Catalysts, April 1983

PROCESS
ECONOMICS
PROGRAM
SRI INTERNATIONAL
Abstract MenloPark, Calfornia
94025
Process Economics Program Report No. 153

CATALYSTS

(April 1984)

Catalysts are essential to about 90% of modern chemical and

petroleum refining processes. Annual catalyst sales in the United
States exceed $1 billion. Major consumers, in order of volume and
value are:

0 Petroleum refining
l Chemical processing
l Emissions control.

A wide variety of substances can be used as catalysts. This re-

port summarizes the major catalytic processes and typical catalysts
used for them. It lists the major U.S. catalyst manufacturers and their
products. Detailed discussions and descriptions are included for:

Zeolite catalysts--Includesprocess description and economic

evaluation of 8 plant to make 50,000 short tOnS/yr of a ZeOlite
cracking catalyst.
Platinum group metals catalysts--Data on production, consump-
tion, and applications of platinum group metal catalysts.
Olefin polymerieation catalysts--Information on manufacture and
applications of Phillips and Ziegler-Natta catalysts for poly-
merization of ethylene and propylene.
Ammoxidation catalysts--Processdescription and economic evalua-
tion of a process for 2 million lb/yr of a bismuth molybdate
type catalyst for acrylonitrile production.
Recovery of metals from catalysts--Descriptions of processes
for recovery Of platinum group metals from industrial and auto-
motive emissions control catalysts and recovery of molybdenum,
vanadium, and other metals from petroleum hydroprocessing cata-
lysts.

gUmm8rieS of recent patents are included for each type of catalyst

shown above.

PEP'81 GER/LAW
 Catalysts, April 1983

l
Report No. 153

CATALYSTS

by GRANT E. RUSSELL
and LEONARD A WASSELLE

I0 I
a
April 1984

A private report by the

PROCESS ECONOMICS PROGRAM

Menlo Park, California 94025

 Catalysts, April 1983

For detailed marketing data and information, the reeder is

referred to one of the SRI programs specialieing in marketing
research. The CHEMICAL ECONOMICS HANDBOOK Program covers
most major chemicals and chemical products produced in the
United States and the WORLD PE'lROCHEMICALSProgram covers
major hydrocarbons and their derivatives on a worldwide basis.
In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company, prod-
uct, and plant for the United States and Western Europe.

ii
 Catalysts, April 1983

0
CONTENTS

0 1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 SUMMARY ........................... 5
Processes for Zeolite Catalysts ............... 5
Platinum Group Metals (PGM) ................. 6
0 Olefin Polymerization Catalysts ...............
Ammoxidation Catalysts ....................
7
9
Catalyst Metals Red8MtiOn ................. 10
PGM Recovery ........................ 10
Molybdenum and Vanadium Recovery .............. 11

3 INDUSTRY STATUS ....................... 13

Major Catalyst Manufacturers ................. 16
American Cyanamid Company, Wayne, New Jersey ........ 16
BASF Wyandotte Corporation, Parsippany, New Jersey ..... 18
Calsicat Division, Mallinkrodt, Inc.,
Erie, hlIl8ylV8ni8 ..................... 18
Catalyst Resources, Inc., Affiliate of Phillips Chemical,
0 Houston, Texas .......................
Davison Chemical Division, W. R. Grace,
18

Baltimore, Maryland .................... 18

Degussa Corporation, South Plainfield, New Jersey ..... 19
Engelhard Corporation, Iselin, New Jersey ......... 19
H8lcon Catalyst Industries, Little Ferry, New Jersey .... 19
H8rshaw/Filtrol, Cleveland, Ohio .............. 19
Johnson Matthey, Inc., West Deptford, New Jersey ...... 19
Katalco Corporation, Oakbrook, Illinois .......... 20
Katalistiks International, B8lthoTe, Maryland ....... 20
Lucid01 Division, Pennwalt Corporation,
Buffalo, New York ..................... 20
Shell Chemical Company, Houston, Texas ........... 20
Stauffer Chemical Company, Westport, Connecticut ...... 20
Union Carbide Corporation, Danbury, Connecticut ...... 20
United Catalysts, Inc., Louisville, Kentucky ........ 21

