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Historical Overview
Year
1750
1870
1880
1885
1900
1910
1920
1930
1940
1950
Process
H2SO4 lead chamber processa
SO2 oxidation
Deacon process (Cl2 from HCl)
Claus process (H2S and SO2 to S)
Fat hydrogenation
Methane from syngas
Coal liquefaction
Upgrading of coal liquids
NH3 synthesis (Haber-Bosch)
NH3 oxidation to nitric acid
MeOH synthesis (HP process)
Fischer-Tropsch synthesis
SO2 oxidation
Acetaldehyde from acetylenea
Catalytic cracking (fixed bed, Houdry)
Ethylene epoxidation
Polyvinyl chloride
Polyethylene (low density, ICI)
Oxidation of benzene to maleic anhydride
Alkylationa
Hydroformylation, alkene to aldehydea
Catalytic reforming (gasoline)
Cyclohexane oxidation (nylon 66 production)a
Benzene hydrogenation to cyclohexane
Synthetic rubber
SBR
BNR
Butylrubber
Polyethylene (high density)
Ziegler-Natta
Phillips
Polypropylene, Ziegler-Natta
Polybutadiene, Ziegler-Natta
Hydrodesulphurisation (HDS) of naphtha
Naphthalene oxidation to phthalic anhydride
Ethylene oxidation to phthalic anhydridea
p-Xylene oxidation to terephthalic acida
Ethylene oligomerisationa
Catalysis and Catalysts - History
Catalyst
NO/NO2
Pt
ZnCl2-CuCl2
bauxite
Ni
Ni
Fe
WS2
Fe/K
Pt
ZnO, Cr Oxide
promoted Fe, Co
V2O5
Hg2+/H2SO4
Clays
Ag
peroxide
peroxide
V oxide
HF/H2SO4
Co
Pt
Co
Ni, Pt
Li, peroxide
peroxide
Al
Ti chloride
Cr oxide
Ti chloride
Ti, Co, Ni
CoS-MoS2/Al2O3
V, Mo oxides
Pd, Cu
Co, Mn oxide
Al(Et)3
Historical Overview
Year
1960
1970
1980
1990
Process
Butylene oxidation to maleic anhydride
Acrylonitrile via ammoxidation of propylene (Sohio)
Propylene oxidation to acrolein/acrylic acid
Xylenes hydroisomerisation
Propylene metathesis
Adiponitrile via butadiene hydrocyanisation
Improved reforming catalysts
Improved cracking catalysts
Acetic acid from MeOH (carbonylation)a
Vinyl chloride via ethylene oxychlorination
Ethylene oxidation to vinyl acetate
o-Xylene oxidation to phthalic anhydride
Propylene oxidation to propylene oxidea
Hydrocracking
HT Water-Gas Shift process
LT Water-Gas Shift process
MeOH synthesis (Low pressure, ICI)
Acetic acid from MeOH (carbonylation, low
pressure process, Monsanto)a
Improved process for xylene isomerisation
-Alkenes via ethylene oligomerisation/
Isomerisation/metathesis (SHOP)
Improved hydroformylationa
Auto exhaust gas catalysts
L-DOPA (Monsanto)
Cyclooctenamer (metathesis)a
Hydroisomerisation
Selective reduction of NO (with NH3)
Gasoline from MeOH process (Mobil)
Vinyl acetate from ethylene and acetic acida
Methylacetate (carboxylation)a
Methylacrylate via t-butanol oxidation
Improved coal liquefaction
Diesel fuel from syngas
Coal gasification
Polyketone (from Co and ethylene)a
Fuel ethers, MTBE, etc.
Phenol from benzene and N2O
Cyclohexene from benzene
Diesel soot combustion
via oxidation with NO2
Deep desulphurisation
N2O decomposition
Catalysis and Catalysts - History
Catalyst
V, P oxides
Bi, Mo oxides
Bi, Mo oxides
Pt
W, Mo, Re oxides
Ni
Pt, Re/Al2O3
zeolites
Co
Cu chloride
Pd/Cu
V, Ti oxides
Mo
Ni-W/Al2O3
Fe2O3/Cr2O3/MgO
CuO/ZnO/Al2O3
Cu-ZnO/Al2O3
Rh
zeolite
Ni, Mo
Rh
Pt/Rh
Rh
W
Pt/zeolite
V2O5/TiO2
zeolite
Pd
Rh
Mo oxides
Co, Mo sulfides
Co
K, Na
Pd
H2SO4, zeolite
Cu-ZSM-5
Ru
Ceria
Pt
Pt-Pd
Fe-ZSM-5
Change in Raw Materials
1900
1950
Acetic acid
1960 1970 1980 1990
Fermentation
Ethylene
Acetylene
Methanol
Butane oxidation
Butanol
Fermentation
Propylene
Ammonia
Coke oven gas
Steam reforming
Coal gasification
Partial oxidation
Vinyl chloride
HCl + CC
CC oxychlorination
Toluene
Distillation of coal tar
Naphtha refining
Catalysis and Catalysts - History
From biomass
From coal
From petroleum
From natural gas