Maleic anhydride is produced by the vapour

phase reaction of benzene with air (take as

21% oxygen and 79% nitrogen). The fresh
feed of benzene has the following
composition: 99.5% w/w benzene, 0.5% w/w
toluene.
The vapour phase catalysed reaction takes
place isothermally in a fluidised bed reactor
(to avoid hot spots) at 340C and 0.2 MPa,
with a pressure drop of 30 kPa. The
idealised reactor operates at 73%
conversion per pass of benzene. Assume
there is no oxygen in the reactor outlet. The
reactor temperature is maintained by
circulating liquid Dowtherm A with a
temperature leaving the reactor at 330C.
Assume a 10 change in the Dowtherm A
temperature between the inlet and outlet of
the reactor.
The reactor efflux is cooled and partly
condensed to 150C and then (ideally)
separated into two streams: a gas stream
containing all the nitrogen, carbon dioxide,
toluene and the unreacted benzene and a
liquid stream containing the crude maleic
anhydride and water. Assume the gas stream
is cooled to about 35C and all the nitrogen
and carbon dioxide leave the process, leaving
the benzene and toluene in the liquid phase.
Part of this stream is recycled, but the rest is
purged to avoid a build-up of toluene.
What is the chemical equation for the
production of maleic anhydride?
Draw a block diagram and annotate the
streams for your mass balance..
Calculate the rate and composition of the
purge stream.
The feeds to the process are at 20C.
The 10C change in the Dowtherm A stream
occurs in an external heat exchanger. Decide
how this temperature change can be
achieved. High pressure steam is more
valuable/costs more than lower pressure
steam. Note: Use Steam Tables and a
moderate temperature difference approach
(T) to decide on the steam pressure.
Calculate (not using a process simulator) the
heat to be removed to maintain this optimum
temperature for a crude maleic acid
production of 1,600 kg/h.
Draw a PFD and add the flows and conditions
of all streams to the PFD.
From an estimate of the overall heat transfer
coefficient, arrive at a layout for the heat
exchanger(s) using standard lengths and tube
diameters.
Calculate the overall heat transfer coefficient
and compare it with 4. above. Iterate using
the last calculated overall heat transfer
coefficient until the calculated value is
Draw a PFD and add the flows and conditions
of all streams to the PFD.
From an estimate of the overall heat transfer
coefficient, arrive at a layout for the heat
exchanger(s) using standard lengths and tube
diameters.
Calculate the overall heat transfer coefficient
and compare it with 4. above. Iterate using
the last calculated overall heat transfer
coefficient until the calculated value is
between 0 and +15% of the assumed
(previous value for same layout) value of the
heat transfer coefficient.
Draw an isometric sketch to determine the
piping lengths and the number of bends and
other fittings
Specify the duty of the Dowtherm A pump,
based on the pressure drop across the steam
generating heat exchanger, allowing for a
pressure drop across the reactor heat
removal system of 0.5 bar, that across the
control valve of 0.18 bar and the rest of the
piping and fittings.
Discuss how you would improve the process.
Thread:Isothermal reaction Post:RE: Isothermal reactionAuthor: Gerhart Goltz
Instructor Manager Posted Date: 20 November 2015 14:18Status:Published
The term isothermal reaction means that the temperature is maintained at the
reaction temperature. For an exothermic reaction the reactants are often fed at
below the reaction temperature, but the heat of reaction brings them to the
isothermal temperature. The reactor temperature is maintained by an external
cooling (or heating) loop.
In general gas phase fluidised bed reactors are not fed with liquid streams as
that might cause problems to the catalyst and to the fluidisation. My
recommendation would be to vaporise and preheat the combined fresh feed of
benzene and the recycle stream to a temperature some 10 to 20C above the
boiling point of the mixture at slightly above the reactor pressure. This will
compensate for any heat losses and pressure drop between the vaporiser and
the reactor inlet.
For the reactor energy balance you can then assume a benzene/toluene feed
temperature into the reactor and use that. You do not need to do an energy
balance over the vaporiser. The air does not have to be preheated. All the feeds
and the reactor outlet are thus in the vapour phase.

