PRODUCTION OF PHENOL FROM

CHLOROBENZENE
Shikhar Prakash (101446)
Sumit Verma (101449)

DEPARTMENT OF CHEMICAL ENGINEERING

JAYPEE UNIVERSITY OF ENGINEERING & TECHNOLOGY,
A-B ROAD, RAGHOGARH, DT. GUNA 473226, M.P., INDIA
Production of Phenol from Chlorobenzene

Natural occurrences
Natural occurrences:
During fractionation of coal tar, carbonic oil fraction is
separated containing 30-35wt% phenolic components and liquid
byproducts from gasification process.

Applications:
Used as an disinfectant in household cleaners and in mouthwash,

used forsynthesis of dyes, aspirin (C9H8O4).

Used for making picric acid , Used in the manufacturing of
Bisphenol - A

Phenol is also used to produce Aniline

Product specifications & standards

Phenol

is classified as a Class B poison.

The US Pharmacopeia (USP) specifications for phenol
include:
a) Purity is to be no less than 98 wt%.
b) Clear solubility of 1 part of phenol in 15 parts of
water.
c) A congealing temperature to be not lower than 39C.
d) A content of non volatiles is no more than 0.05 wt%.

Phenol demand forecast in India

300,000

250,000

200,000

Metric
tonnes

150,000

Demand
Production
Import

100,000

50,000

0
2011

2012

2013

2014

2015

Year

Graph 1: Production / Import of phenol in metric ton

per year.

Plant capacity on demand - supply

basis (for 2014)

Demand: 240,000 TPA
Production: 80,000 TPA
Import: 160,000 TPA
Plant Capacity: 200,000 TPA (To meet the demand).

S.
Specification
No.

Units

Cumene Oxidation

Processes
Toluene
SulphoBenzoic
nation
Acid

Chloro
Benzene

Rasching

Feed Stocks
1.
2.
3.
4.

Toluene
Benzene
Chlorine
Propylene

T/T
T/T
T/T
T/T

0.67
0.38

1.45
-

0.95
-

1.01
1.04
-

0.925
-

Steam
Cooling water
Process water
Electricity
Fuel Oil
Inert gas
(High Pressure)

Tonne
m3
m3
KWh
106 KJ
SCF

3.5
35
0.02
350
4.5
80

9.0
65
650
3.5
40

2.7
80
6.5
100
15
-

9.0
250
1.0
3900
5.5
-

16.5
50
350
14
-

Natural Gas

BTU

2100

10000

4000

Utilities
(Consumption per
tonne of phenol)

The most widely accepted technology for producing phenol is cumene

oxidation process because of better economics due to by-product acetone. If
one wants to avoid acetone, the choice will be toluene oxidation process.

Selected process
Phenol from chlorobenzene
There aretwo reactions to convert chlorobenzene to phenol using
chlorination route:
Causticization

C6H5 Cl+ NaOH C6H5ONa

NaOH is in aqueous media (Operating conditions: 425C and 350 atm,
Exothermic reaction)

Hydrolysis
C6H5ONa + HCl (aq) C6H5 Cl + NaCl (aq)
(Operating conditions: 1 atm & 60 C)

Fig1. PFD for production of Phenol from

Chlorobenzene

Material Balance

Various assumptions and values taken from

literature:
Phenol production with a purity of 99% = 2,00,000 TP
All

calculations are done on per hour operation.

Working

days in a year = 330 days.

Molecular
Per

weight of phenol = 94.

hour production = 25252.53 kg/hr.

= 268.644 kg mol/hr.

Overall material balance

Component

In (Kg/h)

Out (Kg/h)

Chlorobenzene

32113.143

1605.668

Sodium hydroxide

14263.810

3423.303

Diphenyl oxide

2575.277

2575.277

Phenol

--------

25507.566

Sodium chloride

--------

15839.168

48952.230

48950.982

Total

Energy balance
H 298 = -114.567 KJ/mol
H C6H5Cl = 285.297(230.0238) (373-303) = 17718836.42 J/mol
H NaOH = 356.622 (86.0937) (573-303) = 3243363.955 J/mol
HC6H5OH =271.033 (239.334)(353-303) = 3243363.955 J/mol
H NaCl = 271.033(84.4090) (353-303) = 1143881.74 J/mol
Heat of reaction = Heat of product Heat of reactant+ H

