Sultan Qaboos University

College of Engineering
PCE Department
Chemical Reaction Engineering

PBR Design for Phthalic

Anhydride Production

Ahmed Hamed Al-Qasmi

88805

Abdullah Ghusen Al-Abri

89672

Abdullah Mohammed Al-Kharosi 90033

Abstract
These papers illustrate a reactor design to produce Phthalic anhydride (PAN) in
continuous plant through the oxidation of o-xylene. Maleic anhydride is also obtained
as by-product in this process. Pressure drop, side reactions and maintaining a
relatively constant driving force for heat transfer are considered in this design. The
production of phthalic anhydride is approximately 20,000 tons/year as required. The
process was simulated using the process simulator Aspen plus.

Table of Contents
Abstract ................................................................................................................................. I
Table of Contents .................................................................................................................. II
List of Tables ....................................................................................................................... III
List of figures ....................................................................................................................... IV
Introduction .......................................................................................................................... 1
Uses .................................................................................................................................. 1
Manufacturing company .................................................................................................... 2
The feed stock ................................................................................................................... 2
Process description ............................................................................................................ 3
Reactions path way............................................................................................................ 3
Type of reactors ................................................................................................................ 4
Catalyst ............................................................................................................................. 5
Kinetics ............................................................................................................................. 6
First Design: Reactor Volume Using Simple Reaction Rate Expression .................................... 7
Mass balance: .................................................................................................................... 8
Calculating the volume ...................................................................................................... 8
The simulation .................................................................................................................. 9
Second Design: Pressure Drop and Reactor Configuration .................................................... 11
Splitting the Reactor into Tubes ....................................................................................... 13
Tube Length effect .......................................................................................................... 13
Particle Diameter effect ................................................................................................... 14
The simulation ................................................................................................................ 16
Third Design: Multiple Reactions ........................................................................................ 18
Plot Flow ........................................................................................................................ 19
Effect of Temperature in Selectivity ................................................................................ 20
Aspen simulation............................................................................................................. 21
Final Design: Energy Balance............................................................................................. 23
Temperature profile ......................................................................................................... 23
Dynamic stability ............................................................................................................ 24
Aspen Simulation ................................................................................................................ 25
Economic analysis............................................................................................................... 30
Design summary.................................................................................................................. 31
Conclusion .......................................................................................................................... 31
II

References........................................................................................................................... 32
Appendix ............................................................................................................................. 33

List of Tables
Table 1: Component Price ..................................................................................................... 2
Table 2: Fixed-Bed. vs. Fluidized-Bed Reactors for Selective Hydrocarbon Oxidation
Reactions .............................................................................................................................. 4
Table 3:Catalyst Properties and Behavior in o-Xylene Oxidation .......................................... 5
Table 4: Mass Balance Results .............................................................................................. 8
Table 5:Polymath design results ............................................................................................ 8
Table 6: Heat and material balance ...................................................................................... 9
Table 7: Design Results without Sipliting to Tube ................................................................ 11
Table 8: Heat and material balance .................................................................................... 16
Table 9: Heat and material balance .................................................................................... 17
Table 10: Third Design Results ........................................................................................... 19
Table 11: Heat and Material Results in Aspen Plus ............................................................. 21
Table 12: Components Properties ....................................................................................... 23
Table 13: Gain Calculation ................................................................................................. 24
Table 14: Gain Calculation after Modification .................................................................... 25
Table15 :Aspen Results ....................................................................................................... 29
Table 16: Total Cost Results................................................................................................ 30
Table 17: Reactor Configurations ....................................................................................... 31
Table 18: Feed Rates........................................................................................................... 31
Table 19: Products Rates .................................................................................................... 31
Table 20 : Coolant Specification ......................................................................................... 31

III

List of figures

Figure 1: Major uses of phthalic anhydride[1] ...................................................................... 1

Figure 2: Major product chain of phthalic anhydride ............................................................ 2
Figure 3: Reactions Pathway ................................................................................................ 4
Figure 4:Effect of temperature in the conversion ................................................................... 9
Figure5 : Aspen Reactor Model............................................................................................. 9
Figure6 : conversion versus heat duty ................................................................................. 10
Figure 7:Effect of temperature in the conversion ................................................................. 12
Figure 8:Effect of Pressure Drop in the conversion at Different Temprature ....................... 12
Figure 9:The effect of number of tubes in the pressure drop ................................................ 13
Figure 10:Effect of Tube Length in Pressure Drop. ............................................................. 14
Figure 11: Comparing two paticle diameters effect in pressure drop. .................................. 14
Figure 12: Final design results............................................................................................ 15
Figure 13: Shows the Catalyst Weight Effects in Pressure Drop and Conversion ................. 15
Figure 14: Molar flow rate of each component versus the catalyst weight............................ 19
Figure 15: Selectivity of Phthalic Anhydride at Different Temperature ................................ 20
Figure 16: Selectivity of Phthalic Anhydride at Different Temperature ................................ 20
Figure 17: Molar Flow of each Component with Reactor Length obtained from Aspen ........ 22
Figure 18: Temperature Profile........................................................................................... 23
Figure 19:Coolant Temperature Profile .............................................................................. 24
Figure 20: Reactor and Coolant Temperature Profiles ........................................................ 24
Figure 21:Aspen Flowsheet ................................................................................................. 25
Figure 22 : Model Type ....................................................................................................... 26
Figure 23 : Design Dimensions ........................................................................................... 26
Figure 24: Pressure Drop Calculation ................................................................................ 27
Figure 25: Catalyst specification......................................................................................... 27
Figure26 : Reactions in Aspen............................................................................................. 28
Figure 27: Kinetics Specification ........................................................................................ 28
Figure28 : Temperature Profile........................................................................................... 29

IV

Introduction
Phthalic anhydride (PAN) is an organic compound with the formula C6H4(CO)2O. It is
the anhydride of phthalic acid. This colorless solid is an important industrial chemical.
It is one of the most important products of modem large-scale organic synthesis, and
it has a wide application in various branches of chemical industry.

