Soran University

Faculty of Engineering
Chemical Engineering DlkazcvhbjzkLXMKjepartment

CHLOROBENZENES FROM BENZENE AND CHLORINE

Prepared by: Aram Nasih Muhammad,k;nbuoi;cvyuto7x56riydchgb

Supervisor: Mr. Ali Hossin

30/11/2020
Introduction
Chlorobenzene was one of the earliest heavy organic chemicals that is, those chemicals which
were produced industrially in large amounts. The former United Alkali Company first produced
chlorobenzene industrially at Widnes, England, in 1909. Chlorobenzene first acquired
importance during the World War I, when it was required in high tonnage 8 making phenol in
picric acid manufacture.
Chlorobenzene is a colorless, mobile liquid with an almond like odor. At ordinary temperature
and pressure chlorobenzene is unaffected by the presence of air, moisture, or light, and upon
prolonged boiling, shows no tendency to split off chlorine. The chlorine atom in chlorobenzene
is unreactive at ordinary temperatures and pressures. At moderate temperatures, chlorobenzene is
unaffected by steam, alkalis, hydrochloric acid, and dilute sulphuric acid. Even boiling for
several hours with alcoholic KOH has no effect on chlorobenzene. It is soluble in all proportions
in ether, chloroform, benzene, alcohol and carbon disulphide. It is insoluble in water. Hydrolysis,
with the formation of Phenol takes place at 450°C to 500°C in the presence of a catalyst or with
alcoholic alkalis or with water under pressure at high temperatures. Aniline may be prepared by
reaction with concentrated ammonium hydroxide under pressure in the presence of copper
catalyst. Of technical importance is the preparation of DDT by condensation of chlorobenzene
with chloral in the presence of fuming Sulphuric Acid. Chlorination of chlorobenzene in the
presence of a variety of catalysts produces prominently o and p-Dichlorobenzene isomers.
Chlorobenzene forms both binary and ternary azeotropic mixtures with water and a number of
organic liquids. Chlorobenzene are less toxic than benzene. Liquid chlorobenzene produces mild
to moderate irritation upon skin contact. Contact with eye tissue at normal temperature cause s
pain, mild to moderate irritation, and possibly some transient corneal injury. Prompt washing
with large quantities of water is extremely helpful. Continued contact may cause roughness or a
mild burn. Absorption through the skin is slow and with short-term exposure over a limited
period of time, no significant amounts will enter the body. Since the mono chlorobenzene vapor
forms explosive mixtures with air, open flames and smoking should not be allowed where
chlorobenzene is stored or used.

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  Description of Process Equipment
The process flow diagram of the chlorination process is shown in Figure 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 + 𝐻2𝑂

 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.

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 Mixer (A): This is used to combine raw benzene feed and recycle benzene prior to drying column.

Figure 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

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 MATERIAL BALANCE

To design a chemical process plant, the material balance analysis enables the process designer to

calculate the flow rate of process streams.

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.

MCB produced in kg/hr: 20,000 𝑡𝑜𝑛 𝑀𝐶𝐵𝑦𝑟 × 103 𝑘𝑔 𝑀𝐶𝐵1 𝑡𝑜𝑛 𝑀𝐶𝐵 × 1 𝑦𝑟320 𝑑𝑎𝑦𝑠 × 1 𝑑𝑎𝑦24 ℎ𝑟 =

2604.17 kg/hr

MCB produced in kmol/hr: 2604.17 𝑘𝑔 𝑀𝐶𝐵ℎ𝑟 × 1 𝑘𝑚𝑜𝑙 𝑀𝐶𝐵112.56 𝑘𝑔 𝑀𝐶𝐵 = 23.14 kmol/hr

DCB produced in kg/hr: 2,000 𝑡𝑜𝑛 𝑀𝐶𝐵𝑦𝑟 × 103 𝑘𝑔 𝑀𝐶𝐵1 𝑡𝑜𝑛 𝑀𝐶𝐵 × 1 𝑦𝑟320 𝑑𝑎𝑦𝑠 × 1 𝑑𝑎𝑦24 ℎ𝑟 =

