PHENOL

STRUCTURE OF PHENOL

Phenol also known as carbolic acid is an aromatic organic compound with the molecular formula C6H5OH and molecular 94.11. The molecule consists of a phenyl group (-C6H5) bonded to a hydroxyl group (-OH). It is a white crystalline solid that is volatile. Although similar to alcohols, phenols have unique distinguishing properties. Unlike in alcohols where the hydroxyl group is bound to a saturated carbon atom, in phenols the hydroxyl group is attached to an unsaturated benzene ring or other arene ring. Consequently, phenols have greater acidity than alcohols due to stabilization of the conjugate base through resonance in the aromatic ring.

WHY PHENOL?
Synthesis of dyes, aspirin, explosives, ink, rubber, Extensive thermosetting and phenolic resins Applications Used in commercial disinfectants, in the antiseptics, lotions, ointments, market sclerosing agents, chemical face peeling

Easy Benzene and Toluene are used availabilityas raw materials that are easily of raw available in petrochemical materials plants.
Cumene Process for Phenol Production: Toluene two-stage Oxidation Wide range Rasching : vapor phase of processes hydrochlorination and hydrolysis to choose Chorobenzene-caustic Hydrolysis from Benzene Sulfonate-caustic Fusion Benzene-direct Oxidation

PHYSICAL PROPERTIES
Property Molecular weight Value 94.11

Melting point
Boiling point Density @ 25C

42C
181C 1.07

CHEMICAL PROPERTIES
Phenol is weakly acidic and at high pH's gives the phenolate anion C6H5O (also called phenoxide) PhOH PhO + H+ (K = 1010) Phenol exhibits keto-enol tautomerism with its unstable keto tautomer cyclohexadienone, but only a tiny fraction of phenol exists as the keto form.

IMPORTANT REACTIONS OF PHENOL

Reaction of phenol with A base Zinc dust Product Neutralises to give a metallic phenolate Reduces to benzene

Diazomethane in the presence of Anisole is obtained boron triflouride

Ferric chloride Violet coloured iron complex is formed that is a characteristic of the existence of the keto-enol tautomer

Ammonia in the presence of Zinc Gives Anniline(Bucherer reaction) Chloride at 300C Alkyl halides PhenylEthers(Williamsons Synthesis)

Methods of Production

Cumene peroxidationhydrolysis Raschig: vapor phase hydrochlorination & hydrolysis Benzene sulfonate-caustic fusion

Toluene twostage oxidation

Chlorobenzenecaustic hydrolysis

Benzene-direct oxidation

Cumene Process for Phenol Production

REACTIONS

PROCESS

Oxidation in presence of air. Cumene peroxide formed is cleaved in an acidifier. Mixture of products is separated in four distillation units.

MAJOR ENGINEERING PROBLEMS

Gas with two-phase liquid contact Peroxide handling to avoid explosions.

ECONOMICS

Produces 0.6 ton of acetone per ton of phenol.

Toluene Oxidation Process for Phenol Production

REACTION

RAW MATERIALS

Toluene Air

PROCESS
Two-stage air oxidation process is used. Reactor is run at 150 degree centigrade and 3 atms. Liquid from the reactor continuously passes to a distillation column which strips the toluene. Purified benzoic acid is separated by extracting the bottoms with hot water. The crude acid is melted, mixed with cupric benzoate catalyst, and then charged to an air- sparged tower.

MAJOR ENGINEERING PROBLEMS Efficient gas liquid contacting design Economic recovery of organics

ECONOMICS

High cost Two stage oxidation Abundant and low cost availability of toluene

Raschig phenol process using hydro chlorination of benzene

REACTIONS
First reaction Benzene + HCl + Oxygen Benzyl chloride + Water Catalyst: FeCl3 + CuCl2 Operating conditions: 240C and atmospheric pressure Second reaction Benzyl chloride + water Phenol + HCl Catalyst: SiO2 Here, HCl is regenerated and will be recycled. Operating conditions: 350C and atmospheric pressure

PROCESS
Two vapor-phase catalytic stages Purified benzene is fed to a heated, packed reactor containing ferric chloride and cupric chloride catalyst Chlorination with HCl-O2 Fractionation separates unreacted benzene from chloro benzene and poly chloro benzene. Crude Chlorobenzene is hydrolyzed to form phenol. It is washed and purified by two stage distillation.

