The lower catalysts and hydrogen consumptions Technical and economic studies carried out to evaluate the
translate into lower operating costs [30,31]. application of IMP technology in a heavy crude oil upgrader and
in a typical refinery scheme show important advantages of IMP’s
process in comparison with the main technologies commercially
3.5.1. History available for bottoms-of-the-barrel processing.
IMP started developing exploratory studies in heavy crude oil All of the components of IMP’s heavy crude oil upgrading
upgrading since 1990, and was granted its first Mexican patent technology have been demonstrated at the industrial level in
in 1995 (No. 9,200,929: an approach for hydroprocessing of heavy hydrotreatment/hydrocracking units. The key elements of the tech-
crude oils to produce synthetic crude oil). From 1995 to 2003, the nology (the activity and selectivity of the catalysts system, the
process was extensively studied and optimized for its application operation at moderate conditions with very low sediments for-
for a wide range of heavy and extra-heavy crude oils. The techno- mation and the ability to process very difficult feedstocks) have
logical development of the IMP process was performed from 2003 been extensively tested at the pilot plant level and confirmed in a
to 2006, which included long-term pilot plant experiments (about 6 semi-industrial unit.
months). Two semi-commercial demonstration tests were carried The possibilities of application of this technology in a first indus-
out in 2006 and in 2008 in a 10 barrels per day unit with high metal trial unit are being analyzed with Petroleos Mexicanos (PEMEX).
and asphaltenes content crude oils having API gravity ranging from
10 to 16◦ . The results of these tests indicated that the IMP process
produces an upgraded crude oil having a consistently high quality. 3.5.4. Results
Optimization and engineering have been carried out during Table 6 shows the results of IMP process for upgrading of heavy
2008–2011, and the IMP process is ready for commercial applica- crude oils in the range of 10–16 API gravity at moderate reaction
tion. conditions.
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 257
Table 6
Results of upgrading of different heavy crude oils with IMP process.
Property Crude oil Upgraded oil Crude oil Upgraded oil Crude oil Upgraded oil
Metals, ppm
Ni 69.2 26 91.2 22 94.2 28
V 361.0 71 452.7 76 494.0 71
Ni + V 430.2 97 543.9 98 588.2 99
3.6. NexGen-ultrasound process Once the asphaltenes and heavy oil have been partially cracked
by the CP process, they are sent to the next cracking process which
The NexGen technology is a new system invented for upgrading has great control on the type of hydrocarbon formed. Energy Quest
heavy oil employing ultrasonic waves to break the long hydro- calls the second ultrasound upgrader the HOG. The 10 step HOG
carbon chains and simultaneously adds hydrogen generated from followed by the 4 step HOG produces a finished product that only
purified water to the molecules. has to be separated by distillation.
The fundamentals for the NexGen technology derived of a The 10 step HOG allows the operator to control the
project undertaken by the developer group to overcome fuel sta- paraffin–olefin–naphthenic–aromatic (PONA) ratio of the formed
bility problems in MIG fighter jets. Further, this group developed products. The 4 step HOG allows the operator to control the purity
this technology for using within the oil upgrading sector [32]. of the products by eliminating sulfur, nitrogen and oxygen.
Fig. 7 shows the physical basis of NexGen Technology, which
is a cavitation process. It uses ultrasonic energy waves to create 3.6.1. History
cavitation bubbles within the working fluid, in this case, oil. By NexGen’s team has developed and proven the technology over
further application of this energy the bubbles are taken to collapse the last 5 years. Scientists of NexGen have proven the ability to
at high temperature and pressure. This collapse causes the breaking upgrade heavy oil from 8 to 42 ◦ API gravity at an energy input of
of the long chain hydrocarbon molecules. 20 kWh/bbl.
The prototype heavy oil upgrader (HOG) shown in Fig. 8 is fed
with heavy crude oil. The crude contains salt water and small
amounts of solids. To remove the salt water and solids, the crude is 3.6.2. Patents
heated to about 200 ◦ C which causes the water and solids to drop So far, the corresponding patent claiming this technology was
out of the oil. The material is removed by the fresh water circuit unavailable to be retrieved.
shown at the front of the process.
Once the water and solids are removed the crude oil is passed 3.6.3. Current situation
through a membrane separation process where the asphaltenes are NexGen is now designing a 10,000 barrels per day commer-
separated from the lighter crude oil. The pure asphaltenes form cial upgrading plant that plans to install in Edmonton, Alberta,
small crystals which in volume behave much like a low viscos- near the Athabasca tar sands. The estimated cost of this com-
ity liquid. The two separate streams are first sent to what Energy mercial plant is about $45 million, and will be sufficiently large
Quest calls the Cracking Process (CP) which is a chemical–magnetic enough to demonstrate the capabilities of the system. Upon suc-
induced process. The CP process will be operated differently for the cessful completion of this upgrader unit NexGen will promote
two streams. the systems, including NexGen-owned and operated systems, joint
venture partnerships with other petroleum companies, and licens- The technology can process feedstocks such as bottoms, heavy
ing and royalty arrangements. oil, extra-heavy oil (bitumen), and light oil, and eliminate the need
for condensate. It considerably improves oil quality before the oil
3.6.4. Results refining takes place; significantly improves yields and coking is not
The system operates at lower temperatures and pressures, present.
avoiding the need of the complex and expensive hardware in tradi- Due to viscosity reduction, this technology substantially reduces
tional refineries, hence, investment costs will represent a fraction or eliminates blending during oil transportation along pipelines. No
of conventional upgraders. down time to replace catalyst.
