GAZİ UNIVERSITY

FACULTY OF ENGINEERING
2023-2024 FALL SEMESTER
CHE451- CHEMICAL ENGINEERING DESIGN I
ASSIGNMENT II

Reactor Design for Phthalic Anhyride Production

GROUP D
191142007 – Eren AYKUT
191142054 – Selda UÇARAVCI
201142050 – Melikşah ASLAN
201142055 – Yasemin KARADAĞ
201142755 – Ibraheem NACHAT

INSTRUCTORS
Prof. Dr. Sena YAŞYERLİ
Res. Asst. İrem Koçyiğit ÇAPOĞLU

Team Leader: Melikşah ASLAN

Edited by: Yasemin KARADAĞ

Due Date: 15.12.2023

1
 ABSTRACT
The objective of this report is to develop a reactor, serving as the central component of a
process, aimed at the conversion of ortho-xylene to phthalic anhydride using oxygen at 5 atm
and 300°C. This design emphasizes safety by considering a lower explosion limit of 1% o-
xylene/air and efficiency with a flow rate of 75x10^6 kg/year over a Vanadium Pentoxide
(V2O5) catalyst at the minimum cost possible. The approach involved a comprehensive
literature review and market analysis, identifying main and side reactions, with the process
being deemed irreversible due to the determined k value. The catalytic nature of the reaction
led to the selection of a V2O5 catalyst, and kinetic expressions from academic research
guided the design. The reaction's occurrence in a heterogeneous environment was
acknowledged.

Operational conditions were set at a 5 atm inlet, an outlet temperature of 300 ℃, and an
isothermal reaction within a non-adiabatic environment. To maintain isothermality, a molten
salt was chosen to absorb the released heat. The reactor type selected was a Plug Flow
Reactor (PFR) with a multi-tubular fixed bed configuration. Material and energy balances
were meticulously performed, resulting in a single reactor design with a diameter of 4.8 m,
length of 10 m, and a total volume of 50 m^3. The tube diameter was calculated at 0.02574 m,
and the pressure drop was determined to be 0.1933 atm. Rigorous safety measures were
implemented.

In terms of performance metrics, a conversion rate (Xa) of 10% was achieved. The associated
costs were detailed, including a reactor cost of $4.62x10 5/year, a catalyst cost of
$1.2x106/year, and a utility cost of $3.4x10 7/year. This report reflects a systematic and
thorough approach to reactor design, encompassing safety, efficiency, and cost
considerations.

Keywords: Phthalic anhydride, ortho-xylene, vanadium penta-oxide, PAN.

i
 CONTENT

ABSTRACT................................................................................................................................i
CONTENT.................................................................................................................................ii
LIST OF FIGURE...................................................................................................................iii
LIST OF TABLE.....................................................................................................................iii
LIST OF GRAPH....................................................................................................................iv
LIST OF CHART....................................................................................................................iv
NOMENCLATURE..................................................................................................................v
1.INTRODUCTION..................................................................................................................1
2. METHOD OF ATTACK......................................................................................................2
3. CALCULATION...................................................................................................................3
3.1. Material Balance............................................................................................................3
3.2. Design Equation for PFR...............................................................................................5
3.3. Energy Balance..............................................................................................................6
3.3.1. Heat Capacites.........................................................................................................6
3.3.2. Enthalpy and Gibbs Energy of Formation............................................................8
3.4. Pressure Drop...........................................................................................................13
3.5. Cost Calculations..........................................................................................................14
3.5.1. Cost of the Reactor................................................................................................14
3.5.2.Cost of Catalyst.......................................................................................................15
3.5.3. Utility Cost..............................................................................................................15
3.5.4.Valve Cost................................................................................................................16
3.5.5. Total Annual Cost..................................................................................................16
4. RESULTS AND DISCUSSION.........................................................................................17
5. CONCLUSION...................................................................................................................31
6. REFERENCES....................................................................................................................33
7. APPENDIX..........................................................................................................................35
Appendix.A. Heuristic and Phase Diagram......................................................................35
Appendix.B.Calculations....................................................................................................36

ii
 Appendix.B.1. Heat Capacity of Gas.............................................................................36
Appendix.B.2. Enthalpy of Formation of Gas...............................................................37
Appendix.B.3. Gibb’s Energy of Formation of Gas.....................................................37
Appendix.B.4.Pressure Drop..............................................................................................38
Appendix.B.5. TEMA Standards.......................................................................................39
Appendix.C.Cost Estimation..................................................................................................40
Appendix.C.1. Cost Estimation of Reactor.......................................................................40
Appendix.C.2. Cost Estimation of Valve...........................................................................40
Appendix.C.3. Estimation of Capital Investment Cost....................................................41
Appendix.C.4. Chemical Engineering Plant Cost Index (CEPCI).................................42
Appendix.C.5. POLYMATH RESULTS...........................................................................43

LIST OF FIGURE

Figure 1. Method of Attack for the Reactor Design..................................................................2

Figure 2. Flow Sheet for Multi-tubular Fixed Bed Reactor.....................................................23
Figure 3. Polymath Equations..................................................................................................25

LIST OF TABLE
Table 1. FA0 /-ra at Different Conversion Value.......................................................................5
Table 2. Correlation for individual Cp Values [4].......................................................................6
Table 3. Thermodynamic Properties of Each Components [4]....................................................8
Table 4. Project Management and Risk Assessment................................................................17
Table 5. Risk Assessment.........................................................................................................18
Table 6. Catalyst Equipment Summary Table.........................................................................19
Table 7. Reactor Equipment Summary Table..........................................................................20
Table 8. Reactor Specification Sheet.......................................................................................21
Table 9. Utility Specification Sheet.........................................................................................22
Table 10. Flow Summary Table for Multi-tubular Fixed Bed Reactor....................................23
Table 11. Polymath Equations Results....................................................................................26
iii
 LIST OF GRAPH
Graph 1. (XA1-XA2-XA) vs. z Graph....................................................................................26
Graph 2. P vs. Z Graph............................................................................................................27
Graph 3. DP vs. z Graph..........................................................................................................27
Graph 4. FA0/ra vs. Xa1..........................................................................................................28
Graph 5. FA0/ra vs. Xa1 , Enlarged Version...........................................................................28

LIST OF CHART

Chart 1. Pie Chart of Cost of Reactor......................................................................................29

Chart 2. Pie Chart of Total Cost of Design..............................................................................30

iv
 NOMENCLATURE
ρ : Density, kg/m 3

MW: Molecular Weight, g/mol

d: Diameter, m

ṁ: Mass Flow Rate, kg/h

V: Volume, m3

h: Height, m

D: Diameter, m

L: Length, m

r: Radius, m

P: Pressure, bar

g: Gravity, m/s2

A: Area, m2

t: Thickness, m

∆ P: Pressure Drop, atm

µ: Viscosity, kg/m.s

q: Volumetric Flow Rate, m3/s

T: Temperature, °K

ε : Void Fraction

RA: Rate equation,

F: Flow rate, mol/s

k: Equilibrium constant

y: Yield

v
XA: Conversion

°G: Gibbs’s Free Energy, kJ/kg

°H: Enthalpy

Cp: Specific Heat, kJ/kg

Q: Energy, kJ/h

PA, B, C, D, E: Pressure, atm

PT: Total Pressure

R: Gas Constant, J/mol-K

S: Cross-Sectional Area, m2

vi
 1.INTRODUCTION

In this report, the complex problem was producing phthalic anhydride (PAN) by oxidation of
o-xylene with a flow rate of 75,000,000 kg/year by using the vanadium penta-oxide (V 2O5)
catalyst and designing a reactor system with taking into account safety precautions and
economical evaluation.

Phthalic anhydride is an organic compound obtained from naphthalene and ortho-xylene.

Naphthalene continued to be the feedstock of choice until the late 1950s, when a shortage of
naphthalene coupled with the availability of xylenes from a burgeoning petrochemical
industry forced many companies to use o-xylene. [1]

Phthalic anhydride is widely used worldwide for an extremely broad range of applications
spanning from the plastics industry for plasticizer to the synthesis of resins, agricultural
fungicides, and amines. Its production is currently based on the vapor phase oxidation of o-
xylene.[2] The demand for phthalic anhydride is rising in the building, furniture, automotive,
and aviation industries due to its advantages over other materials, including its low weight,
resistance to chemical rot, high transparency, and resilience to weather, corrosion, abrasion,
and impact.[3] Due to its versatile uses in various industries, phthalic anhydride is considered
an important raw material.

