Process Technology &

Economics
Dr Saurabh Joglekar
Assistant Professor,
Department of Chemical Engineering,
Laxminarayan Institute of Technology, Nagpur
Compounds from C1 (Methane & Syn gas)

• Methanol
• Formaldehyde
• Methyl chloride, Methylene chloride, Chloroform & Carbon
tetrachloride
• Perchloroethylene from pyrolysis of Carbon tetrachloride
Methanol

• Catalytic hydrogenation of carbon monoxide

• H2 to CO ratio of 2.25 is compressed to 3000-5000 psi, mixed
with recycle gas and fed to high pressure converter
• Internal preheat is usually employed
• Reactor: Copper lined
• Catalyst: Zn, Chromium, Mn or Alumina Oxide
• Temp is 300-375 Deg Cel
• Exit gases are cooled by exchange of heat with reactant
• Liquid methanol is depressurized, ketones and aldehydes are
removed by permagnate & sent to stripper to remove DME
Methanol
• Fractionater is used to remove heavier fractions
• Reactions
• CO+2H2 CH3OH ΔH=-26.4 kCal
• CO+3H2CH4 + H2O ΔH=-50 kCal
• 2CO + 2H2  CH4 + CO2 ΔH=-60.3 kCal
• xCO+yH2 higher alcohol & hydrocarbons

• 1 tonne of methanol  0.127 tonne of H2 & 0.89 tonnes of CO

Methanol
Formaldehyde

• Used as raw material for phenolic, urea & melamine resin

• CH3OH+ 1/2O2 HCHO + H2O ΔH=-37 kCal
• CH3OH HCHO + H2 ΔH=19.8 kCal
• CH3OH+ 3/2O2 HCHO + CO2 ΔH=-162 kCal

• 1tonne product – methanol (1.04 tonnes) ; Air 1760Nm3

Formaldehyde

• Air is preheated at 0.2 atm guage and added to methanol

evaporator
• Methanol to oxygen ratio is 30-50%
• Mixed gases preheated are sent to reaction over catalyst –
solver, copper guaze
• Temperature is maintained by endothermic dehydrogenation
and exothermic oxidation to 450-600 Deg cel
• A catalyst of mixed oxide catalyst of Mo, Vanadium and or Iron
gives higher yield of more than 90%
Chloromethane
• Methyl chloride (CH3Cl)
• Methylene Chloride (CH2Cl2)
• Chloroform (CHCL3)
• Carbon Tetrachloride (CCl4)
• Chlorination of methane
• Reaction
• CH4+ Cl2 CH3Cl + HCl
• CH3Cl + Cl2 CH2Cl2 + HCl
• CH2Cl2 + Cl2 CHCl3 + HCl
• CHCl3 + Cl2 CCl4 + HCl
Chloromethane
• Thermal chlorination of natural gas is accomplished by
different cycles depending on desired product ratio and state
of by product
• Chlorination is performed in adiabatic furnace
• Exotherm is used to preheat the feed to 280 deg cel
• Reaction temperature is 370-410 deg cel
• Typical feed ratio CH4/Cl2 ; (CH3Cl – 60 wt% CH2Cl2- 28 wt %
• (CHCL3 – 9 wt % CCl4- 3% wt.
• 1 tonne product : 1.53 tonnes of chlorine & 0.305 tonnes of
Methane
Perchloroethylene
• Pyrolysis of CCl4
• Reactions: 2 CCl4 Cl3C. CCl3 + Cl2
• Cl3C. CCl3 Cl2C=CCl2+ Cl2
• 2 CCl4 Cl2C=CCl2+ 2Cl2
• 1 tonne of product = 0.86 tonnes of Cl2 & 2 tonnes of CCl4\
• CCl4 is vaporized and passed into resistively heated carbon
electrode furnace at 800-900 deg cel
• Pyrolysis takes place to form perchloroethylene,
hexachloroethane
• Effluent is cooled in partial condenser at 80-85 deg cel
• Chlorine, hexachloroethane and CCl4 is recycled
Compounds from C2

