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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
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
100.00
80.00
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
100.00
80.00
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
4.00
3.50
3.00
2.00
3.00
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
3.00
2.50
2.00
1.50
2.50
2.00
1.50
1.00
0.50
0.00
1.2 0 0.2 0.4 0
Purge R
of Maleic Anhydride
gnificantly by
h November 2015].
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)
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
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
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
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
apourisation (toluene)
apourisation (benzene)
apourisation (water)
halpy (Water)