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Types Of Phenol Manufacturing Process

Phenol can be manufactured through five different processes. The processes are mentioned
below.

Cumene Peroxidation process

Rasching process

Toluene two stage oxidation process

Sulphonation process

1.Cumene Peroxidation process:

Benzene and purified propylene obtained from petroleum industry are mixed in liquid or
vapor phase in presence of phosphoric acid on kieselguhr. As a result, cumene or iso propyl
benzene is formed. The cumene thus formed is made in to the form of an emulsion with dilute
aqueous sodium carbonate solution, using sodium stearate as an emulsifier. The emulsion is
then oxidized in an oxidizer with air under atmospheric pressure for 3 4 hours in presence
of catalyst, such as copper, cobalt or manganese salt.

The temperature and pH of the reaction are maintained between 160-260c and 8.5-10.5
respectively. As a result of oxidation, cumene hydro peroxide is formed. The peroxide thus
formed is then decomposed by 5-50%sulphuric acid in an acidifier at 45-65c under pressure.
As a result of decomposition, phenol (15%), acetone (9%), cumene (73%) are formed along
with some -methylstyrene and acetophenone. These separated in a separator. The cumene is
recycled to be used again and phenol is either extracted or recovered by distillation. The yield
is about 92%. Acetone is formed as a byproduct (0.6 lb. per lb of phenol).

2.Rasching process:

This process was developed in Germany in 1940. Benzene is first converted into
Chlorobenzene by passing a mixture of benzene vapor, hydrochloric acid vapour and air
under normal pressure at about 23c in presence of a copper iron catalyst, supported on
alumina. The reaction is exothermic in nature and so the temperature is maintained constant
by external cooling. The conversion .the per pass is 10%
The Chlorobenzene after separation from unchanged reactants is hydrolyzed into phenol by
heating with steam at about 400-500c in presence of silica catalyst. The conversion is again
about 10% per pass in this second step. Hydrogen chloride set free in the reaction is
recovered and recycled. Crude phenol (97%) obtained according to the above reaction is
purified by distillation under vacuum. The yield is about 75-85% on benzene. A small amount
of HCl is sufficient to convert large amounts of benzene into phenol.

3.Toluene two stage oxidation process:

Toluene in liquid phase is oxidized with air in a reactor under 40-70 p.s.i in presence of a
soluble cobalt catalyst maintained at 150c. benzoic acid and water are thus formed. The
reaction is exothermic and temperature is maintained by external cooling. The crude molten
benzoic acid at about 150-200c is transfered from the reactor to distillation column, where
separation of benzoic acid from un reacted toluene and produced water take place . The
toluene is separated and recycled to the first oxidizing reactor. The pure benzoic acid is fed to
a second reactor, where it is oxidized to phenol by air and steam under 20-25 p.s.i at 230c in
presence of cupric benzoate catalyst promoted with manganese. The reaction mass is
periodically withdrawn from the second reactor into an extractor, where it is washed with
water to remove unwanted tars and benzoic acid and steam are returned to second reactor.
The phenol, water and unreacted benzoic acid are conducted overhead to two distillation
columns in series. In the first column, crude phenol is separated from overhead and unreacted
benzoic acid is recycled to the second oxidizing reactor. Pure form phenol is obtained at the
second distillation column as overhead product and supply's aromatics compounds and
benzoic acid as a feed to crude phenol rectification column. The yield of phenol on benzoic
acid is about 75- 80%.

4.Sulphonation process:

It is one of the oldest methods of manufacture of phenol. Benzene sulphonic acid is first
prepared by passing vapour of benzene into concentrated sulphuric acid is about 150-
170c.the water formed during sulphonation process is distilled out because sulfuric acid gets
diluted and conditions accelerates backward reaction of the process. Benzene sulphonic acid
should be neutralized by reacting it with aqueous sodium sulphite to form salt of benzene
sulphonic acid. The sodium salt is filtered off and then fused with caustic in a cast iron vessel
at about 340-380c in the ratio (1:3) for about 5-6 hours. As a result, sodium phenate is
formed. The melt is cooled, extracted with water and then acidified with sulphur dioxide. The
latter is obtained as a result of neutralization of benzene sulphonic acid with sodium
sulphite.the upper oily layer of crude phenol is distilled under vacuum to get pure phenol.
The yield is about 80-90% on benzene. The lower layer contains sodium sulphite which is
separated and used for the neutralization of benzene sulphonic acid.
S.No Existing Methods Raw Materials/ Catalyst Yield Products Comments
Cumene, Air, H2SO4 and Phenol and Produces valuable co-
1 Cumene peroxidation 92%
Emulsifying agents acetone product acetone
Toluene, Air, Cobalt Low cost operation by
Toluene two stage
2 napthalate, Cupric benzoate 80% Phenol and CO2 direct toluene
oxidation
catalyst application
Rasching phenol Phenol and HCl Feasible under large
3 Benzene, Air, HCl 75%
process as recycle units
Chlorobenzene Benzene, Chlorine, NaOH,
4 95% Phenol, NaCl Economically feasible
caustic hydrolysis HCl
Phenol,
Benzene sulfonate Operates on large
5 Bezene, H2SO4, NaOH 87% Na2SO3,
process batch cycles
Na2SO4
http://enggyd.blogspot.co.id/2010/09/cholorobenzene-caustic-process-for.html

Cholorobenzene and Caustic Process for Phenol Production

Phenol by Chlorobenzene-NaOH

Process Description of Chlorobenzene and Caustic process for phenol production:

For 1 ton of phenol production approximately the following raw materials are required as per the
process described:
Benzene = 0.90 tons
Chlorine = 0.82 tons
NaOH = 0.67 tons
HCl = 0.51 tons
The main reactions which take place for this process are:
1. Chlorination
C6H6 + Cl2 ---> 850C , Fe- --> C6H5Cl (Chlorobenzene)
2. Causticization
C6H5Cl +NaOH (aq)---> C6H5NaO
3. Hydrolysis
C6H5NaO + HCl(aq) ---- > C6H5OH + NaCl(aq)
A Short Process Description for Phenol Production:

Benzene which is in dry state, reacted with chlorine at the presence of the catalyst iron or anhydrous
ferric chloride at about 85 deg centigrade temperature to form Chlorobenzene in a chlorination
tower, unconverted benzene is recycled and monochlorobenzene is with drawn all excess chlorine is
used in neutralizer and about 10% solution of dilute caustic soda is mixed with Chlorobenzene which
is reacted with caustic solution where chlorine present at the benzene ring is reacted with hydrogen
and produce water vapors which is removed a tail gas. The result product diphenly oxide is pumped
to the preheater and than passed to multi tube reactor where causticization reaction occurs at the
parameters 425 deg centigrade and 350 atm pressure, then the reacted mixture is passed to the
neutralizer through the effluent heat exchangers.

Phenol is obtained from hydrolysis occurs at the neutralizer where reaction with concentrated
hydrochloric acid take place to form phenol and sodium chloride.

Sodium chloride is formed as side product, this salt is separated and send to electrolysis.

Upstream from separator is send to vacuum distillation column where phenol is stripped out. About
95% yield is obtained and diphenyl oxide is removed from the bottom of the column to recycle.

Major engineering problems in this process are:

HCl corrosion in Chlorobenzene plant section