Abstract Process Economics Program Report No. 153 CATALYSTS (April 1984) PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, Calfornia 94025 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 Chemical processing 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--includes process 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, consumption, and applications of platinum group metal catalysts. Olefin polymerieation catalysts --Information on manufacture and applications of Phillips and Ziegler-Natta catalysts for polymerization of ethylene and propylene. Ammoxidation catalysts--process description and economic evaluation 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 automotive emissions control catalysts and recovery of molybdenum, vanadium, and other metals from petroleum hydroprocessing catalysts. gumm8ries of recent patents are included for each type of catalyst shown above. PEP'81 GER/LAW
Report No. 153 CATALYSTS by GRANT E. RUSSELL and LEONARD A WASSELLE I I a 0 A private report by the April 1984 PROCESS ECONOMICS PROGRAM Menlo Park, California 94025
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'lROCHEMICALS Program 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
CONTENTS 1 INTRODUCTION......................... 1 2 SUMMARY... 5 Processes for Zeolite Catalysts... 5 Platinum Group Metals (PGM)... 6 Olefin Polymerization Catalysts... 7 Ammoxidation Catalysts... 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, Houston, Texas... 18 Davison Chemical Division, W. R. Grace, 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 iii
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-Kaolin Matrix... 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
CONTENTS 5 PLATINUM GROUP METAL CATALYSTS (continued) Consumption Data for the United States... 84 Prices... 87 Catalyst Applications... 89 Automobile Emission Converters... 90 Catalytic Converter Geometry... 91 Catalyst Formulations... 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 New Applications... 117 PGM Catalyst Costs... 118 6 OLEPIN POLYMERIZATION CATALYSTS... 121 Polyolefin Properties... 123 Polyethylene... 124 Polypropylene... 127 Polymerization Processes... 129 Suspension Polymerization... 131 V
CONTENTS 6 OLEFIN POLYMERIZATION CATALYSTS (continued) Solution Polymerization... Gas-Phase Polymerization... Phillips Type Catalysts... Catalyst Preparation... Preparation of the Support... Metal Addition and Activation... Catalyst Performance... Summary of Recent Phillips Patents... Organotransition Metal Catalysts... Ziegler-Natta Catalysts... Stereospecific Ziegler Catalysts... Summary of Recent Montedison Patents on Ziegler Catalysts.. 134.. 135.. 136.. 136.. 137.. 137.. 138.. 140.. 141.. 142.. 145.. 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 Vi
ILLUSTRATIONS 4.1 4.2 4.3 4.4 4.5 4'. 6 5.1 5.2 6.1 6.2 6.3 6.4 6.5 6.6 7.1 7.2 8.1 Block Flow Diagram, W.R. Grace Technology.......... Block Flow Diagram, Filtrol Technology........... Block Flow Diagram, Engelhard Technology.......... Block Flow Diagram and Simplified Material Balance..... Flow Sheet......................... Effect of Plant Capacity on Total Fixed Capital....... Platinum Losses from Nitric Acid Plants........... Reforming Catalyst Performance............... Polyethylene Chain Branching................ Effect of Branching Type and Concentration on Density of Ethylene-*Olefin Copolymers......... Molecular Structures of Polypropylene............ Generalized Olefin Polymerization Process.......... Generalized Monomer and Solvent Recovery.......... Effect of Catalyst Activation Temperature on Melt Index... Simplified Process Flow Diagram of the Sohio Acrylonitrile Process................. Manufacture of Ammoxidation Catalyst Flow Sheet......................... Recovery of Platinum and Palladium from Catalysts by Acid Leaching............... 37 40 42 265 267 70 102 115 126 128 130 132 133 139 156 271 180 Vii
ILLUSTRATIONS 8.2 Recovery of Platinum from Catalysts by Digestion h Acid.................... 182 8.3 Recovery of Molybdenum and Vanadium from Spent Desulfurization Catalysts............ 189 Viii
1.1 Summary of Catalytic Processes.............. 2 3.1 Major Catalyst Suppliers in the United States... 3.2 Projected Catalyst Consumption in the United States 3.3 Estimated Catalyst Sales in the Free World.... 4.1 Zeolite Properties................. 4.3 4.4 4.5 4.6 4.7 List of ZSM Zeolites with Organic Template and Si02/A1203 Mol Ratio.............. ZSM and Other Zeolite Catalysts Summary of Mobil Patents.............. Design Bases and Assumptions............ Major Equipment and Utilities Summary....... Cracking Activity of Zeolites.............. 14... 15... 17... 26 4.2 Zeolite Catalysts Summary of Patents Other than Mobil's.......... 195... 46... 202... 48... 57... 66 4.8 Capital Investment.................... 69 4.9 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
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 X
TABLES 8.6 Recovery of Metals from Desulfurization Catalysts by Acid Processes Patentsummary... 239 8.7 Recovery of Metals from Desulfurization Catalysts by Chlorination Patent Summary... 240 Xi