Uses
PAN is an intermediate petrochemical used for the production of plasticizers
especially for polyvinylchloride (PVC), unsaturated Polyesters, dyes and alkyd resins
which are used in the manufacture of reinforced plastics and in specialized
applications such as surface coatings. It is trade in either molten form or as a white
powder. About 50% of all phthalic anhydride produced is used in the manufacture of
plasticizers for PVC processing. Unsaturated polyester resins are uses (15-20) % of all
PAN produced and (10-15) % used in alkyd resins.[1]

Figure 1: Major uses of phthalic anhydride[1]

The figure below shows the major product chain of phthalic anhydride in chemical
industry.

Figure 2: Major product chain of phthalic anhydride

Manufacturing company
PAN is currently produced in many region of the world. In Australia one company
has two plants were built in 1960s and use naphthalene as the feed. Several large
producers of PAN operate in Japan, Korea, and Taiwan. The major company that
produce PAN are NCP coatings inc , Arkema inc, Esco company and Durcon inc .
In 2006, the worldwide production of PAN has slowly increased with production
approaching the estimated capacity of 3,600,000 tones/year.[2]
The selling price has varied due fluctuating demands and production rates but is
currently around $(850-950)/ton with purity of 99.5%.[3]
The feed stock
PAN is produced from o-xylene feedstock or naphthalene. In 1896 the feed stock for
the liquid phase oxidation was naphthalene. In the United State and Germany they try
to come up with process to oxide naphthalene using vapor phase and they success in
1930.The shortage of naphthalene with availability of o-xylene the company forced to
use it. Since the 1960s o-xylene has replaced naphthalene as feedstock more and
more. The selling price of pure o-xylene around $5.05/kg while the price for
naphthalene around $5.96/kg[1].Currently 90% of phthalic anhydride is produced
from o-xylene because of the yield since it is the main factor affecting the choice of
the feed stock and the price.
Table 1: Component Price

Component
O-xylene
Naphthalene

Price($)
5.05/kg
5.96/kg

Process description
The manufacturing of Phthalic Anhydride (PAN) is done in several steps. As
simplicity, mixture of O-xylene and air is preheated and converting o-xylene to vapor
knowing that the boiling point of the o-xylene is 144.4 C. Then, the mixture is fed to a
catalytic reactor. The reaction is highly exothermic, so to maintain the temperature,
the reactor is designed as packed bed reactor with heat exchanger. Water is used to
cool the reactor. The products then purified using other units like distillation.
There are five reactions happen beside the production of phthalic anhydride by
oxidation of o-xylene. These reactions are listed below.[6]

+
+

+ .

+ .
+

+
+

The first reaction is the main reaction and it is assumed 70% selectivity. The second
Reaction refers to the formation of the by-product maleic anhydride (MA) and a 10%
selectivity is considered. The third and the fourth reactions represent the complete and
incomplete combustions of o-xylene with 15% and 5% selectivity, respectively.

Reactions path way

In the reactor, the o-xylene is subject to a variety of oxidation reaction to the desired
product of Phthalic anhydride; by product Maleic anhydride and products of
combustion. The oxidation of o-xylene feed with the air produce Phthalic anhydride.
The reactor effluent containing pure Phthalic anhydride reacts with excess oxygen to
produce water and carbon dioxide. Also, o-xylene reacts with the oxygen to produce
the Maleic anhydride as by product that also react with excess oxygen to produce
water and carbon dioxide.

Figure 3: Reactions Pathway

Type of reactors
In the past, phthalic anhydride (PAN) was produced in a slurry. After o-xylene has
replaced naphthalene as feedstock, the reactors were developed and fluidized bed and
fixed bed reactors were used. Naphthalene-based feedstock is made up of vaporized
naphthalene and compressed air. It is transferred to the fluidized bed reactor and
oxidized in the presence of a catalyst.
In PAN production using o-xylene as the basic feedstock, filtered air is preheated,
compressed, and mixed with vaporized o-xylene and fed into the fixed-bed tubular
reactors. Nowadays, fixed bed catalytic reactor is commonly used. The table below
shows comparison between fluidized bed and fixed bed for many parameters.[5]
Table 2: Fixed-Bed. vs. Fluidized-Bed Reactors for Selective Hydrocarbon Oxidation Reactions

Hydrocarbon
concentration
Oxygen concentration
Temperature control
Catalyst effectiveness
Catalyst cost
Capital investment
Raw material Cost
Raw material availability
CO2 emission
PAN Yield

Fixed-bed
reactor
Below flammability

limit Flammable region possible

Large excess
Hot spot
Poor to average
Least expensive
Expensive
Lower
More available
Less
Higher

Near stoichiometric
Nearly isothermal
Good
More expensive
Less expensive
Higher
Less available
More
Lower