All processes are carried out at T = 0–70 ◦ C and P = 1–5 bar,
consequently energy consumption is reduced and operating and 3.7. Sulph-ultrasound process
maintenance costs are reduced by 50%.
Volumetric yields are 20–50% higher than the traditional pro- SulphCo has developed an economic process employing ultra-
cess, therefore profits are increased and the use of petroleum sound technology for desulfurization and hydrogenation of crude
supplies is maximized. Profit margins are greatly increased, initial oil and other oil related products. The technology upgrades sour
construction time is reduced, and harmful environmental emis- heavy crude oils into sweeter, lighter crudes, producing more gal-
sions virtually eliminated. lons of oil per barrel. Fig. 9 shows a flow diagram of the process.
The technology takes place in oil pipelines during pumping and
no catalyst is engaged. The systems are modular with processing 3.7.1. History
capacities of 500–100,000 bbl/day or more, so they can be sized to SulphCo was founded in 1999 leading most of the testing at
meet the local demand. its facility in the United Arab Emirates and some also in Nevada.
Solvent
Peroxide & Make up
Catalyst
Solvent
Regeneration
Feed
SulphCo
Sonocracking Purge
Assembly
O/W
Separator Regenerating
Bed
Water
Make up
Desulfurized
Purge Converted Product
Water Adsorbing
Recycle Feed Bed
Fig. 9. Process block flow diagram and applications of Sulph-Ultrasound process [34].
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 259
110 hydrogenated. Outlet gas products from top of the reactor are con-
100 densed and separated. In the first stage of separation, unreacted
hydrogen and light hydrocarbon are separated, treated in amine
90
contactor and recycled to the system by a compressor. In the second
Conversion of DBT to DBTO, %
0
3.8.1. History
0 1 2 3 4 5 6 7 8 The HRH process has been run with a variety of feeds in dif-
Time, min ferent capacities. In 1991 a 200 BPD semi-industrial pilot plant
was located in Russia to evaluate this technology. Further, 1 L lab
Fig. 10. Conversion of DBT to DBTs with and without the use of ultrasound.
batch unit and 2 BPD pilot unit were used in Teheran, and a 5 L/day
continuous pilot plant was located in Russia. The basic design was
SulphCo has conducted four separate series of sonocracking tri- completed on a 10,000 BPD heavy oil upgrader in Persian Gulf area
als recognizing that Sonocracking is almost ready since 2002. In and the final completion of this development was obtained in a 200
February 2008 SulphCo signed a deal with Pt. Isis Megah, an oil dis- BPD refinery residue demo plant located at Bandas–Abbas refinery.
tributor in India, Malaysia, Singapore, and Indonesia to implement Currently, an 180,000 BPD unit is under basic design at heavy oil
sonocracking technology in their plants. The technology has not yet upgrading and refining complex in Iran.
been installed.
3.8.2. Patents
3.7.2. Patents Patent US 7,585,406 B2 (September 2009), Publication No. EP
SulphCo has five U.S. patents issued to cover the development 1,754,770 A1 (February 2007) and Application No. EP 05,107,538.0
and production of its high-powered ultrasound technology and (August 2005), process for hydroconverting of a heavy hydrocar-
equipment: 6,402,939 (2002), 6,500,219 (2002), 6,652,992 (2003), bonaceous feedstock. Further during 2006 year the invention was
6,827,844 (2004), and 6,897,628 (2005). SulphCo’s Sonocracking protected in other countries such as USA, Canada, Venezuela, Cuba,
ultrasound process increases the distillate yield while at the same Mexico, China, Iraq, Japan and South Korea as well in the Gulf Coop-
time reducing sulfur and nitrogen content. The patent granted eration Council countries (GCC).
in 2005, “High-Power Ultrasound Generator and Use in Chemi-
cal Reactions”, covers the electromagnets and other machinery in 3.8.3. Current situation
SulphCo ultrasound generator and how the mechanism works to Industrial projects on conversion of heavy crude oil to light
produce a chemical reaction when ultrasonic waves are introduced. crude and also heavy vacuum residue to synthetic crude has
The company has six other patents pending plus corresponding been studied and designed for several commercial scales from
applications pending around the world. 10,000 to 180,000 BPD. The technology can be licensed through
Mobis in Canada. Research Institute of Petroleum Industry (RIPI)
3.7.3. Current situation offers opportunities for cooperation in its HRH process in technol-
SulphCo has already contracted its sonocracking technology to ogy transfer, process development package, carrying out detailed
Pt. Isis Megah which operates in India, Malaysia, Singapore and design, and other related engineering activities.
