PES Lecture 3

Raw Materials I Catalysts,Solvents, Monomerrs I

Polymer Engineering and Science

This subject consists of two major divisions: Polymer Manufacturing Polymer processing or making the final product from raw polymer.

Polymer Manufacturing
This involves catalysts, solvents or diluents and monomers. Reactor design involves kinetics and other engineering operations such as mixing, fluid mechanics, heat transfer, material of construction, process control etc.

Polymer Processing
This involves selection of material for a given application, compounding of additives and other ingredients and a proper processing technique such as extrusion, molding, calendaring etc. Polymer properties and product design influence the selection of process. Decorative processes also play a role.

Solvents and Diluents

Solvents or diluents are used during manufacturing of polymers. They may also be part of final formulations of paints, inks or adhesives. The solubility of monomer, polymer, the reaction conditions and health issues influence the choice of solvents. Recovery of solvent during the manufacture of polymer is very important factor in selecting the solvent.

 Solvents dissolve the polymer / monomer while diluents may only suspend the polymer and reduce the viscosity of medium. Viscosity of solution increases as the polymer concentration increases or at a given concentration the if molecular weight is higher. When good solvents are used, viscosity rise is minimal. However, the removal of solvent by evaporation or by drying at room temperature becomes difficult. It is a common practice to use mixture of solvents to suit the needs. The vapor pressure of solvent and its boiling point decide the use in a given formulation.

 Some of the materials like benzene, toluene or xylene are solvents as well as starting materials for other monomers or chemicals. Benzene is used in making ethyl benzene and subsequently styrene. Some polymers precipitate if the molecular weight increases beyond certain limit. The solution polymerization can yield a control over the molecular weight of a polymer during the manufacturing.

Monomers
Most of monomers are obtained using crude oil as feedstock. Ethylene, propylene and C4 fractions are manufactured by pyrolysis of different feedstocks. Benzene, toluene and xylene are manufactured by reforming of naphtha and similar feedstock.

Ethylene and Propylene

Both ethylene and propylene are produced from pyrolysis of light gases, (ethane, propane, n-butane), naphtha, gas oil or part of crude. Process conditions can change to optimize the production of ethylene or propylene. Ethylene and propylene account for 60% of all monomers produced from feedstocks

Pyrolysis
Feed is mixed with steam which acts as a diluent. Quantity of steam per kg of feed is important parameter. Vapors of feed and steam are mixed and heated to desired temperature. Steam controls the formation of coke. The pyrolysis takes place inside the tubes which are present in a furnace.

 Pyrolysis temperature is in the range of 700 to 9500C. The mean residence time is 0.05 to 1 seconds. The furnace temperature is in the range of 11000C Pyrolysis tubes are 2025 mm in diameter and 1015 meter in length. The tubes are arranged like hair pins.

 Coke which is formed is removed periodically Formation of coke depends upon feed composition and also material of construction of pyrolysis tubes. A typical flow sheet of the process for the manufacturing of ethylene, propylene and other products is shown.

Steam, H2, CH4 Feed Pyrolysis Gases Quench Coke Purification Ethylene

Separation Process

Separation Process

Propane

Purification

Multistage Compression

Acidic Gases

Ethane Caustic Wash Purification

Separation Process

Separation Process

Propylene

Purification

H2

Acetylene Convertor

Separation Process

C4 Recovery

Higher Fraction to recovery/ treatment/ fuel

Methane Purification

Schematic Diagram for Pyrolysis Process

 Effluents from the pyrolysis are quenched so as to arrest further coke formation. Cooled gases are compressed in about 5 stages. Around third stage or so, acid gases like hydrogen sulfide,H2S, and carbon dioxide,CO2, separate out.

 Compressed gases are washed with caustic solution and water to remove remaining acid gases. The cleaned and compressed gases are subject to distillation at low temperatures to recover methane, ethane, ethylene, propane, propylene, C4 and higher fractions.

