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ETHYLENE AND DERIVATIVESEthylene is one of the most versatile petrochemicals and itsproduction has steadily increased over the years.

Ethylene is called as king of chemicals and surpasses all organicchemicals in production and in amount sold.

Ethylene is the basic building block for petrochemicals.

Because of its ready availability at low cost and high purity &reactivity, ethylene has become one of the important raw materialsfor large number of petrochemicals and products

Ethylene has replaced the earliest route of production of vinylchloride, acetaldehyde, vinyl acetate and other chemicals throughacetylene route. Large tonnage of ethylene is being used for themanufacture of polyethylene, ethylene oxide, ethylene glycol andstyrene.

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Region wise Ethylene CapacityGrowth (million tonnes)

Region Capacity(in 2004)

Capacity 2010

America Europe MiddleEast/Africa

Asia

pacific

38.47 29.80 12.18 31.10

41.42 32.00 32.68 43.89

WorldTotal

111.55 149.99

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Ethylene

P V C

Industrial solventand

Chemicalintermediates

A c e t i c a c i d (

P e r a c e t i c

a c i d ), A c e t i

c a n h y d r i d e ,

C e l l u l o s e a c

e t a t e , V i n y l

a c e t a t e , P y r

i d i n e,

B u t y r a l d e h y

d e ( E t h y l

h e x a n o l )

V i n y l

C h l o r

i d e

S y n t h e t i c r u b b e r a n

d

p o l y s t y r e n e S t yre n e

A c e t a l d

e h y d e

( f r o m e

t h y l

a l c o h o

l )

EthylChlorideTetraethyl lead,

Chemical intermediates

V i n y l A c e t a t e

P o l y v i n y l a c e t a t e ,

P o l y v i n y l a l c o h o l

Ethylalcohol

E t h y l e

n e

o x i d e

&

E t h y l e

n e

g l y c o l

PolyethyleneLDPE, LLDPE,HDPE

Films, moldings,pipes, cablecovering, netting

A n t i f r e e z e ,

p o l y e s t e r ,

s o l v e n t s ,

d e t e r g e n t

t e x t i l e , e t h a n o l

a m i n e

C h l o r

i n a t e d

S o l v e n

t s

O l e f i

n

T r i c h l o r

o e t h y l

e n e ,

P e r c h l o r o

e t h y l e

n e

n - b u

t e n e s ,

S y n t

h e t i c

d e t e

r g e n

t ,

O x o a

l c o h o

l s ,

S y n t

h e t i c

l u b r i c

a n t s

Product Profileof Ethylene

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EthyleneOxide

P o l y e s t e r, S t

a p l e f i b e r y a

r n,

P E T B o t t l e s

, F i l m

Natural gas,Plasticizer,Conditioning agent

P h a r m a c e u t i

c a l s ,

B r a k e F l u i d,

c o s m e t i c s

Textile auxiliaries,

Binders, Dyes,

Pesticides,

Pharmaceuticals,

Cosmetics

Non-ionicsurfactants,Ethoxylates

M o n o

E t h y l e n e

G l y c o l

C o o l a n

t s ,

P e s t i c i

d e s ,

R u b b

e r

C o m p o u n

d i n g ,

P l a s t i c i z e

r ,

P o l y u r

e t h a n e ,

A l k y l R

e s i n

D i e t h y

l e n e

G l y c o l

P o l y e t

h y l e n e

G l y c o l

GlycolEthers

Brake Fluid

and

Protective Coating

E t h a n o l A m i n e

s

D e t e r g e n t , S o a p s o l v e n t ,

C o s m e t i c s , M o r p h o l i n e

TriethyleneGlycol

Product Profileof Ethylene Oxide andEthylene Glycol

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EthyleneThere are two basic routes for manufacture of

ethylene:(i) Fermentation of molasses to ethanol and then

dehydrogenation of ethanol to ethylene

(ii) Thermal cracking of alkanes, naphtha, and gas oil .

Major portion of the ethylene is still met through

cracking of naphtha and natural gas - ethane andpropane. In India, naphtha and natural gas are thetwo major sources of ethylene.

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Ethylene Oxide by Direct Oxidation Process In the direct oxidation process, ethylene (after

removal of sulphur) and oxygen produced byair separation are reacted safely underoptimum conditions for making ethylene oxidein presence of silver catalyst containing an

initiator, which is usually alkaline earth oralkaline metal deposited on solid support.Various steps involved in manufacture ofethylene oxide are

Ethylene oxide synthesis, Ethylene oxide scrubbing, Ethylene oxide purification, and CO2 recovery.

