` IHS CHEMICAL Aromatics Upgrading Technologies Process Economics Program Report 25E December 2016 ihs.com PEP Report 25E Aromatics Upgrading Technologies Rajesh Kumar Verma Principal Analyst Downloaded 20 December 2016 03:27 AM UTC by Ellen Blue, IHS INC ([email protected]) IHS Chemical | PEP Report 25E Aromatics Upgrading Technologies PEP Report 25E Aromatics Upgrading Technologies Rajesh Kumar Verma, Principal Analyst Abstract Transalkylation, disproportionation, alkylation, and dealkylation are the most widely used processes in a refinery complex for C7, C9, C10 aromatics upgrading, and xylene isomerization is used to increase the para- xylene content of streams from low to high. Many licensors and technology developers provide process technologies and proprietary catalysts for these processes, each with advantages and disadvantages over other technologies. In this report, the technological advancements and production economics are updated for the following three processes: • The UOP Tatoray™ process for upgrading toluene, C9, and C10 aromatics, by catalytic disproportionation and transalkylation, to a commercial grade mix of xylene product (>98 wt% C8 content) and high-purity benzene by-product (>99.9 wt% purity) • The UOP isomerization process for isomerizing xylenes in a para-xylene-lean stream to provide a para- xylene-rich stream, by converting meta- and ortho-xylenes to an equilibrium mixture of xylenes, with ethylbenzene either dealkylated to benzene or isomerized to xylenes. • The CB&I Detol® process for converting a toluene-rich stream to high-purity benzene product. This report also provides an industry review of p-xylene and benzene, including the market shares of various licensors for the selected processes, process PFDs, patent summaries, and an upfront Summary section. For the process analyses, we evaluate and discuss patent and other non-proprietary information, particularly to extract key process conditions and parameters necessary to forming the design basis for each process. An Aspen simulation model is developed and engineering judgement is applied to define the detailed material and energy balances. Plant construction costs (CAPEX), including ISBL and OSBL costs, are estimated for each processes by individual equipment sizing and costing with the aid of IHS’s proprietary software PEPCOST®. Operating costs are calculated based on unit consumption of raw materials, utilities, and direct costs as well as depreciation and return on investment. Production economics presented in the report are based on cost data for the US Gulf Coast (USGC) region. However, an Excel-based data module iPEP NavigatorAromaticsUpgrading is included as an attachment to the electronic report, to allow our clients to convert the economics of the discussed upgrading processes to the corresponding economics in five other regions (Canada, China, Germany, Japan, and the Middle East). © 2016 IHS 1 December 2016 Downloaded 20 December 2016 03:27 AM UTC by Ellen Blue, IHS INC ([email protected]) IHS Chemical | PEP Report 25E Aromatics Upgrading Technologies Contents 1 Introduction 10 2 Summary 13 Commercial aspects 13 Benzene 14 Xylenes 14 C7A and C9A upgrading to benzene and xylene 16 Process economics summary 16 UOP’s transalkylation process 17 UOP’s xylene isomerization process 18 CB&I’s Detol® process 18 Process summary 18 3 Industry status 20 Specifications of major streams in an aromatics complex 20 Naphtha reformate 20 Mixed xylenes 21 Benzene 22 para-Xylene 23 Supply and demand 24 Mixed xylenes 24 Benzene 26 Toluene 27 Toluene disproportionation and hydrodealkylation 27 List of producers and plant capacities 29 Price trends for feedstock and products 36 4 Technology review 38 Feedstock and products 38 Aromatics complex unit configurations 39 Aromatics complex process description 42 Benzene and toluene recovery unit 43 Toluene column 44 Xylene, ortho-xylene, and heavy aromatics columns 44 p-Xylene recovery unit 45 Xylene isomerization unit 48 Aromatics upgrading to xylene and benzene 50 Overview 50 Catalytic hydrodealkylation of toluene 50 Thermal hydrodealkylation of toluene 50 Toluene disproportionation and transalkylation of C7 and C9 aromatics 51 Selective toluene disproportionation 52 Toluene methylation 52 Transalkylation process 53 Chemistry 53 Alkylation 57 Hydrocracking 58 IHS™ CHEMICAL COPYRIGHT NOTICE AND DISCLAIMER © 2016 IHS. 