Heterogeneous Catalysis

Lecturer – 3
 History of Industrial Catalytic Processes
Year Process Catalyst (Prime
constituent)
1750 H2SO4 lead Chamber Process (Homogeneous) NO/NO2
1870 SO2 oxidation Pt
1880 Deacon process (Cl2 from HCL) ZnCl2/CuCl2
1885 Claus process (H2S and SO2 to S) Bauxite (Al2O3)
1900 Fat Hydrogenation. Methane from syngas Ni
1910 Coal Liquefaction. Upgrading Coal liquids Fe. WS2
NH3 Synthesis (Haber-Bosch). NH3 oxidation to nitric Fe/K. Pt
acid
1920 Methanol Synthesis (high pressure process) Zn, Cr oxide
Fischer-Tropsch synthesis Co,Fe
Oxidation of SO2 to SO3 (H2SO4 production) V2O5
1930 Catalytic Cracking of oil (fixed-bed Houdry process) Montmorillonite clays
Epoxidation of ethylene Ag
1940 Catalytic reforming of hydrocarbons (gasoline) Pt/Al2O3
Hydrogenation of benzene to cyclohexane Ni, Pt
 History of Industrial Catalytic Processes (contd.)

Year Process Catalyst

1950 Polymerization of ethylene to PE Ziegler- Ti / Cr
Natta/Phillips
HDS, Hydrotreatment of Naphtha (CoMo/Al2O3
Oxidation of Naphthalene to phthalic anhydride (V, Mo) oxides
1960 Oxidation/Ammoxidation of lower alkenes (V, P);(Bi,
Mo)oxide
Metathesis of alkenes (W, Mo or Re)Ox
Production of vinyl acetate from ethylene Pd/Cu
Hydrocracking; WGSR(LT; HT) Ni-W/Al2O3
1970 Xylene isomerization H-ZSM-5
(zeolite)
Methanol from CO +H2 Cu-Zn/Al2O3
Disproportionation of toluene to Bnz and p-xylene H-ZSM-5
Production of MTBE Acidic IE resins
1980 Methanol to gasoline (MTG) H-ZSM-5
Conversion of ethylene and acetic acid to vinyl Pd
acetate
 History of Industrial Catalytic Processes (contd.)
Year Process Catalyst
1980 Catalytic distillation (in MTBE Production) Aciic IE resins
(Contd.)
Vitamin K4 production Pd membrane
Dehydrocyclization (“Cyclar”) of alkanes Ga-ZSM-5
1990 Production of acrylamide from vinyl cyanide (V, P);(Bi,
Mo)oxide
Methanol to light alkenes (MTO) SAPO-5, zeolites
Production of dimethyl carbonate Cu chloride
Hydrocracking; WGSR(LT; HT) Ni-W/Al2O3
Ammoxidation of cyclohexanone to its oxime Ti-silicalite
Conversion of phenol to hydroquinone and Ti-silicalite
catechol
2000 p-methoxyacetophenone by acetylation of anisole BEA zeolite
3,4-dimethoxyacetophenone from veratrole BEA, FAU
zeolites
Polymerization for desired tacticity Metallocenes
Market value of the top 10 chemical companies worldwide in 2014
(in million U.S. dollars)
2014 ranking of the global top 10 chemical companies based on
net income (in billion U.S. $)

Source: Statista 2015

2014 ranking of the global top 10 chemical companies based on
revenue (in billion U.S. $)

Source: Statista 2015

 Global Top 20
CHEMICAL HEADQUART CHEMICAL OPERATI
2016 2015 COMPANY SALES ($ ERS OPERATING NG
MILLIONS) PROFITS($ PROFIT
MILLIONS) MARGIN
1 1 BASF $60,653 Germany $6,395 10.5%
2 2 Dow Chemical 48,158 U.S. 5,629 11.7
3 3 Sinopec 42,815 China 3,106 7.3
4 4 SABIC 30,985 Saudi Arabia 10,101 32.6
5 5 Formosa Plastics 27,141 Taiwan 2,620 9.7
6 7 ExxonMobil 26,058 U.S. 5,917 22.7
7 8 LyondellBasell 24,624 Netherlands 5,638 22.9
8 6 Ineos 23,530 Switzerland 4,780 20.3
9 9 Mitsubishi Chemicals 23,358 Japan 1,954 8.4
10 10 DuPontf 19,679 U.S. 4,081 20.7
11 12 Air Liquide 19,554 France 1,914 9.8
12 11 LG Chem 18,111 South Korea 1,718 9.5
13 15 Toray Industries 16,533 Japan 1,427 8.6
14 13 Linde 16,488 Germany 2,453 14.9
15 14 AkzoNobel 15,719 Netherlands 1,663 10.6
16 17 PPG Industries 14,270 U.S. 2,356 16.5
17 16 Evonik Industries 14,097 Germany 1,726 12.2
18 22 Reliance Industries 13,769 India 1,934 14.0
19 18 Braskem 13,692 Brazil 2,760 20.2
20 21 Sumitomo Chemicals 13,396 Japan 831
Selected Heterogeneous Catalysts of Industrial Importance
Reaction Catalyst and reactor type
(Continuous operation unless otherwise noted)

