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

153 CATALYSTS by GRANT E. Catalysts. California 94025 . April 1983 - l Report No. RUSSELL and LEONARD A WASSELLE I0 I a April 1984 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park.

ii . prod- uct. April 1983 For detailed marketing data and information. and plant for the United States and Western Europe. the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company. 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. Catalysts. In addition.

Connecticut ......... 20 United Catalysts. Ohio ... Little Ferry................. 23 Chemical Composition . 19 Engelhard Corporation....... Kentucky .. .. Maryland ....... ...... 19 H8rshaw/Filtrol. ... 18 Baltimore.. 7 9 Catalyst Metals Red8MtiOn .... Inc... 16 BASF Wyandotte Corporation.... ..... hlIl8ylV8ni8 .. ... 18 Catalyst Resources... ....... Maryland .... Wayne........ 20 Katalistiks International...... . Houston........ New Jersey . .............. Illinois . 16 American Cyanamid Company..... Cleveland... Affiliate of Phillips Chemical. 18 Calsicat Division.... 10 Molybdenum and Vanadium Recovery ... .... ... .... 20 Union Carbide Corporation...................... 20 Stauffer Chemical Company. 27 Methods of Preparation ......... . 25 Structure ...... New Jersey ................ Oakbrook. ........................ Buffalo.... Davison Chemical Division.. Texas ...... 6 0 Olefin Polymerization Catalysts ... 19 Johnson Matthey..................... Mallinkrodt......... New Jersey ................ South Plainfield. Pennwalt Corporation. .. Inc.. Ammoxidation Catalysts ........... Inc. Grace. New Jersey . New Jersey .... Texas . Louisville... Inc.. 20 Lucid01 Division........ 19 Katalco Corporation............. ...... 18 Degussa Corporation........................ .............. 25 Catalytic Activity . .... Connecticut ........ ....... 20 Shell Chemical Company..... 13 Major Catalyst Manufacturers . 10 PGM Recovery .................... . Westport.... 19 H8lcon Catalyst Industries.... Iselin...... West Deptford. 21 4 ZEOLITE CATALYSTS ...... W... B8lthoTe. 0 Houston.... 11 3 INDUSTRY STATUS .... New Jersey ..... 29 0 iii ... New York .......... Danbury... ....... April 1983 0 CONTENTS 0 1 INTRODUCTION ... R. 1 2 SUMMARY .... Catalysts.. Erie........ 5 Processes for Zeolite Catalysts ..... 5 Platinum Group Metals (PGM) ............... . ...... .. Parsippany.... ..

....... 53 Product Drying and Handling ................................. 47 Sodium Aluminate ....... 60 Spray Drying ..................................... 78 United States........................................... .......... 77 USSR ..... 39 Zeolite Moving Bed Catalysts ............... 59 Zeolite Seeding ............... 51 Ammonium/Sodium Ion Exchange .......................... 33 Protection from Contaminants . 55 Process Discussion ......... 61 Rare Earth Exchanged Zeolites . 74 South Africa ............................ April 1983 4 ZEOLITE CATALYSTS (continued) Effects of Formulation on Performance ............. 43 ZSM Synthetic Zeolites ............ 36 In Situ Zeolite Clay Based Fluid Bed Catalysts ...................... 80 Refining Processes .. 67 Capital Costs........... 36 Silica/Alumina Hydrogel Based Zeolite Fluid Bed Catalysts ........... .............. Catalysts.......... 31 Effects of Zeolite Composition ......... 78 Canada ........ 83 IV ................ 59 Production of Synthetic Type X and Y Zeolites ....... 62 Cost Estimates ..... 67 Production Costs ......................................... 51 Silica-Alumina-KaolinMatrix .............. .............. 82 Rustenburg .............. 32 Effects of Matrix Composition ......... 53 Rare Earth Ion Exchange ........................... 55 Materials of Construction ....... 31 Effects of Zeolite Content ...................................................................... 34 Review of Processes ..................... 78 Ore Concentration .... 73 Sources and Production ....... ... 54 Product Composition ............ 50 Zeolite Y Synthesis ....... 67 5 PLATINUMGROUP METAL CATALYSTS ................... 47 Zeolite Seeding ................................................................... 81 INCO Ltd ..................... 50 Zeolite Preparation ...................... 44 Process Description .....