 The products from pyrolysis process depend upon feed, temperature and many other factors. Ethane yields more of ethylene. The unreacted ethylene is recycled. Propylene yields are higher if propane is used. Typical product distribution is shown now.

Typical product distribution from the pyrolysis of different feedstock Feedstock Ethane Propane n-Butane isobutane light naphtha Product (% wt) Hydrogen, H2 Methane, CH4 Acetylene, C2H2 Ethylene, C2H4 Ethane, C2H6 Propylene, C3H6 Propane, C3H8 Methyl-Acetylene, C3H4 C4 fractions C5 and higher -fractions *

3.72 3.47 0.42 48.81 40.0 0.99 0.03

0.20 1.58

1.56 23.65 0.77 41.33 3.48 12.88 7.0

1.09 3.71

1.49 19.30 1.07 40.59 3.82 13.64 0.48

1.07 10.05 8.59 100

1.08 16.56 0.72 5.65 0.88 26.35 0.38

2.34 40.0 4.04 100

1.0 18.0 0.95 34.30 3.80 14.1 0.35

1.02 8.35 18.13 100

0.78 4.44 100 100 Benzene, toluene, xylene etc.

 Overall yields for different fedstocks after recycling Feedstock Yields Ethane Propane Ethylene 80 40 Propylene 3 18 C4 fractions 2.5 6

 Properties of ethylene and propylene are listed now.

ETHYLENE
Chemical formula Formula weight CAS Registry No Boiling Point Melting Point C2H4 28 [74 85 1] - 103.710C - 169.150C

PROPYLENE
Chemical formula Formula weight CAS Registry Number Boiling Point Melting Point C3H 6 42 [115 07 1] - 47.70C - 185.30C

Other Processes
Ethylene: Dehydration of ethanol:-catalytic (zinc oxide with alumina) dehydration of ethanol C2H5OH ------------ C2H4 + H2O Disproportion :- Ethylene can be made from propylene or vice versa 2C3H6 -- C2H4 + C4H8 (disproportion)

Other Processes
Propylene: Metathesis reaction C2H4 + C4H8 --- 2C3H6 (metathesis) Advanced cracking:- Temperature around 20000C and residence time of few milliseconds yields C1-C5 fractions and gasoline.

Other processes
Methanol to olefins:- A process developed by Union Carbide. A catalytic fluid bed reactor employing

VINYL CHLORIDE
This is the monomer for Poly Vinyl Chloride, PVC Most of monomer is produced from ethylene and chlorine.

Chlorine is produced from chlor-alkali industry by electrolysis of salt solution.

Vinyl Chloride
Chemical Formula CH2=CHCl Formula weight 62.5 CAS Registry Number [75 01 4] Boiling Point - 13.50C Melting point -153.50C Solubility sparingly soluble in water but it is soluble in organic solvents

Process
The reactions are shown below CH2=CH2 + Cl2 -------2ClCH2CH2Cl (1,2, ethane dichloride, EDC) CH2=CH2 +2HCl + 0.5 O2 --- CH2ClCH2Cl + H2O (Oxychlorination,) CH2Cl CH2Cl ------- CH2=CHCl + HCl (Pyrolysis)

2HCl + 0.5 O2 -----H2O + Cl2 (Oxidation step)

Process
The overall reaction is 2 CH2=CH2 + Cl2 + 0.5 O2 -- 2 CH2=CHCl + H 2O

Manufacturing
Direct chlorination: Catalyst is Ferric Chloride. Reaction temperature is 50-600C and pressure of 4-5 atmospheres. EDC is liquid at its boiling point. Evaporation of EDC helps to remove heat of reaction. Traces of oxygen improves the selectivity.

 Either ethylene or chlorine is reacted completely by keeping one of these two in excess. EDC is purified at the end of reaction by distillation. The catalyst is also removed.

 Oxychlorination: Cupric chloride is used as a catalyst. Reaction temperature is 220-2400C and the pressure is about 1.5- 5 atmospheres. Ethylene, dry HCl and air react to produce EDC. EDC is purified

 Pyrolysis: Temperature is 475-5000C and pressure of 20 atmospheres. Separation of Vinyl chloride and EDC is a key issue of the process. Unreacted EDC contains chlorinated products. VCM is quenched with liquid EDC and then distilled to purify it.