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Downloaded 20 December 2016 03:27 AM UTC by Ellen Blue, IHS INC ([email protected]) IHS Chemical | PEP Report 25E Aromatics Upgrading Technologies Isomerization 58 Ring saturation 59 Coking 59 Process variables 59 Temperature and pressure dependency 59 Feed quality 60 Reaction severity 61 Temperature 61 H2 partial pressure 62 Space velocity 62 Methyl/phenyl or methyl/ring ratio in the feed 62 Process development 63 Major commercial processes 66 SM ExxonMobil’s TransPlus process 66 SM ExxonMobil’s toluene disproportionation process MTDP-3 67 UOP TAC9™ process 68 SM GTC-Transalkylation process (GTC-TransAlk ) 68 Catalyst development 69 Summary of technology development 76 Xylene isomerization 77 Chemistry 78 Xylene isomerization 78 Ethylbenzene conversion 79 Side reactions 79 Process variables 79 Temperature 79 H2 partial pressure and reactor pressure 80 H2/HC ratio 80 Reaction severity 80 Space velocity 80 Process and catalyst development 80 Liquid phase xylene isomerization 81 Vapor phase xylene isomerization 81 Vapor phase isomerization without a hydrogen atmosphere 81 Vapor phase isomerization with a hydrogen atmosphere 81 Major commercial processes 86 SM ExxonMobil’s XyMax process 86 Axens-Engelhard Octafining™ process 88 SM GTC GT-IsomPX technology 88 JSC SIE Neftehim process 89 Summary of technology development 89 Toluene hydrodealkylation 90 Catalytic hydrodealkylation versus thermal hydrodealkylation 91 Chemistry 91 Side reactions 92 Process variables 94 Feed composition 94 Temperature 94 Pressure 95 Toluene conversion 95 H2/HC ratio 95 Process and catalyst development 95 © 2016 IHS 3 December 2016 Downloaded 20 December 2016 03:27 AM UTC by Ellen Blue, IHS INC ([email protected]) IHS Chemical | PEP Report 25E Aromatics Upgrading Technologies Summary of technology development 98 5 UOP’s transalkylation process 99 Scope 99 Process description 109 Feed 109 Reaction 110 Product fractionation 110 Process discussion 111 Process scheme 111 Catalyst 111 Feed composition 112 Reactor 112 Recycle gas compressor 112 Make-up H2 112 Cost estimates 112 Fixed capital costs 113 Production costs 113 Economic discussion 113 6 UOP’s xylene isomerization process 119 Scope 119 Process description 126 Feed section 126 Reaction section 127 Product fractionation section 127 Process discussion 128 Process scheme 128 Catalyst 128 Feed composition 128 Reactor 128 Recycle gas compressor 128 Make-up H2 129 Cost estimates 129 Fixed capital costs 130 Production costs 130 Economic discussion 130 7 CB&I’s Detol® process 136 Scope 136 Process description 144 Feed section 144 Reaction section 145 Product fractionation section 146 Process discussion 147 Catalyst 147 Feed composition 147 Reactor 147 Recycle gas compressor 147 Make-up H2 147 Cost estimates 147 Fixed capital costs 148 Production costs 148 Economic discussion 148 Appendix A—Patent summaries 153 © 2016 IHS 4 December 2016 Downloaded 20 December 2016 03:27 AM UTC by Ellen Blue, IHS INC ([email protected]) IHS Chemical | PEP Report 25E Aromatics Upgrading Technologies Appendix B—Design and cost basis 181 Design conditions 182 Cost basis 182 Capital investment 182 Production costs 183 Effect of operating level on production costs 184 Appendix C—Cited references 185 Appendix D—Patent references by company 195 Appendix E—Process flow diagrams 199 Tables Table 2.1 Economics summary for the studied processes 17 Table 2.2 Process summary for the studied processes 19 Table 3.1 Major properties and composition of naphtha reformate 21 Table 3.2 Major specifications for mixed xylenes product 22 Table 3.3 Major specifications for benzene product 23 Table 3.4 Major specifications for p-xylene product 24 Table 3.5 World supply and demand for mixed xylene by region 25 Table 3.6 World supply and demand for