Abstract Process Economics Program Report No. 226 INNOVATIVE REACTORS (June 2001)

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1 Abstract Process Economics Program Report No. 226 INNOVATIVE REACTORS (June 2001) This report examines potential applications and economic potential for the use of innovative chemical reactors in existing processes. A technology review profiles major design features and operational characteristics of conventional and innovative continuous chemical reactors including down flow, radial flow, tubular, fluidized bed, membrane, and porous wall reactors. Also breifly reviewed are static mixer, monolithic, microreactors, and reactive distillation. The report then focuses on the use of catalytic membrane reactors for potential large scale dehydrogenation applications including production of styrene from ethylbenzene, production of ethylene from ethane, and production of isobutene from isobutante. Following a review of membrane types and example applications, technical barriers and R&D needs are identified, and an economic analysis developed to define the current state of the art. Finally, an identification of potential applications by reaction class and chemical product is presented along with a conceptual techno-economic evaluation for SRI's novel porous wall reactor technology. Comparative process economics are reported for the sulfonation of methyl laurate for conventional and SRI's proposed process design to illustrate the commercial potential for SRI's reactor with process intensification. PEP'97 RMS

2 Report No. 226 INNOVATIVE REACTORS SUPPLEMENT By Ron Smith June 2001 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

3 SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client s use of the reports or other deliverables produced by SRIC pursuant to this agreement For detailed marketing data and information, the reader is referred to one of the SRI Consulting programs specializing in marketing research. THE CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons and their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.

4 CONTENTS GLOSSARY... x 1 INTRODUCTION PROCESS INTENSIFICATION REPORT FOCUS INTRODUCTION OVERVIEW TECHNOLOGY STATUS ECONOMICS TECHNOLOGY REVIEW CONVENTIONAL REACTORS Down Flow Reactors Radial Flow Reactors Tubular Reactors Fluidized Bed Reactors Exothermic Reaction Endothermic Reaction INNOVATIVE REACTORS Membrane Reactors Equilibrium Enhancement with Non-Catalytic Reactors Equilibrium Enhancement in Catalytic Reactors Selectivity Enhancement with Catalytic Reactors Inorganic Porous Wall Reactors Butane Oxidation to Maleic Anhydride Other Innovative Separative Reactor Systems Static Mixer Reactors Large Scale Monolithic Reactors iii

5 CONTENTS (continued) Microreactors Reactive Distillation CATALYTIC MEMBRANE REACTORS DENSE MEMBRANES Hydrogenation Dehydrogenation POROUS MEMBRANES Dense vs. Porous Membranes Gas-Gas Reaction systems Thermal Incinerators for VOC Waste Emissions Gas-Liquid Reaction Systems ALTERNATIVE POROUS MEMBRANE MATERIALS Glass Membranes Ceramic Membranes Zeolite Membranes Perovskite Membranes DEVELOPMENT STATUS OF SEPARATIVE REACTORS Technical Barriers and R&D Needs DEHYDROGENATION APPLICATIONS Comparative Technical Specifications Conceptual Catalytic Membrane Reactor Systems PROCESS ECONOMICS Basis for Estimates and Evaluation Review of Commercial Processes Styrene Production from Ethylbenzene Ethylene Production from Ethane Isobutene Production from Isobutane iv

6 CONTENTS (continued) Butadiene Production from 1-Butene Review of Developmental Catalytic membrane Based Processes Styrene Production from Ethylbenzene Ethylene Production from Ethane Isobutene Production from Isobutane ECONOMIC ANALYSIS POROUS WALL REACTORS PROGRESSIVE ADDITION ALTERNATIVE REACTOR CONFIGURATIONS Heat Balances Permeability Reduction and Control Conceptual Scalability POTENTIAL APPLICATIONS SULFONATION OF METHYL LAURATE Falling Film Reactor Chemistry Process Description Process Discussion Cost Estimates Porous Wall Reactor Sulfonation Process Chemistry Process Description Process Discussion Cost Estimates Cost Comparison APPENDIX A: PATENT SUMMARY TABLES... A-1 APPENDIX B: DESIGN AND COST BASES... B-1 v

7 CONTENTS (concluded) APPENDIX C: CITED REFERENCES... C-1 APPENDIX D: PATENT REFERENCES BY COMPANY... D-1 APPENDIX E: PROCESS FLOW DIAGRAM... E-1 vi

8 ILLUSTRATIONS 3.1 Plug Flow Membrane Reactor-Exothermic Reaction Temperature/Conversion Profile Perfect Mixing Membrane Reactor-Exothermic Reaction Temperature/Conversion Profile Plug Flow Reactor-Endothermic Reaction Temperature/Conversion Profile Perfect Mixing Membrane Reactor-Endothermic Reaction Temperature/Conversion Profile Fluidized Bed Membrane Reactor Methanol to Gasoline Gas to Liquids Processes Membrane Reactor Furnace for Dehydrogenation of Methane Basic New Porous Wall Reactor Concept Porous Wall Reactor Module Porous Wall Reactor Single Stage Process for Heat Removal Porous Wall Reactor Multi-Stage Process for Heat Removal Sintered Metal Filter-Unit Cell Layers of Unit Cells Forming Barrier Wall Sulfonation of Methyl Laurate Conventional Falling Film Reactor Design Sulfonation of Methyl Laurate New SRI Reactor Design vii

9 TABLES 2.1 Comparison of Design Parameters for the Sulfonation of Methyl Laurate Sulfonation of Methyl Laurate Process Economics Comparison Innovative Reactors Patent Summary: Catalytic membrane Reactors... A Inorganic Membrane Manufacturers Examples of Potential Applications For Dense Palladium Based Catalytic Membrane Reactors Examples of Potential Applications For Zeolite Based Catalytic Membrane Reactors Technical Barriers for Catalytic Membrane Reactors and Catalytic Distillations R&D Needs for Catalytic Membrane Reactors and Catalytic Distillations Technical Specifications of Dehydrogenation Processes Commercial Processes for Producing Styrene from Ethylbenzene Styrene from Ethylbenzene by Adiabatic Dehydrogenation Ethylene from Ethane by Oxydehydrogenation Isobutylene from Isobutane by Oleflex Dehydrogenation Styrene from Ethylbenzene Membrane Reactors Ethylene from Ethane: Catalytic Membrane Reactors Variable Operating Costs Isobutylene from Isobutane: Membrane Reactors Variable Operating Costs Catalytic Membrane Reactors Economic Analysis Results Potential Porous Wall Reactor Applications by Reaction Class Potential Porous Wall Applications Product Reactions Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Design Bases and Assumptions Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Stream Flows viii

10 TABLES (concluded) 5.5 Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Major Equipment Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Utilities Summary Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Total Capital Investment Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Production Costs Sulfonation of Methyl Laurate: Porous Wall Reactor Design Bases and Assumptions Sulfonation of Methyl Laurate: Porous Wall Reactor Stream Flows Sulfonation of Methyl Laurate: Porous Wall Reactor Major Equipment Sulfonation of Methyl Laurate: Porous Wall Reactor Utilities Summary Sulfonation of Methyl Laurate Comparison of Reactor Design Parameters Sulfonation of Methyl Laurate: Porous Wall Reactor Total Capital Investment Sulfonation of Methyl Laurate: Porous Wall Reactor Production Costs Sulfonation of Methyl Laurate Cost Comparison ix

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