IHS Chemical Process Economics Program Report 291 Aromatics from Light Hydrocarbons By Syed Naqvi November 2014 ihs.com/chemical
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PEP Report 291 Aromatics from Light Hydrocarbons By Syed Naqvi November 2014 Abstract This report presents a technical and economic evaluation of three technologies used in the production of benzene, toluene, and xylenes (BTX). The feedstocks for the BTX processes are C 3 -C 4 range aliphatic/olefinic hydrocarbons. PEP Reports 129A, 129B, and 182B (published in 1996, 2006, and 2008, respectively), covered BTX technologies based on the catalytic reforming of light naphtha or pyrolysis gasoline. The current report, however, focuses on BTX produced from liquefied petroleum gas (LPG) as individual, refined products that serve as feedstocks for several other commercially important derivative chemicals. Hence, the starting materials covered in this report differ from those in previous reports covering aromatics. From the perspective of feedstocks, LPG has a cost advantage over light naphtha-range hydrocarbons. However, many LPG production regions are remote, resulting in high transportation costs, leading LPG producers to look for ways to convert LPG (or C 3 -C 4 -rich streams) into more valuable products that are in higher demand, such as BTX.The three technologies analyzed in this report are UOP-BP Cyclar technology, SINOPEC Luoyang GTA technology, and Mitsubishi-Chiyoda Z-Forming technology. UOP-BP s Cyclar technology is based on a bifunctional catalyst consisting of a metal (gallium) modified zeolite (ZSM-5) base material. The highlight of this process is the proprietary continuous catalyst regeneration system (CCR system), a feature used by UOP for the last 40 years. Another important feature of the process is the type of reforming system, which consists of a series of vertically stacked reactors in which catalyst flows down under gravity in the form of a dense medium and reactants flow through the catalyst bed in a radial direction. Operating conditions are 896-1,022 F (480-550 C) at <100 psia. BTX yield can be up to 60-65 wt%. Feed to process is LPG or light naphtha. For BTX separation, only simple distillation (SD) is used. SINOPEC Luoyang s GTA technology is also based on a bifunctional catalyst consisting of a metal (undisclosed, but likely zinc or gallium) modified zeolite (ZSM-5) base material. The reforming reactors are of an adiabatic, fixed-bed type. Operating conditions are 860-986 F (460-530 C) at <70 psia. BTX yield can be up to 55-60 wt%. Feed to process is C 4 -rich olefinic streams. For BTX separation, only SD is used. Mitsubishi-Chiyoda s Z-Forming technology is also based on a bifunctional catalyst consisting of a metal (undisclosed, but likely zinc) modified zeolite (ZSM-5) base material. The reforming reactors are of an adiabatic, fixed-bed type. Operating conditions are 932-1,112 F (500-600 C) at <100 psia. BTX yield can be up to 55-58 wt%. Feed to process is LPG or light naphtha. For BTX separation, only SD is used. November 2014 iii 2014 IHS
Contents 1. Introduction... 1 2. Summary... 2 Feedstocks... 3 Reaction conditions... 4 Catalysts... 4 Design conditions... 5 Light-naphtha-based processes... 7 Process economics... 8 Overall economic conclusion for the Cyclar process... 9 Overall economic conclusion for the GTA process... 9 Overall economic conclusion for the Z-Forming process... 10 3. Industry status... 13 Capacity, production and consumption... 13 Benzene... 13 Toluene... 17 Xylenes (mixed)... 22 4. Technical review... 26 Catalysts... 26 Monofunctional catalysts... 27 Dual-function catalysts... 27 Feedstocks... 28 Reaction conditions/parameters... 30 Selectivity and conversion... 30 Staged aromatization... 32 Reactors... 37 5. UOP process for BTX production by catalytic reforming of LPG... 39 Process description... 39 Process discussion... 49 Process design choices... 49 Feedstock... 49 Conversion parameters... 50 Reformer heaters sizing... 50 Fired-heaters fuel consumption efficiency... 51 Product recovery... 51 Refrigeration... 51 Materials of construction... 51 Cost estimates... 51 November 2014 iv 2014 IHS
Fixed capital costs... 52 Production costs... 52 Overall economic conclusion... 52 6. SINOPEC Luoyang GTA process for BTX production by catalytic reforming of C 4 raffinate-ii... 58 Process description... 58 Process discussion... 67 Process design choices... 67 Catalyst... 67 Reactor... 68 Feedstock... 68 Product recovery... 68 Product spectrum... 68 Refrigeration... 68 Materials of construction... 69 Cost estimates... 69 Fixed capital costs... 69 Production costs... 70 Overall economic conclusion... 70 7. Mitsubishi-Chiyoda Z-Forming process for BTX production by catalytic reforming of C 4 (butanes)... 75 Process description... 76 Process discussion... 85 Process design choices... 85 Catalyst... 85 Reactor... 85 Feedstock... 86 Product recovery... 86 Product spectrum... 86 Refrigeration... 87 Materials of construction... 87 Cost estimates... 87 Fixed capital costs... 87 Production costs... 88 Overall economic conclusion... 88 Appendix A: Patent summary tables... 93 Appendix B: Design cost bases... 109 Design conditions... 109 Cost bases... 109 Capital investment... 109 Production costs... 110 November 2014 v 2014 IHS
