University of Engineering & Technology Lahore

(New Campus)

Aspen Plus Complex Engineering Problem

Topic:
Production of 50,000 Tonnes/year of Phthalic Anhydride from O-Xylene

Submitted By:
2022-CH-238
2022-CH-204
2022-CH-250

Submitted to: [Link] Tabish

 TABLE OF CONTENT

1 TABLE OF CONTENTS
Abstract ................................................................................................................................................... 3
1 Process Description ........................................................................................................................ 4
2 Process Simulation........................................................................................................................ 10
2.1 methodology ........................................................................................................................ 10
2.2 Process Simulation Results .................................................................................................. 12
2.3 Key findings .......................................................................................................................... 12
3 Sensitivity Analysis ........................................................................................................................ 13
3.1 Study Selection..................................................................................................................... 13
3.2 Sensitivity Analysis Results .................................................................................................. 13
4 Economic Analysis ........................................................................................................................ 14
5 CONCLUSIONS............................................................................................................................... 16
REFERENCES .......................................................................................................................................... 16

2
 ABSTRACT
This study presents a steady-state simulation of the vapor-phase catalytic oxidation of o-xylene to
phthalic anhydride using Aspen Plus V14, with a modified process flow excluding an intermediate
heat exchanger. The model replicates a typical industrial setup, beginning with separate conditioning
of o-xylene and air. O-xylene is pumped and vaporized to 360 °C, while air is compressed to 3 bar.
These streams are combined in a mixer and directed into a plug flow reactor (RPlug) operating
isothermally at 360 °C and 3 bar.

Within the reactor, o-xylene undergoes exothermic oxidation in the presence of air, forming phthalic
anhydride, maleic anhydride, water, and carbon dioxide. The hot reactor effluent is directly cooled to
50 °C in a downstream cooler without any intermediate heat recovery. The cooler efficiently
condenses a portion of the products and prepares the stream for phase separation by reducing its
vapor fraction to approximately 0.68.

A Flash2 separator (V-DRUM1) operating at 160 °C and 3 bar separates condensed phthalic
anhydride and water from unreacted gases and light byproducts. The liquid phase is subsequently
sent to a RadFrac distillation column comprising 33 stages and operating at 3 bar. With maleic
anhydride as the light key and phthalic anhydride as the heavy key, the column effectively purifies
the product, achieving a bottom stream flow rate of approximately 38.67 kmol/h of phthalic
anhydride.

The results demonstrate that even without an intermediate heat exchanger, the system maintains
efficient thermal and phase behavior. The simulation validates the feasibility of this streamlined
process design for industrial-scale application.

3
1 PROCESS DESCRIPTION
Brief Overview:
Phthalic anhydride appears as a colorless to white lustrous solid in the form of needles with a mild
distinctive odor. Moderately toxic by inhalation or ingestion and a skin irritant. Melting point 64 °F
Flash point 305 °F. Forms a corrosive solution when mixed with water. Used in the manufacture of
materials such as artificial resins.
Phthalic anhydride is the cyclic dicarboxylic anhydride that is the anhydride of phthalic acid. It has a
role as an allergen. It is a cyclic dicarboxylic anhydride and a member of 2-benzofurans.

Hazards:
Exposure to phthalic anhydride may occur during its use as a chemical intermediate in the plastics
industry. The acute (short-term) effects from exposure to phthalic anhydride in humans consists of
irritation to the eyes, respiratory tract, and skin, but no permanent injury is observed. Chronic (long-
term) effects observed in workers exposed to phthalic anhydride included conjunctivitis, rhinitis,
rhinoconjunctivitis, bronchitis, and irritation of the skin and mucous membranes of the respiratory
tract. Animal studies indicate that chronic exposure to phthalic anhydride vapor causes congestion,
irritation, and injury to lung cells. No studies are available on the reproductive, developmental, or
carcinogenic effects of phthalic anhydride in humans.
Applications:

❖ Phthalic anhydride is a toxic, white crystalline compound used in the manufacture of phthaleins
and other dyes, resins, plasticizers, and insecticides. Phthalic anhydride is the anhydride of
phthalic acid. This colorless solid is an important industrial chemical, especially for the large–
scale production of plasticizers for plastics. It is presently obtained by catalytic oxidation of
ortho–xylene or naphthalene. Phthalic anhydride can also be prepared from phthalic acid.
❖ Phthalic anhydride is a versatile intermediate in organic chemistry, in part because it is
bifunctional and readily available. The primary use of phthalic anhydride (PA) is as a chemical
intermediate in the production of plasticizers from polyvinyl chloride (PVC).
❖ The primary use of phthalic anhydride (PA) is as a chemical intermediate in the production of
plastics from vinyl chloride. Phthalate esters that function as plasticizers are derived from
phthalic anhydride. Phthalic anhydride has another major use in the production of polyester
resins and other minor uses in the production of alkyd resins used in paints and lacquers, certain
guys, insect repellents, and urethane polyester polyols.
❖ Phthalic anhydride has also been used as a rubber scorch inhibitor and [Link] second
largest outlet for PA is in unsaturated polyester resins (UPR) which are usually blended with glass
fibers to produce fiberglass-reinforced plastics. Principal markets are construction, marine and
transportation.
❖ The third largest outlet is PA-based alkyd resins that are used in solvent-based coatings for
architectural, machinery, furniture and fixture [Link] volume uses for PA include the
manufacture of dyes and pigments, detergents, herbicides and insecticides, fire retardants,
saccharin and polyester resin cross-linking agents

4
Molecular Formula:

C6H4(CO)2O

IUPAC Name:

2-benzofuran-1,3-dione

Reaction scheme and kinetics:

The catalysis and reaction engineering group has obtained the following kinetic information
regarding the o-xylene to phthalic anhydride reaction. The reactions are

In addition, the complete combustion reaction for each organic component occurs. The reaction
network is given below. As you can see, a major advantage of our catalyst is that CO formation is
essentially eliminated and no heavy impurity is made.

The catalyst must operate between 300°C and 400°C, and at pressures between 1 atm and 3 atm. In
this range, the kinetics are as follows: (partial pressures in atmospheres, ri in kmol hr-1 (kg catalyst)-
1, k0 = 1 kmol hr-1(kg catalyst)-1atm-2, R = 1.987 cal/K mole, and T is in K)

5
Boundary Stream specifications:
Table 1: Boundary stream specifications

Stream No. Type Specifications

S1 O-Xylene Feed Stream Temp: 25 C
Pressure: 1 bar
Benzene: 330 kmol/hr
S2 Air Temperature: 25 C
Pressure: 1 bar
Air flow rate: 1260 kmol/hr

S13 Phathalic anhydride Phthalicanhydride: 50213.6 tones/year

(Product) Temperature: 337.771 C
Pressure: 3 bar
S10 Flah2 Vapour stream Temperature: 160C
Pressure: 3 bar
Composition:
CO2: 66.1777 kmol/hr
O-Xylene: 240.941 kmol/hr
N2: 995.325 kmol/hr
PHTHA-02: 9.53 kmol/hr
MALEI-01: 0.2177 kmol/hr
Water: 216.697 kmol/hr
S12 Liquid Distillate Temperature: 121.424 C
Pressure: 3 bar
CO2: 0.161650963549259
O-XYLENE: 21.5951019215524
N2: 0.0747442823224938
PHTHA-02: 10.8233122216536
MALEI-01: 0.0674405345222305
WATER: 2.27775007640006

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Detailed description of each unit operation/process involved in the production process including purpose
and typical operating condition:

1. P1 – Feed Pump (for o-Xylene)

• Purpose: Increases the pressure of liquid o-xylene from ambient (1 bar) to the reactor
operating pressure.

• Typical Conditions:

o Inlet: 25 °C, 1 bar

o Outlet: 3 bar

o Phase: Liquid

2. C1 – Compressor (for Air)

• Purpose: Compresses air to match the reactor operating pressure.

• Typical Conditions:

o Inlet: 25 °C, 1 bar

o Outlet: 3 bar

o Composition: Oxygen and nitrogen (O₂/N₂)

3. F1 – Heater Furnace

• Purpose: Vaporizes and heats o-xylene to the required reaction temperature.

• Typical Conditions:

o Inlet: 25 °C (liquid)

o Outlet: 360 °C (vapor)

o Pressure: 3 bar

4. B6 – Mixer

• Purpose: Combines the vaporized o-xylene and compressed air into a single feed stream for
the reactor.

• Typical Conditions:

o Outlet Temperature: 359.3 °C

o Pressure: 3 bar

o Phase: Vapor

7
5. ICON1 – RPlug Reactor

• Purpose: Carries out catalytic vapor-phase oxidation of o-xylene to produce phthalic

anhydride.

• Typical Conditions:

o Temperature: 360 °C (isothermal)

o Pressure: 3 bar

o Residence Time: 0.028 hr

o Reaction: Highly exothermic

o Products: Phthalic anhydride, maleic anhydride, water, CO₂

6. B3 – Cooler

• Purpose: Reduces reactor effluent temperature from 360 °C to 50 °C to facilitate

condensation.