I am sure you have all found that maleic anhydride is a solid a 25C. Thus the
heat of formation will be for the solid. To calculate the enthalpy at the reactor
outlet, you need the sensible heat from 25 to the melting point, then the heat of
fusion, followed by the sensible heat from the melting point to the boiling point,
the latent heat of vaporisation at the boiling point and finally the sensible heat
of the vapour from the boiling point to the reaction temperature.
 Steam Inlet

2
n_3
(O_2)
n_4
20C (N_2)

1
n_1
(B)
n_2 130C Re
(T) 3
Pre Heater n_5 (B)
3
20C n_6 (T) 0.2
n_7
(O_2)
n_8
(N_2)
10
n_27 (B)
n_28 (T)

9
(Purge)
n_25 (B)
n_26 (T)
Equation

2b + 9o2 --> 2Ma + 4 Co2 + 4H2O

 H.E
Steam Outlet

4
Downtherm A n_9 (B)
320C n_10 (T)
n_11
(N_2)
n_12 (Ma)
n_13 (H_2
O)
n_14
Reactor (CO_2) Condenser &
340C Separator
0.2MPa 150C

330C

Separator
8 35C
n_23
(B)
n_24
(T)
 5
n_15
(Ma)
n_16
Condenser & (H_2 O)
Separator
150C

6
n_17 (B)
n_18 (T)
n_19
(N_2)
n_20
(CO_2)

Separator
35C

7
n_21
(N_2)
n_22
(CO_2)
 7
n_21
(N_2)
n_22
(CO_2)
 Fresh Feed Basis 100 kmol/hr
Purge Ratio 0.1

1 2 3
Benzene n1 99.6 n5
Toulene n2 0.4 n6
Oxygen n3 432.21 n7
Nitrogen n4 1626 n8
MA
Water
Carbon Dioxide
 4 5 6 7 8
131.57 n9 35.524 n17 35.524 n23
4 n10 4 n18 4 n24
432.21
1626 n11 1626 n19 1626 n21 1626
n12 96.048 n15 96.048
n13 192.1 n16 192.1
n14 192.1 n20 192.1 n22 192.1

Graph 1: The Effect

120.00

100.00

80.00

Flow Rate MA Product (n15) (kmol/hr) 60.00

 80.00

Flow Rate MA Product (n15) (kmol/hr) 60.00

40.00

20.00

0.00
0
 Purge Ratio

9 10 0.1
35.524 n25 3.5524 n27 31.972 0.2
4 n26 0.4 n28 3.6 0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

Graph 1: The Effect of Purge Ratio on the Flow Rate of Product

120.00

100.00

80.00

(n15) (kmol/hr) 60.00

 80.00

(n15) (kmol/hr) 60.00

40.00

20.00

0.00
0 0.2 0.4 0.6 0.8 1 1.2

Purge Ratio
Flow Rate MA Toluene Flow Rate Benzene Flow
Product (n15) to Reactor (n6) Rate to Reactor
(kmol/hr) (kmol/hr) (kmol/hr)
96.05 4.00 131.57
92.74 2.00 127.04
89.65 1.33 122.81
86.76 1.00 118.85
84.06 0.80 115.14
81.51 0.67 111.66
79.12 0.57 108.38
76.86 0.50 105.29
74.73 0.44 102.36
72.71 0.40 99.60

Graph 2: The Effect of Purge Ratio on the Flo

4.50

4.00

3.50

3.00

Toluene Flow Rate to Reactor 2.50

(n6) (kmol/hr)

2.00
 3.00

Toluene Flow Rate to Reactor 2.50

(n6) (kmol/hr)

2.00

1.50

1.00

0.50

0.00
0 0.2 0.4
 Graph 1 illustrates that by increasing the rati
Overall is reduced proportionally. However, from Gra
% Toluene to Liquid Conversion increasing the purge ratio, this could have im
Reactor Feed
By operating the process at a purge fraction
2.95 0.96 liquid feed. This purge ratio also balances th
1.55 0.93 to scale with the flow rate in the recycle stre
rate of 96% is produced at this purge ratio, a
1.07 0.90 whilst the market prices Benzene remains lo
0.83 0.87 acceptable ; the cost of the 4% wasted benz
this purge rate cannot be increased further,
0.69 0.84 this, due to the enviromental an safety hazar
0.59 0.82 known carcinogen and disposal of large quan
benefits.
0.52 0.79
0.47 0.77 1. SunSirs Commodity Data Group. 2015. Chi
Availabe from: www.sunsirs.com
0.43 0.75
0.40 0.73