Fluidized-bed reactor

Catalyst
There are different types of catalysts which are used for the oxidation of o-xylane to
PAN. Types that contain V2O5 supported on TiO2 are common and affective
catalysts for this process. The amount of V2O5 is used affects the selectivity of PAN
and carbon dioxide and the temperature for total conversion. Table (3) shows some
comparison. It seems that the catalyst contain 5.6% is more active. It has selectivity of
50% PAN when 100% conversion of o-xylene and the best temperature is 553K.[8]
Table 3:Catalyst Properties and Behavior in o-Xylene Oxidation

Catalyst

Vanadium
(wt%)
VPTGA(1)
0.68
VPTGA(5)
2.85
VPTGA(10) 5.6
VPTGB
0.58
VP25
0.13

Surface
(m2/g)
111
96
104
152
56

area Yield of PA
(%)
26
17
50
25
18

Temp.
(K)
558
513
553
568
593

Kinetics
The kinetic of the five reactions are:[7]

First Design: Reactor Volume Using Simple Reaction Rate Expression

In this design we develop an isothermal reactor model to estimate the reactor volume
for the production of phthalic anhydride by oxidation of o-xylene based on the
reaction below
C H

+ 3O C H O + 3H O

A catalyst weight of a packed bed reactor model is obtained and then converts the
weight to a reactor volume using catalyst bulk density. In this design we will explore
a reactor with a single reaction. However, reactions to byproducts will be added in the
third design.
The designing of fixed bed reactor depend on the following rate of the reaction that
obtained from literature:
r

= k P P

ln

+ 19.837

k =4.1219e8 kmole /(kg catalyst).atm2 hr. The activation energy is 27000 cal/mol[1].
The design differential mole balance equation is

With the following specifications:

T=673K

d(x) r
=
d(w) Fa

P=3atm

W (f) =21071kg

Polymath solved the differential equation and gave the relation between the weight of
catalyst and the conversion. The typical conversion is 85%. The calculations were
repeated at different temperatures to visualize the effect of temperature in the
conversion and the weight of the catalyst required to achieve the specified conversion.
The calculations can be obtained in matlab which is easier and the code is in the
appendix. Table (4) shows the results at 400 C and 3 atm. Figure (4) shows the effect
of temperature in the conversion. From figure (4), the weight of the catalyst required
to reach 85% conversion decrease with increasing in temperature. At 633 K, 75 000
kg of catalysts is needed however; 21000 kg is only required to achieve the specified
conversion.

Mass balance:
Table 4: Mass Balance Results

species

Total

Initial
(Kmol/s)
0.0523
0.7259
0
0
2.7308
3.509

Change
(kmol/s)
-0.04453
-0.1333
0.0444
0.1333
0
0

Final
(Kmol/s)
7.858 10
0.5925
0.0444
0.1333
2.7308
3.509

Table 5:Polymath design results

1
2
3
4

Variable
w (kg)
X
T (K)
P (atm)

Final value
2.107E+04
0.8500067
673
3

Calculating the volume

To calculate the volume of the packed bed reactor, we use the weight catalyst, the
density of the particle and the porous media coefficient by the following equation:
V=

w
21071
=
= 12.55m
(1 ) 3357(1 0.5)

Where the (w) is the weight of catalyst in kg

The is the density of the particle in kg/m3 [2]

is the porose media of the catalyst (V2O5/TiO2)[2]

Figure 4:Effect of temperature in the conversion

The simulation
We simulate the packed bed reactor in Aspen Plus using the RPLUG reactor. The
specifications of the feed are 673K and 3 atm. The table below shows the result
obtained of heat and material balance.
Table 6: Heat
balance
Heaand
t anmaterial
d Material
Ba la nce Table

Strea m ID
Tem perature C
P ressure
Vap or Frac

ba r

Mole Flo w
Ma ss Flo w

FEED

P RODUCT
39 9. 9
399. 9
3.040
1.000

3.00 0
1.00 0

km ol/hr
kg/hr

12 686.36 0
38 0541.6 02

12686.360
380541 .602

Volum e Flow cu m /hr

23 3529.3 66

236623 .630

37 .683

-4.82 6

188. 597
2612.819

30 .1 43
21 37.456

Enthalpy
Mole Flo w
C8H10 -01
O2

Gca l/hr
km ol/hr

C8H4O-01
H2O
N2

15 8. 454
47 5. 363
9884.945

98 84.945

Figure5 : Aspen Reactor Model

The conversion can be calculating using the flow rate of the o-xylene obtained from
aspen plus by the equation below, and we get very close answer to the calculated
result.
x=

188.597 30.143
= 0.84
188.597

To construct the plot of conversion versus heat duty we use the data composition
obtained and multiplied by the total flow of the outlet and use it to find the
conversion.

0.9
0.8
0.7
0.6

0.5
0.4
0.3
0.2
0.1
0
0

10000

20000

30000

40000

50000

60000

Q (KW)
Figure6 : conversion versus heat duty

The figure above shows the relationship between the conversions versus heat duty. As
can be seen from the figure, as we increase the conversion the heat duty increase.
Actually there is a proportional linear relationship between them.

