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
Report No. 226 INNOVATIVE REACTORS SUPPLEMENT By Ron Smith June 2001 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025
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CONTENTS GLOSSARY... x 1 INTRODUCTION... 1-1 PROCESS INTENSIFICATION... 1-1 REPORT FOCUS... 1-3 2 INTRODUCTION... 2-1 OVERVIEW... 2-1 TECHNOLOGY STATUS... 2-1 ECONOMICS... 2-4 3 TECHNOLOGY REVIEW... 3-1 CONVENTIONAL REACTORS... 3-1 Down Flow Reactors... 3-1 Radial Flow Reactors... 3-2 Tubular Reactors... 3-2 Fluidized Bed Reactors... 3-3 Exothermic Reaction... 3-3 Endothermic Reaction... 3-4 INNOVATIVE REACTORS... 3-4 Membrane Reactors... 3-4 Equilibrium Enhancement with Non-Catalytic Reactors... 3-5 Equilibrium Enhancement in Catalytic Reactors... 3-7 Selectivity Enhancement with Catalytic Reactors... 3-14 Inorganic Porous Wall Reactors... 3-23 Butane Oxidation to Maleic Anhydride... 3-23 Other Innovative Separative Reactor Systems... 3-24 Static Mixer Reactors... 3-24 Large Scale Monolithic Reactors... 3-26 iii
CONTENTS (continued) Microreactors... 3-26 Reactive Distillation... 3-28 4 CATALYTIC MEMBRANE REACTORS... 4-1 DENSE MEMBRANES... 4-4 Hydrogenation... 4-5 Dehydrogenation... 4-6 POROUS MEMBRANES... 4-8 Dense vs. Porous Membranes... 4-8 Gas-Gas Reaction systems... 4-9 Thermal Incinerators for VOC Waste Emissions... 4-9 Gas-Liquid Reaction Systems... 4-10 ALTERNATIVE POROUS MEMBRANE MATERIALS... 4-11 Glass Membranes... 4-12 Ceramic Membranes... 4-12 Zeolite Membranes... 4-13 Perovskite Membranes... 4-14 DEVELOPMENT STATUS OF SEPARATIVE REACTORS... 4-16 Technical Barriers and R&D Needs... 4-16 DEHYDROGENATION APPLICATIONS... 4-20 Comparative Technical Specifications... 4-20 Conceptual Catalytic Membrane Reactor Systems... 4-22 PROCESS ECONOMICS... 4-23 Basis for Estimates and Evaluation... 4-24 Review of Commercial Processes... 4-25 Styrene Production from Ethylbenzene... 4-25 Ethylene Production from Ethane... 4-28 Isobutene Production from Isobutane... 4-28 iv
CONTENTS (continued) Butadiene Production from 1-Butene... 4-30 Review of Developmental Catalytic membrane Based Processes... 4-34 Styrene Production from Ethylbenzene... 4-34 Ethylene Production from Ethane... 4-35 Isobutene Production from Isobutane... 4-35 ECONOMIC ANALYSIS... 4-40 5 POROUS WALL REACTORS... 5-1 PROGRESSIVE ADDITION... 5-1 ALTERNATIVE REACTOR CONFIGURATIONS... 5-3 Heat Balances... 5-4 Permeability Reduction and Control... 5-6 Conceptual Scalability... 5-9 POTENTIAL APPLICATIONS... 5-10 SULFONATION OF METHYL LAURATE... 5-11 Falling Film Reactor... 5-11 Chemistry... 5-13 Process Description... 5-14 Process Discussion... 5-21 Cost Estimates... 5-23 Porous Wall Reactor Sulfonation Process... 5-27 Chemistry... 5-27 Process Description... 5-28 Process Discussion... 5.34 Cost Estimates... 5-35 Cost Comparison... 5.40 APPENDIX A: PATENT SUMMARY TABLES... A-1 APPENDIX B: DESIGN AND COST BASES... B-1 v
CONTENTS (concluded) APPENDIX C: CITED REFERENCES... C-1 APPENDIX D: PATENT REFERENCES BY COMPANY... D-1 APPENDIX E: PROCESS FLOW DIAGRAM... E-1 vi