• Typical Conditions:

o Inlet Temp: 360 °C

o Outlet Temp: 50 °C

o Pressure: 3 bar

o Heat Duty: –1.86 × 10⁶ cal/sec

o Vapour Fraction Out: 0.686

7. DRUM1 – Flash2 Separator

• Purpose: Separates condensed product (liquid) from unreacted gases and volatile
byproducts.

• Typical Conditions:

o Temperature: 160 °C

o Pressure: 3 bar

o Valid Phases: Vapor–Liquid

o Output:

▪ Bottoms: Phthalic anhydride + water

▪ Tops: Unreacted gases (CO₂, N₂, traces of o-xylene)

8
8. FRACT1 – RadFrac Distillation Column

• Purpose: Purifies phthalic anhydride by separating light impurities (mainly water and maleic
anhydride) from the product.

• Typical Conditions:

o Number of Stages: 33

o Pressure: 3 bar

o Light Key: Maleic anhydride

o Heavy Key: Phthalic anhydride

o Condenser Temp: 121.4 °C (Duty: –1.73 × 10⁵ cal/sec)

o Reboiler Temp: 337.8 °C (Duty: 2.53 × 10⁵ cal/sec)

o Reflux Ratio: 0.01

o Bottom Product: Phthalic anhydride (38.67 kmol/hr)

2 Summary of Purpose per Unit:

Unit Code Unit Operation Purpose

P1 Pump Pressurize o-xylene feed

C1 Compressor Compress air for reaction

F1 Heater Furnace Vaporize and preheat o-xylene

B6 Mixer Combine o-xylene and air

ICON1 RPlug Reactor Oxidize o-xylene to phthalic anhydride

- Cooler Further reduce temperature for flash

DRUM1 Flash2 Separator Separate product liquid from vapor

FRACT1 RadFrac Distillation Purify phthalic anhydride

9
3 PROCESS SIMULATION

3.1 METHODOLOGY

Process modelling was executed in Aspen Plus V14 using the SYSOP0 base method with
the IDEAL activity-coefficient model, which gives reliable VLE and enthalpy predictions
for the non-electrolyte, low-pressure system (≤ 3 bar). Seven pure components were declared:
o-xylene, O₂, N₂, CO₂, water, phthalic anhydride (PHTHA-02) and maleic anhydride
(MALEI-01).

Feed specification. Stream S1 delivers 35 035.2 kg h⁻¹ of liquid o-xylene at 25 °C, 1 bar,
while Stream S2 supplies 36 351.5 kg h⁻¹ of ambient air (O₂ 8 466.8 kg h⁻¹, N₂ 27 884.6 kg h⁻¹)
under identical conditions.

Conditioning units. Pump P1 elevates S1 to 3 bar; compressor C1 raises S2 to the same

pressure. The o-xylene is vaporised in furnace F1 and exits at 360 °C (Stream S5). Air is
simultaneously pre-heated to 176.2 °C (Stream S4).

Reactive section. Hot feeds are combined in mixer B6, producing Stream S8 at 359.26 °C,
3 bar. This enters the RPlug reactor ICON1, constrained isothermally at 360 °C with a
residence time of 0.028 h. The highly exothermic oxidation releases –6.81 × 10⁶ cal s⁻¹,
converting o-xylene to phthalic anhydride plus by-products.

Heat recovery and cooling. Reactor effluent (Stream S9: 160 °C, vapour fraction 1) is first
flashed across DRUM1 conditions in a heat-integrated loop, then cooled further in cooler B3
to 50 °C with a duty of –1.86 × 10⁶ cal s⁻¹ (vapour fraction 0.686).

Phase separation. Flash vessel V-DRUM1 operates at 160 °C, 3 bar with vapour–liquid
equilibrium convergence to 10⁻⁴ tolerance, yielding a liquid product stream (S12: 7 331 kg h⁻¹
phthalic anhydride, 41 kg h⁻¹ water) and a gaseous overhead rich in CO₂ and N₂.

Purification. The liquid enters a 33-stage RadFrac column (FRACT1) at 3 bar. Using
maleic anhydride as light key and phthalic anhydride as heavy key, the condenser
(121.42 °C, –1.73 × 10⁵ cal s⁻¹) and reboiler (337.77 °C, 2.53 × 10⁵ cal s⁻¹) achieve a bottoms
purity of 38.67 kmol h⁻¹ phthalic anhydride with a minimal reflux ratio 0.01.