.................................. Hydrotreating............. 107 Electrochemical Processes ....... 121 Polyolefin Properties ...... April 1983 0 CONTENTS 0 5 PLATINUM GROUP METAL CATALYSTS (continued) Consumption Data for the United States .............................. 117 0 New Applications .............................. 117 118 6 OLEPIN POLYMERIZATION CATALYSTS ... 89 Automobile Emission Converters .... Catalyst Formulations ....... 84 Prices ............. 113 Hydrocracking.... 112 Catalyst Preparation ............... and Isomerization ................. 107 Hydrogenation and Dehydrogenation ...... 105 Acetic Acid by Carbonylation of Methanol .............. 101 Catalytic Reduction of Tail Gases of Nitric Acid Plants..................................... Catalysts.................. 110 Naphtha Reforming .... 103 Hydrogen Cyanide ....... 96 Nitric Acid ........................ 95 Chemical Plants ......... 116 Hydrocracking ................................. 96 Platinum Gauze Catalyst ... 106 Oxo Alcohols ............... 91 82 Three-Way Catalyst System ................... 99 Platinum Recovery ......... 96 Catalyst Usage and Performance ........................... 127 Polymerization Processes .... 116 Hydrotreating (Hydroprocessing) .............................. 131 0 V ............................ 110 Catalyst Usage and Life .................... 105 Wacker-Hoechst Olefin Oxidation ........ 104 Other Chemical Processes ... 116 Isomerization ............. 90 0 Catalytic Converter Geometry ........ 108 Hydrogen Peroxide .............................. .............. ..... Recovery . 123 Polyethylene .. 109 Petroleum Refineries ........................ 87 Catalyst Applications ....... 109 Miscellaneous Catalytic Applications ... 124 Polypropylene ..... 129 Suspension Polymerization ............................ ........................... PGM Catalyst Costs ...............................

...... .. 149 7 AMMOXIDATION CATALYSTS FOR ACRYLONITRILE ....... 171 Cost Estimates .................. 140 Organotransition Metal Catalysts . 134 Gas-Phase Polymerization .......................................................... 160 Commercial Requirements .. ... .... 145 Summary of Recent Montedison Patents on Ziegler Catalysts ....... Catalysts................ .... ....... 135 Phillips Type Catalysts ................. ...................... 193 CITEDREFERENCES ............... . 183 Patent Summary .................................. 179 Solution of Catalyst Support ..... 155 Catalyst Evaluation .............................. ..... 159 Commercial Catalysts . 157 Catalyst Preparation ...... 136 Preparation of the Support ........... 154 Patent Summary ... 137 Metal Addition and Activation .......... ....... 142 Stereospecific Ziegler Catalysts . . ........ 164 Process Description ..... 181 Treatment of Monolithic Catalysts ..... ...... 166 Process Discussion ..... 136 Catalyst Preparation ... 158 Catalyst Regeneration ............................ 177 Recovery of Platinum Group Metals from Industrial and Automotive Catalysts ........ 241 PATENT REFERENCES ................ 172 8 CATALYSTMETALS RECLAMATION..... 185 PATENT SUMMARY TABLES ................. ...... ....... . ...... 141 Ziegler-Natta Catalysts ..... ... April 1983 CONTENTS 6 OLEFIN POLYMERIZATION CATALYSTS (continued) Solution Polymerization .............. .................. .................... 177 Acid Leaching of Metals ........ 138 Summary of Recent Phillips Patents .... 137 Catalyst Performance .... .. ................ 153 Chemistry . ....... 184 Recovery of Metals from Petroleum Hydroprocessing Catalysts ........ 259 Vi ..... ........................... ... ...........................

.1 Polyethylene Chain Branching . . . . . . . .1 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Block Flow Diagram. . . . . .2 Manufacture of Ammoxidation Catalyst Flow Sheet . 156 7. . . . . . . . .6 Effect of Catalyst Activation Temperature on Melt Index . . .4 Generalized Olefin Polymerization Process . April 1983 ILLUSTRATIONS 4. . . . . W. . . . . . . . . . . . . . . 102 5. . . . . . Filtrol Technology . . . . 6 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Effect of Plant Capacity on Total Fixed Capital . . . . 70 5. 133 6. . . . . . . . . . . . . . . . .3 Molecular Structures of Polypropylene . . . . .5 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Flow Sheet . 42 4. .3 Block Flow Diagram. . . . . . . . . . . . . 180 0 Vii . . . . . . . . 126 6. . 128 6. . 265 4. . . . . . . . . . . . . 271 0 8. . FCC Catalyst Based on Addition of Synthetic Zeolite 40 to Matrix Block Flow Diagram. . . . . . . . . . . .2 Reforming Catalyst Performance . .1 Recovery of Platinum and Palladium from Catalysts by Acid Leaching . . . . .4 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Block Flow Diagram and Simplified Material Balance . Catalysts. . . . . . .1 Simplified Process Flow Diagram of the Sohio Acrylonitrile Process . . . . . 130 6. . . . 267 4'. . .1 Platinum Losses from Nitric Acid Plants . . . . . .2 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix 0 4. . . . . . . . .R. . . . . . . . . 37 4. . . . Grace Technology . . . . . . . . . . 115 6. . . . 139 0 7. . . . . . . . . . . . Engelhard Technology . . . . 132 6.5 Generalized Monomer and Solvent Recovery . . . . . .2 Effect of Branching Type and Concentration on Density of Ethylene-*Olefin Copolymers . .