ILLUSTRATIONS 3.1 Plug Flow Membrane Reactor-Exothermic Reaction Temperature/Conversion Profile... 3-8 3.2 Perfect Mixing Membrane Reactor-Exothermic Reaction Temperature/Conversion Profile... 3-9 3.3 Plug Flow Reactor-Endothermic Reaction Temperature/Conversion Profile... 3-10 3.4 Perfect Mixing Membrane Reactor-Endothermic Reaction Temperature/Conversion Profile... 3-11 3.5 Fluidized Bed Membrane Reactor... 3-12 3.6 Methanol to Gasoline... 3-19 3.7 Gas to Liquids Processes... 3-20 4.1 Membrane Reactor Furnace for Dehydrogenation of Methane... 4-22 5.1 Basic New Porous Wall Reactor Concept... 5-2 5.2 Porous Wall Reactor Module... 5-3 5.3 Porous Wall Reactor Single Stage Process for Heat Removal... 5-4 5.4 Porous Wall Reactor Multi-Stage Process for Heat Removal... 5-5 5.5 Sintered Metal Filter-Unit Cell... 5-7 5.6 Layers of Unit Cells Forming Barrier Wall... 5-8 5.7 Sulfonation of Methyl Laurate Conventional Falling Film Reactor Design... 5-12 5.8 Sulfonation of Methyl Laurate New SRI Reactor Design... 5-29 vii
TABLES 2.1 Comparison of Design Parameters for the Sulfonation of Methyl Laurate... 2-3 2.2 Sulfonation of Methyl Laurate Process Economics Comparison... 2-4 3.1 Innovative Reactors Patent Summary: Catalytic membrane Reactors... A-3 4.1 Inorganic Membrane Manufacturers... 4-3 4.2 Examples of Potential Applications For Dense Palladium Based Catalytic Membrane Reactors... 4-7 4.3 Examples of Potential Applications For Zeolite Based Catalytic Membrane Reactors... 4-14 4.4 Technical Barriers for Catalytic Membrane Reactors and Catalytic Distillations.. 4-17 4.5 R&D Needs for Catalytic Membrane Reactors and Catalytic Distillations... 4-18 4.6 Technical Specifications of Dehydrogenation Processes... 4-21 4.7 Commercial Processes for Producing Styrene from Ethylbenzene... 4-26 4.8 Styrene from Ethylbenzene by Adiabatic Dehydrogenation... 4-31 4.9 Ethylene from Ethane by Oxydehydrogenation... 4-32 4.10 Isobutylene from Isobutane by Oleflex Dehydrogenation... 4-33 4.11 Styrene from Ethylbenzene Membrane Reactors... 4-37 4.12 Ethylene from Ethane: Catalytic Membrane Reactors Variable Operating Costs... 4-38 4.13 Isobutylene from Isobutane: Membrane Reactors Variable Operating Costs... 4-39 4.14 Catalytic Membrane Reactors Economic Analysis Results... 4-40 5.1 Potential Porous Wall Reactor Applications by Reaction Class... 5-10 5.2 Potential Porous Wall Applications Product Reactions... 5-10 5.3 Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Design Bases and Assumptions... 5-15 5.4 Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Stream Flows... 5-17 viii
TABLES (concluded) 5.5 Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Major Equipment... 5-19 5.6 Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Utilities Summary... 5-20 5.7 Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Total Capital Investment... 5-24 5.8 Sulfonation of Methyl Laurate: Conventional Falling Film Reactor Production Costs... 5-25 5.9 Sulfonation of Methyl Laurate: Porous Wall Reactor Design Bases and Assumptions... 5-30 5.10 Sulfonation of Methyl Laurate: Porous Wall Reactor Stream Flows... 5-32 5.11 Sulfonation of Methyl Laurate: Porous Wall Reactor Major Equipment... 5-33 5.12 Sulfonation of Methyl Laurate: Porous Wall Reactor Utilities Summary... 5-34 5.13 Sulfonation of Methyl Laurate Comparison of Reactor Design Parameters... 5-35 5.14 Sulfonation of Methyl Laurate: Porous Wall Reactor Total Capital Investment... 5-37 5.15 Sulfonation of Methyl Laurate: Porous Wall Reactor Production Costs... 5-38 5.16 Sulfonation of Methyl Laurate Cost Comparison... 5-41 ix