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Reactions The reactions involved are:

C2H4 + O2 C2H4O ; H = -105 kJ/mol

The above reaction is highly exothermic. To remove the heat ofreaction water is passed from shell side and steam is generatedwhich is used in the process.

The reactor temperature is one of the most critical parameter in

ethylene oxide synthesis and is measured at large number oflocations in the catalyst bed. Efficient and reliable heat transfersystem is also very important.

The gas stream leaving the reactor contains CO 2, acidiccompounds, formaldehyde, ethylene, etc., is sent to absorberand stripping section for further purification and removal of

impurities like CO 2, acid compounds, and formaldehyde. In the reactor, about 10.5% conversion of ethylene occurs perpass with a design selectivity of 79.6%. The reaction systemoperates on a recycle process and the conversion of ethylene-to-ethylene oxide is about 6% only.

o250 290 C

Ag

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Others8%

Surfactants13%

Ethanolamine7%

Glycols65%

OtherPetro

chemicals7%

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Mono-, Di- Tri- Ethylene Glycols(MEG,DEG,TEG )

A major petrochemicals and find application in manufactureof polyester and as antifreeze.Accounts for 70% of Ethylene oxide production.

Ethylene oxide preheated to 195 oC

EO:H 20 ratio 10:1 to maximise MEG productionBy Products DEG,TEG

C 2H 4O + H 2O CH 2OH CH 2OH

MEGCH 2OH CH 2OH + C 2H 4O HO(C 2H 4O)2H

DEG

HO(C 2H 4O) 2H + C 2H 4O HO(C 2H 4O) 3HTEG

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EthyleneOxide

Water

Inhibitor

Dilution

GlycolReactor200 oC

1.5 MPaResidenceTime: 45min-1h

MultipleEffect

Evapora

tor

Dehydration

MEGDistillation

Column

Recycle WaterMonoethyleneGlycol (MEG)

DEGDistillation

Column

Diethylene Glycol(DEG)

TEGDistillation

Column

Triethylene Glycol(TEG)

HeavyEnd Vacuum Columns

Raw Material

Vapor

Ethylene Glycol from Ethylene Oxide

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Vinyl Chloride Vinyl chloride is one of the major ethylene derivatives

and has gained worldwide importance because of itsindustrial use as raw material for Polyvinyl Chloride(PVC) polymer.

The second largest tonnage commercial polymer afterpolyethylene. About 95% of the present vinyl chlorideproduction worldwide is used in polymer productionor copolymer application.

Another important use of vinyl chloride is in theproduction of vinylidiene chloride.

Worldwide vinyl chloride production andconsumption in 2001 was 30.704 lakh tonnes and27.843 lakh tonnes respectively

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Process Technology

The original process of manufacture of vinyl chloridewas by reaction of acetylene derived from calciumcarbide with hydrochloric acid in gaseous phase inpresence of mercuric chloride catalyst at temperature

around 100-180 oC.

However, because of the cost of acetylene and theavailability of ethylene from steam crackers, the aboveprocess has been replaced commercially either bychlorination of ethylene and cracking of the ethylenedichloride or by oxychlorination and cracking ofethylene dichloride.

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Vinyl Chloride by Ethylene Chlorinationand Cracking of Ethylene Dichloride

The process of vinyl chloride manufacture takesplace in two stages.

First stage: Ethylene is reacted with chlorine ineither liquid or vapor phase in presence of ferricchloride. However, the liquid phase process ismore common and the reaction takes place ataround 50-90 oC and 3-5 atm pressure.

Seond stage: Vinyl chloride is produced bypyrolysis of vaporised ethylene dichloride in a setof tubular furnaces at temperature of about 400-500 oC.

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Ethylene Oxide Process Technology Chlorohydrin Process

Cl 2 + H 2O HOCl + HClC 2H4 + HOCl CH2OH-CH2Cl

CH 2OH-CH 2Cl + Ca (OH) 2 CH 2 CH 2 + CaCl2 + H2O

Direct Oxidation

CH 2+CH 2 +1/2O 2 C 2H4O

C2H 4 + 3 O 2 2CO 2 + 2 H 2O ; H = -135 kJ/moC2H 4O + 5/2 O 2 2 CO 2 + 2 H 2OC 2H4 + O 2 CH 3CHOC2H 4 + O 2 2 HCHO

Ag, 260-290 0C

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OXYCHLORINATION PROCESS The original process of manufacture of vinyl chloride

by ethylene chlorination and cracking of ethylenedichloride has been replaced by oxychlorinationprocess in which no hydrochloric acid is formed asbyproduct.

The process involves production of ethylenedichloride by exothermic reaction of ethylene,hydrochloric acid and oxygen

Liquid phase: at about 170-180oC in at 15-20 atm

pressure in presence of copper chloride in either fixedor fluidised bed reactor.

