Production of maleic anhydride from benzene

Gonzalo Moreno, Adesuwa Omosigho, David Ortiz, Sal Ortiz, Alexis Cordero*
*Facultad de Ciencias Qumicas, Universidad Autnoma de Nuevo Len, Nuevo Len, Mxico
29 November 2016

Abstract
The production of maleic anhydride from benzene was analysed and the design of the
pumps, packed bed and compressor were obtained. The data suppositions as several
numbers of pipes longitude or diameters they helped to estimate the operation size and the
data obtain its very close to the reported in the process. We also calculate the installation
cost with the approximate prices of the equipment taking into consideration areas where
improvements could be made, adding or replacing equipment. For the calculation of every
situation we use equations based on books and for gases or liquids properties also giving
place if the flow type is turbulent or laminar.
Keywords: maleic anhydride, compressor, pumps, packed bed.

CONTENTS

1. Introduction
2. Justification
3. Objective
4. Process Diagram
5. Methodology
6. Results and discussions
7. Conclusions and suggestions
8. References
9. Attachments

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1. Introduction
Maleic anhydride is an organic compound. It is a colourless or white solid with an acrid
odor. It is produced industrially on a large scale for applications in coatings and polymers
Maleic anhydride is produced by steam-phase oxidation of n-butane. The overall process
converts the methyl groups to carboxylate and dehydrogenates the backbone. The
selectivity of the process reflects the robustness of maleic anhydride, with its conjugated
double-bond
system.
Traditionally
maleic
anhydride
was
produced
by
the oxidation of benzene or other aromatic compounds. As of 2006, only a few smaller
plants continue to use benzene.
The traditional method using benzene became uneconomical due to the high and still rising
benzene prices and by complying the regulations of benzene emissions. In addition, in the
production of maleic anhydride (4 C-atoms) a third of the original carbon atoms is lost as
carbon dioxide when using benzene (6 carbon atoms). The modern catalytic processes start
from a 4-carbon molecule and only attaches oxygen and removes water; the 4-C-base body
of the molecule remains intact. Overall, the newer method is therefore more material
efficient.
Around 50% of world maleic anhydride output is used in the manufacture of unsaturated
polyester resins (UPR). Chopped glass fibres are added to UPR to produce fibreglass
reinforced plastics which are used in a wide range of applications such as pleasure boats,
bathroom fixtures, automobiles, tanks and pipes.

2. Justification
The calculation and design of process as the maleic anhydride which are precisely based on
the fluid mechanics is important since like many other because this helps us to control an
improve all the aspects on which we depend and thus not only economize on production,
but also manage the resources in a sustainable way.

3. Objective
Analyse, calculate and design different stages of unit operations in the production of maleic
anhydride from benzene and compare the results with the reported process accuracy
complementing it with what we have learned.

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4. Process diagram

Figure 1. Pipe and Instrumentation diagram (DTI) of production of maleic anhydride

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Process description
The benzene is vaporized in a heat exchanger, mixed with compressed air, and then heated in a fired heater,
prior to being sent to a packed-bed catalytic reactor, where the following reactions take place:
9
C6 H 6 + O C 4 H 2 O 3 +2 CO2 +2 H 2 O
2 2
C6 H 6 +

15
O 6 C O 2 +3 H 2 O
2 2

C 4 H 2 O3 +3 O 2 4 CO 2+ H 2 O
3
C6 H 6 + O2 C 6 H 4 O2 +2 H 2 O
2

All the reactions are highly exothermic. For this reason, the ratio of air to benzene entering the reactor is kept
very high. A typical inlet concentration of approximately 1.5 vol% of benzene in air is used. Cooling is achieved
by circulating molten salt (a mixture of sodium nitrite and sodium nitrate) concurrently through the shell of the
reactor and across the tubes containing the catalyst and reactant gases. This molten salt is cooled in two external
exchangers prior to returning to the reactor.
The reactor effluent, containing small amounts of unreacted benzene, maleic anhydride, quinone, and
combustion products is cooled and then sent to an absorber column, which has both a reboiler and condenser,
the vapor feed is contacted with recycled heavy organic solvent (dibutyl phthalate), This solvent absorbs the
maleic anhydride, quinone, and small amounts of water. Any water in the solvent leaving the bottom of the
absorber, reacts with the maleic anhydride to form maleic acid, which must be removed and purified from the
maleic anhydride. The bottoms product from the absorber is sent to a separation tower, where the dibutyl
phthalate is recovered as the bottoms product, and recycled back to the absorber. A small amount of fresh
solvent, is added to account for losses. The overhead product from the tower, is sent to the maleic acid column,
where 95 mol% maleic acid is removed as the bottoms product. The overhead stream is taken to the quinone
column, where 99mol% quinone is taken as the top product and 99.9mol% maleic anhydride is removed as the
bottoms product.