298

Heat of reaction = -21735942.74 J/mol

Production of Phenol from

Chlorobenzene

11

Heat balance across

exchanger

Heat balance across heat

heat exchanger inlet

outlet reactor inlet

Tref = 303 K

Tref = 303K,

Tin = 313 K

T= 573K

QNaOH = 310595.5465 J

Q NaOH = 8342126.471 J

QC6H5Cl = 5449157.38 J

QC6H5Cl = 14019901.52 J

QC12H10O = 1358477.399 J

C12H10O

= 45211.0613 J

Heat balance reactor outlet

neutralizer in
Tref = 303 K, T = 698 K
QHCl = 19671615.81 J
Q

C6H5Cl

= 1190158.848 J

QNaOH =2920034.506 J
Q

C12H10O

= 2147280.632 J

Heat balance

ref

= 303K, T= 333 K

QHCl = 309069.2717 J
QNaOH = 223550.9719 J
Q

C12H10O

= 136762.8128 J

Production of Phenol from

Chlorobenzene

12

QC6H5OH = 3116121.024 J
QNaCl = 115353535.308 J
QC6H5Cl = 111834.3687 J
QNaOH = 372452.6559 J
Q

C12H10O

= 229770.867 J

Energy balance across distillation column

Assumptions:
Temperature of distillate = 460 K
Boiling point of Diphenyl oxide = 531.46 K
Boiling point of phenol =455 K
Feed enters at =353 K

Production of Phenol from

Chlorobenzene

13

Utility required in reactor

Heat of reaction = -21735942.74 J/mol
Cp of water = -75.327 J/mol K
H = n*Cp*dT
-21735942.74 = n*(-75.327)*(40)
n = 7213.861 moles
Weight of water required = 7213.861*18 = 129849.5126 g/hr

Production of Phenol from

Chlorobenzene

14

Process & mechanical design of neutralizing tank

C6H5ONa + HCl

C6H5Cl + NaCl

EQUIPMENT - Cylindrical vessel with a drain valve and a turbine agitator

Total weight of the reacting mass = 48950.587 kg/h

Average density at 60oC= 1.4006 kg/litre
Total volume of reacting mass= Total weight of the reacting mixture
Average Density

Let residence time (T) = 2 hours

Vo= mav/dav =34.949 m3/hr
T = V / Vo
V = 69.898 m3
Where V = Volume of reactor
L/D = 1.25
D= 4.14 m,

H=5.18 m

Mechanical design
The maximum pressure in the tank is 14.70 psi (1
atm)

ts=[{(14.70 x 4.14)/(2 x 20000 x 0.8)}+0.005] x 2.54 =5.13 mm

Take shell thickness= 5mm

Design pressure is above 100 Kpa, ellipsoidal head would be an
ideal choice
Major axis: Minor axis=2:1
Inside depth (B=A/2), A=D/2,

B=D/4

B=1.035 cm
Volume V of the ellipsoidal head
V = (3.14 x 4.142 x 5.18/4) + (3.14 x 4.143/12)
= 88.306 m3

Design of agitator
Let diameter of the agitator= 0.6 x D
Da= 0.6 x 4.14= 2.484 m
Speed of the agitator=75 rpm = 1.2 rps
Average Viscosity =3.6 cp
Average density of the slurry=1.1747 kg/lt
Calculating Reynolds Number Nre
Nre = 112584.00
Calculating Froude number Nfr
Nfr = n2 x Da/g = 1.252 x 2.484/9.81 = 0.3956

1 cm=1/30.8 ft
1 kg/lt= 62 lb/ft3
9.81 m/s2=32.17 ft/s2
Power=[(0.123)-0.0935 x 1.253 x (8.1710)5 x 1.4006 x 62]/32.17
Power=331.52 ft/lbf
Power=0.513 HP
Assuming frictional losses
Power= 1.5 HP
Torque in the shaft=2 x 550/2 n
Torque in the shaft= 140 ft/lbf

Distillation Column: Process

design
Feed

components:
Phenol 271.0333 kmol/hr
Diphenyl oxide 15.13 kmol/hr
Total feed = 286.163 kmol/hr

Distillate

components:
Phenol 265.64 kmol/hr
Diphenyl oxide 2.683 kmol/hr
Total = 268.323 kmol/hr

Bottom

components:
Phenol 5.393 kmol/hr
Diphenyl oxide 12.447 kmol/hr
Total = 17.84 kmol/hr

Component

Feed, xf

Distillate, xd

Bottom, xb

Phenol

0.947

0.99

0.302

Diphenyl oxide

0.053

0.009

0.698

Using Antoine Equation, we find vapor pressure:

P = A-(B/ (T+C)) T in Kelvin, Pressure in bar.