In the field of reactor design, which the reactor is the heart of a process, the overarching
strategy involves the creation of a specific mathematical model that accurately characterizes
the unique reaction system associated with that specific type of reactor. This approach
includes consideration of primary and ancillary aspects of reactor design, as well as their
corresponding cost implications, for the process involving the oxidation of o-xylene to
phthalic anhydride.

At the beginning of the design, a working plan was prepared in order to proceed in a planned
manner, and the necessary literature research was conducted in this direction, the operating
conditions of the reactor were determined and calculations were made accordingly.

In the report, calculations were made under isothermal, non-adiabatic conditions using a
multitubular fixed bed reactor at 5 atm 300°C with 10% conversion.

1
 2. METHOD OF ATTACK

Within this section of the report, Figure 1. outlines the procedural steps for designing a reactor
to production phthalic anhydride from ortho-xylene. It delineates the approach to be taken and
highlights the factors to be taken into account in the reactor design process. These steps create a
correct direction in reaching the result. The values obtained from the previous steps and the
selected values are used to perform some calculations. For this reason, the steps should be
followed carefully.

Figure 1. Method of Attack for the Reactor Design

2
 3. CALCULATION
3.1. Material Balance

C8H10 + 3O2 → C8H4O3 + 3H2O (Main Reaction)

( A ) + ( 3B ) → ( C ) + ( 3D )
C8H10 + 7.5O2 → C4H2O3 + 4H2O + 4CO2 (Side Reaction)
( A ) + ( 7.5 B ) → ( E ) + ( 4D ) + ( 4F )

FA = FA0 - FA0Xa1 - FA0Xa2

FB = FB0- 3FA0Xa1 – 7.5FA0Xa2

FC = FC0 - FA0Xa1 = FA0Xa1

FD = FD0 + 3FA0Xa1 + 4FA0Xa2 = 3FA0Xa1 + 4FA0Xa2

FE = FE0 + FA0Xa2 = FA0Xa2

FF = FF0 + 4FA0Xa2 = 4FA0Xa2

The lower explosive limit of o-xylene is 1 mole % of o-xylene in air, there for we need to
keep the reaction mixture below it; hence: FAir,0= FA0 *99

FI0 = FI = FA0 *99* 0.79 (N2) (I is inert, which is 79% moles nitrogen in air)

FB0 = FA0 *99* 0.21 (O2)

We have

FC =(75∗10 ¿ ¿ 6
kg
year
)∗ (
1 kmole
148.1 kg)(
∗
1 year
8000 h )
=63.29
kmole
h
¿

kmole
FC = 63.29 = FA0Xa1
h
63.29 kmole
F A 0=
Xa 1 h
Selectivity:

Xa1 4
s = 0.8 = =
Xa1+ X a 2 5
5∗Xa1=4∗Xa1 +4∗Xa2 , 4 Xa2=Xa1

Xa = Xa1 + Xa2 = 0.1 , for Xa1 =0.08

3
 kmole
F A 0=791.25
h
F T =F A + F B + F C + F D + F E + F F + F I

F T =F A 0 −F A 0 Xa1 −F A 0 Xa2 + F B 0 −3 F A 0 Xa1−7.5 F A 0 Xa2 + F A 0 Xa1+ 3 F A 0 Xa1 +4 F A 0 Xa 2+ F A 0 Xa2 +4 F A 0 X

F T =F A 0 +20.79 F A 0−7.5 F A 0 Xa2 +8 F A 0 Xa2+ F A 0∗99∗0.79

F T =21.79 F A 0 +0.5 F A 0 Xa2 +78.21 F A 0

F T =100 F A 0 +0.5 F A 0 Xa2=F A 0 (100−0.5 Xa2 )

If Xa1 is written in terms of Xa2 ;

F T =F A 0 (100−0.125 Xa1 )

P1= y 1∗P T

FA F A 0 (1−Xa1−Xa 2) 1−Xa1−0.25 Xa1 1−1.25 Xa1

y 1= = = =
F T F A 0 ( 100−0.125 Xa1 ) 100+ 0.125 Xa1 100+0.125 Xa1

P2= y 2∗PT

F A 0∗99∗21
F B 0= =20.79 F A 0
100
F B F B 0−3 F A 0 Xa1−7.5 F A 0 Xa2 F A 0 (20.79−3 Xa1−7.5 Xa2) 20.79−4.375 Xa1
y 2= = = =
FT F A 0 ( 100−0.125 Xa1) F A 0 ( 100−0.125 Xa1 ) 100+0.125 Xa1

PT =5 atm is selected since the catalyst working conditions is suitable,

− Ea −E a

−r A =k 0 e R∗T p1 p2 =k 0 e R∗T y1∗PT ∗y 1∗PT

For main reaction

−27000
4.12∗1011∗e 1.987∗573 ∗1−1.25 Xa1
∗20.79−4.375 Xa1
100+0.125 Xa1 2
−r A 1= ∗5
100+0.125 Xa1

For side reaction

4
 −27900
2.25∗1011∗e 1.987∗573 ∗1−1.25 Xa1
∗20.79−4.375 Xa1
100+0.125 Xa1 2
−r A 2= ∗5
100+0.125 Xa1

Compining both reactions

−27000 −27900
(4.12∗e 1.987∗573 +2.25∗e 1.987∗573 )∗1011∗52∗(1−1.25 Xa1)∗(20.79−4.375 Xa1 )
−r A ,T = 2
(100+ 0.125 Xa1)

647.1277∗(1−1.25 Xa1 )∗(20.79−4.375 Xa1)

−r A ,T = 2
(100+0.125 Xa1 )

3.2. Design Equation for PFR

dF A
=r A
dV
F A=F A 0 −F A 0 Xa

d F A =0−F A 0 dXa

dXa dXa dXa

−F A 0 =r A , F A0 =−r A , F A0 =dV
dV dV −r A

t=0, Xa=0, V=0

Xa
dXa
V =F A 0∫
0 −r A

For our system is represented as Xa1

Xa 1
dXa 1
V =F A 0 ∫
0 −r A ,T
Xa 1
dXa 1
V =F A 0 ∫
0 −r A ,T
Xa 1 2
791.25∗(100+ 0.125 Xa1)
V=∫ dXa1
0 647.13∗(20.79−4.375 Xa1 )∗(1−1.25 Xa1)

Using Simpson 1/3 rule

b

∫ f (x )dx ≅ h3 [f ( x 0 ) +4 ( f ( x 1 ) + f ( x3 ) + f ( x 5 ) +f ( x 7 ) )+ 2 ( f ( x 2 ) + f ( x 4 ) +f ( x 6 ) )+ f ( x 8 ) ]
a

Xa = Xa1 +Xa2 = 0.1 is selected. Because in the industry, the conversion of o-xylene to
phthalic anhydrite using V2O5 is mostly seen as conversion 0.1. From the ratio of Xa 1/Xa2 ,
Xa1 = 0.08.

5
 b−a 0.08−0
h= = =0.01
n 8

The value Fa0/-ra is calculated for different values of Xa1 in increments of 0.01. The results
are shown in Table 1.

Table 1. FA0 /-ra at Different Conversion Value

Xa1 f(x)=FA0/-ra Xa1 f(x)=FA0/-ra
0 588.12 0.05 634.85
0.01 596.98 0.06 644.98
0.02 606.08 0.07 655.39
0.03 615.41 0.08 666.10
0.04 625.00

∫ f (x )dx ≅ 0.01
3
[588.12+ 4 ( 596.98+615.41+634.85+ 655.39 ) +2 ( 606.08+625.00+644.98 ) +666.10 ]
a

V=50.056 m3 ≅ 50 m3
Vanadium Pentoxide (V2O5) catalyst:

Bulk density: ρbulk = 1350 kg/m3

Particle density: ρp = 2400 kg/m3

Particle size: dp = ½ inch = 0.0127 m , spherical

Void fraction selected to be ℇ =0.5 .

