UNIT-I

PROPYLENE & ITS

DERIVATIVES
Introduction
 Propylene is one of the key “ building block” petrochemicals used as
feedstock for a variety of polymers and chemical intermediates.
 Propylene often referred as the crown prince of petrochemicals.
 Propylene is used in many of the world’s largest and fastest growing
synthetic materials and thermoplastics.
 The demand of propylene has increased rapidly during the last twenty
years and primarily driven by polypropylene demand.
 Propylene is always a byproduct of refinery FCC and steam cracking of
ethane/propane as well as naphtha cracking.
 In 2003, the world propylene market of 57.6 million tonnes came from
steam cracking as byproduct of ethylene(67%), refinery FCC units as a
byproduct of gasoline and distillate production (30%) and on purpose
unit such as propane dehydrogenation and metathesis(3%).
Global Propylene demand
 Global propylene demand grew
from 37,2 million tons in 1995
to approximately 52 million tons
in 2000, corresponding to an
AAG of 5.5%.
 From 2000 to 2006 – AAG of
4.6 % per year, reaching almost
67 million tons.
 Global propylene consumption is
forecast to average growth of
around 5.1% per year from 2009
to 2014 and 8.5% per year from
2014-19.
 According to CMAI consulting 2010 global production and
consumption of propylene in 2009 was both approximately 71
million tones with capacity utilization of 78.5%.
 Consumption of refinery grade propylene made up 9% of total
consumption in 2009, chemical grade 23% and polymer grade
68%.
 Refinery grade propylene is consumed mainly for production of
cumene and isopropyl alcohol. Chemical grade propylene
mostly goes into oxo-alcohol, propylene oxide and acrylonitrile.
Global propylene demand by derivatives

 This increase will be driven by

the demand for derivatives,
especially polypropylene and
propylene oxide, the demand
for which growing at the rate of
5.5% and 4.3 %, respectively
for the period of 2007 - 2015
Global Propylene consumption trends by region
Product profile of propylene
Product profile of Propylene
Sources of propylene
 Propylene is a byproduct of steam crackers and varying amount
of olefins is produced from steam crackers depending on the type
of feedstock. Other sources of propylene may be recovery of
propylene from FCC light ends, Propane dehydrogenation,
Metathesis.
 According to CMAI analysis, out of the total demand of 50.2
million tonnes, 34.2 million tonnes is recovered as byproduct
from crackers, 14.7 million tonnes as byproduct from refinery
FCC units, 0.8 million tonnes from propane dehydrogenation
and 0.5 million tonnes from metathesis.
Propylene Production Technologies
Propylene Production Technologies
Propylene Production Technologies
 Propylene: Lummus’ Olefin Conversion Technology
Application:
 To produce propylene from ethylene and butenes using Lummus’ olefin
conversion technology (OCT).
Yields:
 OCT process selectivity to propylene is typically greater than 98%.
Overall conversion of n-butenes is 85 – 92%.
 Ethylene and butenes feed streams can come from steam crackers or
many refinery sources and in varying concentrations.
 In the Automet Technology, butenes yield about 10% ethylene, 38%
propylene and 47% hexene-1. The balance is C6 and heavier material.
 Based on a 300,000-mtpy propylene plant, US Gulf Coast.
 Two plants have recently started up:
690 MM lb/yr unit for BASF Fina Petrochemical in Port Arthur, Texas
&
320 MM lb/yr unit for Mitsui Petrochemical in Osaka, Japan.
Description:
 Ethylene feed stream (plus recycle ethylene) and butenes feed
stream (plus recycle butenes) are introduced into the fixed-bed,
metathesis reactor. The catalyst promotes reaction of ethylene and
2-butene to form propylene and simultaneously isomerizes 1-
butene to 2-butene.
 Effluent from the metathesis reactor is fractionated to yield high-
purity, polymerization-grade propylene, as well as ethylene and
butenes for recycle and small byproduct streams. Due to the
unique nature of the catalyst system, the mixed C4 feed stream
can contain a significant amount of isobutylene without impacting
performance of the OCT process.
 A variation of OCT & Auto-met Technology can be used to
generate ethylene, propylene and the co-monomer hexene-1 by
metathesis of n-butenes.
Propylene: Lummus’ Olefin Conversion Technology
 Propylene: Methanol to Propylene (MTP)