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 1. Simulation approach of all unit operations as per Table 2.
Table 2: Simulation approach of the process

Sr. # Unit in the flowsheet Block in the simulation diagram Input specifications of the block
1 Separator Flash 2 (V-DRUM1) Temperature: 160C
Pressure: 3bar
Valid phases: Vapour-Liquid
Maximum iterations: 30
Error tolerance: 0.0001
2 Distillation Column RadFrac ( FRACT1) No. of stages: 33
Pressure: 3 bar
Light key: Maleic
Heavy Key: Phtha-02
Condensor Top stage:
Temperature: 121.423681C
Heat duty: -172853.3cal/sec
Distillate rate: 35
Reflux rate: 0.35
Reflux ratio: 0.01
Reboiler/ Bottom stage:
Temperature: 337.771015
Heat duty: 252907.487 cal/sec
Bottoms rate: 38.67339 kmol/hr
Boilup rate: 71.3656905 kmol/hr
Boilup ratio: 1.8453435

3 B3 Cooler Outlet Temp: 2C

Outlet Pressure: 3 bar
Vapour Fraction: 0.685617738
Heat Duty: -4358585.77 cal/sec
Net Duty: -4358585.77 cal/sec

4 B6 Mixer Outlet Temp: 359.26046C

Pressure: 3 bar

5 B7 Reactor RPlug (ICON1) Heat Duty: -6811696.32cal/sec

Reactor Temperature:
Maximum Temp: 360C
Minimum Temp: 360C
Residence Time: 0.02798318 hr

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 3.2 PROCESS SIMULATION RESULTS
Table 3: Stream summary

Parameter S1 S2 S3 S4 S5 S7 S8 S9 S10 S11 S12 S13 S21

Temperature 25 25 25.1 176.2 360 360 359.26 360 160 160 121.424 337.441 2
(⁰C)

Pressure (bar) 1 1 3 3 3 3 3 3 3 3 3 3 3

Vapor 0 1 0 1 1 1 1 1 1 0 0 0 0.38159
fraction

Mass flow 35035.2 36351.5 35035.2 36351.5 36351.5 35035.2 71386.7 71393.1 61712.2 9680.9 3952.68 5728.22 71393.1
(kg/hr)

Mole flow 330 1260 330 1260 1260 330 1590 1602.5 1528.8 73.6 35 38.67 1602.5
(kmol/hr)

Comp 0 8466.8 0 8466.8 8466.8 0 8466.8 0 0 0 0 0 0

(O2)(kg/hr)

Comp 0 0 0 0 0 0 0 2919.5 2912.4 7.11 7.11 1.6E-38 2919.5

(CO2)(kg/hr)

Comp 35035.2 0 35035.2 0 0 35035.2 35035.2 27872.8 25580.1 2292.6 2292.6 7.6E-08 27872.8
(O-XYLENE
)(kg/hr)
Comp 0 27884.6 0 27884.6 27884.6 0 27884.6 27884.6 27882.5 2.09 2.09 1.8E-56 27884.6
(N2)(kg/hr

Comp 0 0 0 0 0 0 0 8743.1 1411.8 7331.3 1603.1 5728.2 8743.1

(PHTHA-
02)(kg/hr
Comp 0 0 0 0 0 0 0 27.9 21.3 6.61 6.61 1.3E-07 27.96
(MALEI-
01)(kg/hr
Comp 0 0 0 0 0 0 0 3944.9 3903.8 41.03 41.03 1.7E-21 3944.9
(Water)(kg/hr

3.3 KEY FINDINGS

The simulation of phthalic anhydride production from o-xylene was successfully performed
using Aspen Plus V14, modeling a continuous process from feed preparation through to
product purification. The process involves the catalytic vapor-phase oxidation of o-xylene,
followed by multistage cooling, phase separation, and distillation.

The plug flow reactor (ICON1), operating isothermally at 360 °C and 3 bar, facilitated the
oxidation of o-xylene in the presence of compressed air. The reactor demonstrated high
conversion efficiency, with a heat duty of approximately –6.81 × 10⁶ cal/sec, underscoring the
exothermic nature of the reaction. The reactor outlet was cooled to 160 °C using a heat
exchanger and further reduced to 50 °C via a cooler before entering the flash separator
(DRUM1). The heat exchanger utilized a cold stream at 2 °C and achieved a calculated duty
of 1.69 × 10⁶ cal/sec, confirming effective heat recovery.

In the flash separator, a vapor-liquid split was achieved at 3 bar and 160 °C, isolating non-
condensable gases and water from a liquid phase rich in phthalic anhydride. The RadFrac
distillation column (FRACT1), configured with 33 stages and operating at 3 bar, successfully
12
separated maleic anhydride (light key) in the overhead stream and phthalic anhydride (heavy
key) as a purified bottom product. The column performance was robust, yielding
38.67 kmol/hr of phthalic anhydride in the bottom stream at 337 °C with a low reflux ratio of
0.01.