HCl recycle

Air or Oxygen

Oxychlorination

Light ends

Ethylene

Water

Ethylene dichloride purification

Pyrolysis

vinyl chloride purification

vinyl chloride to PVC or storage

Chlorine Gas

Direct chlorination

Heavy ends

Block diagram for a balanced vinyl chloride process

Other Process
Acetylene route: Reaction is shown here C2H2 + HCl ---------- CH2=CHCl + HCl This route is followed at limited places only. Acetylene can be used in more gainful way.

Ethylene Oxide and Ethylene Glycol

Ethylene oxide is a precursor for ethylene glycol.
Ethylene glycol is a raw material for the manufacture of PET, Poly ethylene terephthalate, and also for poly urethanes.

Ethylene oxide
Formula Formula weight Boiling Point Melting Point CAS Registry No Solubility CH2OCH2 44 10.70C - 1120C [75 - 21- 8] Soluble in water.

Manufacturing Process:
It is direct oxidation of ethylene with oxygen. The reaction is given below 5 CH2=CH2 + 5O2 -------- 4CH2OCH2 + 2CO2 + 2H2O

Silver deposited on silica alumina acts as catalyst.

 Feed ethylene should not contain sulfur, acetylene or carbon monoxide more than 2 ppm. Reaction temperature is 260 2900C. Pressure is 10 to 30 atmospheres. Concentration of ethylene or ethylene oxide is less than 2.5 % so as to avoid explosion limits.

 Molar ratio of oxygen to ethylene oxide in the feed is from 7 to 10. Methane gas is used an inert gas to maintain lower concentration of ethylene. Tubular reactors are used. Reactor effluents are absorbed in water. Unabsorbed ethylene is recycled. Ethylene oxide is recovered by desorption.

Ethylene, methane and traces of ethylene oxide for recycle Ethylene & methane for recycle Carbon dioxide absorption Water Ethylene Air Reactor (Tubular)

Water absorption column

Desorption column

Ethylene oxide for purification

Methane (Inert gas)

Water for recycle to absorption tower

Block diagram for the manufacture of ethylene oxide

Ethylene Glycol
Formula Formula weight Boiling point Melting point CAS Registry no Solubility HOCH2CH2OH 62 197.60C - 130C [107 21 1] soluble in water

 Ethylene Glycol is manufactured by hydration of ethylene oxide. CH2OCH2 + H2O ---- HOCH2CH2OH Water to ethylene oxide molar ratio is 20 to 25. This suppresses the side reactions.

 Reaction temperature is 150 2000C. Reaction time is 45 to 50 minutes. Dilute solution of ethylene glycol is concentrated in evaporators.

(Mono) Ethylene glycol is separated from di- and tri- ethylene glycols by distillation.

Water Water for recycle

Ethylene Oxide

Reactor

Evaporation

Refining by vacuum distillation

Ethylene Glycol Higher Glycols

Block diagram for the manufacture of ethylene glycol

Acrylic Acid and derivatives

Acrylic Acid: It is a monomer to prepare polyacrylic acid and also esters such as methyl acrylate or butyl acrylate which are polymerized. These polymers find applications in textiles and as speciality additives.

Acrylic Acid
Chemical formula Formula weight CAS Number Melting point Boiling point Solubility H2C=CHCOOH 72 [79 10 7] 13.50C 1410C Soluble in water

It has a very pungent odor.

Manufacturing methods
Vapor phase oxidation of propylene: Two stage oxidation is industrially followed. The reactions are: H2C=CHCH3 + O2 --- H2C=CHCHO + H2O (First stage) H2C=CHCHO + 0.5 O2 ---- H2C=CHCOOH (Second stage)

 Catalysts are based on metals such as copper, tin or bismuth. Reaction conditions in two stages are different. This enhances the selectivity.

