CHAPTER THREE

METHODOLOGY

3.1 Process Description

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

bottom of the drying column is charged to the reactor system.

3.2 Feed Specifications

 Chlorine: 293 K, atmospheric pressure, 1 atm, 100% purity.

  Benzene: 293 K, atmospheric pressure, 1 atm, 99.95 wt% benzene, 0.05 wt% water.

3.3 Product Specifications

 Monochlorobenzene: 99.7 wt% purity.

 Dichlorobenzene: 99.6 wt% purity.

 Hydrogen chloride gas: less than 250 ppm by weight benzene.

3.4 Utilities

 Steam: dry saturated at 8 bar and at 24 bar.

 Cooling water: 293 K.

 Process water: 293 K.

 Caustic soda solution: 5 wt% sodium hydroxide, 293 K.

 Electricity: 440 V, 50 Hz, 3 phases.

3.5 Data Supplied

𝐹𝑒𝑟𝑟𝑖𝑐 𝑐ℎ𝑙𝑜𝑟𝑖𝑑𝑒 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡,2.4 𝑏𝑎𝑟,328 𝐾

 𝐶6 𝐻6 + 𝐶𝑙2 → 𝐶6 𝐻5 𝐶𝑙 + 𝐻𝐶𝑙

𝐹𝑒𝑟𝑟𝑖𝑐 𝑐ℎ𝑙𝑜𝑟𝑖𝑑𝑒 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡,2.4 𝑏𝑎𝑟,328 𝐾

 𝐶6 𝐻5 𝐶𝑙 + 𝐶𝑙2 → 𝐶6 𝐻5 𝐶𝑙2 + 𝐻𝐶𝑙

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

concentration of dissolved chlorine remains essentially constant. Thus,

𝑟𝐵 = 𝑘1 𝑥𝐵

𝑟𝑀 = 𝑘1 𝑥𝐵 − 𝑘2 𝑥𝑀
𝑟𝐷 = 𝑘2 𝑥𝑀

Where r = rate of reaction.

𝑘1 = rate constant for reaction (1) at 328 K, 1.00 × 10−4 𝑠 −1.

𝑘2 = rate constant for reaction (2) at 328 K, 0.15 × 10−4 𝑠 −1.

X = mol fraction.

The subscripts B, M and D represent benzene, monochlorobenzene and dichlorobenzene

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

constraints of the plant are:

 The plant is designed to minimize harmful emission to the air.

 The plant is designed to minimize DCB yield which forms at high temperatures and

maximize MCB yield which is desirable for industrial purposes.

 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)

Temperature (K) 293 303 313 323

g 𝐻2 𝑂/100 g 𝐶6 𝐻6 0.050 0.072 0.102 0.147

g 𝐶6 𝐻6 /100 g 𝐻2 𝑂 0.175 0.190 0.206 0.225

Table 3.2: Thermodynamic and Physical Properties

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

Density (𝑘𝑔/𝑚3 ) 298 K 872 1110

350 K 815 1040 1230
400 K 761 989 1170
450 K 693 932 1100
500 K 612 875 1030

Viscosity (Ns/𝑚2 ) 298 K 0.598 × 10−3 0.750 × 10−3

350 K 0.326 × 10−3 0.435 × 10−3 0.697 × 10−3
400 K 0.207 × 10−3 0.305 × 10−3 0.476 × 10−3
450 K 0.134 × 10−3 0.228 × 10−3 0.335 × 10−3
500 K 0.095 × 10−3 0.158 × 10−3 0.236 × 10−3

Surface tension (N/m) 298 K 0.0280 0.0314

350 K 0.0220 0.0276 0.0304
400 K 0.0162 0.0232 0.0259
450 K 0.0104 0.0177 0.0205
500 K 0.0047 0.0115 0.0142
3.7 Description of Process Equipment

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

the respective equipment as follows:

 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

catalyst. As a result of the exothermic nature of the chlorination, water is used as a

cooling medium to maintain the system at desired temperature. After considerable

quantity of MCB has formed, the chlorine combines with the MCB produce p-DCB as

shown in the reaction stoichiometry.

 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.

Also, gaseous chlorine reacts with MCB to yield p-DCB.

 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.

HCl + NaOH → NaCl + 𝐻2 𝑂

Figure 3.1: Process Flow Diagram of the Chlorination Process
Legend:

A mixer

B drying distillation column

C reactor 1

D reactor 2

E neutralizer (washer)

F cooler

G activated carbon adsorber

H benzene distillation column

I chlorobenzene distillation column

 Benzene column (H): The feed to the system consists of MCB, DCB and unreacted

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

products are charged to chlorobenzene column.

 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

plant for use elsewhere.