Indonesia, however, the technology has not yet been installed. The
company also is expecting opportunities in Austria, South Korea, 3.8.4. Results
South America, and Canada [33]. The HRH process has been investigated in pilot plant and demo
scales. Experimental data for hydroconversion of Bandar–Abbas
3.7.4. Results vacuum residue is shown in Table 8.
Table 7 shows the efficiencies and recoveries of the sonoc-
racking technology in ultrasound assisted oxidative desulfurization 3.9. CCU process
(UAOD) on diesels and Fig. 10 shows the conversion of DBT to diben-
zothiophene sulfone (DBTO) with and without the use of ultrasound The UOP catalytic crude upgrading process (CCU) offers a solu-
[34]. tion to trapped nontraditional crude production. The process is
based on traditional FCC principles processing only enough of the
3.8. HRH process crude to create sufficient accumulation to produce a synthetic crude
meeting pipeline specifications.
Heavy residue hydroconversion (HRH) developed by Research The process has a high coke yield, which results in the opportu-
Institute of Petroleum Industry (RIPI) of Iran, is a catalytic hydroc- nity to produce large quantities of both steam and electrical power.
racking process, which targets conversion of heavy and extra-heavy The produced steam and power supply the utility needs of the com-
crude to valuable crude. In this process, shown in Fig. 11, the hydro- plex as well as the surrounding oil field, the upgrading complex and
gen, feed and the catalytic complex are heated separately. Then feed the infrastructure necessary to support the project [37].
and the catalytic complex are mixed and heated again. Finally, the The process can be adapted to meet the needs of a number of
mixture of feed, catalytic complex and hydrogen are heated and stranded oil projects where natural gas and electricity supplies are
entered into the reactor where heavy residue feed is cracked and unavailable. The CCU process is applicable to heavy oil projects
260 L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273
Table 7
Efficiencies and recoveries of the sonocracking technology in ultrasound.
Sonication time (min) Sulfur content (wt%) Sulfur removal (%) Recovery of oil (%)
Residue
Gasification
Fig. 11. Scheme of HRH process for heavy crude oil upgrading [35].
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 261
Table 9 Table 10
Properties of the crudes obtained in the CCU process. EST process performances.
Properties Rubiales crude CCU product crude Feedstock Zuata crude Maya crude Athabasca bitumen
Products upgrading
The Eni Slurry Technology (EST) process was developed by %HDS 86 84 83
Snamprogetti and EniTecnologie, both companies of the Eni Group. %HDN 59 52 47
%HDN >99 >99 >99
Fig. 12 shows a scheme of this process. The EST process enables an % removal of CCR 98 96 95
almost complete conversion of the feedstock (>95%) and guaran-
tees an excellent level of upgrading of the products. The process
proved extremely flexible in treating different types of heavy feed- 3.10.4. Results
stocks, such as vacuum residues, heavy crudes, extra-heavy crudes Table 10 shows the performance of the EST process on different
and bitumens from oil sands [39,40]. feedstocks [47].
The heart of the process consists of a hydrotreating reactor
in which the heavy crude feedstock undergoes a hydrogenation
3.11. HOUP process
treatment in relatively mild conditions (410–420 ◦ C and 160 bar).
The hydrotreating is carried out in the presence of several thou-
The Heavy Oil Upgrade Project (HOUP) developed by Pre-
sand ppm of a molybdenum based catalyst finely dispersed in
mium Engineering-Research and Development focuses on two
the liquid mass so as to promote the upgrading reactions (metal
main areas: first, the upgrading of high viscosity and low API grav-
removal, desulfurization, denitrogenation and reduction of the car-
ity heavy oils at the production site by converting them into lighter
bon residue).
synthetic crude oil, and second, the refining of heavy oil residues
Typical overall performances achieved in the reaction system,
at refineries.
by recycling unconverted bottoms show:
The HOUP process is based on a major modification of the ther-
mal cracking process and does not require the use of catalysts nor
• Metal removal (HDM) > 99%; of hydrogen, and has a minimal infrastructure requirement which
• Conradson carbon residue reduction (HDCCR) > 97%; means that it can be used at production sites.
• Sulfur reduction (HDS) > 85%; The most important feature of the process is the manner in
• Nitrogen reduction (HDN) > 40%. which feedstock molecules receive energy required for cracking.