4 ZEOLITE CATALYSTS ...................... 23

Chemical Composition ..................... 25
Structure .......................... 25
Catalytic Activity ...................... 27
Methods of Preparation .................... 29

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 Catalysts, April 1983

4 ZEOLITE CATALYSTS (continued)

Effects of Formulation on Performance ............. 31
Effects of Zeolite Content ................. 31
Effects of Zeolite Composition ............... 32
Effects of Matrix Composition ................. 33
Protection from Contaminants ................ 34
Review of Processes ...................... 36
Silica/Alumina Hydrogel Based Zeolite Fluid Bed Catalysts . . 36
In Situ Zeolite Clay Based Fluid Bed Catalysts ....... 39
Zeolite Moving Bed Catalysts ................ 43
ZSM Synthetic Zeolites ................... 44
Process Description ...................... 47
Sodium Aluminate ...................... 47
Zeolite Seeding ....................... 50
Zeolite Preparation ..................... 50
Zeolite Y Synthesis ..................... 51
Silica-Alumina-KaolinMatrix ................ 51
Ammonium/Sodium Ion Exchange ................ 53
Rare Earth Ion Exchange ................... 53
Product Drying and Handling ................. 54
Product Composition ..................... 55
Materials of Construction .................. 55
Process Discussion ...................... 59
Zeolite Seeding ....................... 59
Production of Synthetic Type X and Y Zeolites ........ 60
Spray Drying ........................ 61
Rare Earth Exchanged Zeolites ................ 62
Cost Estimates ........................ 67
Capital Costs. ....................... 67
Production Costs ...................... 67

5 PLATINUMGROUP METAL CATALYSTS ................ 73

Sources and Production .................... 74
South Africa ........................ 77
USSR ............................ 78
Canada ........................... 78
United States. ; ...................... 78
Ore Concentration ....................... 80
Refining Processes ...................... 81
INCO Ltd ........................... 82
Rustenburg ......................... 83

IV
 Catalysts, April 1983

0
CONTENTS

0 5 PLATINUM GROUP METAL CATALYSTS (continued)

Consumption Data for the United States ............ 84
Prices ............................ 87
Catalyst Applications .................... 89
Automobile Emission Converters ............... 90
0 Catalytic Converter Geometry ...............
Catalyst Formulations ..................
91
82
Three-Way Catalyst System ................
Recovery ......................... 95
Chemical Plants ....................... 96
Nitric Acid ....... ; ................ 96
Platinum Gauze Catalyst ................. 96
Catalyst Usage and Performance .............. 99
Platinum Recovery .................... 101
Catalytic Reduction of Tail Gases of Nitric Acid Plants. . 103
Hydrogen Cyanide ...................... 104
Other Chemical Processes .................. 105
Wacker-Hoechst Olefin Oxidation ............. 105
Acetic Acid by Carbonylation of Methanol ......... 106
Oxo Alcohols ....................... 107
Hydrogenation and Dehydrogenation ............ 107
Electrochemical Processes ................ 108
Hydrogen Peroxide .................... 109
Miscellaneous Catalytic Applications ........... 109
Petroleum Refineries ..................... 110
Naphtha Reforming ..................... 110
Catalyst Usage and Life ................. 112
Catalyst Preparation ................... 113
Hydrocracking, Hydrotreating, and Isomerization ...... 116
Hydrocracking ...................... 116
Hydrotreating (Hydroprocessing) ............. 116
Isomerization ...................... 117
0 New Applications .....................
PGM Catalyst Costs ......................
117
118

6 OLEPIN POLYMERIZATION CATALYSTS ............... 121

Polyolefin Properties .................... 123
Polyethylene ........................ 124
Polypropylene ....................... 127
Polymerization Processes ................... 129
Suspension Polymerization ................. 131

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 Catalysts, April 1983

CONTENTS

6 OLEFIN POLYMERIZATION CATALYSTS (continued)

Solution Polymerization ................. . . 134
Gas-Phase Polymerization ................ . . 135
Phillips Type Catalysts .................. . . 136
Catalyst Preparation .................. . . 136
Preparation of the Support .............. . . 137
Metal Addition and Activation ............. . . 137
Catalyst Performance ................... . . 138
Summary of Recent Phillips Patents ............ . . 140
Organotransition Metal Catalysts ............. . . 141
Ziegler-Natta Catalysts .................. . . 142
Stereospecific Ziegler Catalysts ............. . . 145
Summary of Recent Montedison Patents on Ziegler Catalysts . . 149