10

Second Design: Pressure Drop and Reactor Configuration

Based on the previous design (isothermal reactor), the pressure drop consideration is
taken into account in this design. The minimum pressure ratio (P/P0) is 0.9 that give
us the outlet pressure of 2.7atm.The consideration of pressure drop is important to get
the suitable outlet pressure that needed for downstream operation. Moreover, if we
have very large pressure drop, we have to increase the pressure before it fed to the
next operation hence increase the capital and operating cost. The optimization will be
done in this design to find the typical conversion which is 0.85 and reasonable reactor
configuration using multiple tubes, changing weight of catalyst and the temperature.
The differential mole balance equation is
d(x) r
=
d(w) Fa

And the momentum balance Ergun equation is

( )

( )

(1+x)

With the following specifications:

T=673K

P=3atm

W (f) =21071kg

= y (0) =1

Polymath solved the differential equations and gave the relation between the weight
of catalyst and the conversion. The calculations were repeated at different
temperatures to visualize the effect of temperature in the conversion with
consideration of pressure drop and compare it with the result of previous design.
Table 7: Design Results without Sipliting to Tube

1
2
3
4
5
6
7
8
9

Variable
w (kg)
x
y
T (K)
N
P0 (atm)
D (m)
V (m3)
L (m)

Final value
2.107E+04
0.7044096
0.4936886
673
1
3
3.5
12.55347
1.304257

11

Weight VS conversion

0.8
0.7
0.6

T=673K
T=650K
T=630K
T=600K
T=573K

0.5

0.4
0.3
0.2
0.1
0
0

5000

10000

15000

20000

W(kg)

25000

Figure 7:Effect of temperature in the conversion

Figure (7) above shows the effect of catalyst weight on the conversion at different
range of temperature with consideration of pressure drop. As can be seen, the
conversion increases as the catalyst weight increase. When the pressure drop
increased the concentration decreased resulting in a decreased rate of reaction. As a
result of this smaller reaction rate, the conversion will be less with pressure drop than
without pressure drop as we observed that on figure (8).

Weight VS conversion

0.9
0.8
0.7
0.6

T=673K without (y)

T=673K with (y)
T=630K without(y)
T=630K with(y)

0.5
0.4
0.3
0.2
0.1
0
0

5000

10000

15000

W(kg)

20000

Figure 8:Effect of Pressure Drop in the conversion at Different Temprature

12

25000

Splitting the Reactor into Tubes

After the calculation of conversion and pressure drop, it can be seen that the pressure
drop is less than 10%. The proper solution is to split the flow in tubes to decrease the
pressure drop since it function of mass flow rate. From figure (9), it is clear that
dividing the flow rate into tubes affect the pressure drop. Pressure drop is decreasing
with increasing the number of tubes. So, using banks of tubes will solve the pressure
drop problem and the design will meet the specifications.

Figure 9:The effect of number of tubes in the pressure drop

Tube Length effect

After optimizing the design to achieve the required conversion 85% and the pressure
drop constrain 10% maximum, the number of tubes was chosen to be 25140 tubes.
The weight of catalyst is 5.8 kg in each tube. The tube diameter was selected as 1.5
inches. The length of the tube is changing to discuss the effect of tube length in the
pressure drop. Figure (10) shows the results of different tube length in pressure drop.
As can be seen from the figure, increasing the tube length will increase the pressure
drop and that due to the friction. Also, since the volume of the reactor is fixed,
increasing the length will decrease the diameter and as a result the friction will be
greater and pressure drop will increase. From the calculation, a length of three meters
gives a pressure drop of 0.2885 atm which is a proximately 10%.
13

Figure 10:Effect of Tube Length in Pressure Drop.

Particle Diameter effect

As well known theoretically that particles with smaller size will minimize the spacing
between them and as a result the fluid needs more force to pass through them. A large
pressure drop will gain if smaller particle is used. For studying the particle size effect,
the particles diameter that was used is doubled and the calculation is repeated. Figure
(11) gives the result of both diameters used to calculate the pressure drop. As
expected, the higher diameter has a less pressure drop of 0.1365 atm which is 5%
approximately.

Figure 11: Comparing two paticle diameters effect in pressure drop.

14

After optimizing all parameters, the result shows below

1
2
3
4
5
6
7
8
9

Variable
w (kg)
x
y
T (k)
N
P0 (atm)
D (in)
L (m)
Vt (m3)

Final value
2.152E+04
0.8507969
0.9009362
617
2.514E+04
3
1.5
0.653
86.87042

Figure 12: Final design results

The number of tubes is considered to be 25140 tubes and contains 5.8 kg of catalyst in
each one. The conversion is calculated and gives 85% and the pressure ratio is 0.9.
Figure (13) shows the catalyst weight effects in pressure drop and conversion. The
tube diameter of each tube is 1.5 inches and a length of 0.653 meter.