Appendix C: Cited references... 112 Appendix D: Patent references by company... 113 Appendix E: Process flow diagrams... 114 Tables Table 2.1: BTX Technologies Salient Operating Features... 3 Table 2.2: Cyclar Process... 5 Table 2.3: GTA Process... 6 Table 2.4: Z-Forming Process... 7 Table 2.5: Comparative Economics of C 3 -C 4 Hydrocarbons-based BTX Technologies Total Capital Investment... 11 Table 2.6: Comparative Economics of C 3 -C 4 Hydrocarbons-based BTX Technologies Production Costs... 12 Table 2.7: Carbon Footprint for Different BTX Production Technologies... 12 Table 3.1: Global Annual Capacities for Benzene... 14 Table 3.2: Global Benzene Production and Consumption... 16 Table 3.3: Global Annual Capacities for Toluene... 18 Table 3.4: Global Toluene Production and Consumption... 21 Table 3.5: Regional Mixed Xylenes Capacities, Production and Consumption... 23 Table 4.1: Ethane Conversion on Different Types of Pt-Sn Catalysts... 29 Table 4.2: Ethane Conversion on Different Types of Pt-Ga Catalysts... 30 Table 4.3: Performance Test Results of Aromatization Catalysts for Two-staged Reformers... 33 Table 4.4: Performance Comparison of One-Stage and Two-Stage Aromatization Reactors... 36 Table 5.1: UOP Process for BTX Production by Catalytic Reforming of LPG Design Bases... 43 Table 5.2: UOP Process for Production of BTX by Catalytic Reforming of LPG Stream Flows... 44 Table 5.3: UOP Process for Production of BTX by Catalytic Reforming of LPG Equipment List... 46 Table 5.4: UOP Process for Production of BTX by Catalytic Reforming of LPG Utilities Summary... 48 Table 5.5: UOP Process for Production of BTX by Catalytic Reforming of LPG Total Capital Investment... 54 Table 5.6: UOP Process for Production of BTX by Catalytic Reforming of LPG Production Costs... 55 Table 6.1: SINOPEC Luoyang GTA Process for BTX Production by Catalytic Reforming of C 4 Raffinate Design Bases... 61 Table 6.2: SINOPEC Luoyang GTA Process for Production of BTX by Catalytic Reforming of C 4 Raffinate Stream Flows... 62 Table 6.3: SINOPEC Luoyang GTA Process for Production of BTX by Catalytic Reforming of C 4 Raffinate Equipment List... 64 Table 6.4: SINOPEC Luoyang GTA Process for Production of BTX by Catalytic Reforming of C 4 Raffinate Utilities Summary... 66 Table 6.5: SINOPEC Luoyang GTA Process for Production of BTX by Catalytic Reforming of C 4 Raffinate Total Capital Investment... 71 November 2014 vi 2014 IHS
Table 6.6: SINOPEC Luoyang GTA Process for Production of BTX by Catalytic Reforming of C 4 Raffinate Production Costs... 72 Table 7.1: Mitsubishi-Chiyoda Z-Forming Process for BTX Production by Catalytic Reforming of C 4 (butanes) Design Bases... 79 Table 7.2: Mitsubishi-Chiyoda Z-Forming Process for BTX Production by Catalytic Reforming of C 4 (butanes) Stream Flows... 80 Table 7.3: Mitsubishi-Chiyoda Z-Forming Process for BTX Production by Catalytic Reforming of C 4 (butanes) Equipment List... 82 Table 7.4: Mitsubishi-Chiyoda Z-Forming Process for BTX Production by Catalytic Reforming of C 4 (butanes) Utilities Summary... 84 Table 7.5: Mitsubishi-Chiyoda Z-Forming Process for BTX Production by Catalytic Reforming of C 4 (butanes) Utilities Summary... 89 Table 7.6: Mitsubishi-Chiyoda Z-Forming Process for BTX Production by Catalytic Reforming of C 4 (butanes) Production Costs... 90 Table A.1: Production of BTX from C 3 -C 4 Hydrocarbons Patent Summary... 93 Figures Figure 3.1: Global Benzene Capacity by Process (2013)... 15 Figure 3.2: Global Benzene Production by Feedstock Type (2013)... 16 Figure 3.3: Global Benzene Demand by Derivative Products (2013)... 17 Figure 3.4: Global Toluene Demand by Derivative Products (2013)... 20 Figure 3.5: Global Toluene Production by Feedstock Type (2013)... 21 Figure 3.6: Global Toluene Supply and Demand (2013)... 22 Figure 3.7: Global Mixed Xylenes Demand by Derivative Products (2013)... 24 Figure 3.8: Global Mixed Xylenes Production by Feedstock Type (2013)... 25 Figure 3.9: Global Mixed Xylenes Supply and Demand (2013)... 25 Figure 4.1: Single-Stage Aromatization Process Flow Schematic... 35 Figure 4.2: Two-Stage Aromatization Process Flow Schematic... 36 Figure 5.1: UOP Process for BTX Production by Catalytic Reforming of LPG... 115 Figure 5.2: UOP Process for Production of BTX by Catalytic Reforming of LPG... 57 Figure 6.1: SINOPEC Luoyang GTA Process for BTX Production by Catalytic Reforming of C 4 Raffinate... 117 Figure 6.2: SINOPEC Luoyang GTA Process for Production of BTX by Catalytic Reforming of C 4 Raffinate... 74 Figure 7.1: Mitsubishi-Chiyoda Process for BTX Production by Catalytic Reforming of C 4 (butanes).. 119 Figure 7.2: Mitsubishi-Chiyoda Z-Forming Process for BTX Production by Catalytic Reforming of C 4 (butanes)... 92 November 2014 vii 2014 IHS