Overall, the simulation demonstrated high product purity, efficient thermal integration, and
accurate phase behavior, validating the process design and supporting its potential for
industrial application.

4 SENSITIVITY ANALYSIS

4.1 STUDY SELECTION

Define study objectives for the sensitivity analysis as per Table 4
Table 4: Scope of sensitivity analysis

Case No. Manipulated variable Study Objective

1 Stream-Var Stream=S13 To study the effect of Feed change in mole flow on the
Substream=MIXED Phathalic anhydride Production from O-Xylene
Variable=MASS-FLOW
Units=kg/hr

4.2 SENSITIVITY ANALYSIS RESULTS

Sensitivity Results Curve
1.00 450
0.95 445
VARY 1 S1 MIXED TOTAL MO LEFLOW KMOL/HR
440
0.90 S19
435
0.85
430
0.80 425
VARY 1 S1 MIXED TOTAL MO LEFLOW KMOL/HR

0.75 420
0.70 415
410
0.65
405
0.60
400
0.55 395
S19

0.50 390
0.45 385
380
0.40
375
0.35
370
0.30 365
0.25 360
0.20 355
350
0.15
345
0.10
340
0.05 335
0.00 330
330 335 340 345 350 355 360 365 370 375 380 385 390 395 400 405 410 415 420 425 430 435 440 445 450
VARY 1 S1 MIXED TOTAL MO LEFLOW KMOL/HR

13
5 ECONOMIC ANALYSIS
Perform preliminary economic calculation and investment analysis for the process. Report following
information.

1. Assumption of the boundary stream and utility prices

2. Equipment mapping
3. Assumption made regarding desired rate of return, APEA template, plant life, operational
hours/year etc.
4. Key economic indicators as per investment analysis

Utility 1
Electricity Purchase Price= 0.06 $/kWhr
Utility 2
Gas Purchase Price= 0.10625 $/kg
Utility 4
Steam Purchase Price= 0.0198 $/kg

14
15
6 CONCLUSIONS
The process utilizes essential unit operations such as a feed pump, air compressor, heater
furnace, reactor, cooler, flash separator, and distillation column to model a continuous and
thermally integrated system.

O-xylene is pumped and vaporized to 360 °C, then mixed with compressed air and fed to a
plug flow reactor operating at 3 bar and 360 °C. In the reactor, catalytic vapor-phase
oxidation of o-xylene occurs, generating phthalic anhydride, maleic anhydride, water vapor,
and CO₂ as products. Despite the removal of the heat exchanger, thermal control is
maintained using a downstream cooler that directly reduces the reactor effluent temperature
from 360 °C to 50 °C. The cooler efficiently handles a heat duty of approximately –
1.86 × 10⁶ cal/sec and brings the vapor fraction down to 0.68, preparing the stream for phase
separation.

A Flash2 separator operating at 160 °C and 3 bar separates the liquid-rich product phase from
gaseous byproducts. The bottom stream, containing phthalic anhydride and water, is further
purified in a RadFrac distillation column. Operating at 3 bar with 33 stages, the column
successfully isolates phthalic anhydride as a bottom product with high purity, while removing
maleic anhydride and water as overheads.

This simulation demonstrates a simplified yet robust design, maintaining conversion and
separation efficiency even in the absence of an intermediate heat exchanger, and forms a valid
basis for further optimization and economic assessment.

REFERENCES
1. Ulrich, G. D., and P. T. Vasudevan. Chemical Engineering Process Design and Economics: A
Practical Guide. 2nd ed., Process Publishing, 2004.

2. Peters, Max S., et al. Plant Design and Economics for Chemical Engineers. 5th ed., McGraw-
Hill, 2003.

3. Seider, Warren D., et al. Product and Process Design Principles: Synthesis, Analysis and
Design. 3rd ed., Wiley, 2009.

4. Turton, Richard, et al. Analysis, Synthesis and Design of Chemical Processes. 5th ed., Pearson
Education, 2018.

5. Towler, Gavin, and R. K. Sinnott. Chemical Engineering Design: Principles, Practice and
Economics of Plant and Process Design. 2nd ed., Elsevier, 2013.

6. Sinnott, R. K., and Gavin Towler. Chemical Engineering Design. 6th ed., Butterworth-
Heinemann, 2020.

7. Al-Malah, Kamal I. Aspen Plus: Chemical Engineering Applications. Wiley-AIChE, 2016.

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