Abstract Process Economics Program Report 190C ADVANCES IN MEMBRANE TECHNOLOGY FOR CHEMICAL SEPARATION APPLICATIONS (June 2001)

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1 Abstract Process Economics Program Report 190C ADVANCES IN MEMBRANE TECHNOLOGY FOR CHEMICAL SEPARATION APPLICATIONS (June 2001) Membrane separation process technology has an enormous variety of applications. During the last decade, there have been significant breakthroughs and incremental improvements for conventional applications in water and wastewater purification, industrial gas separations (H 2, N 2, CO 2 ) and chlor-alkali electrolytic cells. However, there has been general disappointment in the commercial success of membranes for hydrocarbon processing, especially in olefins and aromatics processing. In this PEP report, we focus on commercial hydrocarbon separations using membranes, and review improvements in other fields of application (water and wastewater, industrial gases, chlor-alkali). We also provide an assessment of the commercial status of existing industrial membrane applications, and we highlight recent developments in the industry that are likely to be commercialized in the near future. Three potential uses for membrane separations are examined in detail. The report provides a techno-economic evaluation of the VaporSep process offered commercially by Membrane Technology and Research Company (MTR) for hydrocarbon separations in the petrochemical industry. The VaporSep process is used for condensing propylene monomer contained in purge gases (generally from polymer processing and storage tanks). We also evaluate other MTR applications using the basic technology platform provided by VaporSep. The report also examines the use of membranes for industrial gas separations, primarily to produce high purity nitrogen and enriched oxygen. Membranes for hydrogen purification are also well commercialized. More recently, CO 2 rejection membranes have been applied commercially in natural gas production. We include a techno-economic evaluation of the Prism-Cactus membrane technology commercialized by Air Products & Chemicals for dehydrating methane during the production of natural gas. Prism-Cactus is similar to the Prism-Alpha process originally commercialized by Monsanto for removing hydrogen from ammonia plants. PEP 98 AP

2 Report No. 190C ADVANCES IN MEMBRANE TECHNOLOGY FOR CHEMICAL SEPARATION APPLICATIONS By ANTHONY PAVONE June 2001 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

3 CONTENTS GLOSSARY... xii 1 INTRODUCTION PREVIOUS PEP MEMBRANE STUDIES PEP PEP 190A PEP 190B SUMMARY BACKGROUND HISTORICAL BACKGROUND THERMODYNAMICS OF OSMOTIC PRESSURE PERFORMANCE PARAMETERS CONCENTRATION POLARIZATION PROCESS DESIGN CONSIDERATIONS INDUSTRY STATUS COMMERCIAL APPLICATIONS Competing Technologies for Water Treatment Commercial Membrane Market Size GLOBAL MEMBRANE COMPETITORS Microfiltration Ultrafiltration Reverse Osmosis Nanofiltration Electrodialysis Gas Separation/Contacting Electrolysis iii

4 CONTENTS (Continued) Pervaporation Hemodialysis RECENT MEMBRANE TECHNOLOGY DEVELOPMENTS NEW MEMBRANE SYSTEMS Carbon Molecular Sieve Membranes Nuclear Waste Decontamination Organic Acid Drying Pervaporation Biomedical Applications Liquid Membranes Bulk Liquid Membranes Emulsion Liquid Membranes Supported Liquid Membranes Ceramic Membranes VAPORSEP PROCESS TO RECOVER PROPYLENE MONOMER COMPANY BACKGROUND MTR'S POLYSULFONE MEMBRANE SPIRAL WOUND MEMBRANE CONFIGURATION CLAIMED ADVANTAGES OF MTR SYSTEM MTR'S PATENT POSITION VAPORSEP PROCESS TO RECOVER PROPYLENE FROM PP PLANTS VAPORSEP PROCESS MATERIAL BALANCE VAPORSEP PROCESS LIMITS PROCESS SEQUENCE FOR THE DSM PP APPLICATION FEESTOCK COMPOSITION FOR POLYPROPYLENE DEGASSING PROCESS DESCRIPTION FOR A VAPORSEP PROPYLENE RECOVERY UNIT iv

5 CONTENTS (Continued) VAPORSEP PROCESS ECONOMICS COMPETING PROCESSES APPLICATIONS OTHER THAN PROPYLENE FOR VAPORSEP Vent Gas Purge Streams VaporSep for Removing Organics from Contaminated Air Streams VaporSep for Air Streams in Contaminated Soil Remediation Hydrocarbons Recovery from Distillation Tower Non-Condensable Products VaporSep System for Natural Gas Conditioning PRISM CACTUS PROCESS FOR NATURAL GAS DEHYDRATION COMPANY AND PROCESS BACKGROUND Commercial Experience of Prism-Cactus Membranes in Natural Gas Dehydration Rationale for Gas Dehydration Permea's Patent Position Characteristics of Commercial Prism-Cactus Membranes Configuration of Commercial Permea Membranes DESIGN OF A PRISM-CACTUS DEHYDRATION SYSTEM FOR NATURAL GAS PRISM-CACTUS PROCESS ECONOMICS COMPETING PROCESSES Non-Membrane Competing Processes Absorption Using Liquid Glycols Solid Desiccant Dryers Calcium Chloride Dehydration Other Prism Membrane Gas Separations Prism-Cactus Membrane for Air Drying Prism Membranes for H 2 S Removal Prism Membranes for Nitrogen Generation Prism Membranes for Hydrogen Purification v