Component

Phenol

4.24688

1509.677

-98.949

Diphenyl oxide

4.13678

1800.415

-95.324

Calculated Vapour Pressure in bar:

Top temp at 123C

Bottom temp at 150C

Phenol

0.14599

0.3948

Diphenyl oxide

0.01409

0.04487

Heavy key component Diphenyl oxide

Light key component Phenol
Relative volatility calculation :
top = 10.36
bottom = 8.798
avg = ( top* bottom)0.5
= (10.36*8.798)0.5
= 9.5475.

Fenske equation :
Nm = log [(XLK/ XHK)d*( XHK/ XLK)b] / log avg
(XHK) d = 0.302
(XLK) d = 0.698
(XHK) b = 0.990
(XLK) b = 0.009
Nm = log [(0.698/ 0.302)*( 0.990/ 0.009)] / log 9.5475
= 2.52
Nm 3

Underwoods Method:
(i*xif)/ (i-) = 1-q
We get, =1.4960

(i*xif)/(i-) = Rm+1

We get, Rm = 0.138

Gillilands correlation:

On solving, we get
N = 8.983
9
Assuming, tray efficiency = 0.5
Therefore, actual no. of trays = 9/0.5 = 18

Tower diameter required at

top:
Distillation: Vacuum distillation at
100mm Hg
Molar flow rate of vapor & liquid at top in enriching
section
L = R*D = 0.2074*268.323 = 55.650 kmol/hr
V = (R+1)*D = 1.2074*268.323 = 323.973 kmol/hr
L/V = 55.650/323.973 = 0.172
Mavg = xiMi = 94.7621

Assuming tray spacing = 0.6 m

From Figure 11.27 of R.K Sinnott (Coulson & Richardsons) page568
K1 = 0.08
uf = flooding velocity

uf = 3.6 m/sec
Now, Actual velocity = 0.85 * uf = 2.88 m/sec
Volumetric flow rate of vapor at the top, Qv = (V+Mavg) / v = 2.168
m3/s
An = net area required at the top
An = Qv/V = 0.753 m2
Down comer area, Ad = 0.12*Ac (Reference: Sinnott)
An = A c Ad
On solving, Ac = 0.856 m2
Di = 0.98 m

Tower diameter required at

bottom:
Similar procedure was followed to calculate
bottom
diameter:
Bottom diameter comes out to be 1.02 m
Height of Distillation Column:
Height of column, Hc = no. of trays * tray
spacing
Actual no. of plates = 18
Tray spacing = 0.6 m
So, height of column = 18 * 0.6 =10.8 m

Mechanical design
Calculation of Thickness:
Allowable design stress, f= 1.18MN/m2
Welding joint efficiency factor, J=0.85
t = [PDi/ (2*f*J-P)]
= [(13.33*103*1.02)/ (2*1.18x106*0.85)(13.33*103)]
= 0.06 m

Economic Analysis
Costing of distillation column
Thickness of shell = 0.06 m
Weight of vessel = = x 10.8 x 0.06 x 7850
= 16292.003 Kg
Where r is the internal radius of distillation
column, L is the length of column, t is the
thickness of shell.
Density of carbon steel = 7850 Kg/m3
Weight of head, skirt = 10% weight of vessel.
Total weight of column without tray = 1.1 x
16292.003 = 17921.23 Kg
Production of Phenol from
Chlorobenzene

31

Therefore, Purchased cost of distillation column without trays (1990) = $ 105

Production of Phenol from
Chlorobenzene

32

Production of Phenol from

Chlorobenzene

33

Purchased cost of tray = $ 300 per/tray

Total cost of trays = 18 x $ 300 = $ 5400
Quantity factor of each tray = 1.10
Total cost of the trays = 1.10 x $ 5400 = $ 5940
Total cost of distillation column in 1990 = $ (10 5 + 5940) =$
105940
Cost index in 1990 (C1) = 356 (Chemical engineering plant cost
index refer Klaus D.Timmerhaus Page 163)
Cost index in 1990 (C2) = 588.6
P1 = Purchased cost of distillation column in 1990
P2 = Purchased cost of distillation column in 2014
Present Cost = Original Cost
P2 =105940 = $ 17518 = Rs 17518 59 = Rs 10,334,327

Production of Phenol from

Chlorobenzene

34

Costing of various equipments

1.
2.
3.
4.