Dehydrogenation
C4H10 (butane) → butenes Cr2O3 ∙ Al2O3 (fixed bed, cyclic)
C6H6C2H5 → C6H6CH =CH2 Fe2O3 promoted with Cr2O3 and K2CO3 (fixed
(ethyl benzene → styrene) bed, in presence of steam)

CH4 or other hydrocarbons + H2O → CO + H2 Supported Ni (fixed bed)

(steam reforming)

(CH3)2CH(OH) → CH3COCH3 + H2
ZnO
(isopropanol → acetone + hydrogen)

Hydrogenation
Of edible fats and oils Ni on a support (slurry reactor, batch)
Various hydrogenations of fine organic Pd or Pt on carbon (slurry reactor, usually cals
chemicals batch)
Fe promoted with A12O3, K2O, CaO, and MgO
N2 + 3H2 → 2NH3 (adiabatic fixed beds)

C2H2 → C2H6 (selective hydrogenation of C2H2 Pd on Al2O3 or sulfided Ni on support (adiabatic

impurity in C2H4 from thermal-cracking plant) fixed bed)
Selected Heterogeneous Catalysts of Industrial Importance (Contd.)
Oxidation
V2O5 plus K2SO4 on silica (adiabatic, fixed
SO2 + ½ O2 (air) → SO3
beds)
90% Pt - 10% Rh wire gauze, oxidizing
2NH3 + 5/2 O2 (air) → 2NO + 3H2O
conditions
NH3 + CH4 + air→ HCN (Andrussow 90% Pt - 10% Rh wire gauze, under net
process) reducing conditions
C10H8 or 1,2-C6H4(CH3)2 + O2 →
C6H4(CO)2O (naphthalene or o-xylene + V2O5 on titania (multitube fixed bed)
air → phthalic anhydride
n-C4H10 + O2 → C4H2O3 Vanadia-phosphate (multi tube fixed bed or
(butane + air → maleic anhydride) fluidized bed)
C2H4 + ½ O2 → (CH2)2O (ethylene Ag on α-Al2O3 promoted with Cl and Cs
oxide) (multitube fixed bed)
C3H6 + O2 → CH2=CHCHO (acrolein)
Bismuth molybdate plus other components
and/or CH2=CHCOOH (acrylic acid)
Complete oxidation of CO and
Pt or Pd, or both, on monolith support
hydrocarbons for pollution control
C4H8 + 1/2O2 → C4H6 + H2O Promoted ferrite spinels
Selected Heterogeneous Catalysts of Industrial Importance (Contd.)

Acid-catalyzed Reactions
Zeolite in SiO2-AI2O matrix plus other
Catalytic cracking
ingredients (transport reactor)

Pd on zeolite in an amorphous matrix; NiMo

Hydrocracking on silica alumina, various other dual-
function catalysts (adiabatic fixed beds)

Paraffin isomerization Pt on H-mordenite zeolite in alumina matrix

Pt, Pt-Re or Pt-Sn on acidified Al2O3 or on
Catalytic reforming zeolite in matrix (adiabatic, fixed beds, or
moving bed, with interstage heating)

Polymerization H3PO4 on clay (fixed bed)

Hydration, eg., propylene to isopropyl Mineral acid or acid-type ion-exchange resin

alcohol (fixed bed)
CH3OH + isoC4H8 → methyl tert.
Acid-type ion-exchange resin
butyl ether
 Selected Heterogeneous Catalysts of Industrial Importance (Contd.)

Reactions of Synthesis Gas

CuI-ZnO promoted with Al2O3 (adiabatic, fixed
CO + 2H2 → CH3OH beds with interstage cooling or multitube fixed
bed)

CO + 3H2 → CH4 + H2O (methanation) Supported Ni (fixed bed)

CO + H2 → paraffins, etc. (Fischer- Fe or Co with promoters (multitube fixed bed or

Tropsch synthesis) transport reactor)

Other
Oxychlorination (e.g., C2H4 + 2HCl + CuCl2/Al2O3 with KCl promoter
1/2O2 → C2H4CI2 + H2O)

Hydrodesulfurization, CoMo/ Al2O3 or NiMo/ Al2O3, sulfided (adiabatic,

hydrodenitrogenation, hydrotreating
SO2 + 2H2S → 3S + 2H2O (Claus
process)
H2O + CO → CO2 + H2 (water-gas shift)
fixed beds with interstage cooling)
Al2O3 (fixed beds)
Fe3O4 promoted with Cr2O3 (adiabatic fixed
bed); for a second, lower temperature stage, Cu-
ZnO on Al2O3; CoMo on support