Application:
 To produce propylene from natural gas via methanol. This route
delivers dedicated propylene from nonpetroleum sources, i.e.,
independently from steam crackers and FCCs.
 Current studies and projects are based on a combined
MegaMethanol / MTP plant with a capacity of 5,000 mtpd of
methanol (1.667 million mtpy), yielding approximately 519,000
mtpy of propylene and 143,000 mtpy of gasoline.
Description:
 Methanol feed from a MegaMethanol plant is sent to an adiabatic DME
pre-reactor where methanol is converted to DME and water. The high-
activity, high-selectivity catalyst nearly achieves thermodynamic
equilibrium.
 The methanol/water/DME stream is routed to the first MTP reactor
stage where the steam is added. Methanol/DME are converted by
more than 99%, with propylene as the predominant hydrocarbon
product.
 Additional reaction proceeds in the second and third MTP reactor
stages.
 Process conditions in the three MTP reactor stages are chosen to
guarantee similar reaction conditions and maximum total propylene
yield. The product mixture is then cooled, and product gas, organic
liquid and water are separated.
 The product gas is compressed, and traces of water, CO and
DME are removed by standard techniques. The cleaned gas is
then further processed yielding chemical- or polymer-grade
propylene as specified.
 Several olefin-containing streams are recycled to the MTP
reactor as additional propylene sources.
 To avoid accumulation of inert materials within the loop, a
small purge removes light-ends, further purge streams of C4
and C5/C6. High-grade gasoline is produced as a byproduct.
 Water is recycled to steam generation; excess water from the
methanol conversion is purged. This process water can be used
for irrigation after appropriate and inexpensive treatment.
Methanol to propylene (MTP) Process
 Propylene: Oleflex Process
Application:
 To produce polymer-grade propylene from propane using the Oleflex
process in a propylene production complex.
Yields:
 Propylene yield from propane is approximately 85 wt% of fresh feed.
Hydrogen yield is about 3.6 wt% of fresh feed.
 US Gulf Coast inside battery limits are based on an Oleflex complex unit
for production of 350,000 mtpy of polymer-grade propylene.
Commercial plants:
 Eleven Oleflex units are in operation to produce propylene and
isobutylene. Six of these units produce propylene.
 These units represent 1.25 million mtpy of propylene production. Three
additional Oleflex units for propylene production are in design or under
construction.
Description:
 The complex consists of a reactor section, continuous catalyst
regeneration (CCR) section, product separation section and fractionation
section.
 Four radial-flow reactors (1) are used to achieve optimum conversion and
selectivity for the endothermic reaction.
 Catalyst activity is maintained by continuously regenerating catalyst (2).
 Reactor effluent is compressed (3), dried (4) and sent to a cryogenic
separation system (5). A net hydrogen stream is recovered at
approximately 90 mol% hydrogen purity.
 The olefin product is sent to a selective hydrogenation process (6) where
dienes and acetylenes are removed.
 The propylene stream goes to a deethanizer (7) where light-ends are
removed prior to the propane-propylene splitter (8). Unconverted
feedstock is recycled back to the depropanizer (9) where it combines
with fresh feed before being sent back to the reactor section.
 Platinum in alumina promoted by lithium and arsenic.