Graph 2: The Effect of Purge Ratio on the Flow Rate of Toluene to the Reactor
0.2 0.4 0.6 0.8 1 1.2

Purge Ratio
 by increasing the ratio of feed which is purged from the recycle stream the flow rate of Maleic Anhydride
ly. However, from Graph 2, it is clear that the toluene feed to the reactor decreases significantly by
tio, this could have impacts on the efficiency of the reactor or catalyst.

ss at a purge fraction of 10% the amount of toluene fed to the reactor is only limited to 2.95% of the total
atio also balances the costs of running pumps and infrastructure for the recycle loop, which are assumed
ate in the recycle stream, with the increased production rate of Maleic Anhydride. An overall conversion
at this purge ratio, as can be seen in Table 1. As current prices of Maleic Anhydride are increasing radiply
s Benzene remains low, and in some cases appears to be falling, a overall conversion of 96% is more than
f the 4% wasted benzene feed would not outweight the extra costs accociated with recycling it. However,
be increased further, despite the apparent reduced costs of infrastructure that could be achieved by doing
mental an safety hazards associated with disposing of a feed rich in benzene and toluene. Benzene is a
disposal of large quanties of purge mixture would greatly outweigh any of the previously apparent cost

Data Group. 2015. Chinese Benzene/ Maleic Anhydride Prices. [Online]. [Accessed 15th November 2015].
nsirs.com

Graph 3: The Effect of the Purge Ratio of the Compositi

3.50

3.00

2.50

2.00

% Toluene in Liquid Reactor Feed

1.50
 2.50

2.00

% Toluene in Liquid Reactor Feed

1.50

1.00

0.50

0.00
1.2 0 0.2 0.4 0

Purge R
of Maleic Anhydride
gnificantly by

o 2.95% of the total

which are assumed
overall conversion
re increasing radiply
of 96% is more than
ecycling it. However,
be achieved by doing
ne. Benzene is a
usly apparent cost

h November 2015].

atio of the Composition of Liquid Feed to Reactor

0.4 0.6 0.8 1 1.2

Purge Ratio
Feed B n1=0.996(n1+n2)
T n2=0.004(n1+n2)

Air O2 n3=0.21(n3+n4)
N2 n4=0.79(n3+n4)

Overall Balance B n1=n15+n25

T n2=n26

First Mixing T B n5=n27+n1

T n6=n28+n2
O2 n3=n7
N2 n4=n8

Balance Benzene Over Reactor

(73% Conversion Benzene Feed)
Reacted B n12=0.73n5
Unreacted B n9=0.27n5
H2O n13=4*n12
CO2 n14=4*n12
N2 n8=n11
O2 n14=(4/9)n7

First Condensor/Seperator B n9=n17

T n10=n18
N2 n11=n19
MA n12=n15
H2O n13=n16
CO2 n14=n20

Second Seperator B n17=n23

T n18=n24
N2 n19=n21
CO2 n20=n22

Purge Fraction (X) X=n25/n9

Purge T B n23=n25+n27 n25=X*n23

T n24=n26+n28 n26=X*n24
n23=Xn25+(1-X)n27
n24=Xn26+(1-X)n28
Basis: 1600 kg/hr Maleic Anhydride Product Purge Ratio

Maleic Anhydride
Mr 98 g/mol 1
Mass 1600 kg/h Benzene n1s
Moles Required 16.32653 kmol/h Toulene n2s
Current Moles 96.04756 kmol/h Oxygen
Scale Ratio 0.169984 Nitrogen
Required Fresh Feed 16.99838 kmol/h MA
Water
Carbon Dioxide
 0.1

1 2 3 4 5 6
16.93039 n5s 22.4 n9s 6.0 n17s
0.067994 n6s 0.7 n10s 0.7 n18s
n3s 73.5 n7s 73.5
n4s 276.4 n8s 276.4 n11s 276.4 n19s
n12s 16.3 n15s 16.3
n13s 32.7 n16s 32.7
n14s 32.7 n20s
6 7 8 9 10
6.0 n23s 6.0 n25s 0.6 n27s 5.4
0.7 n24s 0.7 n26s 0.1 n28s 0.6