6 CONTENTS (Concluded) APPENDIX A: CITED REFERENCES... A-1 APPENDIX B: DESIGN AND COST BASES... B-1 APPENDIX C: PROCESS FLOW DIAGRAM... C-1 vi

7 ILLUSTRATIONS 4.1 Regional Distribution of Membrane Module Sales in Regional Forecast Growth of Membrane Module Sales Estimated Global Membrane Module by Process Technology Estimated Global Growth Rate in Membrane Sales ( ) Relative Solubility of VaporSep Polysulfone Membrane Three-Layer Sandwich Configuration for VaporSep Membrane VaporSep Spiral Wound Membrane Bundle Configuration General Configuration of VaporSep System Process Flow for Bulk Slurry Polypropylene Process Flow Diagram for VaporSep Hydrocarbon Recovery from PP Purge VaporSep System Incorporating Feed/Product Heat Exchanger Effect of Pressure Ratio on VaporSep Enrichment Factor Raffinate Concentration and Recovery Permeate Concentration and Recovery PP Production Incorporating VaporSep Membrane Recovery System Vapor Separation System to Recover Propylene from Polypropylene Purge Gas...C Distribution of VaporSep Total Fixed Capital Cost by Type of Equipment Distribution of VaporSep Production Costs Activated Carbon for Recovery of VOCs from Vent Streams Integrated Thermal Oxidation System for Halogenated Solvent Removal VaporSep Process for VCM Recovery VaporSep Process to Remove VOCs from Air Stream Permea Prism Simplified Flow Diagram for Air Dehydration vii

8 ILLUSTRATIONS (Concluded) 7.2 Hollow Fiber Membrane Incorporating Sweep Fluid Permea Membrane Dehydration Process Recovering Sweep Gas Stage Prism-Cactus Dehydration with Compression/Condensing Relative Permeability of Gases Through Prism Membranes Prism-Cactus Membrane Dehydration Syste,... C Natural Gas Dehydration Flow Diagram Using Glycol Solid Desiccant Drying System for Wet Natural Gas Prism Membrane System for Removing H2S from Natural Gas Prism Membrane for Nitrogen Generation Prism Membrane System for Hydrogen Purification viii

9 TABLES 2.1 Conventional Membrane Material and Applications Flux Rates of Membrane Systems List of Membrane Process Scientific Developments List of Significant Membrane Commercializations Driving Forces for Membrane Technologies Representative Pressure Driving Forces for Commercial Membranes Listing of Major Membrane Applications Emerging Membrane Applications Water Treatment Technologies Regional Distribution of Global Membrane Module Sales Major Global Membrane Competitors Significant Commercial Microfiltration Competitors Significant Commercial Ultrafiltration Competitors Significant Commercial Reverse Osmosis/Nanofiltration Competitors Significant Nanofiltratio Producers Significant Commercial Electrodialysis Competitors Significant Gas Separation/Contacting Competitors Significant Electrolysis Competitors Significant Pervaporation Competitors Significant Hemodialysis Competitors Membrane Component Separation Systems Representative MTR VaporSep Customers VaporSep Propylene Recovery Raffinate Concentration and Recovery Permeate Concentration and Recovery Polypropylene Vent Gas Composition Design Bases and Assumptions ix

10 TABLES (Continued) 6.7 VaporSep Propylene Recovery Stream Flows VaporSep Propylene Recovery Major Equipment VaporSep Propylene Recovery Total Capital Investment Recovery Propylene Using VaporSep Technology Production Costs Recovery Value of Competing Technologies VOC Concentration Dictates Choice of Technology Stream Characteristics that Preclude Use of Separation Technologies Activated Carbon Adsorption Capacity for Organic Contaminants Chemical Applications for the VaporSep Process Potential Vent Gas Purge Applications Basic Process Data on 3 VaporSep Applications for VCM Recovery Specifications for Pipeline Natural Gas MTR Pilot Testing for Dewpoint Control Hydrocarbon Removal Efficiency of VaporSep Process Commercial Specification for Pipeline Natural Gas Raw Natural Gas Composition for Prism-Cactus Membrane System Design Design Permeation Rate for Prism-Cactus System Selectivity of Prism-Cactus Membrane to Light Gases Versus Water Prism-Cactus Natural Gas Dehydration Design Bases Prism-Cactus Natural Gas Dehydration Stream Flows Prism-Cactus Natural Gas Dehydration Major Equipment Prism-Cactus Natural Gas Dehydration Total Capital Investment x

11 TABLES (Concluded) 7.9 Prism-Cactus Natural Gas Dehydration Production Costs xi

MEMBRANE SEPARATION PROCESSES. PHI Learning PnfaO Mmfei. Kaushik Nath. Professor and Head

MEMBRANE SEPARATION PROCESSES. PHI Learning PnfaO Mmfei. Kaushik Nath. Professor and Head MEMBRANE SEPARATION PROCESSES 1 1 %%^\^imte!#as#l=a^ Kaushik Nath Professor and Head Chemical Engineering Department GH Patel College of Engineering and Technology Vallabh Vidyanagar, Gujarat PHI Learning