This approach is based on conventional pre-heating and the use of
3.10.1. History superheated steam as an energy source which results in uniform
Eni Slurry Technology (EST) is a process developed in the early and almost simultaneous heating. The level of the supplied energy
1990s, after catalyst screening studies in laboratory microreactor is adjusted to crack only the weakest bonds of large molecules.
and bench-scale autoclave tests [41,42]. Further a pilot plant with In other words the level of energy supplied minimizes excessive
a capacity of 0.3 bbl/day was started up in 1999. Eni/Snamprogetti cracking and increases the yield of distillate fractions. The HOUP
has proposed conceptual designs for the processing of Athabasca process can be used to convert different heavy residues at refineries
bitumen and Venezuela Zuata heavy crude oil. In 2005 it was com- [48].
pleted and started up a 1200 BPSD of a Commercial Demo Plant
(CDP) at Eni Taranto Refinery [43,44]. 3.11.1. Patents
Additional information of this emerging technology is not acces-
sible in the open literature, however, it is expected that this process
3.10.2. Patents
would be patented in the short time to be competitive with other
U.S. Patent 8,017,000 B2, (Sep, 2011). Process for the conver-
similar technologies under the name “Method and apparatus for
sion of heavy feedstocks such as heavy crude oils and distillation
heavy oil processing”.
residues. U.S. Patent 7,691,256 B2, (Apr, 2010). Process for the con-
version of heavy charges such as heavy crude oils and distillation
residues. U.S. Patent 8,147,675 B2, (Apr, 2012). Process for the total 3.12. Uniflex process
conversion of heavy feedstocks to distillates. U.S. Patent 8,057,660
B2, (Nov, 2011) process for the total conversion of heavy feedstocks The UOP Uniflex process, a high-conversion slurry hydrocrack-
to distillates [45,46]. ing technology resulted from a combination of elements from the
Canmet process reactor section and UOP Unicracking and Unionfin-
ing process technologies [49,50]. The typical Uniflex process flow
3.10.3. Current situation scheme is shown in Fig. 13, which is similar to that of a conven-
The implementation of the first EST industrial plant (23,000 tional UOP Unicracking process unit. In this scheme liquid feed and
BPSD capacity) is in progress at Eni Sannazzaro de’ Burgondi Refin- recycle gas are heated to temperature in separate heaters, with a
ery (Pavia, Italy) expecting to be in operation by the end of 2012. small portion of the recycle gas stream and the required amount
262 L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273
of catalyst being routed through the oil heater. The outlet streams 100
from both heaters are fed to the bottom of the slurry reactor.
3.12.1. History
In 2000 UOP evaluated several options focused on a slurry 3.13. WRITE process
hydrocracking technology concluding that the most efficient
approach involved Canmet hydrocracking process. In 2006 UOP WRITE is an upgrading process that produces residuum-free oil
worked with NRCan to evaluate and improve the process technol- from heavy oil and bitumen with undiluted density and viscos-
ogy package before UOP acquired the exclusive worldwide rights ity that exceed general pipeline specifications. WRITE uses two
to license the Canmet process. processing stages to accomplish low and high temperature con-
Further, UOP has invested significant effort in improving catalyst version of heavy oil or bitumen. The first stage Distillate Recovery
performance, engineering design and feedstock processing flexi- Unit (DRU) operates at mild thermal cracking conditions, yielding a
bility with financial support and strategic input from the Alberta light overhead product and bottoms material. These bottoms flow
Energy Research Institute (AERI) as part of its Hydrocarbon Upgrad- to the second stage, a coker that operates at severe pyrolysis condi-
ing Demonstration Program. This program is aimed at developing tions, yielding light products (pyrolizate) and coke. The combined
and demonstrating commercially viable advanced technologies pyrolyzate and mildly cracked overhead streams yield synthetic
that convert bitumen and bitumen-derived products into higher- crude oil (SCO).
valued products. An application of the WRITE process for partial upgrading would
The Uniflex process catalyst costs are lower relative to other eliminate the need for diluents step, and could possibly eliminate
slurry hydrocracking technologies because expensive catalytic the need for a coker at the upgrader, since a coker is already integral
materials, such as molybdenum, are not required. to the WRITE process itself. Fig. 15 shows a block diagram of the
WRITE process for upgrading a bitumen stream [52,53].