. . . Catalysts.2 Recovery of Platinum from Catalysts by Digestion h Acid . . . . . . . . . . . . . . 189 Viii . . . . . April 1983 ILLUSTRATIONS 8. . . . . 182 8. . . . . . .3 Recovery of Molybdenumand Vanadium from Spent Desulfurization Catalysts .

.3 List of ZSM Zeolites with Organic Template and Si02/A1203 Mol Ratio . . . 86 5. . . . 14 3. . . . . .3 Estimated Catalyst Sales in the Free World . . . . . . Catalysts. . .9 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Production Cost . . . . . . . . . . . . . . . . . . . . .6 Platinum Group Metals for Automotive Uses . . . . . .1 Major Catalyst Suppliers in the United States . . . . . . . 66 4. . . . . . . . 71 5. . . . 69 4. . 48 a 4.S.1 Platinum Group Metals: World Production. 77 :. . . . . . . .5 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Design Bases and Assumptions . . 5. 88 5. . 57 4. . .1 Zeolite Properties .3 Platinum Group Metals: U. . . . . . . . . . . . .8 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Capital Investment . . . . . 91 5. . . . . . . . . . .2 Distribution of Individual Metals in PGM Ores . . . . . . 26 4. . .7 Federal Emission-Control Requirements for Light-Duty Vehicles . . . . . . . . . 17 4. . . . . . 92 IX c . . .7 Cracking Activity of Zeolites . .2 Zeolite Catalysts Summary of Patents Other than Mobil's .4 ZSM and Other Zeolite Catalysts Summary of Mobil Patents . . . . . . . . Domestic Review . . 195 4. . . . . 202 4. . . . . . . . . .2 Projected Catalyst Consumption in the United States . . . . . .4 Platinum Group Metals Sold to Consuming Industries in the United States . . 2 3. . . . . . . . . . . . . . . . . . . . . . by Country . . . . . . . . . . . . . 75 5. 85 5. . . . . . . . . . . . . . . . .1 Summary of Catalytic Processes . .6 FCC Catalyst Based on Addition of Synthetic Zeolite to Matrix Major Equipment and Utilities Summary . . . . . . . . . April 1983 0 l 1. . . . . . 46 4. . . . . . . . . . . . . . 15 e 3. . . . . .5 Average Yearly Producer and Dealer Prices of Platinum Group Metals . . . .

. . . . . . . . 234 8. . . . . . . . .2 Ammoxidation Catalyst Stream Flows . . . . . . . . . . . 236 X . . 174 8. . . . . . . 212 6. . . . . . .1 Ammoxidation Catalysts Patent Summary . . . . . . . . . . . .4 Range of Composition for Spent Hydrotreating Catalysts. . . .9 Optimum Operating Data for Ammonia Conversion to Nitric Acid . . . 208 6. . . . . . . . .1 ASTM Classification of Polyethylene8 . . . . . . . . . . .2 Chromium Oxide Catalysts Summary of Phillips Patents . 98 5. . . . . . Catalysts. . . . .4 Ammoxidation Catalyst Capital Investment . . . . . . 220 7. . 214 7. . . . 187 8. . . . .5 Recovery of Metals from Desulfurization Catalysts by Alkaline Processes Patent Summary . . . . . . . . 100 5.8 Standard Platinum and Rhodium-Platinum Alloy Gauzes . . . . . . . . . . . . . . . . . . . . . . 125 6. . . . . . 169 7. April 1983 TABLES 5. . . . .3 Recovery of Platinum Group Metals from Catalysts by Miscellaneous Methods Patent Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Ziegler-Natta Catalyst Systems . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Recovery of Platinum Group Metals from Catalysts by Leaching with Acids Patent Summary . . .3 Ammoxidation Catalyst Major Equipment Summary. . 173 7. . . . . . . . . . .10 Platinum Group Metals Catalysts Patent Summary .2 Recovery of Platinum Group Metals from Catalysts by Chlorination Patent Summary . . . . . . . . . . . 142 6. . . . . . . . . . . 8. . . 230 8. . . . . .5 Ammoxidation Catalyst Production Cost . . . . . . . . . . . . .4 Ziegler-Natta Catalysts Summary of Montedison Patents . 232 . . . . . . . 170 7. . . . . . . . . . . . . .

April 1983 - TABLES 0........... 240 - 0- 0 Xi ........ 8... 239 8...7 Recovery of Metals from Desulfurization Catalysts by Chlorination 0 Patent Summary....... Catalysts.............6 Recovery of Metals from Desulfurization Catalysts by Acid Processes Patentsummary......