 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

calculate the flow rate of process streams.

4.1 Material balance across reactor system

Basis: 20,000 tonnes MCB/yr and 2,000 tonnes DCB/yr.

On-stream time (i.e. operating period per year) is 320 days.

20,000 𝑡𝑜𝑛 𝑀𝐶𝐵 103 𝑘𝑔 𝑀𝐶𝐵 1 𝑦𝑟 1 𝑑𝑎𝑦

MCB produced in kg/hr: × × × = 2604.17 kg/hr
𝑦𝑟 1 𝑡𝑜𝑛 𝑀𝐶𝐵 320 𝑑𝑎𝑦𝑠 24 ℎ𝑟

2604.17 𝑘𝑔 𝑀𝐶𝐵 1 𝑘𝑚𝑜𝑙 𝑀𝐶𝐵

MCB produced in kmol/hr: × = 23.14 kmol/hr
ℎ𝑟 112.56 𝑘𝑔 𝑀𝐶𝐵

2,000 𝑡𝑜𝑛 𝑀𝐶𝐵 103 𝑘𝑔 𝑀𝐶𝐵 1 𝑦𝑟 1 𝑑𝑎𝑦

DCB produced in kg/hr: × × × = 260.42 kg/hr
𝑦𝑟 1 𝑡𝑜𝑛 𝑀𝐶𝐵 320 𝑑𝑎𝑦𝑠 24 ℎ𝑟

260.42 𝑘𝑔 𝐷𝐶𝐵 1 𝑘𝑚𝑜𝑙 𝐷𝐶𝐵

DCB produced in kmol/hr: × = 1.77 kmol/hr
ℎ𝑟 147 𝑘𝑔 𝐷𝐶𝐵

Reaction stoichiometry: 𝐶6 𝐻6 + 𝐶𝑙2 → 𝐶6 𝐻5 𝐶𝑙 + 𝐻𝐶𝑙

𝐶6 𝐻5 𝐶𝑙 + 𝐶𝑙2 → 𝐶6 𝐻4 𝐶𝑙2 + 𝐻𝐶𝑙

Benzene used up in kmol/hr: (23.14 + 1.77) kmol/hr = 24.91 kmol/hr

24.91 𝑘𝑚𝑜𝑙 𝐶6 𝐻6 78.11 𝑘𝑔 𝐶6 𝐻6

Benzene used up in kg/hr: × = 1945.72 kg/hr
ℎ𝑟 1 𝑘𝑚𝑜𝑙

Chlorine used up in kmol/hr: assume 100 percent conversion of chlorine.

Chlorine 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 = 𝑎𝑚𝑜𝑢𝑛𝑡 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 = 24.91 + 1.77 = 26.68 𝑘𝑚𝑜𝑙/ℎ𝑟

 26.68 𝑘𝑚𝑜𝑙 𝐶𝑙2 71 𝑘𝑔 𝐶𝑙2
Chlorine used up in kg/hr: × = 1894.28 kg/hr
ℎ𝑟 1 𝑘𝑚𝑜𝑙

Based on 100 percent chlorination, hydrogen chloride produced = 26.68 kmol/hr.

26.68 𝑘𝑚𝑜𝑙 36.5 𝑘𝑔 𝐻𝐶𝑙

HCl produced in kg/hr: × = 973.82 kg/hr
ℎ𝑟 1 𝑘𝑚𝑜𝑙 𝐻𝐶𝑙

Benzene supplied: it is assumed that benzene is supplied in 20% excess.

𝐶6 𝐻6 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑− 𝐶6 𝐻6 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙𝑙𝑦

% excess = × 100
𝐶6 𝐻6 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙𝑙𝑦

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

L + V = 2334.86 + 0.0584 + 1894.28

L + V = 4229.20 kg/hr (1)

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,

0.99975V + 0.015L = 973.82 kg/hr (2)

By solving equations (1) and (2) simultaneously yields;

V = 924.48 kg/hr

L = 3304.72 kg/hr

HCl in liquid product: 0.015 × 3304.72 = 49.57 kg/hr

HCl in vapour product: 973.82 – 49.57 = 924.25 kg/hr

Benzene in vapour product: 924.48 – 924.25 = 0.23 kg/hr

Unreacted benzene: 2334.86 – 1945.72 = 389.14 kg/hr

Benzene in liquid product: 389.14 – 0.23 = 388.91 kg/hr

1945.72
Overall percentage conversion of benzene: 2334.86 × 100 = 83.33 %

4.2 Material balance across neutralizer

Neutralizer reaction stoichiometry: NaOH + HCl → NaCl + 𝐻2 𝑂

From the stoichiometry, 1 kmol NaOH requires 1 kmol HCl

49.57 𝑘𝑔 𝐻𝐶𝑙 1 𝑘𝑚𝑜𝑙 𝐻𝐶𝑙

HCl in liquid product (kmol/hr): × = 1.3581 kmol/hr
ℎ𝑟 36.5 𝑘𝑔 𝐻𝐶𝑙

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

1.6297 𝑘𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 40 𝑘𝑔 𝑁𝑎𝑂𝐻

NaOH supplied in kg/hr: × = 65.19 kg/hr
ℎ𝑟 1 𝑘𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