276.4 n21s 276.4

32.7 n22s 32.7

 Reference: All substances other then Dowtherm A (T = 25 C, P= 0.2
MPa,Vapour); Dowtherm A (T=320, gas)
Substance Phase Nin Hin Nout Hout
Downtherm Vapour 0 0
Benzene Vapour 22.36511 -132516.4324 6.03858 179400.42
Toulene Vapour 0.679935 668.40492444 0.679935 15615.336
Oxygen Vapour 73.46939 -1.79214E+11 0 0
Nitrogen Vapour 276.3848 0 276.3848 56629.452
MA Vapour 0 0 16.32653 1.56E+03
Water Vapour 0 0 32.65306 1.16E+04
Carbon Dioxide Vapour 0 0 32.65306 -4.34E+11

Benzene 80.1
Toulene 110.6
MA 202
Dowtherm 257
 Reference: Steam (T = 330 C, P= ?,Vapour); Dowtherm A
(T=320, gas)
Substance Nin Hin Nout Hout
Downtherm 0 0
Steam 0
Dowtherm A Water
T1 593 T1 373
T2 603 T2 613
Specific Enthalpy 191666416.1 J/kg.K Specific Enthalpy 1998.519
1.92E+05 kJ/kg.K 2.00E+00

heat capacity liquid

4.18 kJ/kg*k
enthaplpy liquid 313.5

Hf (kJ/mol) Heat of reaction

C6H6 0.008288 2747.132
MA -470.41
CO2 -393.776
H2O -57.7979
 Carbon Dioxide Benzene
T1 298 T1 353.1
T2 613 T2 613
J/kg.K Specific Enthalpy -1.328636E+13 J/kg.K Specific Enthalpy 29701565
kJ/kg.K -1.33E+10 kJ/kg.K 29701.56

Toluene Toluene
T1 383.6 T1 383.6
T2 613 T2 403
Specific Enthalpy 22909578.3637 J/kg.K Specific Enthalpy 926705.9
22909.5783637 kJ/kg.K 926.7059

O2 N2
T1 298 T1 298
T2 403 T2 403
Specific Enthalpy -2.439301E+12 J/kg.K Specifc Enthalpy 68286.8
-2439301335.6 kJ/kg.K 68.2868

MA Heat of Fusion
T1 475 13.6 kJ/mol
T2 613
Specific Enthalpy 5827.16768575 J/kg.K Heat of vapourisation
5.83E+00 kJ/kg.K 54.8 kJ/mol

Specific Heat (Solid and liquid)

0.1199 kJ/mol.K

Specific Enthalpy (Solid)

3.30924

Specific Enthalpy (Liquid)

17.91306

Total Enthalpy MA
9.54E+01
 T1 353.1 Heat Capacity (liquid benzene)
T2 403 0.13569 kJ/mol.K
J/kg.K Specific Enthalpy -5932618 J/kg.K
kJ/kg.k -5932.62 kJ/kg.k Specific Enthalpy (liquid benzene)
7.476519

Heat Capacity (liquid) Specific Enthalpy (liquid) Heat of vapourisation (toluene)

0.1571 kJ/mol.K 56.33606 38.01 kJ/mol

J/kg.K Heat of vapourisation (benzene)

kJ/kg.K 22965.914423693 33.83 kJ/mol

Heat of vapourisation (water)

40.6559 kJ/mol
N2
T1 298
T2 613
J/kg.K Specifc Enthalpy 204893.5 J/kg.K Total Enthalpy (Water)
kj/kg.K 204.8935 kj/kg.K 3.56E+02

Total Enthalpy (Toluene in)

983.042

Total Enthalpy (Toluene out)

22965.91

Total Enthalpy (Benzene in)

-5925.14

Total Enthalpy (Benzene out)

29709.04
acity (liquid benzene)

nthalpy (liquid benzene)

apourisation (toluene)

apourisation (benzene)

apourisation (water)

halpy (Water)

halpy (Toluene in)

halpy (Toluene out)

halpy (Benzene in)

halpy (Benzene out)