First stage oxidation

Temperature is 330 4000C. Tubular reactor is packed with bismuth molybdate catalyst. Tubes are 2 to 5 cm in diameter. Air is used an oxidizing agent The feed consists of 5 to 7 % propylene, 10 to 30 % steam and rest air. Effluents are cooled.

Second stage oxidation

Temperature is 280 3300C. Molybdenum vanadium oxides are used as catalyst. Tubular reactor is used. Reaction products from first stage oxidation reactor and additional air are introduced in the second stage reactor.

Absorption
Reaction products are absorbed in water. Acrylic acid is obtained as 20 30 % aqueous solution. Unreacted gases are incinerated or sent for recovery of propylene.

Recovery of Acrylic Acid

Acrylic acid is solvent extracted using solvent such as butyl acetate, xylene or diisobutyl ketone. Solvent and acrylic acid are separated by distillation.

Incineration To Recovery of Propylene for recycle

Propylene

Reactor 1 Packed Bed Temperature Cool 300-430 0C

Reactor 2 Packed Bed Temperature

Cool

Air Steam
Absorption in Water Temp: 600C Solvent

Acrylic Acid Solution Distillation Solvent Extraction

Acrylic Acid

Flow diagram for manufacturing of Acrylic Acid

Other Routes
Oxidative decarboxylation of ethylene Palladium is used as a catalyst. The reaction is given below. H2C=CH2 + CO + 0.5 O2 H2C=CHCOOH

 Acetylene based process temperature is 40 to 500C. C2H2 + H2O + 0.8 CO + 0.05 Ni(CO)4 + 0.1 HCl CH2=CHCOOH + 0.05 NiCl= + 0.05 H2

If alcohol is used instead of water, it produces acrylic ester

 Acetic acid can be condensed with formaldehyde to yield the acrylic acid. Reaction is given below. CH3COOH + CH2O CH2=CHCOOH + H2 O

ACRYLONITRILE
This monomer is also used in copolymers of styrene (SAN, ABS) Formula Formula weight CAS Registry No Boiling Point Melting point Solubility in water at 250C CH2=CHCN 53 [107 13 1] 77.30C - 83.50C 7.3 %

MANUFACTURING PROCESS
Amoxidation of propylene is commercially practiced. C3H6+ NH3+1.5 O2 CH2CHCN + 3 H2O Air, ammonia and propylene are introduced into a fluid bed reactor.

 Reaction temperature is 400 5000C. oxides of bismuth molybdenum or iron antimony are used as catalyst. Heat of reaction is removed as steam. Unreacted ammonia is neutralized with sulfuric acid. Bye products such as acetonitrile are recovered.

Crude Acrylonitrile

Water

Off Gases

HCN

Ammonia Air

Reactor (Fluid bed)

Water absorption

Separation process Acrylo nitrile

Separation column

Propylene

Water and crude acetonitrile

Separation column

Waste

Block Diagram for the manufacture of acrylonitrile

Butadiene
It is a monomer from which polybutadiene is made. It is also used in making of HIPS (High Impact Poly Styrene). Polybutadiene is dissolved in styrene and then styrene is polymerized to form HIPS. It is a co monomer in forming styrenebutadiene-rubber. (SBR)

Formula Formula weight CAS Registry No Melting point Boiling point Solubility

CH2=CHCH=CH2 54 [106 99 0] -108.90C -4.410C soluble in ethanol or methanol

MANUFACTURING PROCESS
Catalytic dehydrogenation of n-butane or n-butene or oxidative dehydrogenation of n-butene is commercially followed. Earlier process based upon ethanol is still used in some places.

 Catalytic dehydrogenation of butenes:

A C4 fraction from catalytic cracking process typically contains about 44 % butane and 45 % butenes. CH2=CHCH2CH3 CH2=CHCH=CH2 + H2 CH3CH=CHCH3 CH2=CHCH=CH2 + H2

 Reaction temperature is around 625 to 6750C. High pressure steam is also introduced along with butenes.hromium based catalysts are used. The reaction is carried out in a cyclic manner. After the dehydrogenation, air and steam flow over the bed of catalyst so that the coke which might get deposited during the dehydrogenation is burnt.