Vapor phase reaction: the temperature and pressureare 200-220 oC and 20-50 atm pressure.

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Vinyl Chloride Processes by OxychlorinationProcess

Direct chlorination:CH 2=CH 2 + Cl 2 ClCH 2-CH2Cl

Oxychlorination:

CH 2=CH2 + 2 HCl + O 2 ClCH 2-CH 2Cl +H 2O Ethylene dichloride pyrolysis:

ClCH 2-CH 2Cl CH 2=CHCl + HCl

Overall reaction:2 CH 2=CH2 + Cl 2 + O 2 2 CH 2=CHCl + H 2O

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Vinyl Chloride by Oxy Chlorination

Direct chlorination:CH2=CH2 + Cl2 ClCH2-CH2Cl

Oxychlorination:

CH2=CH2 + 2 HCl + O2 ClCH2-CH2Cl +H2O Ethylene dichloride pyrolysis:ClCH2-CH2Cl CH2=CHCl + HCl

Overall reaction:2 CH2=CH2 + Cl2 + O2 2 CH2=CHCl +H2O

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Vinyl Chloride by two stage process Ethylene

chlorination and Cracking

CH 2=CH 2 + Cl 2 CH 2Cl-CH 2Cl CH 2=CHCl + HCl Initiation: ClCH 2-CH 2Cl ClCH2- H2 + l Propagation:

l + ClCH2 -CH2Cl ClCH 2-HCl + HClClCH 2-HCl CH2=HCl +l

Termination:l + ClCH2 -H 2 CH 2=CHCl + HCl

The first stage is typical electrophilic addition of ahalogen to an alkene. The second stage is a freeradical chain reaction.

Fi 8 8 Vi l Chl id f

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Ethylene

Chlorine

O x y c

h l o r i n a

t i o n

C r u

d e

E t h y l e n e

D i c h l o r i

d e

D i s t i l l a

t i o n

D i s t i l l a

t i o n

C h l o r i n a

t i o n

Light End

Heavy End

Ethylenedichloride

Ethylene

HCl

Air/O 2

E t h y l e n e

d i c h l o r i d e

E t h y l e n e

d i c h l o r i d e

C r a c k

i n g

Q u e n c h

Residue

V i n y l

C h l o r i

d e

S e p a r a

t i o n

V i n y l c h

l o r i

d e

c o l u m n

Heavy End

VinylChloride

HCl Recycle

Figure 8.8: Vinyl Chloride fromEthylene by Oxychlorination Process

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VINYL ACETATE (CH 2=CHCOOCH 3) Vinyl acetate is one of the important derivatives of ethylene which

is used as intermediate for manufacture of polyvinyl alcohol,polyvinyl acetate, polyvinyl butyral, etc.

Global end use pattern of vinyl acetate is:-

Adhesives (23%), paints and coating (29%), textiles (21%),plastics (17%), paper and board (10%). Consumption pattern ofvinyl acetate in India is polyvinyl acetate emulsions & resins(50%), polyvinyl alcohol (25%), ethylene vinyl acetate (10%),

others (15%).

End use pattern of vinyl acetate in India is:-

adhesives (35-40%), textiles (30-35%), paints and coating (15-

20%), others (10-15%)

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Product Profile of Vinyl Acetate

Vinyl Acetate

S u r f a c e c o a t i n

g

a d h e s i v e s

,

T e x t i l e r e

s i n s

Acrylic Fibers

W a t e r r

e s i s t a n t

i n s u l a t

i o n

e n a m e l

Textile and

Paper Coating

Ethylene Vinyl AcetateCopolymers

P o l y

v i n y l

A c e t a t

e

T e x t i

l e s i z e ,

G r e a

s e p r o o f

i n g

p a p e

r ,

V i n y l

e m u l s

i f i e r ,

T h i c k

e n e r ,

V i s c o

s i t y

r e g u l a

t o r s ,

A d h e

s i v e s

,

P o l y v

i n y l

A l c o h o l

P o l y v i n y l

F o r m a t

e

V i n y l c h l o r i

d e

c o m o n o m e

r s VC-VAC,

LP Records,

VC-VAC Coating

P o l y v i n y l B u t r y a l d e h y d e

S a f e t y G l a s s

Acrylo- nitrileCopolymer

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Process Technology

The ethylene route has replaced the traditionalprocess of manufacture of vinyl acetate. Theproduction of vinyl acetate through acetylene route,

which was developed by Wacker in 1930, involvesreaction of acetylene and acetic acid in liquid phaseat 60-80 oC and 1-2 atm pressure in presence ofmercury salt catalyst.

