METHODOLOGY
Liquid benzene (which must contain less than 30 ppm by weight of water) is charged into a
reactor system consisting of two continuous stirred tank reactors operating in series at 2.4 bar.
Gaseous chlorine is fed in parallel to both reactors. Ferric chloride acts as a catalyst, and is
produced in situ by the action of hydrogen chloride on mild steel. The reactor system is cooled to
maintain the operating temperature at 328 K. The hydrogen chloride gas leaving the reactors is
first cooled in order to condense most of the organic impurities. It then passes to an activated
carbon adsorber where the final traces of impurities are removed before it leaves the plant for use
elsewhere.
The crude liquid chlorobenzenes stream leaving the second reactor is washed with water and
caustic soda solution to remove all dissolved hydrogen chloride. The product recovery system
consists of two distillation columns in series. In the first column (the benzene column), unreacted
benzene is recovered as top product and recycled. In the second column (the chlorobenzene
column), the mono- and dichlorobenzene are separated. The recovered benzene from the first
column is mixed with the raw benzene feed and this combined stream is fed to distillation
column (the drying column) where water is removed as overhead. The benzene stream from the
3.4 Utilities
The dichlorobenzene is assumed to consist entirely of the para-isomer and the formation of
trichlorobenzenes is neglected. The rate equations is written in the first order form when the
𝑟𝐵 = 𝑘1 𝑥𝐵
𝑟𝑀 = 𝑘1 𝑥𝐵 − 𝑘2 𝑥𝑀
𝑟𝐷 = 𝑘2 𝑥𝑀
X = mol fraction.
respectively. The yield for the reactor system was calculated on the basis of equal liquid
residence times in the two reactors, with a negligible amount of unreacted chlorine in the vapour
product streams. It is assumed that the liquid product stream contains 1.5 wt% of hydrogen
chloride.
3.6 Constraints
The design of the facility is based on the feed (benzene and chlorine) and product (MCB, DCB
and HCl) specifications, utilities and constraints. The feed and product specifications along with
utilities are presented in sections 3.2 to 3.4 of this report. The main design and operation
The plant is designed to minimize DCB yield which forms at high temperatures and
The plant is designed to meet product specifications as stated in section 3.3 of this report.
Table 3.1: Solubility of water/benzene system (source: Seidell, 1941)
𝑪 𝟔 𝑯𝟔 𝑪 𝟔 𝑯𝟔 𝑪𝟔 𝑯𝟔 𝑪𝒍 𝑪𝟔 𝑯𝟔 𝑪𝒍 𝑪𝟔 𝑯𝟔 𝑪𝒍𝟐 𝑪𝟔 𝑯𝟔 𝑪𝒍𝟐
liquid gas liquid gas liquid gas
Heat of formation at 293 K (kJ/mol) 49.0 82.9 7.5 46.1 - 42.0 5.0
Heat capacity (kJ/kmol K) 298 K 136 82 152 92 103
350 K 148 99 161 108 193 118
400 K 163 113 170 121 238 131
450 K 179 126 181 134 296 143
500 K 200 137 192 145 266 155
The process flow diagram of the chlorination process is shown in Figure 3.1. The various
processes occurring in each of the equipment along with the reaction path are highlighted under
Reactor 1 (C): The feed to the reactor consists of liquid benzene from the bottom of the
drying column and gaseous chlorine at 293 K and 1 atm. The system is designed to
operate at 328 K and 2.4 bar. The degree of chlorination is controlled by ferric chloride
quantity of MCB has formed, the chlorine combines with the MCB produce p-DCB as
Reactor 2 (D): The feed to the system consists of liquid product at 328 K and 2.4 bar
from the reactor1 and gaseous chlorine at 293 K and 1 atm. The degree of chlorination is
controlled by ferric chloride catalyst. Due to the exothermic nature of the chlorination,
water is used as a cooling medium to maintain the system at desired temperature. The
gaseous chlorine combines with unreacted benzene from reactor 1 to yield more MCB.
Neutralizer (E): The feed to the system consists of crude liquid MCB, DCB, unreacted
benzene and entrained HCl at 328 K and 2.4 bar and caustic soda solution at 293 K and 1
atm. The dissolved HCl is removed by neutralization reaction with caustic soda solution
to sodium chloride and water. This is to protect downstream equipment from corrosion.
A mixer
C reactor 1
D reactor 2
E neutralizer (washer)
F cooler
benzene from the washer. To reduce the work load of the reboiler, the feed is preheated to
saturation temperature, 351 K using dry saturated steam at 8 bar. The unreacted benzene
is recovered as overhead product and recycled back to drying column. The bottom
Chlorobenzene column (I): The feed to the system consists of MCB and DCB from the
benzene column. The feed is preheated to saturation temperature, 351 K using dry
saturated steam at 8 bar in order to reduce the work load of reboiler. The overhead
product contains 99.7 wt% MCB while the bottom product contains 99.6 wt% DCB.