 Dehydrogenation of n-butane:
Houndry process is a single step process. The reaction temperature is 550 to 6000C and the catalyst is mixture of aluminum oxide and chromium oxide. Phillips has developed a two stage process. First butenes are formed and then these are dehydrogenated.

Butenes for recycle

Butenes Steam

Catalytic Reactor

Quench

Oil absorption

Extraction

Air flows intermittently when butenes flow stops

Butadiene

Block diagram for the manufacture of butadiene

Chapter 4
Raw materials, Monomers 2

Terephthalic Acid
This is a monomer for the manufacture of poly esters such as polyethylene terephthalate, PET, or polybutylene terephthalate, PBT

Terephthalic Acid
Formula C6H4(COOH)2 Formula weight 166 CAS Registry No [100 21 - 0] Melting point sublimes at 3000C Boiling point sublimes at 3000C Solubility insoluble in water, soluble in ether & hot alcohol

Manufacturing process
p-Xylene is oxidized in acetic acid solution Temperature is 175 2000C Pressure is about 15 to 30 atmospheres. The catalyst is cobalt or manganese acetate containing sodium bromide as an initiator. Acetic acid and unreacted p-xylene are first separated from the reaction mass.

 Reaction is given below. C6H4(CH3)2 + 3O2 --- C6H4(COOH)2 + 2H2O

Manufacturing process
Terephthalic acid precipitates and it is separated from the reaction mass when products are cooled to 1100C. Crude terephthalic acid is filtered and purified by distillation. The process is practiced by AMOCO Packed bed or stirred tank reactor can be used.

p xylene

Acetic Acid Gases for scrubbing and disposal

Air

Oxidation reactor Crystallization p xylene and acetic acid recovery

Crude terepthalic acid

Crystallization And washing

Pure terepthalic acid

Block diagram for the manufacture of terephthalic acid (amoco process)

DIMETHYL TEREPHTHALATE
Dimethyl terephthalate is used in the manufacture of polyesters instead of terephthalic acid in transesterification process. C6H4(CH3)2 + 4HNO3 --------C6H4(COOCH3)2 + 4H2O + 4NO

DIMETHYL TEREPHTHALATE
Formula C6H4(COOCH3)2 Formula weight 194 CAS Registry No [120 61 - 6] Melting point 1410C Boiling point 2840C Solubility soluble in ether and hot alcohol

Manufacturing process
Reaction consists of four steps. One (CH3) group is oxidized first into ptoulic acid, C6H4CH3COOH. This is esterified with methanol to produce pmethyl toulate. The p-toulate is oxidized to methyl terephthalate. This in turn is esterified to di methyl terephthalate.

Manufacturing process
Temperature in oxidation is 140- 1700C. Pressure is 5 atmospheres. Cobalt naphthanate is used as a catalyst. In esterification step, temperature is 200 to 2500C.The catalyst is toluene sulfonic acid diluted with methanol. Purification of product is by series of distillation columns.

CAPROLACTAM
Nylon 6 is made from caprolactam Formula Formula weight CAS Reg. Number Melting Point Boiling Point Solubility CH2(CH2)4CONH 113 [105 60 2] 69.30C 2700C (decomposes) Soluble in water and organic solvents

Manufacturing Process
Different processes differ depending upon the manufacturing process for the precursor, cyclohexanon. Acidic hydroxylamine sulfate is produced by conventional Raschig process. The acidic hydroxylamine sulfate reacts with cyclohexanone and ammonia to produce cyclohexanone oxime.