3.12.2. Patents
Patent US 8,110,090 B2 (February 2012), Deasphalting of gasoil 3.13.1. History
from slurry hydrocracking and the original Patent US 4,299,685 Western Research Institute (WRI) and MEG Energy Corporation
(1981). Since 2009, the USPTO has given the Uniflex trademark (MEG) have been jointly developing the WRI Thermal Enhancement
serial number of 77,722,028 to UOP LLC, Des Plaines, IL 600,175,017. (WRITE) process upgrader since 2004. WRITE process was devel-
oped in three phases. Phase 1 involves the completion and analysis
of bench-scale tests (1 BPD), the design of a pilot facility for field
3.12.3. Current situation testing, and development of preliminary economics for a commer-
UOP’s engineering efforts have included the development of an cial facility. Phases 2 and 3 involve the construction and operation
updated and improved engineering design. UOP pilot plants are of a pilot plant (5 BPD) sited at a production facility using actual
able to confirm the design basis for new applications because UOP run bitumen.
and NRCan have over 100,000 h of cumulative pilot plant experi- Testing comprised three series: the first series, run with undi-
ence with the Uniflex process technology. Performance of these luted bitumen, explored the effects of sweep gas composition and
pilot plants has been validated against the Petro-Canada demon- space velocity. The second series run with diluted and undiluted
stration unit. bitumen, varied temperature and space velocity. The third series,
UOP announced in January 2012 that its Uniflex process has been run with dilbit (diluted bitumen), explored a range of reduced space
selected by National Refinery Limited (NRL) to maximize diesel and velocities [54].
lubricant production in Pakistan. The NRL facility, scheduled for
start-up in 2016, will produce 40,000 barrels daily of diesel fuel 3.13.2. Patents
and 4500 barrels daily of lube base oils [51]. Patent US 2011/0284425 A1, (November, 2011), hydrocarbona-
ceous material upgrading method.
3.12.4. Results
The Uniflex process employs a proprietary, nano-sized solid cat- 3.13.3. Current situation
alyst which is blended with the feed to maximize conversion of A preliminary economic analysis conducted by MEG and their
heavy components and inhibit coke formation. The catalyst is dual engineering consultant concluded that the WRITE process is a tech-
functional, with its primary function being to impart mild hydro- nically feasible method for upgrading bitumen producing SCO that
genation activity for the stabilization of cracked products while also meets pipeline specifications. Subsequent development stage will
limiting the saturation of aromatic rings. As can be seen in Fig. 14, be to scale-up the 5 BPD pilot plant to a suitable sized demonstra-
this permits the reactor to operate at both very high asphaltene and tion pilot in 2013. The size of the field demonstration unit may
non-distillable conversion levels. range from 300 BPD to 1500 BPD [55].
264 L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273
Pressurize Water
Feed & Hot pressurized feed Flash
Preheat
Distillate
Continuos Recovery
Coke Coker DRU bottoms
Unit
Anhydrous
Flash
Bottoms
Distillate Distillate
product product
customized for broad spectrum of refineries, at the lowest all-in- 3.16. TRU process
costs”.
On March 7, 2007, VCI announced the company is proceeding The TRU Oiltech technology is a mild thermal reagent-based
with its first Athabasca oil sands production project, Terre de Grace upgrading process added to heavy crude oil and oil sand bitumen
(TDG-1), which will combine in situ recovery and field upgrading. in order to improve viscosity for transfer in pipeline systems.
In December 2007, the company filed a joint regulatory appli- A bitumen feedstock and our cracking resistant additive are
cation with the Energy Resources Conservation Board and Alberta introduced into a non-coking visbreaker where the bitumen is
Environment for the development of an integrated in situ bitumen cracked, then sent for distillation. The additive is recovered and the
pilot production and upgrading project on its Terre de Grace Lease. gas oil is sent for blending. H2 S rich off-gases from the non-coking
VCI announces that BA Energy Inc. has become a wholly owned visbreaker and distillation tower functions are re-directed for
subsidiary of Value Creation effective February 26, 2008. BA Energy potential process fuel supply. Next, the gas oil distillation residue is
is constructing the Heartland Upgrader, a commercial bitumen sent to a solvent deasphalter where the residual extractable (dea-
upgrader using proprietary upgrading technologies developed by sphalter pitch) are separated from the asphaltenes. The solvent is
Value Creation in Strathcona County, northeast of Edmonton, recovered and the deasphalter extract is sent for blending with the
Alberta. gas oil. The resulting metal free, low sulfur, ultra high yield blend
Value Creation has submitted its Project Disclosure document is a premium synthetic crude oil [58,59].
and proposed Terms of Reference for review to the Alberta Energy
and Utilities Board and Alberta Environment. After regulatory 3.16.1. History
approvals, the upstream-upgrading project is expected to begin In the third quarter of 2008, the Company Rival Technologies
production in 2011. Inc. (RVTI) commenced preliminary engineering and design for the
The Terre de Grace block is one of several held by Value Creation, pilot plant and construction. The TRU process has been proven in
which entirely owns one of the largest oil sands resources held by the laboratory by the Alberta Research Council, and the intellectual
an independent Canadian company. property is protected by a provisional patent. The next step is a fully
functional pilot plant [59].
3.15.2. Patents
Patent US 7,625,466 B2 (Dec, 2009) “Systems for the decontam- 3.16.2. Patent
ination of asphaltic heavy” assignee to Value Creation Inc. Calgary, U.S. patent WO/2008/124912 issued on 10-23-2008 titled
Alberta, Canada, and US 2012/0048713 A1 (March, 2012) “Pyrolysis “Method of upgrading heavy oil crude”.
of residual hydrocarbons”.