7 AMMOXIDATION CATALYSTS FOR ACRYLONITRILE ........... 153

Chemistry ........................... 154
Patent Summary ........................ 155
Catalyst Evaluation ..................... 157
Catalyst Preparation .................... 158
Catalyst Regeneration .................... 159
Commercial Catalysts .................... 160
Commercial Requirements ................... 164
Process Description ...................... 166
Process Discussion ...................... 171
Cost Estimates ........................ 172

8 CATALYSTMETALS RECLAMATION. ................. 177

Recovery of Platinum Group Metals from
Industrial and Automotive Catalysts .............. 177
Acid Leaching of Metals ................... 179
Solution of Catalyst Support ................ 181
Treatment of Monolithic Catalysts .............. 183
Patent Summary ....................... 184
Recovery of Metals from Petroleum Hydroprocessing Catalysts . . 185

PATENT SUMMARY TABLES ....................... 193

CITEDREFERENCES ....................... 241

PATENT REFERENCES ....................... 259

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 Catalysts, April 1983

ILLUSTRATIONS

4.1 FCC Catalyst Based on Addition of Synthetic Zeolite

to Matrix
Block Flow Diagram, W.R. Grace Technology . . . . . . . . . . 37
4.2 FCC Catalyst Based on Addition of Synthetic Zeolite
to Matrix

0 4.3
Block Flow Diagram, Filtrol Technology . . . . . . . . . . .
FCC Catalyst Based on Addition of Synthetic Zeolite
40

to Matrix
Block Flow Diagram, Engelhard Technology . . . . . . . . . . 42
4.4 FCC Catalyst Based on Addition of Synthetic Zeolite
to Matrix
Block Flow Diagram and Simplified Material Balance . . . . . 265
4.5 FCC Catalyst Based on Addition of Synthetic Zeolite
to Matrix
Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . . 267
4'.
6 FCC Catalyst Based on Addition of Synthetic Zeolite
to Matrix
Effect of Plant Capacity on Total Fixed Capital . . . . . . . 70
5.1 Platinum Losses from Nitric Acid Plants . . . . . . . . . . . 102
5.2 Reforming Catalyst Performance . . . . . . . . . . . . . . . 115
6.1 Polyethylene Chain Branching . . . . . . . . . . . . . . . . 126
6.2 Effect of Branching Type and Concentration
on Density of Ethylene-*Olefin Copolymers . . . . . . . . . 128
6.3 Molecular Structures of Polypropylene . . . . . . . . . . . . 130
6.4 Generalized Olefin Polymerization Process . . . . . . . . . . 132
6.5 Generalized Monomer and Solvent Recovery . . . . . . . . . . 133
6.6 Effect of Catalyst Activation Temperature on Melt Index . . . 139
0 7.1 Simplified Process Flow Diagram of the
Sohio Acrylonitrile Process . . . . . . . . . . . . . . . . . 156
7.2 Manufacture of Ammoxidation Catalyst
Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . . 271

0 8.1 Recovery of Platinum and Palladium

from Catalysts by Acid Leaching . . . . . . . . . . . . . . . 180

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 Catalysts, April 1983

ILLUSTRATIONS

8.2 Recovery of Platinum from Catalysts

by Digestion h Acid . . . . . . . . . . . . . . . . . . . . 182
8.3 Recovery of Molybdenumand Vanadium
from Spent Desulfurization Catalysts . . . . . . . . . . . . 189