 N2O3 + (NH4)2CO3 2 NH4NO2 + CO2 2 NH4NO2 + 4 SO2 + 2 NH3 + 2 H2O 2 HON (SO3NH4)2 2 HON (SO3NH4)2 + 4 H2O (NH2OH)2H2SO4 + H2SO4

 The acidic hydroxylamine sulfate reacts with cyclohexanone and ammonia to produce cyclohexanone oxime. 2 C6H10O + (NH2OH)2.H2SO4 + 2 NH3 2 C6H10NOH + (NH4)2SO4 + H2O cyclohexanon oxime is converted to caprolactam by Beckmann rearrangement in presence of oleum.

 The reaction mass is then neutralized with ammonia.

C6H10NOH + H2SO4 C5H10NHCO + H2SO4 (Caprolactam)

FORMALDEHYDE
This is a monomer for making polyacetal. It is also known as poly oxy methylene.

It is also a reactant in phenoloic and amino resins. It is a pungent gas and is generally available as 37 % solution in water.

FORMALDEHYDE
HCHO 30 [50 00 0] - 190C - 1170C Soluble in water/ alcohol Moderately soluble in non polar solvents such as ether/chloroform Formula Formula weight Chemical Registry No Boiling Point Melting Point Solubility

MANUFACTURING PROCESS
Two commercially used processes based on methanol as the basic raw material. SILVER PROCESS: It involves two reactions: Oxidation of methanol CH3OH + 0.5 O2 CH2O + H2O (exothermic reaction).

 Dehydrogenation of methanol: CH3OH CH2O + H2 (endothermic reaction). The catalyst is silver crystals or gauze. Reaction temperature is 550 to 6250C Pressure is almost atmospheric. Methanol is in excess. All the oxygen added is used to avoid explosion limits.

Methanol and air are heated separately. Steam and reactants enter the reactor. Heat of reaction is removed as steam. Reaction products are quenched and enter the water absorber. Methanol and formaldehyde are separated by distillation. Methanol I srecycled.

OXIDE PROCESS: Air is used in excess and all the methanol is reacted. Oxides of iron and molybdenum are used as catalyst. Temperature is in the range of 225 to 3000C.

 Tubular reactor is used. Reaction products are quenched and absorbed in water. Unreacted air is cooled and recycled. The heat of reaction is removed to generate high pressure steam

Water

Tail Gases

Steam Air

Reactor

Water absorption tower

Distillation Methanol steam for purification and recycle

Formaldehyde

Methanol

Block diagram for formaldehyde manufacturing process (methanol in excess) (silver catalyst)

Water

Tail Gases+ air for recycle Formaldehyde for purification

Air

Reactor

Cool

Absorption Tower

Methanol

Block diagram for formaldehyde manufacturing process (air excess) (metal oxide catalyst)

STYRENE
Also known as phenylethene, styrol, vinylbenzene, or cinnamene. Predominantly used for manufacture of polystyrene It is also a monomer in the production of styrenic coplymers such as SAN, HIPS, ABS or ASA.

STYRENE
Formula C6H5CH=CH2 Formula weight 104 CAS Registry no [100 42 5] Boiling point 1450C Melting point - 30.60C Solubility sparingly soluble in water

MANUFACTURING
Manufacturing of styrene involves manufacture of an intermediate, ethylbenzene. Ethylbenzene is manufacured from benzene. Ethylebenzene is dehydrogenated into styrene.

MANUFACTURING
Manufacturing of ethylbenzene: Reaction involves catalytic alkylation of benzene with ethylene. Excess benzene is used and almost 100 % ethylene is reacted. C6H6 + CH2=CH2 C6H5CH2CH3

 More than one mole of ethylene can react with benzene to form diethyl-, triethyl-, or tetraethyl enzene. These products are colectively called as poly ethyl benzenes, PEB PEB are separated from eyhyl benzene by distillation and reacted with benzene to form ethylbenzene.

 C6H4 (CH2CH3)2 + C6H6 2 C6H5CH2CH3 Excess benzene reduces the formation of side products but enhances the cost of separation. Purity of benzene and ethylene has to be very high. Impurities less than 2000 ppm are essential. Impurites play play significant role in the side raections

 Zeolites are used as catalyst. Vapor Oxidation Process: Reaction temperatures are 350 to 4500C and pressure is in the range of 6 to 25 atmospheres. Reaction products are distilled to separate benzene, and ethylbenzene alongwith PEB.

