Date post: | 02-Jun-2018 |
Category: |
Documents |
Upload: | ishani-gupta |
View: | 221 times |
Download: | 0 times |
of 30
8/11/2019 Ethylene 2010
1/30
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.
8/11/2019 Ethylene 2010
2/30
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
8/11/2019 Ethylene 2010
3/30
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
8/11/2019 Ethylene 2010
4/30
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
8/11/2019 Ethylene 2010
5/30
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.
8/11/2019 Ethylene 2010
6/30
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.
8/11/2019 Ethylene 2010
7/30
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
8/11/2019 Ethylene 2010
8/30
8/11/2019 Ethylene 2010
9/30
Others8%
Surfactants13%
Ethanolamine7%
Glycols65%
OtherPetro
chemicals7%
8/11/2019 Ethylene 2010
10/30
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
8/11/2019 Ethylene 2010
11/30
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
8/11/2019 Ethylene 2010
12/30
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
8/11/2019 Ethylene 2010
13/30
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.
8/11/2019 Ethylene 2010
14/30
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.
8/11/2019 Ethylene 2010
15/30
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
8/11/2019 Ethylene 2010
16/30
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.
8/11/2019 Ethylene 2010
17/30
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
8/11/2019 Ethylene 2010
18/30
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
8/11/2019 Ethylene 2010
19/30
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
8/11/2019 Ethylene 2010
20/30
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
8/11/2019 Ethylene 2010
21/30
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%)
8/11/2019 Ethylene 2010
22/30
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
8/11/2019 Ethylene 2010
23/30
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
8/11/2019 Ethylene 2010
24/30
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
8/11/2019 Ethylene 2010
25/30
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.
8/11/2019 Ethylene 2010
26/30
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
8/11/2019 Ethylene 2010
27/30
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
8/11/2019 Ethylene 2010
28/30
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
8/11/2019 Ethylene 2010
29/30
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
8/11/2019 Ethylene 2010
30/30
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