CH

CHE655
Plant Design Project #5
Summer 2013
DESIGN OF A MALEIC ANHYDRIDE PRODUCTION PROCESS
(Courtesy of the Department of Chemical Engineering at West Virginia University,
University USA)

Introduction
Maleic anhydride is a chemical intermediate that is used to produce resins, surface coatings,
lubricant additives,
es, and agricultural chemicals. The compounds chemical formula is
C2H2(CO)2O and is the acid anhydride of maleic acid. In its pure state, the compou
compound is
colorless or white solid with an acrid odor. Maleic anhydride was traditionally manufactured by
the oxidation of benzene or other aromatic compounds. As of 2006, only a few smaller plants
continue to use benzene; due to rising benzene prices, most maleic
maleic anhydride plants now use nbutane as a feedstock.
The purpose of this project is to do a preliminary analysis to determine the feasibility of
constructing a chemical plant to manufacture 40,000 ton/year
ton/y r maleic anhydride. The raw
material is benzene. Your job is to analyze a simplified maleic anhydride production process, to
suggest profitable operating conditions, and to write a final report summarizing your findings.

Chemical Reactions
The raw material is benzene. The primary reaction is one in which
which benzene is partially oxidized
to form maleic anhydride (Equation 1). There are three undesired side reactions, the subsequent
combustion of maleic anhydride (Equation 2), the complete combustion of benzene (Equation 3),
and the formation of the by-pr
product, quinone (Equation 4).
The reactions and reaction kinetics are:
k

1 C H O ( g ) + 2CO ( g ) + 2 H O ( g )
C6 H 6 ( g ) + 4.5O2 ( g )
4 2 3
2
2

benzene

(1)

maleic anhydride
k

2 6CO ( g ) + 3H O ( g )
C6 H 6 ( g ) + 7.5O2 ( g )
2
2

(2)

benzene
k

3 4CO ( g ) + H O ( g )
C4 H 2O3 ( g ) + 3O2 ( g )
2
2

maleic anhydride

(3)

2
k

4 C H O ( g ) + H O( g )
C6 H 6 ( g ) + 1.5O2 ( g )
6 4 2
2

benzene

(4)

quinone

where
ri = kiCbenzene or r3 = k 3C maleic anhydride

(5)

k1 = 7.7 106 exp( 25,143/ RT )

(6)

k2 = 6.31 107 exp( 29,850 / RT )

(7)

k3 = 2.33 104 exp( 21, 429 / RT )

(8)

k4 = 7.20 105 exp( 27,149 / RT )

(9)

and

The units of reaction rate, ri, are kmol/m3(reactor)s, the activation energy is given in cal/mol
(which is equivalent to kcal/kmol), the units of ki are m3(gas)/m3 (reactor)s, and the units of
concentration are kmol/m3(gas).
The catalyst is a mixture of vanadium and molybdenum oxides on an inert support. Typical inlet
reaction temperatures are in the range of 350-400C. The maximum temperature that the catalyst
can be exposed to without causing irreversible damage (sintering) is 650C. The catalyst
diameter is 5 mm, and the void fraction of the bed is 0.5.

Process Description
The PFD for the (starting) process is given in Figure 1.

E-501
H-501
E-502
R-501
V-501
T-501
T-502
E-503
H-502
C-501
Air Feed
BenzeneFeed Feed Fired Reactor Effluent Maleic Anhydride Dibutyl Phthalate Maleic Anhydride Maleic Anhydride Maleic Tower Maleic Tower
Compressor Vaporizer
Heater
Cooler
Reactor
Mixing Vessel
Absorber
Distillation Column Condenser
Reboiler/Fired
Heater