Figure 13: Shows the Catalyst Weight Effects in Pressure Drop and Conversion

15

The simulation
Based on the simulation done in memo 2 of packed bed reactor in Aspen Plus using
the RPLUG reactor, the pressure drop was including in this memo. We specify Ergun
friction correlation to calculate process steam pressure drop. The specifications of the
feed in the first run are 673K and 3 atm with the following configurations and catalyst
weight.
N (number of tube) =1
W=21071kg

D=3.5m

L=1.304257m

The table below shows the result obtained of heat and material balance.
Table 8: Heat and material balance

Heat and Materi al Balance Table

Stream ID

FEED

P ROD UCT

Temperature

399 .9

399 .9

P res sure

bar

3.0 40

1.4 95

1.0 00

1.0 00

126 86.3 60

126 86.3 60

Vapor Frac
Mole Flow

kmol/hr

Mass Flow

kg/hr

380 541.602 380 541.602

Volume Flow cum/hr

Enthalpy

Gcal/hr

Mole Flow

kmol/hr

233 529.366 474 674.606

C8H10-0 1
O2

37.683

2.3 01

188 .597

56.708

261 2.81 9

221 7.15 3

C8H4O-01

131 .889

H 2O

395 .666

N2

988 4.94 5

988 4.94 5

The conversion can be calculating using the flow rate of the o-xylene obtained from
aspen plus by the equation below, and we get very close answer to those obtained in
POLYMATH.
x=

188.597 56.708
= 0.699
188.597

The conversion obtained using POLMATH was 0.704. As we observed the difference
between them is 0.7%.

16

In the second run, the specifications of the feed are 617K and 3 atm with the
following configurations and catalyst weight that give us the desired conversion
which is 0.85.
N (number of tube) =25140
L=3.03m

D=0.0381m for each tube

W=21520 kg

The table below shows the result obtained of heat and material balance.
Table 9: Heat and material balance

Heat and Material Balance Tab le

Stream ID

FEE D

PRODUCT

Temperature

343. 9

343. 9

Pressure

bar

3. 040

2. 738

1. 000

1. 000

12686. 360

12686. 360

Vapor Frac
Mole Flow

kmol/hr

Mass Flow

kg/hr

Volume Flow cum/hr

Enthalpy

Gcal/hr

Mole Flow

kmol/hr

C8H10-01
O2

380541. 602 380541. 602

214097. 502 237669. 115
31. 909

-10. 926

188. 597

28. 761

2612. 819

2133. 313

C8H4O-01

159. 835

H2O

479. 506

N2

9884. 945

9884. 945

The calculated conversion using flow rate of the o-xylene obtained from Aspen is
0.848 with the difference of 0.2% from POLYMATH result.
In both trails the ratio of the pressure (P/Po) is exactly the same we obtained in
POLYMATH.

17

Third Design: Multiple Reactions

Based on the previous design (isothermal reactor), the side reactions are included in
this design. There are four reactions happen beside the production of phthalic
anhydride by oxidation of o-xylene. The reactions and their kinetics [7] are below.

The differential mole balance equations are

(

( )

( )

( )

=r

=r

( )

=r
(

( )
(

=r

And the momentum balance Ergun equation is

=r

( )

d(y) F T
=
d(w) 2y F T
18

=r

With the following specifications:

Table 10: Third Design Results

1
2
3
4
5
6
7
8

Variable
w (kg)
y
T (k)
N
P0 (atm)
D (in)
L (m)
Vt (m3)

Final value
23055
0.9005
673
2.25E+04
3
1.5
0.653
86.87042

Plot Flow

Figure 14: Molar flow rate of each component versus the catalyst weight

Figure (14) shows the molar flow of each component with the weight of catalyst. The
molar flow rate of all products is always increasing. Water is produced with high
amount. Pressure drop was fixed to be 10% only.

19

Effect of Temperature in Selectivity

As can be seen from figure (15), the selectivity of phthalic anhydride is increasing
with the decrease of temperature. It is as expected since the activation energy of a
reaction that produce phthalic anhydride has the lowest value than the others. The
selectivity of maleic anhydride is decreasing with increase of temperature. The
relation is shown in figure (16).

3
2.5
T=673K

sd_pa

T=655K

1.5

T=640K

1
0.5
0
0

5000

10000

W(kg)

15000

20000

25000

Figure 15: Selectivity of Phthalic Anhydride at Different Temperature

sd_ma Vs W

0.3
0.25

T=673K

sd_ma

0.2

T=655K

0.15

T=640K

0.1
0.05
0
0

5000

10000

W(kg)

15000

Figure 16: Selectivity of Phthalic Anhydride at Different Temperature

20

20000

25000

Aspen simulation
Based on the simulation done in memo 3 of packed bed reactor in Aspen Plus using
the RPLUG reactor, the four side reactions are added in the configuration with their
kinetics. The specifications of the feed are 673K and 3 atm with the following
configurations and catalyst weight.
N (number of tube) =1
W=21071kg

D=5.35m

L=0.558m

The table below shows the result obtained of heat and material balance.
Table 11: Heat and Material Results in Aspen Plus
Heat and Material Balance Table
Stream ID

FEED

PRODUCT

Temp erature

399.9

399.9

Pressure

bar

3.040

2.737

1.000

1.000

22547.160

22626.729

Vap or Frac
M ole Flow

kmol/hr

M ass Flow

kg/hr

676363.053

676363.053

Volume Flow

cum/hr

415046.066

462533.781

Enthalp y

Gcal/hr

66.980

-47.109

M ole Flow

kmol/hr
335.520

92.947

4646.160

3432.062

C8H10-01
O2
C8H4O-01

160.015

H2O

848.566

N2

17565.480

17565.480

CO2

483.391

C4H2O-01

44.268

The conversion can be calculating using the flow rate of the o-xylene obtained from
aspen plus by the equation below, and we get very close answer to those obtained in
POLYMATH.
x=