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 Catalysts, April 1983

l 1.1 Summary of Catalytic Processes . . . . . . . . . . . . . . 2

3.1 Major Catalyst Suppliers in the United States . . . . . . 14
3.2 Projected Catalyst Consumption in the United States . . . 15

e
3.3 Estimated Catalyst Sales in the Free World . . . . . . . 17
4.1 Zeolite Properties . . . . . . . . . . . . . . . . . . . . 26
4.2 Zeolite Catalysts
Summary of Patents Other than Mobil's . . . . . . . . . . 195
4.3 List of ZSM Zeolites with Organic Template
and Si02/A1203 Mol Ratio . . . . . . . . . . . . . . . . . 46
4.4 ZSM and Other Zeolite Catalysts
Summary of Mobil Patents . . . . . . . . . . . . . . . . . 202
4.5 FCC Catalyst Based on Addition of Synthetic Zeolite
to Matrix
Design Bases and Assumptions . . . . . . . . . . . . . . . 48

a 4.6 FCC Catalyst Based on Addition of Synthetic Zeolite

to Matrix
Major Equipment and Utilities Summary . . . . . . . . . . 57
4.7 Cracking Activity of Zeolites . . . . . . . . . . . . . . 66
4.8 FCC Catalyst Based on Addition of Synthetic Zeolite
to Matrix
Capital Investment . . . . . . . . . . . . . . . . . . . . 69
4.9 FCC Catalyst Based on Addition of Synthetic Zeolite
to Matrix
Production Cost . . . . . . . . . . . . . . . . . . . . . 71
5.1 Platinum Group Metals: World Production, by Country . . . 75
5.2 Distribution of Individual Metals in PGM Ores . . . . . . 77
:.
5.3 Platinum Group Metals: U.S. Domestic Review . . . . . . . 85
5.4 Platinum Group Metals Sold to Consuming Industries
in the United States . . . . . . . . . . . . . . . . . . . 86
5.5 Average Yearly Producer and Dealer Prices
of Platinum Group Metals . . . . . . . . . . . . . . . . . 88
5.6 Platinum Group Metals for Automotive Uses . . . . . . . . 91
5.7 Federal Emission-Control Requirements
for Light-Duty Vehicles . . . . . . . . . . . . . . . . . 92

IX

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 Catalysts, April 1983

TABLES

5.8 Standard Platinum and Rhodium-Platinum Alloy Gauzes . . . 98

5.9 Optimum Operating Data for Ammonia Conversion
to Nitric Acid . . . . . . . . . . . . . . . . . . . . . 100
5.10 Platinum Group Metals Catalysts
Patent Summary . . . . . . . . . . . . . . . . . . . . . 208
6.1 ASTM Classification of Polyethylene8 . . . . . . . . . . 125
6.2 Chromium Oxide Catalysts
Summary of Phillips Patents . . . . . . . . . . . . . . . 212
6.3 Ziegler-Natta Catalyst Systems . . . . . . . . . . . . . 142
6.4 Ziegler-Natta Catalysts
Summary of Montedison Patents . . . . . . . . . . . . . . 214
7.1 Ammoxidation Catalysts
Patent Summary . . . . . . . . . . . . . . . . . . . . . 220
7.2 Ammoxidation Catalyst
Stream Flows . . . . . . . . . . . . . . . . . . . . . . 169
7.3 Ammoxidation Catalyst
Major Equipment Summary. . . . . . . . . . . . . . . . . 170
7.4 Ammoxidation Catalyst
Capital Investment . . . . . . . . . . . . . . . . . . . 173

7.5 Ammoxidation Catalyst

Production Cost . . . . . . . . . . . . . . . . . . . . . 174

8.1 Recovery of Platinum Group Metals from Catalysts

by Leaching with Acids
Patent Summary . . . . . . . . . . . . . . . . . . . . . 230
8.2 Recovery of Platinum Group Metals from Catalysts
by Chlorination
Patent Summary . . . . . . . . . . . . . . . . . . . . . 232
.
8.3 Recovery of Platinum Group Metals from Catalysts
by Miscellaneous Methods
Patent Summary . . . . . . . . . . . . . . . . . . . . . 234
8.4 Range of Composition for Spent Hydrotreating Catalysts. . 187
8.5 Recovery of Metals from Desulfurization Catalysts
by Alkaline Processes
Patent Summary . . . . . . . . . . . . . . . . . . . . . 236

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 Catalysts, April 1983

-
TABLES

0- 8.6 Recovery of Metals from Desulfurization Catalysts

by Acid Processes
Patentsummary....................... 239
8.7 Recovery of Metals from Desulfurization Catalysts
by Chlorination
0 Patent Summary....................... 240

0-

0 Xi