9
13

Dibutyl Phthalate
E-501

V-501

Waste Gas

poc

11

10

Benzene

lps

H-501
2

Air

5
6

C-501

E-503

T-501

cw
14

air

ng

T-502

Maleic
Anhydride

12

R-501

poc

cw
8

H-502

7
cw

E-502
air ng

Figure 1: Maleic Anhydride Production Process

2

Process Details
Feed Stream and Effluent Streams
Stream 1: Benzene stored as a liquid at the desired pressure of the reaction. The
cost of benzene is $4.73/L (liquid).
Stream 2: Air or pure oxygen present at 200% excess based on maleic anhydride
formation reaction (note: 100% excess is double the stoichiometric
amount). Consider air to have zero cost and to have 79 mol % N2, 21 mol
% O2. The cost for pure oxygen is $0.20/100 std ft3 (60F, 1 atm).
Oxygen is available at 60F and 1 atm.
Stream 9: Dibutyl phthalate solvent make-up stream for amount lost in Streams 11
and 14. The cost is $1.72/kg.
Stream 11: Waste gas contains unreacted benzene and O2, N2, CO2, and H2O, plus
some dibutyl phthalate sent to treatment process, the cost of which may
be considered negligible.
Stream 14: Maleic anhydride product. Specifications for this stream are given below.
The product is to be sold at $1.08/kg of maleic anhydride in the stream.
Equipment
Compressor (C-501)
The compressor increases the pressure of the feed air or oxygen to the reactor
pressure. The compressor may be assumed to be adiabatic. In that case, the
compressor work, Ws, may be calculated as
Ws = 4.5 R(Tout Tin )

(10)

where Ws is in [kJ/kmol] and the inlet and outlet temperatures, Tin and Tout,
respectively are in [K]. The outlet and inlet temperatures are related through:

Tout

P
= Tin out
Pin

0.286

(11)

The cost of electricity to run the compressor is a utility cost.

Heat Exchanger (E-501)
This heat exchanger vaporizes the benzene feed to 10C of superheat at the stream
pressure. The cost of the heat source is a utility cost.
Fired Heater (H-501)

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This heats reactor feed vapor to reaction temperature. Natural gas is used as the fuel,
and the amount needed is based on the LHV of natural gas. The cost of natural gas is
a utility cost.
Reactor (R-501)
This is where the reactions in Equations 1-3 occur. Details of the reactor are presented
below. There are two possible reactor configurations. The one illustrated in Figure 1
shows heat removal to maintain a constant temperature. In this case, the cost of the
medium to remove heat (cooling water, cw, in Figure 1) is a utility cost. The
alternative reactor configuration is an adiabatic reactor, in which there is no heat
removal. The heat generated by the reaction raises the temperature of the exit stream.
The temperature constraints described below must be obeyed.
Absorber (T-501)
The absorber runs at 1.5 atm and 100C (outlet streams and Stream 8). In the
absorber, 99% of the maleic anhydride in Stream 8 is absorbed into the solvent dibutyl
phthalate. For accounting purposes, all maleic anhydride in the recycle stream
(Stream 13) may be assumed to go to Stream 12. You should assume that 0.001% of
the dibutyl phthalate in Stream 10 is lost into Stream 11. This plus the dibutyl
phthalate in Stream 14 is the amount of dibutyl phthalate needed in Stream 9. The
cost of Stream 9 is a raw material cost.
Distillation Column (T-502)
This column runs at 1 atm. (The pressure is controlled by a valve in the product stream
from R-501.) Separation of maleic anhydride and dibutyl phthalate occurs in this
column. Of the maleic anhydride in Stream 12, 99% enters Stream 14. Similarly,
99% of dibutyl phthalate in Stream 12 enters Stream 13.
Heat Exchanger (E-503):
In this heat exchanger, the contents of the top of T-502 are condensed from saturated
vapor to saturated liquid at the column pressure. It may be assumed that this stream
condenses at the boiling point of maleic anhydride at the column pressure. The
flowrate of the stream from T-502 to E-503 is three times the flowrate of Stream 14.
(That is to say, one-third of the condensate becomes Stream 14, and the remainder is
returned to the column.) There is a cost for the amount of cooling water needed; this
is a utility cost. The cooling water leaving E-503 must always be at a lower
temperature than that of the stream being condensed.
Fired Heater (H-502):
In this heat exchanger, you may assume that the stream that has been vaporized and is
being returned to T-502 has the same flowrate as Stream 13. The stream from H-502
is vaporized from saturated liquid to saturated vapor at the boiling point of dibutyl
phthalate at the column pressure. Natural gas is used as the fuel, and the amount
needed is based on the LHV of natural gas. The cost of natural gas is a utility cost.