260.42 kg/hr

DCB produced in kmol/hr: 260.42 𝑘𝑔 𝐷𝐶𝐵ℎ𝑟 × 1 𝑘𝑚𝑜𝑙 𝐷𝐶𝐵147 𝑘𝑔 𝐷𝐶𝐵 = 1.77 kmol/hr

Reaction stoichiometry: 𝐶6𝐻6 + 𝐶𝑙2 → 𝐶6𝐻5𝐶𝑙 + 𝐻𝐶𝑙

𝐶6𝐻5𝐶𝑙 + 𝐶𝑙2 → 𝐶6𝐻4𝐶𝑙2 + 𝐻𝐶𝑙

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

Benzene used up in kg/hr: 24.91 𝑘𝑚𝑜𝑙 𝐶6𝐻6ℎ𝑟 × 78.11 𝑘𝑔 𝐶6𝐻61 𝑘𝑚𝑜𝑙 = 1945.72 kg/hr

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

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

Chlorine used up in kg/hr: 26.68 𝑘𝑚𝑜𝑙 𝐶𝑙2ℎ𝑟 × 71 𝑘𝑔 𝐶𝑙21 𝑘𝑚𝑜𝑙 = 1894.28 kg/hr

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

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HCl produced in kg/hr: 26.68 𝑘𝑚𝑜𝑙ℎ𝑟 × 36.5 𝑘𝑔 𝐻𝐶𝑙1 𝑘𝑚𝑜𝑙 𝐻𝐶𝑙 = 973.82 kg/hr

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

% excess = 𝐶6𝐻6 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑− 𝐶6𝐻6 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙𝑙𝑦𝐶6𝐻6 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑡ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙𝑙𝑦 ×100

𝐶6𝐻6 𝑠𝑢𝑝𝑝𝑙𝑖𝑒𝑑 = 1945.72 𝑘𝑔 𝐶6𝐻6ℎ𝑟+ (1945.72 × 20100)𝑘𝑔 𝐶6𝐻6ℎ𝑟 = 2334.86 kg/hr

Water in benzene supplied: it is assumed that fresh benzene stream contains 25 ppm water.

2334.86 𝑘𝑔ℎ𝑟 × 251,000,000 = 0.0584 kg/hr

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

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

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

Overall percentage conversion of benzene: 1945.722334.86 ×100 = 83.33 %

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2. Material balance across neutralizer

Neutralizer reaction stoichiometry: NaOH + HCl → NaCl + 𝐻2𝑂

From the stoichiometry, 1 kmol NaOH requires 1 kmol HCl

HCl in liquid product (kmol/hr): 49.57 𝑘𝑔 𝐻𝐶𝑙ℎ𝑟 × 1 𝑘𝑚𝑜𝑙 𝐻𝐶𝑙36.5 𝑘𝑔 𝐻𝐶𝑙 = 1.3581 kmol/hr

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.

NaOH supplied in kmol/hr: 1.3581 𝑘𝑚𝑜𝑙ℎ𝑟 + 20100 ×1.3581 𝑘𝑚𝑜𝑙ℎ𝑟 = 1.6297 kmol/hr

NaOH supplied in kg/hr: 1.6297 𝑘𝑚𝑜𝑙 𝑁𝑎𝑂𝐻ℎ𝑟 × 40 𝑘𝑔 𝑁𝑎𝑂𝐻1 𝑘𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 = 65.19 kg/hr

Since the caustic soda solution contains 5 wt % NaOH; 5 wt % NaOH = 65.19 𝑘𝑔/ℎ𝑟𝑚𝑎𝑠𝑠 𝑜𝑓

𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 ×100.

Mass flow rate of solution = 65.19 ×1005 = 1303.8 kg/hr

Water in caustic soda solution: 1303.8 × 95100 = 1238.61 kg/hr

Unreacted NaOH = 65.19 𝑘𝑔ℎ𝑟 - 40 ×1.3581 𝑘𝑔ℎ𝑟 = 10.87 kg/hr

NaCl formed in kg/hr: 1.3581 𝑘𝑚𝑜𝑙ℎ𝑟 × 58.54 𝑘𝑔 𝑁𝑎𝐶𝑙𝑘𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 = 79.50 kg/hr

Water formed in kg/hr: 1.3581 𝑘𝑚𝑜𝑙ℎ𝑟 × 18.02 𝑘𝑔 𝐻2𝑂1 𝑘𝑚𝑜𝑙 = 24.47 kg/hr

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Table 1: Summary of process streams around reactor system

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 Figure 2: 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 𝐶6𝐻6 will dissolve 0.050 g 𝐻2𝑂 at 293 K.