 Benzene is recycled to the main reactor or reacted with PEB to form ethylbenzene in the transalkylation reactor. Ethylbenzene from the main reactor as well as from the transalkylation reactor is distillled for further reaction.

Benzene PEB

Ethylene

Ethylbenzene

Ethylbenzene for Styrene

Separation column

Reactor

Distillation

Distillation

Benzene vapors Vaporizer

PEB Recycle benzene

Residue for Treatment

Fresh Benzene

Block diagram for manufacture of ethylbenzene (for styrene)

 Liquid Phase Process: Ultra selective Y type (USY) type zeolite catalyst. The reaction temperature is about 2700C and pressure is up to 40 atmospheres. Water is added alongwith benzene to suppress the side reactions.

STYRENE FROM ETHYLBENZENE:

This reaction is endothermic. The manufacturing of ethylbenzene involves exothermic reactions. C6H5CH2CH3 C6H5CH=CH2 + H2 There are two types of processes: adiabatic process and isothermal process

 Adiabatic process: Iron oxide potassium oxide is a catalyst. The reaction temperature is around 550 to 6800C and the pressure is around 2 atmospheres. Steam is added along with ethyl benzene which supplies heat, reduces the partial pressure to derive reaction in the forward direction.

Ethylbenzene

Steam

Off gases

Ethylbenzene for recycle

Series of reactors with interheaters

Distillation Column

Distillation

Crude styrene for purification

Block diagram for the manufacture of styrene by adiabalic process

Other Processes
Isothermal dehydrogenation of ethyl benzene. This is followed by , BASF and Montedison. Styro Plus, developed by UOP uses oxidation of hydrogen to supply the heat for the formation of styrene. Handling of hydrogen at the reaction conditions pose major hurdle for this process.

 Coproduction of STYRENE and Propylene oxide is developed by ARCO. C6H5CH2 + O2 C6H5C(OOH)CH3 Epoxidation of propylene C6H5C(OOH)CH3 + CH2=CHCH3 CH2OCHCH3 + C6H5C(OH)HCH3 C6H5C(OH)CH3 C6H5CH=CH2 + H2O

BISPHENOL A
This is used in making polycarbonates, epoxy and many specialty polymers. The scientific name for bisphenol A is: 4,4 isopropylidenediphenol. It is a product of condensation reaction of phenol with acetone.

Formula C(CH3)2(C6H4OH)2 Formula weight 228 Melting point 1530C Boiling point sublimes above 2250C CAS Registry No [80 05 7] Solubility soluble in alkaline water and organic solvents

MANUFACTURING PROCESS
2 C6H5OH + CH3COCH3 C(CH3)2(C6H4OH)2 + H2O Two processes are described. Ion exchange resin catalyzed process: The reaction is carried out at 750C using a cation exchange resin as a catalyst. Tubular reactor is commonly used.

OTHER BISPHENOLS
Phenol + Acetone Bisphenol A Phenol + Butanone(MEK) Bisphenol B Phenol + o-cresol Bisphenol C Phenol + Formaldehyde Bisphenol F Phenol + o-isopropylphenolBisphenol G Phenol + Cyclohexanone Bisphenol H

 Acid catalyzed process: This process is practiced by GE and Mitsui Company. Phenol and acetone in the molar ratio of 8:1 which are saturated with Hydrochloric acid are reacted at 500C for several hours. Recycled stream contains unreacted phenol, some acetone, bisphenol A and water.

Acetone

Phenol

Reactor (Acid catalyst)

Phenol for recycle

Phenol+ Bisphenol A (organic phase) Water + acetone+ phenol+ traces of bisphenol A Settling tank

Cool Separation process

Filter

Wash

Distillation

BPA

Acetone for recycle Recovered phenol and bisphenol A for purification and recycle

Block diagram for the manufacture of bisphenol A (BPA)