MAJOR ENGINEERING PROBLEMS Design of reactor conditions to minimize poly Chloro benzene. Corrosion from wet HCl at high temperature.

ECONOMICS

Plant investment is 15-20% higher compare to other processes. Large continuously operated units are feasible.

Chloro Benzene Caustic process for phenol production

REACTIONS

RAW MATERIALS: Benzene Chlorine NaOH HCl

PROCESS
Dry benzene and a catalyst of iron turnings or anhydrous ferric chloride are charged continuously into a chlorinator Mono chloro benzene is withdrawn near the bottom plate of the column. Chlorobenzene and dilute caustic soda (10% solution) are mixed in a pump and diphenyloxide is added. Cooled hydrolyzate is acidified in a neutralizer to liberate phenol and sodium chloride.

MAJOR ENGINEERING PROBLEMS

Corrosion from HCl in chloro benzene unit Pressure vessel design for high temperature pressure caustization reactor Separation of saleable by-products

ECONOMICS OF THE PROCESS Competitive if low cost chlorine is available. This means that the process must be coupled to an electrolytic chlorine caustic process so that economics of an integrated plant will apply

Benzene Sulphonate process for Phenol Production

REACTIONS

PROCESS
Benzene sulfonic acid is formed by contact of benzene vapours with H2SO4 liquid in a counter current reactor. The sulfonator is designed so that only a few percent of free H2SO4 remains before the liquid is discharged to the neutralizer. Sulphur dioxide is released and the pot residue contains sodium benzene sulphonate in solution and precipitated Na2SO4. A cast iron fusion pot containing molten caustic is kept at 300C by direct gas or oil fire. The released crude phenol floats on an aqueous solution containing sodium sulphate, sodium sulphite and a small percentage of phenol.

MAJOR ENGINEERING PROBLEMS Operates on large scale batch cycles. Safety design of fusion cycle should be taken care.

ECONOMICS OF THE PROCESS Couldnt compete with modern processes. Installment of NaOH and plants nearby.

Direct Oxidation Of Benzene

Chemical Reactions a) C2H6 +3H2 C6H12 b) 2C6H12 + 11/2O2 C6H11OH + C6H10O + H2O c) C6H11OH C6H5OH + 3H2 Benzene is hydrogenated to cyclohexane which is oxidized with air, yielding a mixture of cyclohexanol, cyclohexanone, and unreacted cyclohexane. The unreacted cyclohexane is separated and recycled. The oxygenated fraction is then dehydrogenated to phenol over nickel or platinum catalyst.

SELECTION OF PROCESS

Yield

Availability of raw materials

Cost of raw materials

Bi-products

Engineering problems

Safety and economics of the process

yield

Yield of a process is the key factor in any production unit Yield by cumene process is 92%

Availability of raw materials

Most of the processes require either benzene or Chloro benzene as initial inputs Toluene is given as input in cumene process which is available within or an adjacent petro chemical plant

Cost of raw materials

The initial cost of production must be low Cumene process uses toluene as the raw material that is easily available and economically viable at the same time.

Cumene process is relatively a new one that produces 0.6 ton of acetone as a co-product per ton of phenol produced.
Bi-products

Engineering problems

care should be taken during the design of reactors, to avoid corrosion, scaling and fouling problems. In this regard, Cumene process has less number of problems.

Safety & economics of the process

Finally it is the economic feasibility of the process that determines the production of a compound by a particular process at a large scale. The raw material of cumene process is alkylated benzene which can be easily obtained from petro chemical industries, thus making cumene process a more feasible and practical one.