• Ethylene and acetylene by steam cracking of hydrocarbon

(naphtha)
• Ethylene dichloride
• Vinyl chloride from Ethylene dichloride pyrolysis
• Vinyl chloride from acetylene and HCl reaction
• Ethylene oxide
• Ethanolamines from ethylene and ammonia
• Acetaldehyde from ethylene
Ethylene and acetylene by steam cracking of hydrocarbon
(naphtha)
• Superheated steam is mixed with hydrocarbon and sent to
pyrolysis section
• Separate pyrolysis is done for C2-C4 residue due to difference
in residence time
• Pyrolysis products are quenched in waste steam boiler
• Gas oil is used to scrub pyrolysis product of any liquid and
solid associated with product
• Compressor increase pressure to 30-35 atm
• Flashed to separate C1- C2 cut and C3-C4 cut
• Both are scrubbed in different vessels using NaOH to remove
associated CO2
Ethylene dichloride

• Ethylene is mixed with chlorine and reacted on catalyst AlCl3

or FeCl3 or ethylene bromide
• Liquid phase reaction ethylene bromide (operated at 45-50
deg cel) – Liquid reactor
• Gas solid- AlCl3 or FeCl3 (operated at 85 deg cel) (Tubular
reactor)
• Traces of AlCl3 or FeCl3 results in higher yield of 90-95 %
Vinyl Chloride

• EDC is vaporized and dried by passing through silica gel

• Dried EDC is sent to tubular reactor where cracking happens
• Temperature is controlled in range 480-520 deg cel
• Catalyst filled in tubes is charcoal or pumice
• Conversion per pass is 50%
• Final yield is 90-95%
• CH2Cl. CH2Cl. CH2=CHCl+ HCl
• HCl is either scrubbed or used for vinyl chloride production
from acetylene
Vinyl Chloride from acetylene &HCl

• Acetylene and dry HCl (5-10% excess) is mixed together by jet

mixing and sent to tubular reactor
• Catalyst is carbon pellets impregnated with HgCl2
• Temperature is 160 deg cel and gradually increased to 215 deg
cel. Leading to catalyst deteriration
• C2H2+ HCl CH2=CHCl
Ethylene oxide from ethylene
• Ethylene and air are compressed and mixed together to form 3% -10%
C2H4 mixture
• Catalyst is silver oxide on alumina
• EDC is added to suppress side reaction products CO2 & H2O
• C2H4+1/2 O2 CH2-CH2O ΔH=-29.2 kCal
• Reaction is highly exothermic and carried out in fixed bed tubular reactor
• Temperature is maintained at 250-300 deg cel
• Residence time is 1sec ultimate yield is 60-70%
• Effluent stream is water washed under pressure
• Desorber fractionator tower removes excess of water
• Stream is purified with high pressure 4-5 atm
Ethanolamine from ethylene oxide and ammonia
• Ethylene oxide and ammonia are mixed together in stirred tank reactor
• Wide range of operating condition to get higher yield of MEA, DEA, TEA
• 1 tonne of product (70% MEA, 25 DEA & 5 TEA)  0.81 tonnes of EO &
0.24 tonnes of Ammonia
• EO+ Ammonia  MEA
• MEA + EO DEA
• DEA+ EO TEA
• M- Monoethanol amine
• D- Diethanolamine
• T- Triethanolamine
• A- Ammonia; E- Ethyleneoxide
Acetaldehyde from Ethylene
• Earlier acetaldehyde was synthesized from acetylene
• 1960s acetaldehyde was synthesized from ethylene : Catalyst Copper salt Liquid with Palladium metal
• first, ethylene is reacted with the catalyst solution under pressure to form acetaldehyde, whereby
copper(II) is reduced to copper(I).
• In a flash tower, the catalyst is brought to atmospheric pressure, and water and acetaldehyde vaporize.
The heat of reaction is utilized to increase the concentration of acetaldehyde in the
water/acetaldehyde mixture to 70 % to 90 % in a distillation column.
• A pump conveys the spent catalyst to the second reactor, where it is reoxidized by air under elevated
pressure.
• The residual air, mainly nitrogen, is separated, while the regenerated catalyst is reacted again with
ethylene
• Residence time is 6-40 minn ; Pressure is <50atm; Temperature 50-100 deg cel