In the following section, 1 m3 cylinder volume was taken as basis for ease of calculation and
then multiplied by real calculated volume.

kg 3
Bulk mass=1350 3
∗1 m =1350 kg
m

1350 kg 3
Particle volume= =0.5625 m
kg
2400 3
m
Volume ( catalyst ) =Volume ( total )∗(1− ℇ )
3 3
V ( catalyst )=50 m ∗(1−0.5 )=25 m
kg 3
m catalyst =ρcatalyst∗V catalyst=2400 3
∗25 m
m
mcatalyst =60 000 kg

6
3.3. Energy Balance
3.3.1. Heat Capacites
Table 2. Correlation for individual Cp Values [4]

Component a (J/mol.K) b (J/mol.K) c (J/mol.K) d (J/mol.K)

C 8 H 10 (o-xylene) 0.182 5.1344x10-1 -2.02x10-4 -2.1615x10-8
C 8 H 4 O3 (phthalic anhydride) 40.083 3.6084x10-2 9.5956x10-4 -1.234x10-6
O 2(oxygene) 29.526 -8.8999x10-3 3.8083x10-5 3.2629x10-8
C 4 H 2 O3(maleic anhydride) -72.015 1.0423 -1.8716x10-3 1.6527x10-6
H 2 O(water) 33.933 -8.4186x10-3 2.9906x10-5 -1.7825x10-8
C O2(carbon dioxide) 27.437 4.2315x10-2 -1.955x10-5 3.9968x10-9
N 2(nitrogene) 29.342 -3.5395x10-3 1.0076x10-5 -4.3116x10-9
Heat capacity calculations were made according to the a, b, c and d values taken from Table 2
for equation Cp=A+bT+cT2+dT3. The data’s were obtained from Appendix Table B.1.1 and
Appendix Table.B.1.2.. [4]

 C8H10 + 3O2 → C8H4O3 + 3H2O (Main Reaction)

∆ Cp ( molK
joule
)=∆ a+∆ bT + ∆ c T + ∆ d T 2 3

∆ Cp Mainrxn=∆ Cp products−∆ Cpreactants

∆ Cp Mainrxn ¿(∆ CpC H 8 4

O3 +3 x ∆ CpH O )−¿ +3 x ∆ CpO ¿
2 2

∆ a=∆ a products −∆ areactants

∆ a=( 40.083+3∗( 33.933 ) ) −¿

∆ a=¿ 53.122

∆ b=∆ b products −∆ b reactants

∆ b=( 3.6084 x 10 + 3∗(−8.4186 x 10 ) )−¿

−2 −3

∆ b=−0.4759 12

∆ c=∆ c products −∆ c reactants

∆ c=¿ ( 9.5956 x 10−4 +3 x ( 2.9906 x 10−5 ) ) −¿

∆ c=¿ 1.13702x10-3

7
∆ d=∆ d products −∆ d reactants

∆ d=¿ (−1.234 x 10−6+ 3 x (−1.7825 x 10−8 ) ) −¿

∆ d=¿-1.3637x10-6

∆ Cp Mainrxn= (53.122 )+ (−0.475912 ) T + ( 1.13702 x 10−3) T 2+ (−1.3637 x 10−6 ) T 3

 C8H10 + 7.5O2 → C4H2O3 + 4H2O + 4CO2 (Side Reaction)

∆ Cp ( molK
joule
)=∆ a+∆ bT + ∆ c T + ∆ d T 2 3

∆ Cp=∆ Cp products −∆ Cpreactants

∆ Cp Siderxn ¿(∆ CpC H 8 2

O3 +7.5 x ∆ CpH O )−¿ + 4 x ∆ CpH O +4 x ∆ CpO
2 2 2

∆ a=∆ a products −∆ areactants

∆ a=¿
∆ a=¿ -48.162

∆ b=∆ b products −∆ b reactants

∆ b=( 1.0423+4 x (−8.4186 x 10 ) + 4 x ( 4.2315 x 10 ) )−¿

−3 −2

∆ b=0.731

∆ c=∆ c products −∆ c reactants

∆ c=¿ (−1.8716 x 10−3 + 4 x ( 2.9906 x 10−5 ) + 4 x ( −1.955 x 10−5 ) ) −¿

∆ c=¿ -2.116x10-3

∆ d=∆ d products −∆ d reactants

∆ d=¿ ( 1.6527 x 10−6 + 4 x ( 2.9906 x 10−5 ) + 4 x ( 3.9968 x 10−9 ) )−¿

∆ d=¿ 1.43 x10-6

∆ Cp Siderxn =(−48.162)+(0.731)T + (−2.116 x 10−3 ) T 2+(1.43 x 10−6) T 3 was found.

8
3.3.2. Enthalpy and Gibbs Energy of Formation
Table 3. Thermodynamic Properties of Each Components [4]
o o
Component ∆ H f ,298 (kJ /mol) ∆ G f ,298 (kJ /mol)
C 8 H 10 ( o−xylene ) 19.0 kJ/mol 122.09 kJ/mol
C 8 H 4 O3 ( pt h alic an h ydride) -393.14 kJ/mol -329.00 kJ/mol
O2 (oxygene ) 0 0
C 4 H 2 O3 (maleic an h ydride) -398.30 kJ/mol -355.00 kJ/mol
H 2 O(water ) -241.8 kJ/mol -228.60 kJ/mol
C O2 (carbon dioxide) -393.5 kJ/mol -394.4 kJ/mol
Heat capacity calculations were made according to the enthalpy of formation and Gibb’s
energy of formation values taken from Table 3. The datas for enthalpy of formation was
obtained from Appendix Table B.2.1 and Appendix Table.B.2.2. and the datas for Gibb’s
energy of formation was obtained from Appendix Table B.3.1 and Appendix Table.B.3.2.. [4]

 C8H10 + 3O2 → C8H4O3 + 3H2O (Main Reaction)

o o o
∆ H r 1 ,298 =∆ H f , products −∆ H f ,reactants
o o o o o
∆ H r 1 ,298 =(∆ H f , C H 8 4
O3 +3∗∆ H f , H O )−(∆ H f , C H +3∗∆ H f ,O )
2 8 10 2

o
((
∆ H r 1 ,298 = −393.14
kJ
mol ) (
+ 3∗ −241.8
kJ
mol
− 19.0
kJ
mol
+3∗0 ¿−1137.54 )) ((
kJ
mol ) )
o o o
∆ Gr 1 ,298 =∆ Gf , products −∆ G f ,reactants

∆ Gro1 ,298 =( ∆ Gof , C H 8 4 O3 +3∗∆ Gof , H 2 O )−( ∆ G of ,C H

8 10
+ 3∗∆ Gof , O )
2

o
((
∆ Gr 1 ,298 = −329.0
kJ
mol ) (
+3∗ −228.60
kJ
mol
− 122.09
kJ
mol
+3∗0 = -1136.89)) ((
kJ
mol ) )
Tref is 25°C = 298K
T
+ ∫ ∆ Cpr 1 dT
o o
∆H r ,T =∆ H r 1, 298
298

∆ Cp=(53.122)+(−0.475912)T + ( 1.13702 x 10−3 ) T 2 +(−1.3637 x 10−6)T 3

(∫ ( )
T
J
53.122−0.475912 .T +1.13702 x 1 0 T −1.3637 x 10 . T ) dT J /mol . K
o −3 2 −6 3
∆ H r ,T =−1137540 +
mol 298

9
 o 2 −4 3 −7 4 J
∆ H r 1 ,T =−1137540+53.122 T −0.237956 T + 3.79 x 10 T −3.4 x 10 T
mol

o
−∆G r ,298
ln k 298=
RT
J
−(−1136890 )
mol
ln k 298= =458.87
( 8.314
J
mol . K
(298 K ) )
199
k 298=1.93 x 10

According to value of k298, we found the main reaction to be irreversible.