1. Four radial-flow reactors 2. Continuously regenerating catalyst 3. Compressor 4. Drier

5. Separation unit 6. Hydrogenation Unit 7. Deethanizer 8. Propane-Propylene splitter
9. Depropanizer
Propylene: ATOFINA/UOP Olefin Cracking Process
Applications:
 To primarily produce propylene from C4 to C8 olefins supplied
by steam crackers, refineries and/or methanol-to-olefins (MTO)
plants via olefin cracking.
Description:
 The ATOFINA/UOP Olefin Cracking Process was jointly
developed by Total Petrochemicals (formerly ATOFINA) and UOP
to convert low-value C4 to C8 olefins to propylene and ethylene.
 The process features fixed-bed reactors operating at temperatures
between 500°C - 600°C & pressures between 1 - 5 bars gauge.
 This process uses a proprietary Zeolite catalyst and provides high
yields of propylene. Usage of this catalyst minimizes reactor size
and operating costs by allowing operation at high-space
velocities, and high conversions and selectivity's without
requiring an inert diluent stream.
 A swing-reactor system is used for catalyst regeneration.
Separation facilities depend on how the unit is integrated into the
processing system.
 The process is designed to utilize olefinic feedstocks from steam
crackers, refinery FCC and coker units, and MTO units, with
typical C4 to C8 olefin and paraffin compositions.
 The catalyst exhibits little sensitivity to common impurities such
as dienes, oxygenates, sulfur compounds and nitrogen
compounds.
Propylene: ATOFINA/UOP Olefin Cracking Process
• Propylene Oxide
• Propylene Glycol [CH3CHOH-CH2OH]
• Propylene Glycol Mono Methyl Ether [CH3CH2OCH2CHOHCH3]
• Isopropyl Alcohol [CH3-CH(OH)CH3]
• Acetone [CH3COCH3]
• Acrylonitrile [CH2=CHCN]
• Cumene
• Methyl Methacrylate(MMA)-[CH2 = C(CH3)COOCH3]
• Butyraldehydes and Butanols
• 2-Ethyl hexanol [CH3CH2CH2CH2-CH(CH2CH3).CH2OH]
• Methyl Iso Butyl Ketone (MIBK)-[CH3COCH2CH(CH3)2]
• Diacetone Alcohol [CH3COCH2C(CH3)2OH]
• Isophorone
• Propylene Carbonate [C3H6CO3]
• Allyl Chloride [CH2=CHCH2Cl]
• Epichlorohydrin
• Acrylic Acid [CH2 = CHCOOH]
• Acrylamide [CH2=CHCONH2]
Propylene Oxide

 There are two major processes for the manufacture of propylene

oxide:
1. Propylene chlorohydrin process
and
2. Propylene oxidation process using peroxides.
Propylene Chlorohydrin Route:
 The chlorohydrination process consists of formation of
propylene chlorohydrin by the reaction between hypochlorous
acid and propylene.
 The propylene chlorohydrin is epoxidised to propylene oxide by
a 10% solution of milk of lime or NaOH.
Various steps involved are
 Propylene hypochlorination: Propylene is reacted with
aqueous chlorine resulting in the formation of propylene
chlorohydrins. Unreacted propylene is recycled.
 Neutralization: Neutralization of propylene chlorohydrins
containing hydrochloric acid which is formed during the
process.
 Dehydrochlorination: Reaction of propylene chlorohydrin
with milk of lime or caustic soda to produce propylene oxide
 Purification: Distillation of crude propylene oxide for
separation heavy ends
• Byproducts formed during the reaction are 1,2-dichloropropane and
chlorinated di-isopropylether.
• Some of the disadvantages and major economic drawbacks of the
process which led to the wide acceptability of epoxidation processes are
use of costly chlorine, production of weak calcium chloride byproduct,
and corrosion problem due to chlorine handling.
Propylene Oxide from Chlorohydrin Route
Epoxidation by Peroxide
 In this process, propylene and Peracetic acid (in ethyl acetate)
which is produced by oxidation of acetaldehyde are reacted in a
series of three specially designed reactors at 50-800C and 90-120
MPa pressure.
 The reaction products are fed to the stripper where a mixture of
propylene and propylene oxide are obtained as top product while
mixture of ethyl acetate and acetic acid is obtained as bottom
product. Both mixtures are fed to two separated columns where
separation of propylene oxide, ethyl acetate, acetic acid, and
heavy end takes place.
In other process: isobutane and methyl benzene are oxidized with air to
yield hydroperoxide which is reacted with propylene in liquid phase at
120-1400C and 350 Mpa pressure using molybdenum naphthenate as
catalyst.
Propylene Oxide from Epoxidation Process
Propylene Glycol[CH3CHOH-CH2OH]

Propylene glycol, also called 1,2-propanediol or propane-1,2-diol,

is an organic compound (a diol or double alcohol) with formula C3H8O2 or
HO-CH2-CHOH-CH3.
It is a colorless, nearly odorless, clear, viscous liquid with a faintly sweet
taste, hygroscopic and miscible with water, acetone, and chloroform.
• Propylene glycol is a component in newer automotive antifreezes and
de-icers used at airports. Like ethylene glycol.
• India manufactures of propylene glycol is in India Manali Petrochemical
Ltd., Tamil Nadu (7800 TPA).
•The total demand of PG is about 11,400 TPA.
Propylene glycol production
Process Technology

Process consists of three steps.