335.520 92.947
= 0.722
335.520

The conversion obtained using POLMATH was 0.726. As we observed the difference
between them is 0.5%.However in this memo we care more about the exit flow rate of
21

our product (phthalic anhydride) to get the desired amount specified (20,000
tons/year). The outlet flow rate obtained using Aspen is 160.0 kmol/hr which is very
close answer calculated by POLYMATH(160.5 kmol/hr).
Figure (17) shows the flow rate of all species except the flow rate of O2 in the
primary axis with reactor length. As can be seen, the reactant flow rate (O-xylene and
Oxygen) are decreasing with the reactor length while the product species increasing
with the reactor length. These results are expected from the reactions since all it are
producing water and four reactions producing CO2
and only one reaction are
producing phthalic anhydride.

flow rate VS Length

5000

800

4500

700

4000

flow rate (kmol/h)

3500

600

3000

500

2500

400

2000

300

1500

200

1000

100

500

0
0

0.1

0.2

0.3
L(m)

0.4

0.5

0.6

Figure 17: Molar Flow of each Component with Reactor Length obtained from Aspen

22

flow rate (kmol/h)

900

f_O-xylene
f_phthalic
f_water
f_CO2
f_o2

Final Design: Energy Balance

Energy balance equation was added to the previous design. All reactions in phthalic
anhydride production are exothermic reactions. The multi tubular reactor acts as a
shell and tube heat exchanger with co-current coolant. The energy balance of the
coolant was considered and steam was used as a coolant. The calculated heat capacity
(Cp) of each component at the inlet temperature ( 673 oC ) are shown in table(12).
Table (13) contains the Heat of formation for each component that was used to
calculate the heat of reactions.

Table 12: Components Properties

Component

o-xylene

Maleic
anhydride
269.9

Carbon
dioxide
48.96

Water

Nitrogen

458.6

Oxygen Phthalic
anhydride
32.73
723.5

Cp
(KJ/kmol.K)
H
(KJ/mol)

37.23

30.6

19.1

-398.2

-393.5

-241.80

-371.4

The overall heat transfer coefficient was found in literature to be 58 (W/m2.K). the
coolant inlet temperature is 655 K. the pressure drop was maintained not to exceed
10%.

Temperature profile
Figure (18) shows the temperature gradient with the weight of catalyst. A hot spot
appear in the reactor. The hot spot temperature which is the highest temperature is
calculated to be 672.8 oC. Then the temperature decreases and goes to constant. The
outlet temperature of the reactor is 656.1 oC which is almost acceptable. Coolant
temperature increases along the reactor and Figure (19) shows the relation.

Figure 18: Temperature Profile

23

Figure 19:Coolant Temperature Profile

Figure 20: Reactor and Coolant Temperature Profiles

Dynamic stability
The reactor was tested dynamically by considering the gain. The inlet temperature of
the coolant was changed to study the effect of changing in the hot spot temperature.
The following results were obtained:
Table 13: Gain Calculation

Ta ( K )
638
636

Th ( K )
715.2
689.1
24

Gain
17
9.1

From the results, the design is not stable dynamically since the gain is more than 2. As
a solution the amount of inert component should be increased and in this case the ratio
of the air to o-xylene was increased from 20 to 25 ( kg.air/kg.xylene). After the air
amount was changed and other parameters were optimized, the dynamic results were
shown in table (14). The coolant inlet temperature was set to be 643 K and hot spot
temperature was found to be 688.1.
Table 14: Gain Calculation after Modification

Ta ( K )
642
644

Th ( K )
681.2
684.8

Gain
1.9
1.7

Aspen Simulation
After the reactor was designed to obtain the target production of phtalic anhydride, the
reactor was simulated in Aspen Plus. The flow sheet of the model was shown in figure
(21). PBR model was used with co-current coolant and specified heat transfer
coefficient U of 3.5 (kw/m2.K). Figure (22) shows the model specification. The
reactor configuration used in Aspen is the calculated dimensions. A length of 0.6 m,
1.5 in diameter and 36000 tubes was considered.

Figure 21:Aspen Flowsheet

25

Figure 22 : Model Type

Figure 23 : Design Dimensions

The inlet reactor pressure is specified to be 3 atm. The Ergun equation was used to
calculate the pressure drop in the reactor. Catalyst weight, porosity and particles
diameter were added in the model specification. Figures (24) and (25) show the
progress.

26

Figure 24: Pressure Drop Calculation

Figure 25: Catalyst specification

The five reactions were added to the design. POWERLAW type of kinetics was
considered and the all kinetics were added. Rate phase, basis and activation energies
were specified for each reaction. Figure (27) explains the kinetics specification way.

27

Figure26 : Reactions in Aspen

Figure 27: Kinetics Specification

After running the simulation, the results were tabulated and then compared with the
calculated values. The production of phthalic anhydride is consistent. The calculated
phthalic anhydride is 163 kmol/hr and Aspen calculated to be 160 kmol/hr. The
pressure drop was 0.3 atm as same as the calculated value. The temperature profile
through the reactor was plotted and a hot spot can be determined. The hot spot
temperature is 391.5 C, 665 K and calculated is 670 K. The results were shown
below.