 C8H10 + 7.5O2 → C4H2O3 + 4H2O + 4CO2 (Side Reaction)

o o o
∆ H r 2 ,298 =∆ H f , products −∆ H f ,reactants

∆ H ro2 ,298 =(∆ H of , C H O + 4∗∆ H of , H O +4∗∆ H of , co )−(∆ H of ,C H +7.5∗∆ H of ,O )

8 4 3 2 2 8 10 2

o
((
∆ H r 2 ,298 = −398.30
kJ
mol ) (
+ 4∗ −241.8
kJ
mol
+4∗ −393.5 ) (
kJ
mol
− −19.0
kJ
mol
+7.5∗0 )) ( ( ) )
o
∆ H r 2 ,298= -2958.5 kJ/mol = -2546360 J/mol

o o o
∆ Gr 2 ,298 =∆ Gf , products −∆ G f ,reactants

∆ Gro2 ,298 =( ∆ Gof , C H 8 4 O3 + 4∗∆ Gof , H O + 4∗∆G of ,CO )−( ∆ G of , C H +7.5∗∆ G of ,O )

2 2 8 10 2

o
((
∆ Gr 2 ,298 = −355.0
kJ
mol ) (
+ 4∗ −228.60
kJ
mol
+ 4∗ −394.4 ) (
kJ
mol
− 122.09
kJ
mol
+ 7.5∗0 )) (( ) )
o
∆ Gr 2 ,298= -2969.09 kJ/mol = -2969090 J/mol

Tref is 25°C = 298K

T
+ ∫ ∆ Cpr 2 dT
o o
∆H r 2 ,T =∆ H r 2 , 298
298

∆ Cp=(−48.162)+(0.731)T + (−2.116 x 10−3 ) T 2+(1.43 x 10−6)T 3

10
 o J
∆ H r 2 ,T =−2546360 +
mol . K

(∫ ( )
T
J
−48.162+ 0.731 .T −2.116 x 10 . T +1.43 x 10 .T ) dT
−3 2 −6 3

298
mol . K

o 2 −4 3 −7 4 J
∆ H r 2 ,T =−2546360−48.162T +0.3655 T −7.053 x 10 T +3.575 x 10 T
mol

o
−∆G r ,298
ln k 298=
RT
J
−(−2969090 )
mol
ln k 298= =¿ 1198.39 According to k298, side reaction is
8.314
J
(
mol . K
(298 K ) )
irreversible.
TR T 1 ,f
F i ,0
∫ ∑ F i C p i ⅆ T +∫ ∑ Fi C pi ⅆ T +Q R=−( Δ H rxn ) γi A
X
T0 İ TR İ

TR Tf

∫ (F A 0 ¿ C PA + F B 0 C PB+ F I C PI )dT +∫ (F A ¿ C PA + F B C PB + FC C PC + F D C PD + F E C PE + F I C PI )dT + QR =−( Δ H rxn)

T0 TR

Since the multi-tubular reactor is at isothermal conditions T R = T0 = Tf = 300°C = 573K is

selected.

573 K

∫ (F A 0 ¿ C PA + F B 0 C PB + F I C PI )dT + ¿ ¿
573 K
573 K
+ ∫ (F A ¿ C PA + F B C PB + F C C PC + F D C PD + F E C PE + F F C PF + F I C PI ) dT +¿ ¿
573 K

+Q R=−( Δ H rxn ,573 K ) F A 0 X A

∆ CpC 8 H 10 =∆ Cp A =¿0.182 + 5.1344x10-1T - 2.02x10-4T2 - 2.1615x10-8T3

∆ CpO =∆ CpB = 29.526 – 8.89994x10-3T + 3.8083x10-5T2 + 3.2629x10-8T3

2

∆ CpC 8 H 4 O3 ¿ ∆ CpC = 40.083+ 3.6084x10-2T +9.5956x10-4T2 – 1.234x10-6T3

∆ Cp H O ¿ ∆ Cp D= 33.933 – 8.4186x10-3T + 2.9906 x10-5T2 – 1.7825x10-8T3

2

∆ CpC 8 H 2O 3 =∆ Cp E=¿ -72.015 + 1.0423T – 1.8716x10-3T2 + 1.6527x10-6T3

11
∆ CpCO ¿ ∆ Cp F= 27.437 + 4.2315x10-2T – 1.955x10-5T2 + 3.9968x10-9T3
2

∆ Cp N ¿ ∆ Cp I = 29.342 – 3.5395x10-3T + 1.0076x10-5T2 – 4.3116x10-9T3

2

573 K

∫ (F A 0 ¿ C PA + F B 0 C PB + F I C PI )dT =¿ ¿
573 K

573 K

∫ ¿¿
573 K

F B 0 ( 29.526 – 8.89994∗10−3 T−3.8083∗10−5 T 2+ 3.2629∗10−8 T 3 ) +¿

F I 0 ( 29.342 – 3.5395∗10−3 T +1.0076∗10−5 T 2−4.116∗10−9 T 3 ) ¿ dT

573 K

∫ (F A 0 ¿ C PA + F B 0 C PB + F I C PI )dT =¿ ¿
573 K

573 K

∫ ¿¿
573 K

( )
−1 −4 −8
5.1344∗10 ( 5732−573 2 )− 2.02∗10 ( 573 3−5733 )− 2.1615∗10 ( 5734 −5734 ) +¿
0.182 ( 573−573 ) +
2 3 4

(
−3 −5 −8
8.89994∗10 ( 5732−573 2 )− 3.8083∗10 ( 5733−5733 )− 3.2629∗10 ( 573 4−573 4 )
FB0 29.526 ( 573−573 )−
2 3 4

(29.342 ( 573−573)− 3.5395∗10 )

−3 −5 −9
FI 0 ( 5732 −5732 ) + 1.0076∗10 (573 3−5733 )− 4.116∗10 (573 4−573 4 ) ¿
2 3 4
573 K

∫ (F A 0 ¿ C PA + F B 0 C PB + F I C PI )dT =0 ¿
573 K

573 K

∫ (F A ¿ C PA + F B C PB + FC C PC + F D C PD + F E C PE + F F C PF + F I C PI )dT=¿ ¿
573 K

573 K

∫ ¿¿
573 K

F B ( 29.526 – 8.89994∗10−3 T−3.8083∗10−5 T 2 +3.2629∗10−8 T 3 ) +¿

F C ( 40.083+3.6084∗10−2 T + 9.5956∗10−4 T 2−1.234∗10−6 T 3 ) +¿

F D ( 33.933 – 8.4186∗10−3 T +2.9906∗10−5 T 2−1.7825∗10−8 T 3 ) +¿

F E (−72.015+1.0423 T −1.8716∗10−3 T 2+1.6527∗10−6 T 3 ) +¿

12
 F F ( 27.437 +4.2315∗10−2 T −1.955∗10−5 T 2 +3.9968∗10−9 T 3 ) + ¿

F I ( 29.342 – 3.5395∗10−3 T +1.0076∗10−5 T 2−4.116∗10−9 T 3 ) ¿ dT

573 K

∫ (F A ¿ C PA + F B C PB + FC C PC + F D C PD + F E C PE + F F C PF + F I C PI )dT=¿ ¿
573 K

( )
−1 −4 −8
5.1344∗10 ( 5732−573 2 )− 2.02∗10 ( 573 3−5733 )− 2.1615∗10 ( 5734 −5734 ) +¿
F A 0.182 ( 573−573 ) +
2 3 4

F (29.526 (573−573 )− 573 −573 ) )