Reaction of propylene oxide with water (15:1 Ratio)
Concentration of reaction product from hydration stage
Distillation for separation of mono propylene glycol, dipropylene
glycol in a series of distillation columns
temperature : 1900C & Pressure: 2.1 Mpa.
Uses of Propylene glycol
• Solvent in the flavor concentrate and fragrance industry, an excipient in elixirs and
pharmaceuticals, and a coupling agent in sunscreens, shampoos, shaving creams and
other personal care products
• Wetting agent for natural gums to simplify compounding

Industrial grade:
Raw material to produce high-performance unsaturated polyester resins (UPR) used for
marine construction, gel coats, sheet molding compounds and synthetic marble castings
Chemical intermediate in the production of resins for paints and varnishes
Solutions with water to make antifreeze, heat-transfer fluids and aircraft and runway deicing
fluids
Solvent in printing inks
Solvent and enzyme stabilizer in laundry detergents
Stabilizer in hydraulic fluids
Plasticizer to improve the process ability of plastics
 Propylene Glycol Mono Methyl
Ether[CH3CH2OCH2CHOHCH3]
It is produced by reaction of Propylene oxide with methanol.

Uses:

Used as solvent for cellulose

Acrylics
Dyes
Inks
Stains and for solvent sealing of cellophanes.
 Isopropyl Alcohol [CH3-CH(OH)CH3]
•Isopropyl alcohol (also isopropanol, propan-2-ol, 2-
propanol, rubbing alcohol ) is a common name for a chemical compound with
the molecular formula C3H8O.
•It is a colorless, flammable chemical compound.

Properties
• Isopropyl alcohol is miscible in water, alcohol, ether and chloroform.
• It will dissolve ethyl cellulose, polyvinyl butyral, many oils, alkaloids,
gums and natural resins. It is insoluble in salt solutions.
• Isopropyl alcohol forms an azeotrope with water, which gives a boiling
point of 80.37 oC and a composition of 87.7 wt% (91 vol%) isopropyl
alcohol.
•Water-isopropyl alcohol mixtures have depressed melting points. It has
a slightly bitter taste, and is not safe to drink.
• Isopropyl alcohol becomes increasingly viscous with decreasing
temperature. At temperatures below -70 °C Isopropyl alcohol resembles
maple syrup in viscosity.
 Process Technology
Two industrial process can be used to manufacture isopropyl alcohol
1. Sulphation of propylene followed by hydrolysis of propylene sulphates
2. Direct hydration of propylene to isopropyl alcohol

❖ Sulphation of propylene followed by hydrolysis of propylene sulphates:

✓ It is reaction of H2SO4 and Propylene in gas phase at ambient temp and
2-3 Mpa pressure.
✓ In the second step, isopropyl acid sulphate is hydrolyzed by reducing
concentration by addition of water or steam
Sulphation of propylene followed by hydrolysis of propylene sulphates
 Either pure propylene or a mixture of Propylene and other
C2, C3 components can be fed to a reactor.
 The hydrocarbon feed is compressed and fed to the reactor
at about 20 – 25 atms pressure.
 Sulphuric acid of about 70% acid strength is fed in a
countercurrent mode to the tray column where reactive
absorption takes place. Here, sulfonation reaction takes
place.
 The reaction is highly exothermic and therefore,
refrigerated brine is used to control the temperature in the
absorber. Jacketed arrangement will be preferred for the
tray absorption column to circulate the refrigerated brine in
the cooling jacket.
 After reaction, the unreacted light ends such as saturated
components will leave the unit as the gas stream.
 The sulfonated product rich stream is then sent to a hydrolyzer cum stripper
where isopropanol is produced and is vaporized due to existing stripper
temperatures.
 The hydrolyzer is fed with water to facilitate the conversion of the sulfonate
product.
 The isopropanol rich vapors then enter a caustic wash unit to remove the acidic
impurities.
 The isopropanol rich vapors then enter a partial condenser which separates the
unreacted propylene from the alcohol + ether mixture. Here, propylene is
separated as the vapor and alcohol + ether is separated as the liquid stream.
 The separated propylene gas is once again subjected to water wash to remove
soluble impurities (such as ethers and alcohols). Subsequently, pure propylene is
sent to mix with the fresh feed stream. Before sending to the unit, the propylene
is cooled to room temperature so as to have identification conditions as the fresh
feed stock.
 The alcohol and ether enter a ether column that separates isopropyl ether which
is returned to the reactor.
 The bottom product consisting of isopropyl alcohol and water is sent to a
isopropyl alcohol column that produces water + heavy ends as the bottom
product and 87 % isopropanol-water azeotrope mixture as the top product.
 The azeotrope is sent to an azeotropic distillation column that
uses isopropyl ether as a azeotropic agent to obtain 99 %
isopropanol as the bottom product. The top product is a mixture
of isopropyl ether and water. The top product is a low boiling
azeotrope. This stream upon gravity settling will produce the
isopropyl ether as the top product which is sent as a reflux
stream to the azeotropic column. The bottom product is a
mixture of isopropanol and water is recycled back to the
isopropyl alcohol column along with the bottom product
generated from the ether separating column.
Uses of Isopropanol :
 It finds use in pharmaceutical applications because of
the low toxicity of any residues. Isopropanol is also
used as a chemical intermediate in some industrial
processes. It is also used as a gasoline additive.
 2. Direct hydration of propylene to isopropyl
alcohol
 Feed propylene, recycled propylene, unreacted propylene are
pressurized to 15-20 Mpa pressure in the liquid state and
prepared just before entering the reactor.
 The pressurized preheated water containing recycled catalyst is
fed to the reactor.
 Water/propylene molar ratio is 12-15% to prevent the
development of polymerization reaction.
 Preheating of propylene and water is done with the aid of a high
temperature.
 Reactor effluent containing catalyst, isopropyl alcohol and
unreacted propylene undergoes heat recovery, pressure
reduction, and separation of dissolved propylene.
 An aqueous solution of isopropyl alcohol and
catalyst goes to purification section after
neutralization with caustic soda where separation of
isopropyl alcohol takes place in the series of
distillation columns.
 The isopropyl alcohol-water azeotropic mixture after
separation of light end and water in two distillation
columns goes to azeotropic distillation column
where benzene is used as entrainer for separation of
isopropyl alcohol.
 Finally benzene is recovered from the last column.