3.16.3. Current situation
3.15.3. Current situation RVTI has recently (2012) started its first license agreement relat-
Based on an independent consultant’s calculation and Value Cre- ing to commercial development and use of TRU Technology. This
ation’s own estimate, TDG-1 has “exploitable bitumen in place” agreement provides the Licensee with worldwide rights to TRU
of 2.45 to 2.77 billion barrels. Economic recoverable bitumen will Technology when used in combination with a separate hydrotreat-
depend on reservoir characteristics and technical cost. ing technology; and allows Rival to continue to develop and license
TDG-1 is expected to be an 80,000 bbl/day upstream-upgrading TRU as a standalone technology to other oil producers and refiners.
project, developed in two 40,000 bbl/day, steam assisted gravity This first license will help advance TRU Technology to commercial
drainage (SAGD) phases and producing light, refinery-ready crudes. use, and provide revenue to Rival through payment of license fees
The capital cost of the Project is projected to be in the range of and royalties. RVTI is now focused on licensing TRU Technology
$3.5–4.0 billion (2007 dollars). to oil producers and other potential users. Rival is also pursuing
266 L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273
Injection of
Cooling ionized air
Commodity
Radiation Gas separator
gases
Oil feedstock chemical
reactor Upgraded
liquid product
Electron
accelerator Commodity
Fractionation
oil products
a financing that will allow it to complete additional testing, final- 3.18. PetroBeam process
ize its worldwide patent and develop its own continuous feed pilot
plant. PetroBeam process is a cold cracking technology, which uses
high-energy electrons instead of energy-intensive catalysts to
reduce the viscosity of heavy oil. The process uses electricity rather
3.16.4. Results
than heat generated from natural gas to effect changes in the crude
Preliminary results show decreased sulfur content 67% and
oil and do not require expensive catalysts. The process is also more
reduced the total acid number 88% for heavy crude oil.
environmentally benign than thermal and chemical-based meth-
ods now in use. A block diagram of this process is shown in Fig. 18.
3.17. Petrosonic process
3.18.1. History
The Petrosonic process developed by Sonoro Energy Ltd., con- E-beam processing has a 50 years history of industrial success
sists of a first phase of rapid de-asphalting of oil that is expected in a wide range of applications. E-beam processing is safe and
to increase the API approximately 6–10 degrees, reduce sulfur economical and has been used in a wide range of commercial appli-
and metal by 40% and lower viscosity by 99%. The second phase cations for many decades.
of the process utilizes a chemical oxidation process which can PetroBeam plans the migration of this industrial process, apply-
upgrade oil by an additional 6–10 ◦ API. The final phase is the ing it to the midstream and downstream sectors of the petroleum
solvent recovery; the recovered solvent is reused at the solvent industry. The technology has been studied and researched by its
de-asphalting stage to complete the closed loop on the Petrosonic scientists for over 15 years. Laboratory scale tests have shown that
upgrading process. A block diagram of the overall process is shown heavy components, such as asphaltenes, in crude oil and bitumen
in Fig. 17. are disrupted and partially decomposed by e-beam processing.
The main advantage of this technology originated in the use The company had expected to complete its next stage of devel-
of its sonic reactor technology and the unique cavitational and opment using its 75 bbl/day rate pilot facility by mid-2009 and
enhanced mass transfer effects that it provides. The sonic reac- further demonstrate the process in its 1000 bbl/day pilot plant,
tor, using its patented low-frequency/high-energy/high-amplitude which was expected to be completed by the end of 2009. How-
reactor design, allows for significant improvement in the mass ever, although they made most of progress from 2007 to 2009 the
transfer efficiency of the solvent de-asphalting step [60,61]. slumping economy has forced them to greatly slow their work and
focus on patent instead of scale-up [62,63].
3.17.1. Patents
3.18.2. Patents
WO/2009/111871 A1, (Sep 2009) “Method for treating heavy
US 8,192,591 B2, (Jun 2012) “Self-Sustaining cracking of
crude oil”, assignee to Sonic Technologies Solutions Inc, Vancouver,
hydrocarbons”, assignee to Petrobeam, Inc., Raleigh, NC (US). Inter-
CA.
national publication number: WO 2007/070698 A2 (Jun 2007)
“Self-sustaining cracking of hydrocarbons”. The Mexican patent
3.17.2. Current situation (MX/a/2008/007791) is proceeding and expecting it to be issued.
Sonoro Energy is commercializing its patented sonic generator
and related technologies through wholly owned subsidiaries and 3.18.3. Current situation
joint ventures. The process has been tested successfully on heavy oil from the
The Company has commenced commercialization of the Pet- Athabasca oil sands and on heaviest from other areas of the world.