−3 −5 −8
8.89994∗10 ( 3.8083∗10 ( 3.2629∗10 (
573 −573 )− 573 −573 )−
2 2 3 3 4 4
B
2 3 4

F (40.083 ( 573−573 ) + 573 −573 ) )+¿

−2 −4 −6
3.6084∗10 ( 9.5956∗10 ( 1.234∗10 (
573 −573 ) + 573 −573 ) −
2 2 3 3 4 4
C
2 3 4

F ( 33.933 (573−573 ) − 573 −573 ) )+

−3 −5 −8
8.4186∗10 ( 2.9906∗10 ( 1.7825∗10 (
573 −573 )− 573 −573 )−
2 2 3 3 4 4
D
2 3 4

F (−72.015 (573−573 ) + 573 −573 ))+¿

−3 −6
1.0423 ( 1.8716∗10 ( 1.6527∗10 (
573 −573 )− 573 −573 ) −
2 2 3 3 4 4
E
2 3 4

F (27.437 ( 573−573 )− 573 −573 ) )+¿

−2 −5 −9
4.2315∗10 ( 1.955∗10 ( 3.9968∗10 (
573 −573 )− 573 −573 )−
2 2 3 3 4 4
F
2 3 4

F (29.342 ( 573−573 )− (573 −573 )) ¿ d

−3 −5 −9
3.5395∗10 ( 1.0076∗10 4.116∗10
573 −573 ) +
2 2 3 3 4 4
I (573 −573 )−
2 3 4
573 K

∫ (F A ¿ C PA + F B C PB + FC C PC + F D C PD + F E C PE + F F C PF + F I C PI )dT=0 ¿
573 K

Hence the energy balance equation become,

Q R=( Δ H rxn ,573 K ) F A 0 X A

o kj
∆ H r ,298 K =−1137.54 (main reaction)
mol
o kj
∆ H r ,298 K =−2546.36 (side reaction)
mol
573 K 573 K
o
∆ H r ,573 K (Total)=∆ H 298 K +
o
∫ ∆C P+ ∆ H 298 K +
o
∫ ∆ CP
298 K 298 K

∆H kj
573 K 573K
+ ∫ ∆ CP+ ∫ ∆ CP¿
o
r ,573 K ( Total ) =¿ −1137540−254636
kmol 298 K 298K

13
∆H kj
r ,573 K ( Total ) =¿o−3683900 +¿ ¿
kmol

o kH kj
∆ H r ,573 K =(−1152718.07−2952981.247 ) =−4105699.31
kmol kmol

Since the reactor is non-adiabatic,

kmol
∗0.1∗1 h
kJ h
Q R=( Δ H rxn ,573 K ) F A 0 X A =−4105699.31 ∗791.25
kmol 3600 s
Q R=−90239.8495 kJ / s ≅ −90240 kW

Q=U∗A∗Δ T LM

Δ T LM =¿ ¿

Δ T LM =−21.64 °C = -21.64 K ≈ -22 K

kw
U =50 2
is selected .
m .K
3
Q −90.24∗10 2
A= = =81.8 m
U∗Δ T LM 50∗(−22)

This is the minimum area needed to keep our reactor isothermal.

3
V reactor =50 m

Radius of the tubes is selected 1 ¼ inch , 11 BWG from TEMA , See Appendix Figure.B.5.1.
[10]

r = 0.01287 m

According to POLYMATH program calculation our reactor length should be 10m (at which,
the desired conversion achieved) (See Appendix Table.C.5.1)

2 2 −3 3
V Tube=π r L=π ¿ 0.01287 ∗10=5.2036 10 m
V reactor 50
Tube number = n = = =9 608.73 ≅ 9 610 tube
V Tube 5.2036 10−3

3.4. Pressure Drop

Ergun Equation is,

14
 2 2
∆P μ (1−ε ) u 0 (1−ε ) ρu0
=150 3 2
+1.75 3 . [5]
L ε dp ε dp

Where, ∆ P is the pressure drop, L is the length of the bed, μ is the fluid viscosity, ε is the
void fraction of the packing, u0 is the fluid superficial velocity, d p is the particle diameter and
ρ is the density of the fluid.

Air physical properties are considered because air represent 99% (by mole) of the system.

According to Appendix Figure.B.4.1.[6] the density of air is ρair =3.6 Kg /m3

( )
F A0 1
u0 = ∗99∗Mw∗
n ρ∗A s

2
A s=π r

( )
F A0 1
u0 = ∗99∗Mw∗
n ρ∗π r 2

( )
3
kmole 28.96 kg 1m
∗99∗ ∗( 2
)∗1 h
791.25 h 1 kmol 3.6 kg∗π∗( 0.012827 m )
u0 =
9 610 3600 s

m
u0 ≅ 35.24
s

According to Appendix Figure.B.4.2.[7] the dynamic viscosity of air is μair =3∗10−5 Pa . s

∆ P=L¿ )

∆ P=( 10 m ) ¿]

∆ P=195.848 Pa ≅ 0.193 atm

3.5. Cost Calculations

3.5.1. Cost of the Reactor

The purchased cost ($) of the 8000 m2 shell-and-tube reactor is read as 1.6 x 10 6 $ from
Appendix Figure.C.1.1.. Since Appendix Figure.C.1.1. values belong to 2002, CEPCI method
15
was applied to reach up-to-date data. Chemical Engineering Plant Cost Index (CEPCI) is
given Appendix Figure.C.4.1.

Index Value at Present (2022)

Purc h ased Cost =Original Cost ×
Index Valueat Original Cost was obtained(2002)

6 816
Purchased Cost =1.6 x 10 $ × =3 300 300 $
395.6
𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒𝑑 𝐸𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡 𝐶𝑜𝑠𝑡= 3 300 300 $
[8]
Direct cost for installation, from the Appendix Table.C.4.1. purchased epuipment cost
range is 25-55%. To found the installation cost, 30% is selected .

𝐼𝑛𝑠𝑡𝑎𝑙𝑙𝑎𝑡𝑖𝑜𝑛 𝐶𝑜𝑠𝑡 = 30% × 𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒𝑑 𝐸𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡 𝐶𝑜𝑠𝑡 = 3 300 300 $∗0.3=¿990 090 $
The value 10% is selected from the Appendix Table.C.4.1. [8]

𝑆𝑎𝑓𝑒𝑡𝑦 𝑃𝑟𝑒𝑐𝑎𝑢𝑡𝑖𝑜𝑛𝑠 𝑎𝑛𝑑 𝐸𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡𝑠 = 10% × 𝑃𝑢𝑟𝑐ℎ𝑎𝑠𝑒𝑑 𝐸𝑞𝑢𝑖𝑝𝑚𝑒𝑛𝑡 𝐶𝑜𝑠𝑡 =

3 300 300 $∗0.1 = 330 030 $

𝑇𝑜𝑡𝑎𝑙 𝐶𝑜𝑠𝑡 𝑜𝑓 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 = 4 620 450 $

3.5.2.Cost of Catalyst
mcatalyst =60 000 kg was found in the Section 3.2.
[9]
Cost of V2O5 catalyst per kg = $20.00/kg (170 kg drums) From Tianjin,China, Hebei
Ruisite Technology at 13.12.2023.

$ 20.00
×60 000 kg catalyst=$ 1,200,000.0
kg
Purchased Cost of Catalyst =$ 1,200,000.0

3.5.3. Utility Cost

Q=mMolten salt∗C P∗∆T =¿ −90239.8495 kJ / s = 90239849.5 J/s

Cp = 5806 – 10.833.T + 7.241 x 10-3 .T2 in the temperature range 426-776 K with an
uncertainty ± 5 %. (J/kg.K) [18]

T 1=260 ° C ,T 2=290 ° C so ∆ T =−30 K

Tmean = (260+290)/2 = 275 °C = 548 K

16
-90239849.5 J/s = ṁ Molten salt x (5806 – 10.833 (548) + 7.241 x 10-3 x (548)2 ) x (-30K)
ṁ Molten salt = (-90 240 kJ/s ) / (- 30 K x 2044.02 kJ/kg.K )

ṁ Molten salt =¿ 1.472 kg/s

Cost of Molten Salt = 40 $/1 drum , 1 drum is 50 kg. [17] From Shanghai, China, Nanjing
Kerun at 13.12.2023.

1.472 kg 8000 h 3600 s 40 $ 1 drum

x x x x ≅ 34 000 000 $ / year
s 1 year h 1 drum 50 kg

3.5.4.Valve Cost
In our design , it used two check valve. Check valve cost is $135 from Appendix
Figure.C.2.1.

( $135 /1 check valve )* 2 check valve= $ 270 for 2 check valve at 2002.