 CH3-CH=CH2 + H2O → CH3-CH(OH)-CH3

Direct hydration of propylene to isopropyl alcohol
Acetone [CH3COCH3]

 Acetone (systematically named propanone) is the organic compound with

the formula (CH3)2CO. It is a colorless, mobile, flammable liquid, and is
the simplest ketone.
 Acetone is miscible with water and serves as an important solvent in its
own right, typically as the solvent of choice for cleaning purposes in the
laboratory.
 About 6.7 million tonnes were produced worldwide in 2010, mainly for
use as a solvent and production of Methyl isobutyl ketone, methyl
methacrylate and bisphenol-A.
 It is an active ingredient in nail polish remover and as paint thinner.
 It is normally present in blood and urine. People with diabetes produce it
in larger amounts.
 Production of acetone in india in 2003-04 was around 46,700 tonnes.
Process Technology:
 Catalytic Dehydrogenation of isopropyl alcohol is an important
route for the manufacture of acetone.
 It can also be prepared by direct oxidation of isopropyl alcohol
and oxidation & dehydration of isopropyl alcohol.
 It is also obtained as a byproduct during manufacture of phenol
by the cumene route, oxidation of propylene, isobutene and
oxidation of propane-butane mixture.
 Acetone in India's is obtained as a
 co-product by Hindustan Organic Co.(Capacity: 24000 Tonnes)
& Herdillia Chemicals (Capacity: 18000 Tonnes) during
manufacture of phenol.
 National Organic Chemical Ltd produces acetone from isopropyl
alcohol.
 Catalytic Dehydrogenation of Isopropyl Alcohol

 By Liquid phase dehydration at 1500 C in the presence of Raney nickel Catalyst

or
- By Vapor phase dehydration using copper-zinc Catalyst at 400-5000
or
- Over a ZnO Catalyst at about 3800 C.

Isopropanol feed is preheated by heat exchanger – then it is

dehydrogenated at 3800 C and 0.2 Mpa in a Multi-tubular reactor
containing ZnO catalyst promoted with Zirconium oxide.