6
Vessel (V-501)
In this vessel, make-up dibutyl phthalate and recycled dibutyl phthalate streams are
mixed.

Additional Constraints

The LFL of benzene may not be exceeded in any stream

No excess steam can be exported from the plant. Therefore, any steam generated
within the process must be used within the process.
The following specifications for products must be met if a product is to be sold:
Maleic Anhydride purity > 99.8 mass%
Quinone purity > 99 mass%
Maleic Acid purity > 99.8 mass%
Any liquid organic stream may be burned in a fired heater as fuel, and a credit may be
taken for the fuel value (LHV) of the stream.
All distillation columns must be simulated using rigorous unit operations (e.g.
RADFRAC in Aspen Plus)

Economic Analysis
When evaluating alternative cases, you should carry out an economic evaluation and
profitability analysis based on a number of economic criteria such as payback period, internal
rate of return, and cash flow analysis. In addition, the following objective function should be
used. It is the equivalent annual operating cost (EAOC), and is defined as
EAOC = (product value feed cost other operating costs capital cost annuity)
A negative value of EAOC means there is a profit. It is desirable to minimize EAOC; i.e., a
large negative value of EAOC is very desirable, although you are not being asked to carry out
optimization.
Utility costs are those for steam, cooling water, boiler-feed water, natural gas, and electricity.
The capital cost annuity is an annual cost (like a car payment) associated with the one-time,
fixed capital cost of plant construction and installation.
The capital cost annuity is defined as follows:

capital cost annuity = FCI

i(1 + i) n
(1 + i ) n 1

(12)

where FCI is the installed cost of all equipment; i is the interest rate; and n is the plant life, in
[y]. For accounting purposes, take i = 0.15 and n = 10.
For detailed sizing, costing, and economic evaluation including profitability analysis, you
may use the Aspen Process Economic Analyzer (formerly Aspen Icarus Process Evaluator) in

7
Aspen Plus Version 8. However, it is also a good idea to independently verify the final
numbers based on other sources such as cost data given below.

Other Information
You should assume that a year equals 8,000 hours. This is about 330 days, which allows for
periodic shut-down and maintenance.

Final Comments
As with any open-ended problem; i.e., a problem with no single correct answer, the problem
statement above is deliberately vague. You may need to fill in some missing data by doing a
literature search, Internets search, or making assumptions. The possibility exists that as you
work on this problem, your questions will require revisions and/or clarifications of the
problem statement. You should be aware that these revisions/clarifications may be
forthcoming.
Moreover, in some areas (e.g. sizing/costing) you are given more data and information than
what is needed. You must exercise engineering judgment and decide what data to use. Also
you should also seek additional data from the literature or Internet to verify some of the data,
e.g. the prices of products and raw materials.

References
1. Felder, R. M. and R. W. Rousseau, Elementary Principles of Chemical Processes (3rd
ed.), Wiley, New York, 2000.
2. Wankat, P., Equilibrium Staged Separation Processes, Prentice Hall, Upper Saddle
River, NJ, 1988.