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

1.3581 𝑘𝑚𝑜𝑙 58.54 𝑘𝑔 𝑁𝑎𝐶𝑙

NaCl formed in kg/hr: × = 79.50 kg/hr
ℎ𝑟 𝑘𝑚𝑜𝑙 𝑁𝑎𝐶𝑙

1.3581 𝑘𝑚𝑜𝑙 18.02 𝑘𝑔 𝐻2 𝑂

Water formed in kg/hr: × = 24.47 kg/hr
ℎ𝑟 1 𝑘𝑚𝑜𝑙
Table 4.1: Summary of process streams around reactor system

Stream names: liquid benzene chlorine vapour product liquid product

Components (kg/hr) (kg/hr) (kg/hr) (kg/hr)
MCB 2604.17

DCB 260.42

Chlorine 1894.28

HCl 924.25 49.57

Water 0.0584 0.0584

Benzene 2334.86 0.23 388.91

Total 2334.92 1894.28 924.48 3303.16

Figure 4.1: Reactor system

Total mass of water in neutralizer: 24.47 + 1238.61 + 0.0584 = 1263.14 kg/hr

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

Water in NaCl solution stream: 1263.14 – 0.19 = 1262.95 kg/hr

4.3 Material balance across benzene column

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.

Overall material balance across the system:

R + 𝐹𝐼 = 3253.69 kg/hr

R = 0.19 kg 𝐻2 𝑂/hr + 388.91 kg 𝐶6 𝐻6 /hr = 389.1 kg/hr

𝐹𝐼 = 3253.69 – 389.1 = 2864.59 kg/hr

4.4 Material balance across chlorobenzene column

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

2604.17 = 0.997D + 0.004B (4)

DCB balance:

260.42 = 0.003D + 0.996B (5)

Table 4.2: Summary of process streams around neutralizer

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

DCB 260.42 260.42

HCl 49.57

Water 0.0584 1238.61 1262.95 0.19

Benzene 388.91 388.91

NaOH 65.19 10.87

NaCl 79.50
Total 3303.16 1303.8 1353.32 3253.69

Figure 4.2: Neutralizer

Table 4.3: Summary of process streams around benzene column

Stream names: benzene column feed recycle chlorobenzene column feed

Components (kg/hr) (kg/hr) (kg/hr)
MCB 2604.17 2604.17

DCB 260.42 260.42

Water 0.19 0.19

Benzene 388.91 388.91

Total 3253.69 389.10 2864.59

Figure 4.3: Benzene column

Solving equations (3) and (4) simultaneously yields;

D = 2610.99 kg/hr

B = 253.60 kg/hr

Overhead products:

MCB = 2603.16 kg/hr

DCB = 7.83 kg/hr

Bottom products:

MCB = 1.01 kg/hr

DCB = 252.59 kg/hr

4.5 Material balance across fresh feed mixer and drying column

Recycle stream:

Benzene = 388.91 kg/hr

Water = 0.19 kg/hr

Reactor feed (B):

Benzene = 2334.86 kg/hr

Water = 0.0584 kg/hr

Benzene balance:

𝐵𝑓 + 388.91 = 2334.86

Where 𝐵𝑓 = benzene in fresh feed.

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

Stream names: chlorobenzene column feed overhead product bottom product

Components (kg/hr) (kg/hr) (kg/hr)
MCB 2604.17 2603.16 1.01

DCB 260.42 7.83 252.59

Total 2864.59 2610.99 253.60

Figure 4.4: Chlorobenzene column

 1945.95 ×0.050
Water in fresh benzene feed (𝑊𝑓 ) = = 0.97 kg/hr
100

Water balance:

0.97 + 0.19 = 0.0584 + 𝑊𝐷

Where 𝑊𝐷 = water removed as the overhead product of the drying column.

𝑊𝐷 = 1.1016 kg/hr

Figure 4.5: Mixer and benzene drying column

Table 4.5: Summary of process streams around mixer and drying column

Stream names: recycle fresh feed reactor feed water removed

Components (kg/hr) (kg/hr) (kg/hr) (kg/hr)
Benzene 388.91 1945.95 2334.86

Water 0.19 0.97 0.0584 1.1016

Total