C 2 H 2 + CH 3 COOH CH 2 =CHCOOCH 3

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Vinyl Acetate through EthyleneRoute

Vinyl acetate is made by reaction of ethylene with acetic acidby liquid phase process or by vapor phase process in presenceof palladium and cupric chloride catalyst. In the vapor phaseprocess, following reactions take place:

CH 2 =CH 2 + CH 3 COOH + PdCl 2 CH 2 =CHCOOCH 3 + 2 HCl + Pd

Pd + 2 CuCl 2 PdCl 2 + 2 CuCl

2 CuCl + 2 HCl + H 2 O 2 2 CuCl 2 + 2 H 2 O

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ETHANOL (C 2H5OH) Ethanol apart from its major use as a beverage is one of the

most versatile chemicals and is one of the basic buildingblocks of the organic chemical industry. Ethanol isgenerally produces by fermentation of molasses, due to thedevelopment of petrochemical industry and availability ofethylene, now ethylene provides another major route offormation of ethanol.

However, ethanol in India is still manufactured throughmolasses route. Some of the important chemicals which aremade through petrochemical route are still made throughethanol route at some places in India. Two such importantcomplexes are Jubilant Organosys Ltd., Gajraula (UttarPradesh) and Indian Glycol Ltd. Kashipur (UttarPradesh), where large number of ethanol derivatives ismanufactured through ethanol route.

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Product Profile ofEthanol

Acetic Acid

Acetaldehyde

Ethyl Alcohol Butadiene

SBR

ABR

Molasses,beats, starch, waste

sulphide, liquor,

forest residue

Ethylene from steamcracker and other routes

Catalytic hydrationor

Esterification & hydrolysisFermentation

Butyraldehyde

n-butane

Butyl acetate

n-butanolEthyl hexanol

AcetoneSolvent,

methyl methacrylate,methyl isobutyl ketone

Ethylene

Ethylene Oxide

Vinyl acetate

Vinyl chloride

StyreneSBR,Polystyrene

Emulsions

PVC

Acrylonitrile

Ethanol amine

Ethylene glycolPolyester

Vinylacetate

Pyridine

Peracetic acid

Acetate ester

Diketone

2,4-D

PTA Polyester

Acetic anhydride Cellulose, aspirin, dye stuff

Vinyl acetate Emulsion

Solvent

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Process Technology

Various routes for manufacture of ethanol Fermentation of molasses Catalytic hydration of ethylene. Ethylene esterification and hydrolysis.

Fermentation of molasses:Ethyl alcohol is made from molasses byfermentation process utilising yeast enzymes.Separation of 8-10% alcohol is achieved in a seriesof distillation columns, as alcohol and water at 95%concentration form azeotropic mixture.

E h l b V Ph H d i f

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Ethanol by Vapor Phase Hydration ofEthylene

An ethylene rich gas is mixed with water and heated to about300 oC and passed on to fixed bed catalytic reactor wherecatalytic hydration of ethylene takes place

C2H4 + H 2O C 2H5OH

The catalyst used is phosphoric acid deposited on silica gel. Thereactor effluents are sent to separator for separation of vapor

and liquid. The gases from the separator are cooled andscrubbed with water to recover traces of alcohol. The alcoholwater mixture is sent to a series of distillation columns whereether is separated in the light end column and finally 95% byvolume ethanol water azeotrope is separated.

Eth l f C t l ti R l H d ti

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Ethanol from Catalytic Recycle Hydrationof Ethylene

R e a c

t o r

Separator S c r u

b b i n g

S t r i p p

i n g

Wastewater

Water

Ethylene

Process water

L i g h t e n

d c o

l u m n

E t h y

l a

l c o

h o l

c o

l u m n

H y

d r o g e n a

t i o n

Hydrogen

Separator

Lightends

Ethylalcohol

P r e

h e a

t e r

E h l b E ifi i d

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Ethanol by Esterification andHydrolysis

Ethylene and sulphuric acid are reacted at 80 oC and 1.5 MPa to form amixture of ethyl sulphates, which are then hydrolysed to ethyl alcohol.

Ethylene and sulphuric acid are reacted in absorber from which themixture of ethylene sulphates thus formed is fed to hydrolyser from

which the crude alcohol and sulphuric acid are fed to stripping sectionand caustic scrubbing section and finally to a series of two distillationcolumns for separation of ether and alcohol .

C 2H4 + H 2SO 4 C 2H5OSO 3H

2 C 2H4 + H 2SO 4 (C 2H5O) 2SO 2C2H5OSO 3H + (C 2H5O) 2SO 2 + 3 H 2O 3 C 2H5OH + 2 H 2SO 4

2 C 2H5OH C 2H5OC 2H5 + H 2O