The reactor product from the reactor containing Acetone,

isopropyl alcohol and hydrogen is passed to an absorber and
then fed to a series of distillation columns where separation of
Acetone from isopropyl alcohol takes place.
Acetone by Catalytic Dehydrogenation of Isopropyl
Alcohol ZnO catalyst promoted with Zirconium
oxide. Temp: 3800C & Pressure: 0.2Mpa
Cumene
Application: High Octane addition for engine fuels;
 To produce cumene from benzene and any grade of propylene including
lower-quality refinery propylene-propane mixtures using the Badger
process and a new generation of Zeolite catalysts from ExxonMobil.
Yield and product purity:
 This process is essentially stoichiometric and product purity above
99.97% weight has been regularly achieved in commercial operation.
Economics:
 Estimated ISBL investment for a 300,000-mtpy unit on the US Gulf Coast
(2004 construction basis), is US$15 million.
 The first commercial application of this process came on stream in 1996.
At present, there are 12 plants operating with a combined capacity
exceeding 5.2 million mtpy.
 Fifty percent of the worldwide and 75% of Zeolite cumene production
are from plants using the Badger process.
 The process includes: a fixed-bed alkylation reactor, a fixed bed
transalkylation reactor and a distillation section. Liquid propylene
and benzene are premixed and fed to the alkylation reactor (1)
where propylene is completely reacted.
 Separately, recycled polyisopropylbenzene (PIPB) is premixed
with benzene and fed to the transalkylation reactor (2) where
PIPB reacts to form additional cumene.
 The transalkylation and alkylation effluents are fed to the
distillation section. The distillation section consists of as many as
four columns in series.
 The depropanizer (3) recovers propane overhead as LPG. The
benzene column (4) recovers excess benzene for recycle to the
reactors. The cumene column (5) recovers cumene product
overhead. The PIPB column (6) recovers PIPB overhead for
recycle to the transalkylation reactor.
 Cumene manufacture from Propylene Alkylation

Reaction: C6H6 + CH3-CH=CH2 → C6H5-CH-(CH3)2 Temp: 200-250C

Cumene Pressure: 3.5-4.0 Mpa
Side reaction: C6H6 + n CH3-CH=CH2 → n C9H12 (Polyisopropyl benzene)
Catalyst: H3PO4 deposited on a solid support or Zeolite catalyst
Acrylonitrile CH2=CHCN
Sohio proess: Propylene Route:

Ammoxidaion reaction

Ethylene Oxide Route:

Ehylene oxide + HCN -→ Ethylenecyanohydrin
Ethylenecyanohydrin → Acrylonitrile + water at 2000C
 Propylene + Propane, Air and Ammonia, Steam are compressed
to required pressure and are sent to the fluidized catalytic reactor
consisting of the Mo-Bi spherical catalyst. The reactor is
maintained at 400 – 500oC.
 Cyclone separator is also kept in the fluidized bed reactor in
which catalyst and product gases are separated after fluidization.
The contact time for fluidization is in the order of seconds
 The product vapors then enter a water scrubber that does not
absorb propane and nitrogen from the products. The products
absorbed in the water include acrylonitrile, acetonitrile and
other heavy ends.
 The very dilute acryolonitrile (about 3 %) solution in water is
sent to a fractionator. The fractionators separates acrylonitrile +
heavy ends + HCN + light ends as a top product stream and
acetonitrile + water + heavy ends as a bottom product.
 The top product then enters an extractive distillation column
with water as extractant.
 The azeotropic distillation column vapour is partially condensed
to obtain a vapour, aqueous and organic layer.
 The vapour consists of Light ends and HCN and is let out. The
organic layer consists of acrylonitrile and heavy ends is sent for
further purification.
 The aqueous layer is sent as a reflux to the azeotropic column. In
other words, addition of water enabled the formation of a
heterogeneous azeotropic mixture at the top.
 The bottom product from the azeotropic distillation column
enters a product purification unit along with oxalic acid where
acrylonitrile is further purified from heavy ends (+ oxalic acid)
and is obtained as a 99.5 % pure product.
 In similarity to this, the bottom product from the
product splitter enters an azeotropic column which
produces water as a bottom product. The total
condenser in this column generates both aqueous and
organic layers. The organic layer is rich in acetonitrile
and heavy ends where as the aqueous layer is sent back
as a reflux to the azeotropic column.
 -The bottom product from the acetonitrile azeotropic
column enters a purification unit where distillation
principle enables the separation of acetonitrile from the
heavy ends.
Sohio proess: Propylene Route
 Butyraldehydes (CH3CH2CH2CHO)
&
Butanols(CH3CH2CH2CH2OH)