Purchased cost
10,334,327
Purchased cost
8283736
Purchased cost
Purchased cost

of distillation column = Rs
of heat exchanger = Rs.
of Neutralizer = Rs 321798
of reactor = Rs 29966100

Cost of raw materials

S No

Raw material

Cost
($/kg)

01

Chlorobenzene

0.5

Total
Rs/Year
Consumption
in Kg/Year
241619202
7127766459

02

Sodium Hydroxide

0.3

85856815.44

1519665633

03

Diphenyl ether

20396193.84

3610126310

Total

12257558402

Total product cost

Component

$/kg

Total production (kg/yr)

Phenol

1.6

202019923

19120683690

Diphenyl ether

20396193.84

3610126310

Total product cost

Rs/year

22730810000

Production of Phenol from

Chlorobenzene

36

Cash flow statement

Production of Phenol from

Chlorobenzene

37

Cash flow statement

Non-discounted parameters
(a) CCP (cumulative cash position) = Rs 38.02 crores
(b) Payback Period
Land + working capital = 1.12 + 3.67 = 4.8
Payback period is the point at which cumulative cash flow is
equal to the sum of land and working capital.
Payback period (PBP) = =3+((4.939-4.8)/(4.939-0.77))
Therefore, PBP = 3.033 years
(c) Rate of return on investment (ROROI)

Where n is the project life.

ROROI = 20.68 %
Production of Phenol from
Chlorobenzene

38

Plant layout

Production of Phenol from

Chlorobenzene

39

First Aid safety measures

Eyes: Get medical aid immediately. Do NOT allow victim to rub or keep eyes closed. Extensive
irrigation with water is required (at least 30 minutes).
Skin: Get medical aid immediately. Immediately flush skin with plenty of soap and water for at
least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Discard contaminated clothing in a manner which limits further exposure. SPEEDY ACTION IS
CRITICAL! Destroy contaminated shoes.
Ingestion: Do NOT induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or
water. Never give anything by mouth to an unconscious person. Get medical aid immediately.
Inhalation: Get medical aid immediately. Remove from exposure to fresh air immediately. If
breathing is difficult, give oxygen. Do NOT use mouth-to-mouth resuscitation. If breathing has
ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and
a mask.
Notes to Physician: Persons with liver or kidney disease should not be exposed to phenol for any
length of time.
Antidote: Activated charcoal, followed by cathartic, may be preferred to ipecac induced emesis or
lavage in decontamination of the GI tract and preventing systemic absorption of phenol.
Production of Phenol from
Chlorobenzene

40

Conclusions
After studying the entire process of
manufacture of phenol, there are a few
recommendations:
Phenol production has a very good scope
in India.
For most of the equipments, the fixed
capital investment is higher but the
payback period is small.

Production of Phenol from

Chlorobenzene

41

.
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a
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References
[1] http://www.helium.com/items/2025739-medical-uses-for-phenol
[2] http://www.greener-industry.org.uk/pages/phenol/1PhenolAnnualProd.htm
[3] Kirk R. E., Othmer D. F., Encyclopedia of Chemical Technology, John Wiley and
Sons, 1994, Volume 18 Page no: 291
[4]http://www.honeywell-pmt.com/sm/chemicalintermediates/phenol-n3/phenolproperties- spec.html?c=21
[5] http://www.icispricing.com/il_shared/Samples/SubPage186.asp
[6] http://en.wikipedia.org/wiki/Phenol#Properties
[7] http://en.wikipedia.org/wiki/Phenol
[8] http://hazard.com/msds/mf/baker/baker/files/p1949.htm
[9] Dryden C. E., Outlines of Chemical Technology, East-West Press, 2008
[10] Kirk R. E., Othmer D. F., Encyclopedia of Chemical Technology, John Wiley and
Sons, 1999-2012
[11] Carl L.Yaws, Chemical Properties Handbook, Tata McGraw Hill publications,
Third Edition.
[12] Max S.Peters, Klaus D.Timmerhaus, Plant design and economics fro chemical
engineers, McGraw-Hill International editions, chemical and petroleum
engineering series, fourth edition.
[13] http://www.matche.com/equipcost/
[14] http://avogadro.chem.iastate.edu/MSDS/phenol.htm
Production of Phenol from
Chlorobenzene

43