rosonic process through a 1000 barrels per day (bpd) joint venture PetroBeam expects to build, operate and license its process to
(60% Sonoro) in Albania. Other commercial applications of this pro- producers and refiners. Since foundation, it has raised more than
cess include converting waste fly ash from coal-fired power stations $9.5 million in capital, including $6 million equity investment from
into a cement substitute and the separation and extraction of oil Ion Beam Applications. The Company has been working in part-
sands from oil. nership with IBA to develop the commercialization plans for a
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 267
Product
Fresh feed
Scrubber
Reactor
product
$30 million 10,000 bbl/day facility. The primary component of the 3.20. EADIEMAC process
facility is the electron beam accelerator, the TT1000 Rhodotron®
produced by IBA. Eadie Oil Inc. licenses the EADIEMAC Process as a practical solu-
tion to the need for field upgrading units, onshore or offshore. This
3.19. IY Q process thermal process is designed to change heavy crude oil by visbreak-
ing into much lower viscosity higher value oil [66].
ETX’s fluid bed coking reactor is a revolutionary technology
developed to convert heavy crude feedstock, such as Athabasca 3.20.1. History
bitumen, into a bottomless synthetic crude oil. ETX systems have Eadie Oil Inc. has successfully run a 1.5 bbl/day pilot unit.
combined cross flow fluidized bed technology with thermal crack-
ing experience, leading the design as IY Q process. Fig. 19 shows a 3.20.2. Patent
scheme of this process where hot solids are introduced at one end US 5,110,447 (May 1992) “Process and apparatus for partial
of the reactor, flowing by gravity through the vessel as a fluidized upgrading of heavy oil feedstock”, assignee to Kasten, Eadie tech-
bed. Pitch is introduced into the bed, reacting to produce liquids nology Ltd., Edmonton Canada.
products, coke and non-condensable gas. The coke remains on the
fluidized solids, while the fluidization gas and other reaction prod- 3.20.3. Current situation
ucts are collected overhead. The solids leave the reactor at a lower Eadie Oil Inc is currently working to commercialize the EAD-
temperature than they were fed, since heat in the solids provides IEMAC Process and related proprietary processes in field units from
the energy required to carry out the chemical reactions [64,65]. 2500 bbl/day up to larger central plants of 20,000 bbl/day capacity
A major advantage of the designs is that the mixing character- or more.
istics of the reactor severely reduce short-circuiting of unreacted
feed compared to competing fluidized bed technologies. 3.20.4. Results
The results of a continuous run using a 13.6 ◦ API “Fort Kent”
3.19.1. History feedstock in a 1.5 bbl/day pilot plant located at the Alberta Research
The technology has followed a rigorous gated development Council, report 17.0 ◦ API and reduction of viscosity from 14,500 to
process over the past 10 years. Having successfully completed a 133 cps.
1 bbl/day pilot with its claims intact, the technology is ready for a
commercial demonstration at a 1000 bbl/day scale. 3.21. CPJ process
liquid yields, reduces or potentially eliminates need for diluents, 3.22.1. History
upgrades heavy crudes to stable lighter oils that can be optimally The Chattanooga process has been developed in two experi-
processed by bottoms constrained refineries. mental plants, Pilot Plant I commissioned in 2000 and Pilot Plant II
commissioned in 2004. This process has the ability to remove 99.8%
of all sulfur.
3.21.2. Patent
US 6,989,091 B2 (Jan 2006) “Deep conversion combining the
demetalization and the conversion of crudes, residues or heavy 3.22.2. Patent
oils into light liquids with pure or impure oxygenates compounds”, US 6319.395 B1 (Nov 2001) “Process and apparatus for convert-
assignee to World Energy Systems Corporation, Scottsdale, AZ. ing oil shale o tar sand to oil” assignee to Chattanooga Corporation,
Bradenton, FL (US).
3.21.3. Results
CPJ process was found to upgrade as much 86% of the crude
to lighter liquids. Test using 8.77 ◦ API vacuum residue yielded 51% 3.22.3. Current situation
gasoil, 23% diesel and 10% kerosene or naphtha for an average grav- Chattanooga Corp. is preparing to design, construct and operate
ity of pipeline grade 20.3 ◦ API, leaving only 16% as sulfur laden pitch a demonstration facility as the next step in the commercialization
to make asphalt or burn for process heat. process. In parallel, Chattanooga will expand its relationship with
selected energy producers, government agencies, financial insti-
tution and investors to promote and establish commercial-scale
3.22. Chattanooga process facilities and create licensing and royalty agreements.
Vent
Makeup
solvent
Colum
Colum
Colum
Colum
Mixer
VR
Cooler
Solid-vapor
separator
Stream Stream
stripper stripper
Table 11
Comparison of emerging technologies for heavy oil upgrading based on the process route.
Table 11 shows a comparison of the most important properties • Technologies for the route of hydrogen addition have experi-
of emerging technologies for upgrading crude oil such as: quality, enced higher test level (demonstration plant) followed by carbon
yields, complexity, flexibility, development level, investment costs rejection.
and operating costs as function of the processing route.