 N-Butyraldehyde and isobutyraldehyde are manufactured

from hydroformylation (also known as oxo synthesis or oxo
process, is an important homogeneously catalyzed
industrial process for the production of aldehydes
from alkenes.) of propylene with carbon monoxide and
hydrogen (Synthesis Gas)
 Butyraldehyde’s are an important intermediates for the
manufacture of n-Butanol, isobutanol and 2-ethyl hexanol
which are being used in surface coating, manufacture of butyl
ester, plasticizers, butyl acrylate and tube oil additive etc.,
Product profile of Butyraldehyde
Butyraldehydes (CH3CH2CH2CHO)
 Butyraldehyde is manufactured by hydroformylation of
propylene with carbon monoxide and hydrogen.
 In the process: Propylene reacts with a 1:1 synthesis gas at
low pressure (<20 kg/cm2) in the presence of a rhodium or
cobalt catalyst.
 The Butyraldehydes are separated from the catalyst and
further separation of Butyraldehydes takes place in the
distillation column.
(1) reactor, (2) catalyst separation, (3) stripper (using fresh syngas to strip unreacted
propylene to recycle), (4) distillation

Hoechst AG and Rhone Poulenc process for

producing Butyraldehydes from propene
 BUTANOLS(n-Butanol & Isobutanol)
 It is manufactured from hydrogenation of a n-Butyraldehyde
and iso-Butyraldehyde mixture obtained by hydroformylation
of propylene and synthesis gas.
 Hydrogenation takes place at 150-2000C and 5-10 Mpa
pressure using copper or nickel catalyst.
 The Butanols from the hydrogenation reactor go through a
series of distillation columns for separation of light effluents
and n-butanol and isobutanol.
 About 88% of n-butanol and 12% isobutanol are obtained.
Butanol from Butyraldehyde Process
 Methyl Iso Butyl Ketone (MIBK) (CH3COCH2CH(CH3)2)

 MIBK has a wide application as solvent for vinyl, epoxy and acrylic
resins and for nitrocellulose.
 It is also used for dye in the printing industry & surface coating agent.
 It is also used as a versatile extracting agent e.g. in the production of
antibiotics, recovery of uranium, and removal of paraffins from
mineral oil.
 The global demand of MIBK is around 0.4 MTPA.
 The production of MIBK in the US(90000 TPA), Europe(96000 TPA)
and Japan (55000 TPA).
 In India NOCL & Herdillia Chemicals Ltd., are produced the MIBK
with a capacity of 75000TPA.
Process Technology:
Various methods used for Manufacture of MIBK are:
 Low temperature condensation of acetone to Diacetone alcohol
followed by dehydration of Diacetone alcohol to methyl oxide
which is hydrogenated to produce MIBK.
 High temperature condensation in liquid phase of acetone in the
presence of either basic or acid catalyst directly to methyl oxide
followed by hydrogenation.
 Vapour phase condensation of acetone and hydrogen in the
presence of catalyst.
 Direct liquid phase condensation hydrogenation of acetone in
the presence of hydrogen using bifunctional catalyst.
MIBK from Acetone by Low Temperature Condensation Route:
 Diacetone alcohol is prepared by low temperature condensation
of acetone in liquid phase by passing over a fixed bed of alkali
catalyst(Ba(OH)2 or Ca(OH)2) impregnated on a suitable carrier
at 0-200C.
 Diacetone alcohol is subsequently dehydrated in the presence of
0.05% H3PO4 or H2SO4 at 100-1200C.
 Methyl oxide is mildly hydrogenated by passing its vapor over a
bed of catalyst based on nickel, copper, chromium or palladium at
temperature of about 120-1700C.
MIBK by low Temperature condensation of Acetone
 Diacetone Alcohol (CH3COCH2C(CH3)2OH)
 It is an important valuable derivative of acetone and is mainly used in
paints, surface coating, break fluids, pesticides.
 It is prepared by Aldol condensation of acetone in the presence of
caustic soda in an alcoholic medium which acts as catalyst in five
reactors in a series.
 Alkaline stream for the reactor is neutralized by ion-exchange resin
and then passed through a series of distillation columns.

Uses:
 It is used as a solvent for nitrocellulose, cellulose acetate, various oils,
fats, dyes, tars, coating composition, wood preservatives, anti freeze
mixtures, extraction of resins, waxes and metal cleaning equipment.
 Isophorone
 It is a high boiling ketone solvent produced by condensation reaction by
trimerization of acetone under 32 bar pressure and 2000C in the
presence of caustic soda.
 The raw materials are acetone, 50% soda and demineralized water.