Therefore, 388.91 kg 𝐶6𝐻6 will dissolve 388.91 ×0.050100 kg 𝐻2𝑂 = 0.19 kg/hr.

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

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 𝐻2𝑂/hr + 388.91 kg 𝐶6𝐻6/hr = 389.1 kg/hr

𝐹𝐼 = 3253.69 – 389.1 = 2864.59 kg/hr

4. 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.

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𝐵𝑓 = 1945.95 kg/hr

From solubility data for water/benzene system, 100 g 𝐶6𝐻6 will dissolve 0.050 g 𝐻2𝑂 at 273 K.

Table 2: Summary of process streams around chlorobenzene column

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 Figure 3: Chlorobenzene column

Water in fresh benzene feed (𝑊𝑓) = 1945.95 ×0.050100 = 0.97 kg/hr

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: Mixer and benzene drying column

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Table 3: Summary of process streams around mixer and drying column

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 ENERGY BALANCE
Assumption is made that the fresh benzene and chlorine to the chlorinator are stored at a

temperature of 30 0C. The reaction temperature is 40 ˚C. The inlet gases are to be heated to

the reaction temperature. Thus the heat required for this process is

Where

H is the heat required.

Cp is the specific heat of component

Specific heat of benzene = 1.7514 kJ/kg K

Specific heat of chlorine = 8.28 + 0.00058T

This heat may be supplied by condensing at atmospheric pressure.

Amount of steam required for producing this much of heat is

Where is the latent heat of vaporization of steam = 2256.9kJ/kg

C6 H6 + Cl2 → C6H5Cl + HCl Hr = -8.5294 x 103 kJ/kmol

C6H5Cl + Cl2 → C6H4Cl2 + HCl Hr = -41.1036 x 103 kJ/kmol

Thus the heat liberated within the reactor is

Σ  = 413.22 x 103 kJ/hr

The reactor is assumed to function under isothermal conditions. Hence cooling water must be

provided via jackets to keep the reactor at the constant temperature of 40 ˚C.

Cooling water flow rate is found out by

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The gases from the chlorinator go out at the temperature of 40 ˚C.

Neutralizer
NaOH + HCl → NaCl +H2O Hr = 54.213 x 103 kJ/kmol

Net heat produced in the neutralizer is H = -171.313 x 103 kJ/hr

This heat produced is utilized to increase the temperature of the outlet stream.

By a process of trial and error we find that the outlet temperature is 345 K.

Benzene Column
Assumption is made that no heat losses occur in the column. For such a column the heat balance

may be written as

Fhf +Qw =DhD +WhW +Qc

F is feed flow rate

D is the distillate flow rate

W is the underflow flow rate.

h indicates the enthalpy of the respective stream

Qw and Qc are the reboiler and condenser heat loads.

h=Σ

Tr is refernce temperature taken as 0 K

hf = 555.4 kJ/kg

hd = 615.33 kJ/kg

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hw = 538 kJ/kg

The condenser heat load may be calculated as

QC = Σ

is the latent heat of vaporization the values for benzene and chlorobenzene are

393.3 kJ/kg and 331.1 kJ/kg respectively.

hence QC is obtained as 7.9588 x 103 kJ/hr

Substituting the values obtained we get

QW = 3.2192 x 106 kJ/hr = 894.22 kW

Chlorobenzene Column

Assumption is made that there are no heat losses. Hence the previous equation

holds.

Fhf +Qw =DhD +WhW +Qc

The values for the enthalpies of various streams are

hf = 505.7 kJ/kg

hd = 508 kJ/kg

hw = 497.3 kJ/kg

The condenser heat load is calculated as

QC = Σ

Thus QC = 1.3226 x 106 kJ/hr = 367.4 kW

Hence QW = 2.8017 x 103 kJ/hr = 778.25 kW

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