From the table, the following comments can be made: Important features such as the API gravity increase and the vol-
umetric yields of the upgraded crude oil are required to evaluate an
• The hydrogen addition processes have better quality and yield of emerging technology. Fig. 23 shows API gravity differential versus
upgraded crude oil, but high investment and operating costs. volume yields of upgrading crude oil of emerging processes. The
• The carbon rejection processes, ultrasound and solvent extrac- following observations can be made:
tion have investment and operating costs more attractive than
hydrogen addition but lower oil quality and yields of upgraded • In general, carbon rejection processes have a range of volumet-
crude oil. ric yields of 65–95% and the API increase is in the range of
• Catalytic or hydrogen addition high-severity processes can be 7–19◦ .
mainly used for full upgrading crude oil, while carbon rejec- • The hydrogen addition processes supply an increase of API gravity
tion, ultrasound and solvent extraction can be applied for partial in the range of 10–25 and volumetric yields between 100% and
upgrading crude oil to transport. Hydrogen addition working at 108%.
moderate severity can also be used for partial upgrading.
Another important aspect to evaluate emerging technologies is
The upgraded crude oil obtained with hydrogen addition tech- economics, particularly the investment and operating costs; Fig. 24
nologies can be mixed with virgin heavy oil in the required volume shows the investment and operating costs associated to emerging
ratio to achieve the specifications for transportation, thus the vol- technologies. It is observed that:
ume of crude to be transported will be greater than that produced
from one partial upgrading technology. The selection of the best • The emerging technologies based on ultrasound involve lower
technology for transportation of crude oil will require a technical
investment and operating costs.
and economic evaluation considering the level of development of • The carbon rejection processes exhibit similar investment cost
each one.
with different values in operating costs derived from the process
Fig. 22 shows the highest test level of different technologies
characteristics.
depending on the processing route. This illustration points out that: • The hydrogen addition technologies have higher investment and
operating costs.
• Most emerging technologies have produced experimental results • The IMP upgrading technology account for investment and oper-
at a laboratory scale. ation costs very similar to those of carbon rejection technology
L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273 271
110
18-25
11-16 API
9-13 API
API 11-18
10-17 API
API
3-5
100 API 7-16
15-18
API
API
9-13
API
11-14
API
10-17
90 API
11-13
API
12-16
API
14-17
API
80
70
60
API Differential
Fig. 23. API differential as function of volumetric yield of upgraded crude oil.
10
8
Operating cost, USD/bbl
21000-26000
7 USD/BPD
9000-11000
6 7000-12000
USD/BPD
UDSD/BPD
10000-13000 ENI
5 Genoil Wildcatter USD/BPD
9000-14000
USD/BPD
9000-12000
4 4000-6500
USD/BPD Viscositor
USD/BPD
IMP
3 Writte
HTL
2
4500-7000
USD/BPD
1 Nexgen
0
Investment cost
because it operates at moderate reaction conditions and conver- them. Thus only basic information can be obtained from the Inter-
sion. net and in the open literature.
Emerging technologies have definitively attracted the attention
5. Final remarks of the refiners. Feasibility studies are being carried out by many
petroleum companies to make proper decision about what tech-
The increased interest in the upgrading of heavy and extra- nology to use. Most of them may be good for one feedstock but not
heavy oils is due to the depletion of light crude oil (conventional for others because of the great variety of properties of the different
oil) in the petroleum production countries, which has forced crude oils.
researchers and refiners to develop new technologies to convert The development of emerging technologies for heavy oil
heavy petroleum into more valuable products. The main objec- upgrading has been traditionally aimed toward the routes of car-
tive in such developments has been to increase the API gravity and bon rejection and hydrogen addition. Emerging processes based
reduce the impurities content, along with high selectivity toward on hydrogen addition have shown higher development performing
gasoline and middle distillates. Detailed information of such tech- tests at demonstration scale with great potential for installation of
nologies is quite difficult to find because most of the work is at the commercial plants in the middle and long term. Emerging processes
laboratory scale or in the scale-up level, and the companies keep it based on carbon rejection exhibit low yields of upgraded crude oil
as secret. (75–95 vol%) and volatile fractions requiring additional processing.
The emerging technologies are either in the development stage While hydrogen addition based technologies achieve more than
or tested at different experimental scales (laboratory, bench, pilot 100 vol% yields and stability of the fractions of upgraded crude oil.
plant, and semi-commercial). Because the details of such processes The investment and operating costs of the hydrogen addition
are limited, it is complicated to infer any conclusion about their processes are greater than those of carbon rejection processes due
commercial applicability and advantages/disadvantages among to its complexity that depends on the operating conditions, type
272 L.C. Castañeda et al. / Catalysis Today 220–222 (2014) 248–273
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