28

Table15 :Aspen Results

392
391
Temperature (c)

390
389
388
387
386
385
384
0

0.1

0.2

0.3
0.4
Tube Length (m)

Figure28 : Temperature Profile

29

0.5

0.6

0.7

Economic analysis
The cost of production phthalic anhydride per year depends on purchase cost of the
packed bed reactor with heat exchanger, annual cost of the raw material (air and oxylene); cooling cost and catalyst cost (V2O5).The cost of production of
20000tons/year can be calculated using the following equation
Cost=Purchase cost of the reactor + Annual cost of raw material + Annual cooling
cost + catalyst cost- annual revenue of by product (malic anhydride)- Annual revenue
of phthalic anhydride
Purchase cost of the packed bed reactor with heat exchanger can be calculated using
the following equation [1] ($) =1.25*1600(As) .
Where N is number of tubes

As = DLN

Cooling cost calculated by obtained first the heat duty then calculate mass flow rate
using the following equation

Cooling cost ($) = 6.70 [1]

m =

Q
C T

Annual cost of the raw material and revenue of by product and the product depend on
the flow rates multiply by it price.
Table 16: Total Cost Results

Purchase cost of the reactor

cost of raw material
cooling cost
catalyst cost
revenue of by product (malic anhydride)
revenue of phthalic anhydride

Cost per year($)

3244210
106,143
365730
670220
3531407
18,000,000

Total

17,145,104

30

Design summary
Table 17: Reactor Configurations

N (tubes)
36000

D (in)
1.5

L (m)
0.6

W ( kg )
40000

T(K)
656

P ( atm)
3

Table 18: Feed Rates

Component
Rate ( kg/s)

O-xylene
10

Air
250

Table 19: Products Rates

Component
Rate (kmol/s)

O-xylene
0.0256

Oxygen
1.4706

PAN
0.0454

MAN
0.0125

CO2
0.1352

Water
0.2395

Table 20 : Coolant Specification

Type of coolant
Water

Inlet temperature (K)

640

Flow rate (kg/s)

0.18

Conclusion
The packed bed reactor design that used for phtalic anhydride production has been
done. Pressure drop, side reactions, temperature variation were considered. After
optimizing all parameters to achieve 20 ton/year of phthalic anhydride, reactor
configurations listed in table (15). The reactor looks like a double pipe heat exchanger
with 36000 tubes with 1.5 in. water steam at 640 K was used to maintain the
temperature with a flow rate of 0.18 kg/s per tube. The feed rates to the reactor shown
in table (16) and products rate tabulated in table (17).

31

References

1.
2.
3.
4.
5.
6.

Chemical Engineering Design Project

Kirk-Othmer Encyclopedia of Chemical Technology Volume 18
Encyclopedia of Chemical Processing
Handbook of Industrial Catalysts By Lawrie Lloyd
CHEMSYSTEMS PERP PROGRAM Report Abstract Phthalic anhydride.
A novel route to produce phthalic anhydride by oxidation of o-xylene with air
over mesoporous V-Mo-MCM-41 molecular sieves.
7. Kinetics of the Selective Oxidation of o-Xylene to Phthalic Anhydride
Doctoral Thesis (Dissertation) to be awarded the degree of Doctor of
Engineering (Dr.-Ing.) submitted by Dipl.-Ing. Robert Marx.
8. THE USE OF MATHEMATICAL MODELLING TO INVESTIGATE THE
EFFECT OF CHEMISORPTION ON THE DYNAMIC BEHAVIOR OF
CATALYTIC REACTORS. PARTIAL OXIDATION OF o-XYLENE IN
FLUIDIZED BEDS By S. S. E. H. ELNASHAIE.
9. Simulation of a Reactor for the Partial Oxidation of o-Xylene to Phthalic
Anhydride Packed with Ceramic Foam Monoliths By A. REITZMANN, A.
BAREISS and B. KRAUSHAAR-CZARNETZKI.
10. Reactors and Separations Design Project, Phthalic Anhydride Production.
11. http://www.alibaba.com/showroom/price-of-phthalic-anhydride.html
12. http://www.metalprices.com/metal/vanadium/vanadium-pentoxide-v2o5-fob
13. Catalyst Deactivation 1994b edited by B. Delmon, G.F. Froment

32

Appendix

Final Design Matlab Code.

function main ()
clear all;close all;clc
%----------------------------------------------% OPERATING CONDITION
%----------------------------------------------To=656;
% k
R1=1.987;
% cal/mol.k
Po=3;
% atm
N=36000;
% Tubes
Ta0=640;
% K
m_c=.01;
% kmol/s
U=3.5;
% Kw/m2.k
Tr=298;
% K
D=.0254*1.5;
% m
w=40000;
% kg
%-----------------------------------------------% O-Xylene FEED
%-----------------------------------------------m_xy=10/N;
% kg/s
%-----------------------------------------------%----------------------------------------------%Reactions
%----------------------------------------------% (1) XY + 3
O2 --->
PA + 3 H2O
% (2) PA + 7.5 O2 ---> 8 CO2 + 2 H2O
% (3) XY + 10.5 O2 ---> 8 CO2 + 5 H2O
% (4) XY + 7.5 O2 --->
MA + 4 CO2 + 4 H2O
% (5) MA + 3
O2 ---> 4 CO2 +
H2O
%
% Stoic
%
XY
O2
PA MA CO2 W
v=[ -1
-3
1
0
0
3
0
-7.5 -1
0
8
2
-1
-10.5 0
0
8
5
-1
-7.5
0
1
4
4
0
-3
0 -1
4
1];
%---------------------------------------------% Cp
%
XY
O2
PA
MA
CO2
Cp=[ 458.588
32.7362
723.474
269.858
48.96
Cpn2=30.5798;
%-----------------------------------------------dCp=v*Cp';
%---------------------------------------------% H
%
XY
O2
PA
MA
CO2
W
Ho=[19.1
0
-371.4
-398.2 -393.51 -241.83]*1e3;
dHrx_o=v*Ho';
%----------------------------------------------% K CALCULATION
%----------------------------------------------ko=[19.837 20.86 18.98 19.23 20.47];
E=[27000 31000 28600 27900 30400];
%-----------------------------------------------%================================================
% CALCULATION
%-----------------------------------------------m_air=m_xy*25;
% kg/s
m_o2=0.232*m_air;
% kg/s
m_n2=(1-.232)*m_air;
% kg/s
%
XY
O2
N2
PA
Mr=[106.16 32 28.02 148.1];
n_xy=m_xy/Mr(1);
% kmol/s
n_o2=m_o2/Mr(2);
n_n2=m_n2/Mr(3);