5. Methodology
We started with the calculation of pumps, with the corresponding divisions in the pipes starts with the balance
corresponding to the Bernoulli equation (Ec.1) taking different number of pipes as well as diameters.
2

nWp+

p
u
+g z+
=hft

Ec.1

Considering the different number of diameters calculated f

( ( ()

f =0.001375 1+ 20000

110
+
D

6 1
3

))

Ec.2

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To calculate the velocity of minimum fluidization in the packed bed we star with the Reynolds number Ec.3
=

v0 D p

Ec.3

We proceed with the minimum fluidization velocity with the Ergun equation (Ec.4), this results were compared
with the velocity in the reactor.
150 v 0 (1)2 1 .75 v 20 (1)
g( )=
+
D2p 3
Dp 3

Ec.4

We also calculate the work of the compressor in an adiabatic way Ec.5:

W Pr=

Pa
( 1) a

[( ) ]
Pb
Pa

Ec.5

And to compare the work and use the data, we also calculate it isothermally according to the equation:

W Pr=

P
RT
ln b
M
Pa

( )

Ec.6

6. Results and discussions

Table 1. Results of the pumps

Pump

Power
(Kw)

Operating point
Q (m3/h)
Efficiency

rpm

Impeller diameter
(m)

P-601 A/B
P-602 A/B
P-603 A/B
P-604 A/B
P-605 A/B
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P-606 A/B
The pumps with nomenclature P-601, P-602, P-604, P-605, P-606, P-606 are centrifugal/ electric drive, the P-603
A/B its a reciprocating7 electric drive.

In the packed bed the reaction no was considered and the results obtained demonstrate that the minimum
fluidization velocity is greater than the velocity achieved inside the reactor making it a fixed bed were the
catalyst particles are not affected by the rate at which the fluid flows.

Table 2. Packaged bed analysis (Reactor R-601)

P
(kPa)
148

Minimum fluidization
velocity

Velocity
(m/s)
1.3449

(m/s)
1.9523

The compressor in this process is adiabatic since the output temperature increases with respect to the input
but this consumes more energy than an isothermal compressor as can be seen in the table 3, but thanks to the
high costs of an isothermal compressor the adiabatic are more profitable, we did the analysis to calculate the
number of stages and considering this we found that three of these would provide greater efficiency to the
process since because they require less power.

Table 3. Compressor C-601

Compressor type
Isothermal
Adiabatic one step
Adiabatic three steps

Power (kW)
2652.78
3099.88
2841.13

Efficiency %
65
65
65

Material
Carbon Steel

Aaaaas

Table 4. Length and diameters of main pipes

Flow
number
2
16
10

Pipe length

Diameters

Material

(m)
1.350
3.351
18.361
17.3205

(in)
0.493
0.090
0.128
0.622

Commercial steel

Aaaaaa

Table 5. Fired Heater

Material
H-601

Length
(m)

Diameters
(m)

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aaaaaa

Table 6. Heat exchangers

Hi

ho

(W/m2k)

(W/m2k)

(W/m2k)

(W)

(m2)

Np

Ns

Length of
pipe

E-601
E-602
E-603
E-604
E-605
E-606
E-607
Aaaaaa

Below is the cost of installation and the annual energy cost that would be spent in the stages analyzed in the
process, (Table 7), the magnitude of the cost is very high giving equally high total expenditure.

Table 7. Cost of unit operations

Unit operations

Installations cost
(USD)

Energy annual
cost
(USD)

Total
(USD)

46.00 E +6

1.2373 E +9

1.2760 E +9

Pumps
Compressor
C-601
Fired heaters

The energy cost in USD varies significantly depending on the type of energy or location in the region

SIMULACION DE ANALISIS DE RIESGO

7. Conclusions and suggestions

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8. References
[1] Geankoplis, C. J. Procesos de transporte y principios de procesos de separacin
(incluye operaciones unitarias), 4a ed., Mxico, Grupo Editorial Patria, 2013.
[2] McCabe, W. L., Smith, J. C. y Harriott, P. Operaciones unitarias en ingeniera
qumica, 7ma ed., Mxico, McGraw-Hill Interamericana, 2007.
[3] White, F. M. Mecnica de Fluidos, 6a ed., Mxico, McGraw-Hill/Interamericana de
Espaa, 2008.
[4] De nevers. N. (1991). Fluid Mechanics for chemical enginners (2nd .Ed). United
States : Mcgraw-hill international Editions.
[5]. The MathWorks, Inc. (2014) MATLAB (Versin R2014a) U.S.A.: 1994-2016 The
MathWorks, Inc.