Appendix 1
Economic Data
Equipment Costs (Purchased)
Note: The numbers following the attribute are the minimum and maximum values for that
attribute. For a piece of equipment with a lower attribute value, use the minimum attribute
value to compute the cost. For a piece of equipment with a larger attribute value,
extrapolation is possible, but inaccurate. To err on the side of caution, you should use the
price for multiple, identical smaller pieces of equipment.
Pumps

Heat Exchangers

Compressors

Compressor Drive

Turbine

Fired Heater

log10 (purchased cost ) = 3.4 + 0.05 log10 W + 0.15[log10 W ]2

W = power (kW, 1, 300)
assume 80% efficiency
log10 (purchased cost ) = 4.6 0.8 log10 A + 0.3[log10 A]2
A = heat exchange area (m2, 10, 1000)
log10 (purchased cost ) = 2.3 + 1.4 log10 W 0.1[log10 W ]2
W = power (kW, 450, no limit)
assume 70% efficiency
log10 (purchased cost ) = 2.5 + 1.4 log10 W 0.18[log10 W ]2
W = power (kW, 75, 2600)
log10 (purchased cost ) = 2.5 + 1.45 log10 W 0.17[log10 W ]2
W = power (kW, 100, 4000)
assume 65% efficiency
log10 (purchased cost ) = 3.0 + 0.66 log10 Q + 0.02[log10 Q ]2
Q = duty (kW, 3000, 100,000)
assume 80% thermal efficiency
assume can be designed to use any organic compound as a fuel

Vertical Vessel

log10 (purchased cost ) = 3.5 + 0.45 log10 V + 0.11[log10 V ]2

V = volume of vessel (m3, 0.3, 520)

Horizontal Vessel

log10 (purchased cost ) = 3.5 + 0.38 log10 V + 0.09[log10 V ]2

V = volume of vessel (m3, 0.1, 628)

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Additional Cost Information
Piping straight pipe

$/m = 5.0 (nominal pipe diameter, in)(1+(sch #)/20)0.25

sch = schedule number for pipe
use the same sch number for fittings and valves

fittings (except valves)

$/fitting = 50.0 (nominal pipe diameter, in)(1+(sch #)/20)0.25

Valves for gate (isolation) valves

for control valve use

$100 (nominal pipe diameter, in)0.8 (1+(sch #)/20)0.25

$1000 (nominal pipe diameter, in)0.8(1+(sch #)/20)0.25

Equipment Bypasses
Bypasses around equipment should consist of a minimum of 20 ft of pipe, 2 standard elbows,
and 1 gate valve. There will also be a tee at each point where the by-pass connects to the
main pipe.

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Utility Costs
Low-Pressure Steam (618 kPa saturated)

$7.78/1000 kg

Medium-Pressure Steam (1135 kPa saturated)

$8.22/1000 kg

High-Pressure Steam (4237 kPa saturated)

$9.83/1000 kg

Natural Gas (446 kPa, 25C)

$6.00/GJ

Fuel Gas Credit

$5.00/GJ

Electricity

$0.06/kWh

Boiler Feed Water (at 549 kPa, 90C)

$2.45/1000 kg

Cooling Water
$0.354/GJ
available at 516 kPa and 30C
return pressure 308 kPa
return temperature is no more than 15C above the inlet temperature
Refrigerated Water
available at 516 kPa and 10C
return pressure 308 kPa
return temperature is no higher than 20C

$4.43/GJ

Deionized Water
available at 5 bar and 30C

$1.00/1000 kg

Waste Treatment of Off-Gas

incinerated - take fuel credit

Refrigeration

$7.89/GJ

Wastewater Treatment

$56/1000 m3

Equipment Cost Factors

Total Installed Cost = Purchased Cost (4 + material factor (MF) + pressure factor (PF))
Pressure < 10 atm, PF = 0.0
(absolute) 10 - 20 atm, PF = 0.6
20 - 40 atm, PF = 3.0
40 - 50 atm, PR = 5.0
50 - 100 atm, PF = 10

does not apply to turbines, compressors, vessels,

packing, trays, or catalyst, since their cost
equations include pressure effects

Carbon Steel MF = 0.0

Stainless Steel MF = 4.0

10

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Appendix 2
Other Design Data
Heat Exchangers
For heat exchangers that are not designed in detail, use the following approximations for
heat-transfer coefficients to allow you to determine the heat transfer area:

situation

h (W/m2C)

condensing steam

6000

condensing organic

1000

boiling water

7500

boiling organic

1000

flowing liquid

600

flowing gas

60

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