% kg/kmol
% kmol/s
% kmol/s

33

W
37.23 ];

% KJ/kmol.K

% KJ/kmol

Ft0=n_xy+n_o2+n_n2;
% kmol/s
%
N2
XY
O2
y0=[n_n2 n_xy n_o2]/Ft0;
%-----------------------------------------------------% Alpha Calculation
%-----------------------------------------------wf=w/N;
P0=Po*101325;
%
R=8.314;
%
por=0.5;
Dp=.006;
%
Vis=(-1e-08*To^2+5e-5*To+0.0039)/1000;
rho_c=3357;
%
rho_b=rho_c*(1-por);
%
V=wf/(rho_c*(1-por));
%
L=4*V/(pi*D^2);
%
M_avg=y0(3)*Mr(1)+y0(1)*Mr(3)+y0(3)*Mr(2);
%
Ac=pi/4*D^2;
%
m=Ft0*M_avg;
%
G=m/Ac;
%
rho_o=P0*M_avg/(R*To)/1000;
%
B0=G/(rho_o*Dp)*(1-por)/por^3*(150*(1-por)*Vis/Dp+1.75*G);%
a=2*B0/(rho_c*Ac*(1-por)*P0);
%
%-----------------------------------------------%-----------------------------------------------------Fn=n_n2;
Fi=[ Ft0*y0(2) Ft0*y0(3) 0 0 0 0 1 To Ta0];

Pa
kPa.m3/kmol.k
m
% Pa.s
kg/m3
kg/m3
m3
m
kg/kmol
m2
kg/s
kg/m2.s
kg/m3
kg/m2.s2
1/kg

ws=0:10/N:wf; n=length(ws);
[w,z]=ode45(@(w,z)rate(w,z,Po,a,v,Ft0,dHrx_o,dCp,rho_b,D,Cp,Fn,Cpn2,To,ko,E,R1,m_c,U,T
r,Ta0),ws,Fi);
%-----------------------------------------------------%======================================================
% RESULTS
%------------------------------------------------------disp('

Fxy

Fo2

table=[z(:,1:6)*N z(:,7:9)]
yf=z(n,7)
Th=max(z(:,8))
D
L
x=(z(1,1)-z(n,1))/(z(1,1))
mp=z(n,3)*Mr(4)*(30326400/1000)*N
q=[z(:,1:6)*N];
plotyy(w,q,w,z(:,7))
plot(w,z(:,8:9))
Vt=V*N
end

Fpa

Fma

Fco2

Fw

% ton/year

%==========================================================================
%==========================================================================
%==========================================================================

function
dzdw=rate(w,z,Po,a,v,Ft0,dHrx_o,dCp,rho_b,D,Cp,Fn,Cpn2,To,ko,E,R1,m_c,U,Tr,Ta0)
for i=1:6
F(i)=z(i);
end
y=z(7);
T=z(8);
Ta=z(9);
Ft=sum(F)+Fn;

34

y ')

% Heat
dHrx=(dHrx_o+dCp*(T-Tr));

% KJ/kmol

k=exp(ko - E/(R1*T))/3600;

% kmol/(kgcat.atm2.s)

Pxy=F(1)/Ft*Po*y*To/T;
Po2=F(2)/Ft*Po*y*To/T;
Ppa=F(3)/Ft*Po*y*To/T;
Pma=F(4)/Ft*Po*y*To/T;

%
%
%
%

atm
atm
atm
atm

% Reactions
rs(1)=k(1)*Pxy*Po2;
rs(2)=k(2)*Ppa*Po2;
rs(3)=k(3)*Pxy*Po2;
rs(4)=k(4)*Pxy*Po2;
rs(5)=k(5)*Pma*Po2;

%
%
%
%
%

kmol/kgcat.s
kmol/kgcat.s
kmol/kgcat.s
kmol/kgcat.s
kmol/kgcat.s

% Rates Evaluation
for i=1:6
r(i)=0;
for j=1:5
r(i)=r(i)+rs(j)*v(j,i);
end
end
% differential
for i=1:6
dzdw(i)=r(i);
end
dzdw(7)=-a/(2*y)*(Ft/Ft0)*(To/T);
dzdw(8)=(((4*U)*(Ta-T)/(D*rho_b))+(sum(-rs.*dHrx')))/(sum(F.*Cp)+Fn*Cpn2);
dzdw(9)=((4*U)*(T-Ta)/(D*rho_b))/(m_c*Cp(6));
dzdw=dzdw';
end

35