Benzene drying column (B): The feed to the column consists fresh liquid benzene at 293
K and 1 atm and recycled benzene from the mixer. The mixture is preheated to saturation
temperature, 351 K using dry saturated steam at 8 bar in order to reduce the work load of
reboiler. Water is removed as overhead product and the bottom liquid benzene is fed to
reactor 1.
Activated carbon adsorber (G): The feed to the unit consists of hydrogen chloride gas and
trace amount of organic impurities from the reactor system. The organic impurities are
retained on the surface of the adsorbent and the purified hydrogen chloride leaves the
Mixer (A): This is used to combine raw benzene feed and recycle benzene prior to drying
column.
CHAPTER FOUR
MATERIAL BALANCE
To design a chemical process plant, the material balance analysis enables the process designer to
1945.72 𝑘𝑔 𝐶6 𝐻6 20 𝑘𝑔 𝐶6 𝐻6
𝐶6 𝐻6 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 = + (1945.72 × ) = 2334.86 kg/hr
ℎ𝑟 100 ℎ𝑟
Water in benzene supplied: it is assumed that fresh benzene stream contains 25 ppm water.
2334.86 𝑘𝑔 25
× = 0.0584 kg/hr
ℎ𝑟 1,000,000
The steady state material balance across reactor system is taken as follows:
B+C=L+V
HCl balance across reactor system: since the vapour product stream contains less than 250 ppm
(0.025 wt %) by weight of benzene and liquid product stream is entrained with 1.5 wt % HCl,
therefore,
V = 924.48 kg/hr
L = 3304.72 kg/hr
1945.72
Overall percentage conversion of benzene: 2334.86 × 100 = 83.33 %
From the reaction stoichiometry, 1.3581 kmol of NaOH is required to remove entrained HCl in
liquid product. To ensure the liquid product is totally free of HCl, 20% excess NaOH is charged
to the neutralizer.
𝑘𝑚𝑜𝑙 20 𝑘𝑚𝑜𝑙
NaOH supplied in kmol/hr: 1.3581 + 100 × 1.3581 = 1.6297 kmol/hr
ℎ𝑟 ℎ𝑟
65.19 𝑘𝑔/ℎ𝑟
Since the caustic soda solution contains 5 wt % NaOH; 5 wt % NaOH = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 × 100.
65.19 ×100
Mass flow rate of solution = = 1303.8 kg/hr
5
95
Water in caustic soda solution: 1303.8 × = 1238.61 kg/hr
100
𝑘𝑔 𝑘𝑔
Unreacted NaOH = 65.19 ℎ𝑟 - 40 × 1.3581 = 10.87 kg/hr
ℎ𝑟
DCB 260.42
Chlorine 1894.28
From the solubility data for water/benzene system, 100 g 𝐶6 𝐻6 will dissolve 0.050 g 𝐻2 𝑂 at 293
388.91 ×0.050
K. Therefore, 388.91 kg 𝐶6 𝐻6 will dissolve kg 𝐻2 𝑂 = 0.19 kg/hr.
100
The feed to the column contains chlorinated products (MCB and DCB), unreacted benzene and
water. The unreacted benzene and water are separated and recycled back to the drying column.
The chlorinated products are fed to the chlorobenzene column.
R + 𝐹𝐼 = 3253.69 kg/hr
𝐹𝐼 = 𝐷 + 𝐵
D + B = 2864.59 (3)
MCB balance: 𝑍𝑓 𝐹𝐼 + 𝑥𝐷 𝐷 + 𝑥𝐵 𝐵
𝑍𝑓 𝐹𝐼 = 2604.17 kg/hr
𝑥𝐷 = 0.997
𝑥𝐵 = 0.004
DCB balance:
Stream names: liquid product caustic soda NaCl solution benzene column feed
Components (kg/hr) (kg/hr) (kg/hr) (kg/hr)
MCB 2604.17 2604.17
HCl 49.57
NaCl 79.50
Total 3303.16 1303.8 1353.32 3253.69
D = 2610.99 kg/hr
B = 253.60 kg/hr
Overhead products:
Bottom products:
4.5 Material balance across fresh feed mixer and drying column
Recycle stream:
Benzene balance:
𝐵𝑓 + 388.91 = 2334.86
𝐵𝑓 = 1945.95 kg/hr
From solubility data for water/benzene system, 100 g 𝐶6 𝐻6 will dissolve 0.050 g 𝐻2 𝑂 at 273 K.
Table 4.4: Summary of process streams around chlorobenzene column
Water balance:
𝑊𝐷 = 1.1016 kg/hr