IndexValue at Present (2022)

Valve Purchased Cost =Original Cost ×
Index Value at Original Cost was obtained (2002)

816
Purchased Cost of Valve=$ 270× =$ 557
395.6

3.5.5. Total Annual Cost

Purchased Equipment Cost of Reactor = 3,300,300 $
𝑇𝑜𝑡𝑎𝑙 𝐶𝑜𝑠𝑡 𝑜𝑓 𝑅𝑒𝑎𝑐𝑡𝑜𝑟 = 4,620,450 $
Utility Cost = 33 914 880 $ / year
Purchased Cost of Catalyst =1,200,000.0 $
Purchased Cost of Valve=557 $
Depretiation is selected as 10 year
1,200,000.0 $+ 4,620,450 $ +557 $ $ $
Total Annual Cost= +33 914 880 ≅ 34 500 000
10 yrear year year

17
 4. RESULTS AND DISCUSSION
Before starting to write the report, it is necessary to divide the main task and sub-tasks of the
report. This preliminary preparation ensures the tracking of tasks at designated times by
designated individuals. Responsible individuals actively participate in task management and
provide necessary guidance to other team members at designated time intervals. Once
responsible individuals are identified, potential risks associated with performing tasks are
determined. Solutions to these risks are developed so that tasks can be successfully
completed. For the production of phthalic anhydride, the main tasks in reactor design include
reaction research, reactor design, cost estimation, preparation for presentation, and report
writing and editing. For this report, the project management and risk assessment table is
provided below in Table 4.

18
Table 4. Project Management and Risk Assessment

The process of locating possible risks and estimating the consequences in the event that a risk
materializes is known as risk assessment. The potential hazards associated with the reactor
utilized in this design are assessed, and the following table outlines the safety measures that
should be implemented. The risk assessment table is given Table 5.

Table 5. Risk Assessment

OPERATIONAL RISK PRECAUTIONS

1 Thermal Runaway Explosion disc and safety valves should be

used

19
 2 Pressure Rise Due To Sudden Safety valves must be opened to relieve
Release Of Energy pressure, explosion disk vents must be
open to the atmosphere
3 Channeling Catalyst must be evenly distributed

4 Deactivation Of Catalyst Due To Feed should be purificated as much as

Poisoning possible
5 Catalyst Life Reduction Periodically regeneration of catalyst

6 Flammability Explosions may occur if the flammability

limit, which should be considered in air-
based processes, is exceeded. For this
reason, care should be taken to stay below
this limit during the design process.

The heart of a process is the reactor. For this reason, the design must be made carefully.The
complex problem of this design was to convert o-xylene at 5 bar 300°C to phthalic anhydride
with a flow rate of 70.000 metric tons/year over a vanadium pentoxide catalyst safely at
minimum cost. Additionaly, reaction mixture is lower explosive limit of 1 mol% of o-xylene
in air. In this direction, a literature search was conducted for optimum reactor design.It was
observed that there was one main reaction and one undesired reactions in the phthalic
anhydride formation reaction from o-xylene. Reaction is total oxidation and reactions and
occur in parallel. In reaction number, consecutive oxidation occurs. Since most of the total
CO2 and H2O comes from o-xylene because the rate value of the reaction number is much
smaller than the other reactions. The K value of the reaction at the reference temperature
(298K) was calculated as 1.93∗10199. Since the K value was much higher than 1 and the
reaction was a combustion reaction, it was found to be irreversible. Also, this reaction is a
catalytic oxidation and it occurs with solid V 2O5 catalyst so this reaction takes place in a
heterogenous environment.

Main reaction: C 8 H 10 +3 O2 → C 8 H 4 O3 +3 H 2 O

o-xylene PA

Side reaction : C 8 H 10 +7.5 O2 → C 4 H 2 O3 +4 H 2 O+ 4 C O2

maleic anhydride

20
Catalyst research, which has a critical importance in determining working conditions, was
started. Supported catalysts were found suitable because the chemical and physical properties
of the support greatly affect catalysts activity and selectivity. Accordingly, low surface area
supports such as V2O5 can be used as they provide high activity by minimizing side reactions
and support phthalic anhydride selectivity. It exhibits multiple oxidation states and forms
unstable intermediates with the reactants which readily change into products. V2O5 is not a
negative catalyst.It increases rate of reaction.So it is a positive catalyst. The catalyst was
diameter of l/2 inch spherical. Also particle density and bulk density values of catalyst are
2400 kg/m3 and 1350 kg/m3 respectively. The pressure range for the high-pressure vapor
phase oxidation of lower aliphatic hydrocarbons using vanadium oxide catalysts is from about
5 to 10 bars. Afterwards, the optimum operating temperature under a 400°C as a result of
literature research.In this direction, 5 bar and 300 ̊C as an initial temperature were found
appropriate as working conditions. Catalyst life is between 5-10 years. Void fraction is
0.4375. Conversion and selectivity values were chosen as 10% and 80%, respectively.
Catalyst equipment summary table is shown in the Table 6. [11]

Table 6. Catalyst Equipment Summary Table

Catalyst
Working Temperature Sinters above a temperature of 400°C
Working Pressure 5-10 bars
Void Fraction 0.5
Catalyst Shape Spherical
Catalyst Service Life 10 year
Selectivity 0.8
Diameter 1/2 inches
Bulk Density 1350 kg/m3
Conversion 0.1

Non-adaibatic and isothermal conditions were preferred for this system.Isothermal conditions
are preferred when the reactions are exothermic, as in the case of phthalic anhydride
production from the oxidation of o-xylene. In an isothermal reactor, the temperature is
maintained constant by efficient heat removal mechanisms, such as cooling coils or tubes.
This allows for better temperature control and minimizes the risk of hot spot formation, which

21
is crucial for safety and product quality.Isothermal conditions also help prevent thermal
runaway, a dangerous situation where the reaction becomes self-sustaining due to the heat
generated. In the case of phthalic anhydride production from o-xylene oxidation, isothermal
conditions are recommended due to the highly exothermic nature of the reactions. This
approach ensures better temperature control, prevents thermal runaway, and promotes safety
and product quality. Reactor equipment summary table shown in the Table 7. [12,13,14]

Table 7. Reactor Equipment Summary Table

Reactor

Material Stainless Steel 304

Insulation (Isothermal)

Catalyst V2O5

D 4.8 m

L 10 m

D/L 0.48

Tube Number 9610

Inlet Temperature 300 °C

Outlet Temperature 300°C

An adiabatic reactor is not used in the production of phthalic anhydride from o-xylene.
Instead, a non-adiabatic reactor is employed. The formation of phthalic anhydride is favored
by the use of a vanadium catalyst, V 2O5, which sinters above 400°C. As a result, the reactor
operates in the chemical regime, and the use of a non-adiabatic reactor allows for efficient
heat management and pressure control during the oxidation process. The non-adiabatic reactor
helps to maintain the desired temperature and pressure conditions for the reaction to occur
efficiently, and it is a major part of the design for the production of phthalic anhydride from
o-xylene.[15]

The choice of reactor type is very important in reactor design. Because every reaction has its
own conditions and if these conditions and needs of the reaction are not observed, the reaction
will not take place. CSTR, PFR and Batch reactors were investigated in determining the
reactor type to be used. CSTR was abandoned due to continuous mixing and batch reactor
was abandoned due to mixing and pressure condition wasn’t suitable (not suitable for

22
operation at high pressures). For irreversible reactions in series the mixing of fluid of different
composition is the key to the formation of intermediate. In PFR, the maximum possible
amount of any and all intermediates is obtained and fluids of different compositions and at
different stages of conversion are not allowed to mix. So PFR is suitable for the production of
phthalic anhydride. Reactor type selected as Multi-tubular fixed bed reactor. Industrial
packed-bed catalytic reactors range in size from small tubes, a few centimetres diameter, to
large diameter packed beds. Packed-bed reactors are used for gas and gas-liquid reactions.
Heat-transfer rates in large diameter packed beds are poor and where high heat-transfer rates
[16]
are required fluidized beds should be considered.(Appendix Heuristic.A.1.) Reactor
specification sheet table is shown in the Table 8.