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9. Attachments
Nomenclature
Wpr

Adiabatic compressor power

Adiabatic dilatation coefficient
Pressure (Pa)

Gas constant

Density
Molecular weight

Length (m)

Diameter (m)

Flow (m3/s)

Reynolds number

Re

Fanning

gravity

height

Hydraulic radius

rH

Minimum fluidization velocity

v0

Porosity

hf

Sphericity
Dynamic viscosity Pa-s
Friction loss J/Kg; hff, in flow through fitting or valve; hfs,
skin friction
Head
Revolutions per minute

Heat transfer coefficient (W/m2K)

rpm

Total heat transfer coefficient (W/m2K)

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Area (m2)

Pipes number

Steps number

Np
Ns
Table 8. Material balance
1
30
101
868
0.000564

Temperature (C)
Pressure (kPa)
Density (kg/m3)
Viscosity (kg/m-s)
Heat capacity
(J/mol-C)
Flow (kg/h)
3304
Flow (kmol/h)
42.3
Flow compositions (kmol/h)
Maleic anhydride
0.0
Dibutyl phthalate
0.0
Nitrogen
0.0
Water
0.0
Oxygen
0.0
Benzene
42.3
Quinone
0.0
Carbon dioxide
0.0
Maleic Acid
0.0
Sodium nitrite
0.0
Sodium nitrate
0.0
9
Temperature (C)
330
Pressure (kPa)
82
Density (kg/m3)
Viscosity (kg/m-s)
Heat capacity
(J/mol-C)
Flow (kg/h)
139191.6
Flow (kmol/h)
500.1
Flow compositions (kmol/h)
Maleic anhydride
0.0
Dibutyl phthalate
500.1
Nitrogen
0.0
Water
0.0
Oxygen
0.0
Benzene
0.

2
30
101

3
30
280

4
170
101

5
460
250

6
608
235

7
608
220

8
270
215

3304
42.3

3304
42.3

80490
2790.0

80490
2790.0

83794
2832.3

83794
2825.2

83794
2825.2

0.0
0.0
0.0
0.0
0.0
42.3
0.0
0.0
0.0
0.0
0.0
10
320
100

0.0
0.0
0.0
0.0
0.0
42.3
0.0
0.0
0.0
0.0
0.0
11
194
82

0.0
0.0
2205.0
0.0
585.0
0.0
0.0
0.0
0.0
0.0
0.0
12
84
75

0.0
0.0
2205.0
0.0
585.0
0.0
0.0
0.0
0.0
0.0
0.0
13
195
80

0.0
0.0
2205.0
0.0
585.0
42.3
0.0
0.0
0.0
0.0
0.0
14
330
82

26.3
0.0
220.5
91.5
370.2
2.6
0.7
129.0
0.0
0.0
0.0
15
419
200

26.3
0.0
2205.0
91.5
370.2
2.6
0.7
129.0
0.0
0.0
0.0
16
562
200
1656
0.0009

30.6
0.1

141866
526.2

81225
2797.9

2597
26.2

139191.6
500.0

391925
5000.0

391925
5000.0

0.0
0.01
0.0
0.0
0.0
0.0

4.8
500.00
0.0
0.0
0.0
0.0

0.5
0.0
2205.0
91.5
370.2
2.6

24.8
0.0
0.0
0.0
0.0
0.0

0.0
500.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0

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Quinone
Carbon dioxide
Maleic Acid
Sodium nitrite
Sodium nitrate

0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0

0.4
0.0
1.0
0.0
0.0

0.4
129.0
0.0
0.0
0.0

0.4
0.0
1.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
2065.6
2934.4

0.0
0.0
0.0
2065.6
2934.4

Environmental impact
Table 8. Compressor C-601
Compressor type

Power (kW-h)
For year

CO2 Emissions
(kg)

Isothermal
Adiabatic one step
Adiabatic three steps

7.7011 E +10
8.9990 E +10
8.2479 E +10

5.0057 E +10
5.8494 E +10
5.3611 E +10

Energy savings and CO2 emissions compared to an one step adiabatic compressor.
Compressor type

Power (kW-h)
For year

CO2 Emissions
(kg)

Isothermal
Adiabatic three steps

1.2979 E +10
7.5114 E +9

7.9236 E +9
4.8525 E +9

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