Uses:
 It is used as a solvent for large number of natural and synthetic polymer
resins, wax, fats and oils.
 It is used in the manufacture of isophorone diamine.
 Another important derivative of isophorone is trimethyl adipic acid and
trimethyl hexamethylene diamine.
 Propylene carbonate (C3H6CO3)
 Propylene carbonate is prepared by reaction of propylene
oxide and carbon dioxide in the presence of ion exchange
resins.
 Temperature: 1000C& Pressure: 8Mpa

Uses:
 It is used as a special solvent in solvent extraction process,
plasticizers, organic synthesis, natural gas purification and
fibre spinning solvent.
 Allyl chloride(CH2=CHCH2Cl)
 Allyl chloride is a colorless liquid, insoluble in water but soluble in
many organic solvents.
 It has a strong pungent odor and an irritating effect on the skin. As a
chemical, allyl chloride is used to make allyl alcohol, glycerol, and
epichlorohydrin.
 The production of allyl chloride could be effected by direct
chlorination of propylene at high temperatures (approximately 500°C
and one atmosphere).
 The reaction substitutes an allylic hydrogen with a chlorine atom.
 The major by-products are cis- and trans- 1,3-dichloropropene, which
are used as soil fumigants.
 Hydrogen chloride is a by-product from this reaction:
The reactor feed must be between 440°C
and 520°C and between 1000 kPa and
1400 kPa.
 Epichlorohydrin
from allyl chloride
Chlorination of propylene
 Allylchloride is obtained by direct chlorination of propylene with
chlorine in gas phase at high temperatures.
 The stream leaving the reactor is fed to a depropanizer tower which
separates overhead hydrogen chloride and propylene from raw
allylchloride.
 This latter is rectified in a two column fractionating system.
 The gas mixture from the depropanizer is washed with water for
absorbing HCl to obtain commercial hydrochloric acid.
 After the washing the resulting wet propylene is compressed,
condensed, dried and recycled to the reaction.
Chlorohydrination of allylchloride
 Chlorohydrination of allylchloride is performed by
reacting allylchloride with hypochlorous acid.
 The rectified allylchloride, water and chlorine react at
nearly ambient temperature to give dichlorohydrins
with relatively high yields.

Dichlorohydrins hydrolysis
 The hydrolysis of dichlorohydrins to epichlorohydrin, using milk of
lime as saponifying agent, is accomplished in a distillation tower where
epichlorohydrin is stripped by live steam injected to the bottom of the
tower.
 Waste water is taken off from the bottom of stripper, while an organic
phase, consisting of raw epichlorohydrin, is separated overhead.
Epichlorohydrin purification
The raw epichlorohydrin is rectified in a fractionation
column system.
In the purification system high purity epichlorohydrin is
separated from water and low and high boiling impurities
Epichlorohydrin from allyl acetate and alcohol route
 Acrylic Acid (CH2=CHCOOH)
 It is a versatile chemical which can be etherified, ammoniated or
otherwise modified and polymerized to complex molecular
arrangement to suit requirement.
 The important route is propylene route is two stage oxidation
process because of availability of propylene from steam cracker.
 The process consists of two stage oxidation of propylene using
molybdenum catalyst.
 Various Routes:
Propylene route; ethylene route; ethylene oxide route;
Formaldehyde & Acetic acid route; Acetylene route;
Acrylonitrile route.
USES:
 It is widely used for the manufacture of an important range of
esters, methyl-, ethyl-, butyl-, and 2-ethylhexyl acrylates.
 It is used in protective coating, paper impregnates, and coating,
floor polishes, fabric binders, plastics, adhesives, additives and
thickener for aqueous emulsifier.
 Acrylic coating have long durability and excellent resistance to
UV light.
 Acrylamide (CH2=CHCONH2)
 The manufacture of acrylamide is hydrolysis of acrylonitrile with
sulphuric acid.

 Another route of acrylamide is by catalytic hydrolysis of acrylonitrile

at 1000C using Copper chromite as Catalyst.

USES:
 The major outlet for Acrylamide is in the manufacture of
polyacrylamide which is made by polymerization of acrylamide.
 It is used as flocculent in industrial & municipal water treatment, in
hair sprays, cosmetics, drilling muds for oil well drilling and soil
stabilizer.