Table 8. Reactor Specification Sheet

REACTOR

Identification: Item: Multitubular Fixed Bed Reactor Date 14.12.2023

Item No. R-1
No required:1
Function: Oxidation of o-xylene for production of phthalic anhydride.
Operation: Continuous
Operation Type: Non-adiabatic, Isothermal
Type: PFR,Fixed Bed
Conversion(XA1): 0.08
Conversion(XA2): 0.02
Operating Conditions:
Pressure: 1 atm Reactor Volume: 50 m3
Temperature: inlet : 260 °C Cross Sectional Area: 81.8 m2
outlet: 290 °C Tube Diameter : 0.01287 m
Diameter: 4.8 m
Length : 10 m
Reactor Inlet (kmol/h) Reactor Outlet (kmol/h)
O-xylene: 791.18 kmol/h O-xylene: 712.06 kmol/h
Oxygen: 16,448.65 kmol/h Oxygen: 16,237.3 kmol/h
Nitrogen: 61,878.28 kmol/h Nitrogen: 61,878.28 kmol/h
Phthalic Anhydride: 63.29 kmol/h

23
 Maleic Anhydridride: 15.82 kmol/h
Carbon Dioxide: 63.29 kmol/h
Water: 253.18 kmol/h
Pressure drops (tube) 0.193 atm

The molten salt as a utility, will absorb the heat released from the reaction.

Table 9. Utility Specification Sheet

UTILITY

Identification: Item: Molten Salt Date 14.12.2023

Function: To cooling the o-xylene whose temperature has increased

Operation: Continuous
Content : 53%KNO3 - 40%NaNO2 - 7% NaNO3
Temperature : inlet : 260 °C
outlet :290 °C
Flow Rate : 1.5 kg/s
Pressure : 1 atm

Figure 2. Flow Sheet for Multi-tubular Fixed Bed Reactor

24
Flow sheet of multi-tubular fixed bed reactor is shown in the Figure 2. And After the
calculations values are given in the Table 10. as flow summary table.

Table 10. Flow Summary Table for Multi-tubular Fixed Bed Reactor

Stream 1 2 3 4
Component O-xylene O-xylene O-xylene O-xylene
P (bar) 5 5 4.98 4.98
T (° C) 300 300 300 300
Phase Gas Gas Gas Gas
FA (kmol/h) 791.18 791.18 712.06 712.06
FB (kmol/h) 16 448.65 16 448.65 16 237.3 16 237.3
FC (kmol/h) 0 0 63.29 63.29
FD (kmol/h) 0 0 253.18 253.18
FE (kmol/h) 0 0 15.82 15.82
FF (kmol/h) 0 0 63.29 63.29
FI (kmol/h) 61 878.28 61 878.28 61 878.28 61 878.28
Vapor Fraction 1 1 1 1

Firstly, a material balance was formulated based on two rate equations due to the presence of
a side reaction. Subsequently, two rate equations were derived using the partial pressures
obtained from the material balance. The reactor volume was then calculated using the
selectivity, the exit flow of phthalic anhydride, and the initial and final flow rates determined
by considering the lower explosive limit.

The rate expressions given above were arranged in XA for the two reactions.

25
For the Plug Flow Reactor (PFR), the design equation was employed, and after substituting
the necessary values, the volume was determined to be 50 m 3 using the Simpson method for
integration.Following this, a void fraction of 0.5 was calculated, leading to an approximate
catalyst volume of 25 m3.

Before the calculation, ΔH values were taken from the literature. At the reference temperature
of 298 K, this value was taken as -1137.54 kJ/mol for the main reaction and -2958.5 kJ/mol
for the side reaction. Then the K value was calculated as 1.93∗10199. The heat value was
reached by establishing an energy balance with heat capacity and enthalpy values. For Q, the
value of -90239.8495 kW was reached. Then, assuming U= 50 kW/(m 2.K), the heat transfer
area was approximately found to be 82 m 2. By using heat transfer area, the number of tubes
was reached to 9610. Since a multi-bular fixed bed is used, we have solid catalysts for our
pipes and these catalysts cause pressure drops inside the tubes. Since it is known that all
molecules in the reactor are in the gas phase, Ergun Equation was deemed appropriate. In
addition, since it is known that 99% of the gas in the reactor is air, velocity and viscosity
values were taken relative to air. At the end of the Ergun equation, the pressure drop reached
0.193 atm.

26
The length and conversion values to be obtained for desired and undesired materials have
been entered in differential and explicit equations on POLYMATH. These equations are given
in Figure 3. The results of the entered equations are also given in Table 11.

Figure 3. Polymath Equations

27
Table 11. Polymath Equations Results

Graph 1. (XA1-XA2-XA) vs. z Graph

28
The D/L ratio was chosen as 0.48. It was considered appropriate diameter value 4.8 should be
m and the length value 10 m. Accordingly, the conversion values corresponding to 10 m in
the graph were read as 0.08 for X A1 and 0.02 for XA2. Graph 1. shows the conversion through
the reactor.

Graph 2. P vs. Z Graph

Graph 2. shows the outlet pressure through the reactor for different length.

Graph 3. DP vs. z Graph

Graph 3. was drawn by entering the Ergun equation into Polymath. Graph 3. shows pressure
drop for different reactor length.

29
 a)

b)

Graph 4. FA0/ra vs. Xa1

Using Graph 4. , it can be find the volume of the reactor represented by the area under the
graph.The a) graph, Xa1 between 0 and 1, shows the transformation if we choose a larger
reactor, while the other one shows the transformation of our current reactor. If the FA0/ra to
XA1 graph is enlarged, Graph 5. is obtained.

Graph 5. FA0/ra vs. Xa1 , Enlarged Version

30
The certain tube diameter was taken from TEMA Standart (Appendix Figure. B.5.1 ) [10]
in
order to defined the pipe diameter that suit our reactor condition also
considering void fraction.

The ratio of reactor length to diameter was determined as 2.083. The length and diameter of
the reactors were calculated from the volumes of the reactors calculated using this ratio.
Pressure drops were calculated as a result of the Ergun equation using different flow rates for
the reactor. The pressure drops are in the expected dimensions and do not pose a problem for
the system.

The cost was calculated by moving from the volume of the catalyst to the mass of the catalyst.
The purchasing costs of the reactors were read from the graph and brought to today's values
using the CEPCI method. Safety measures costs of 10 percent of the purchase cost and
installation costs of 30 percent are foreseen. As a result, the total cost of the reactor is about
$4.65x105/year thousand. A risk assessment table has been created for the risks foreseen for
this system and the measures developed against the risks. The following pie charts were
created over all the calculated cost values.

Chart 1. Pie Chart of Cost of Reactor

A large part of the cost of reactors is the purchase cost.

31
 Chart 2. Pie Chart of Total Cost of Design
When the cost of the whole system was examined, it was seen that catalyst was the equipment
with the highest cost. The reason for this is the, is expensive due to Small particle size,
complex synthesis process, high purity reasons.

32
 5. CONCLUSION
The report took into account the main chemical reaction and side reaction for production of
phthalic anhydride from oxidation of o-xylene over the vanadium penta-oxide catalyst, and
the mass and heat transfer phenomena in both tube side and shell side of the reactor.

Before designing the reactor, we started by investigating the physical and chemical properties
of o-xylene and air. There was a very important limiting factor here. This factor lower
explosion limit of oxylene/ air 1%mole. Concentrations below the LEL are too rare and there
is not enough of the explosive gas. Above the explosive zone, the gas concentration is so high
that there is not enough oxygen to provide flammability, so an explosion will not occur. The
upper limit of the explosive range is defined as UEL (Upper Explosive Limit). Explosion
occurs in the concentration range between LEL and UEL levels. For this reason, this issue
should be taken into consideration when feeding air and o-xylene.

It was decided that 0.1 conversion and 80½selectivity of phthalic anhydride, one of the
products resulting from the main and side reactions, was desired and calculations were made
on the reaction kinetics and catalyst.

As a result of the calculations, the conditions of the reaction were decided. (non-adiabatic,
Inlet and outlet temperature is 300°C since the reaction is isothermal, 5 bar) Material balance
and energy balance equations were made and calculate by hand-calculations for the
isothermal and non-adiabatic reactor. Overall heat transfer coefficients 50 kw/m 2.K were
chosen to calculate area and volume calculations. Above these, the area was found to be
approximately 82 m2, and the reactor volume was 50 m 3. Depending on the type of reactor
(shell-and-tube, multi-tubular fixed bed), material (stainless steel 304), number of tubes for
the tube through which the catalyst and gas mixture will pass (9610 tubes), inside diameter
(11 BWG 1¼ inch) and tube length (It was decided as 10 m).

Since the reactor is non-adiabatic, molten salt is used to absorb the released heat. molten salt
at a flow rate of 1471.6 kg/s. As the catalyst passed through the tube, a pressure drop
occurred. The Ergun equation was used to calculate the pressure drop inside the catalyst bed
with r =0.01287 m. And the pressure drop in a column was calculated to be 0.193 atm.

Equations were made and calculated by hand-calculations for the isothermal and non-
adiabatic multi-tubular fixed bed reactor. Also equations were put in the POLYMATH. Good

33
agreement of phthalic anhydride conversion was achieved between the data of the
POLYMATH model and the hand-calculations.

After all calculations, cost of reactor is found as $4.62x105/year, cost of catalyst is found as
$1.2x106/year, and $3.4x107/year as the utility cost. These details offer a concise overview of
the reactor system and utility components, outlining key design considerations and associated
costs.

The high mass flow rate of Molten Salt seriously affects the cost of Molten Salt. Since
Q=m.Cp.∆ T, Q and Cp values will not change, if the difference between the inlet and outlet
of the molten salt increases, that is, if the molten salt exits by heating much more at the inlet
temperature, the mass flow rate decreases. This directly affects the molten salt cost. However,
if the DeltaT values were changed, the entire calculation would have to be changed. Since this
will not be delivered within the delivery date, this error has been stated and left as is.

34
 6. REFERENCES
[1] Park, C.-M. and Sheehan, R.J. (2000). Phthalic Acids and Other Benzenepolycarboxylic
Acids. In Kirk-Othmer Encyclopedia of Chemical Technology, (Ed.).
Retrieved December 02,2023 from

https://doi.org/10.1002/0471238961.1608200816011811.a01

[2] Krist V. Gernaey, Jakob K. Huusom and Rafiqul Gani (Eds.), 12th International
Symposium on Process Systems Engineering and 25th European Symposium on Computer
Aided Process Engineering. 31 May – 4 June 2015, Copenhagen, Denmark ,2015 Elsevier
B.V.

[3] Data Bridge Market Research. (2022, August) . Global phthalic anhydride market –
ındustry trends and forecast to 2029. Retrieved December 05,2023 from

https://www.databridgemarketresearch.com/reports/global-phthalic-anhydride-
market#:~:text=The%20demand%20for%20phthalic%20anhydride,corrosion%2C
%20abrasion%2C%20and%20impact.

[4] Yaws, C.L., “Chemical Properties Handbook: Physical, Thermodynamic, Environmental,

Transport, Safety, and Health Related Properties for Organic and Inorganic
Chemicals”, .McGraw-Hill, 1995.

[5] Ruya, P. M., Susanto, H., & Purwasasmita, M. (2018). “Experimental study on pressure
drop and flow dispersion in packed bed of natural zeolite”. In MATEC Web of
Conferences (Vol. 156, p. 02006). EDP Sciences.

[6] The Engineering Toolbox (n.d.). Air - density vs. pressure and temperatures. .
Retrieved December 06,2023 from

https://www.engineeringtoolbox.com/air-temperature-pressure-density
d_771.html#google_vignette

[7] The Engineering Toolbox (n.d.). Air - dynamic and kinematic viscosity

Retrieved December 06,2023 from

35
 https://www.engineeringtoolbox.com/air-absolute-kinematic-viscosity-d_601.html?
vA=300&units=C#
[8] Peters, M.,S.; Timmerhaus, K.,D; West, R.,E, “Plant Design and Economics for Chemical
Engineers”, Fifth Edition.

[9] Factory 170kg Packing V2o5 Vanadium -- Pentoxide Powder/Flake for Catalyst with CAS
1314-- 62-- 1. (n.d.). [Video]. Made-in-China.com.
https://rst-tech.en.made-in-china.com/product/jFPaDXkywcUd/China-Factory-170kg-
Packing-V2o5-Vanadium-Pentoxide-Powder-Flake-for-Catalyst-with-CAS-1314-62-1.html
[10] Standards of the Tubular Exchanger Manufacturers Association. (2007). Tubular
Exchanger Manufacturers Association. Inc., Tarrytown (TEMA), New York.
[11] European Patent Office. (2007). European patent specifications (Special edition No. 3).
Retrieved from

https://data.epo.org/publication-server/document?iDocId=2247&iFormat=2

[12] Anastasov, A. I. (2002). A study of the influence of the operating parameters on the
temperature of the hot spot in a fixed bed reactor. Chemical Engineering Journal, 86(3), 287-
297.

[13] Froment, G. F. (1972). Analysis and design of fixed bed catalytic reactors.

[14] Nandi, S. (2012). Modeling and Simulation of Phthalic Anhydride Production in a

Structured Metallic Monolith Reactor. Procedia engineering, 38, 1286-1290.

[15] Phthalic Anhydride Study of a Production Process from o-Xylene Oxidation D. W.

Ateajeu1 , Z. Deckers1 , F. Henin1 , M. Hennuy1 , J. Kalbusch1 , E. Latour1 and M-L.
Weyders1 1 Authors have equally contributed to this work. 1 University of Liège - Master
degree of Science in Chemical and Materials Engineering

[16] Sinnot,R.,K. (2005). Chemical Engineering Design (4th edition). Oxford: Coulson &
Richardsons

[17] Molten Salt Quenchant for heat treatment Kr1129. (n.d.). Made-in-China.com.
https://kerunchem.en.made-in-china.com/product/jNdTKRMEwOpZ/China-Molten-Salt-
Quenchant-for-Heat-Treatment-Kr1129.html

[18] Manohar S. Sohal, Matthias A. Ebner, Piyush Sabhar. Engineering Database of Liquid
Salt Thermophysical 2013. doi:10.2172/1086824.

36
 7. APPENDIX
Appendix.A. Heuristic and Phase Diagram

Table.A.1. O-Xylene Phase Diagram (ChemCAD)

37
 Heuristic.A.1. Heuristics for Reactors [8]

Appendix.B.Calculations
Appendix.B.1. Heat Capacity of Gas

Table.B.1.1. Heat Capacity of Gas – Organic Compounds [4]

Table.B.1.2. Heat Capacity of Gas – Inorganic Compounds [4]

38
Appendix.B.2. Enthalpy of Formation of Gas

Table.B.2.1. Enthalpy of Formation of Gas – Organic Compounds [4]

Table.B.2.2. Enthalpy of Formation of Gas – Organic Compounds [4]

39
Appendix.B.3. Gibb’s Energy of Formation of Gas

Table.B.3.1. Gibb’s Energy of Formation of Gas – Organic Compounds [4]

Table.B.3.2. Gibb’s and Helmholtz Energy of Formation of Gas – Inorganic Compounds

[4]

40
Appendix.B.4.Pressure Drop

Figure.B.4.1. Air Density at Varying Pressure and Temperature [Air - Density vs. Pressure
and Temperatures. (n.d.). [6]

Figure.B.4.2. Air Dynamic Viscosity at Varying Temperature and Constant Pressure [ Air -
dynamic and kinematic viscosity. (n.d.). [7]

41
Appendix.B.5. TEMA Standards

Figure. B.5.1. Tema Standard for Characteristics of Tubing

Appendix.C.Cost Estimation

Appendix.C.1. Cost Estimation of Reactor

42
Figure.C.1.1. Purchased Cost of Reactors (Shell-and-Tube) [8]

Appendix.C.2. Cost Estimation of Valve

Figure C.2.1. Purchased cost of screwed valves for water, oil, and gas [8]

Appendix.C.3. Estimation of Capital Investment Cost

Table.C.3.1. Estimation of Capital Investment Cost (showing individual components) [8]

43
44
Appendix.C.4. Chemical Engineering Plant Cost Index (CEPCI)

Figure.C.4.1. Chemical Engineering Plant Cost Index (CEPCI), October 2023

45
Appendix.C.5. POLYMATH RESULTS

Table.C.5.1. Polymath Results for z-XA1-XA2

46