IHS Chemical Process Economics Program Report 289 New Routes to Styrene and para-xylene By Dipti Dave
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PEP Report 289 New Routes to Styrene and para-xylene By Dipti Dave October 2013 Abstract This report reviews new potentially commercial processes for styrene and para-xylene based on toluene and methanol feedstock. Several technology developments/advances have been announced in the press in the last few years. One of them is in the field of styrene production by the Exelus process. The traditional technology for styrene relies on a two-step process, starting with benzene and ethylene. Both of these hydrocarbon feedstocks are often derived from petroleum refining. In addition to replacing the ethylene and benzene raw materials with toluene and methanol, the Exelus process commercially called ExSyM (Exelus styrene monomer technology) is reportedly based on an improved catalyst technology that avoids the need for a separate dehydrogenation step, resulting in a single-step process with high yields and high conversions. The process reportedly operates at significantly lower temperatures than the conventional route, making the overall process more energy efficient. Although this technology has been demonstrated only at the bench-scale level, if the claims of high selectivity are demonstrated in pilot tests, the costs of production and feedstock savings could be improved significantly over conventional styrene monomer processes. Another technology advancement took place in the field of para-xylene production. SABIC and Lummus Technology announced plans in 2010 plans to jointly develop a new route to para-xylene (PX) that involves methylation of toluene with methanol. Previous catalysts reported in the literature for this conversion tended to deactivate quickly. The SABIC phosphorous-modified zeolites appear to significantly extend the life of such catalysts. Lummus has indicated that this type of process may provide a unique debottlenecking option for an aromatics complex. Typically, toluene is disproportionated to both xylenes and benzene. The SABIC/Lummus approach would allow toluene conversion to just xylenes. Sinopec Yangzi Petrochemical (China) has independently developed and constructed the country s first toluene methanol alkylation plant with the capacity to produce 200 kta of para-xylene. Its successful startup was in December 2012. This report will present technology design and economic analysis of some of the new developing technologies based upon their latest R&D status with economic comparison to their conventional routes. October 2013 2013 IHS
Contents 1. Introduction... 1-1 Background styrene... 1-1 Background para-xylene... 1-1 New developing technologies... 1-1 China status... 1-2 Report overview... 1-2 2. Summary... 2-1 Existing major commercial production styrene... 2-1 World producers... 2-2 New developing technology styrene... 2-3 Exelus styrene monomer technology (ExSyM)... 2-3 ExSyM process scheme... 2-3 Fina Technology... 2-4 Conventional styrene route... 2-4 Economic comparison styrene... 2-5 Conclusion styrene... 2-6 Existing major commercial production para-xylene... 2-7 Producing companies... 2-7 World supply/demand... 2-9 New developing technology para-xylene... 2-9 New para-xylene routes... 2-9 Sinopec Yangzi Petrochemical... 2-10 ExxonMobil para-xylene by methylation... 2-10 Johnson Matthey catalyst contact time... 2-10 Economic comparison para-xylene... 2-11 Conclusion para-xylene... 2-11 3. Industry status... 3-1 Product styrene... 3-1 Background... 3-1 World producers... 3-2 Capacity... 3-3 Producers and plant capacities... 3-4 Product mixed xylenes... 3-9 Background... 3-9 World producers... 3-11 4. Technology review... 4-1 Introduction... 4-1 Styrene properties... 4-1 Conventional styrene route... 4-2 Styrene process reaction chemistries... 4-2 October 2013 iii 2013 IHS
Contents (continued) New styrene routes... 4-3 Exelus styrene monomer technology (ExSyM)... 4-3 ExSyM chemistry... 4-3 ExSyM catalyst... 4-4 Development status... 4-4 ExSyM process benefits... 4-5 ExSyM process scheme and performance... 4-5 Zeolite catalyst... 4-6 Fina Technology... 4-7 Toluene methanol side chain alkylation to produce styrene China... 4-12 para-xylene properties... 4-12 Conventional para-xylene route... 4-13 Toluene disproportionation (TDP) chemistry... 4-14 Selective toluene disproportionation (STDP)... 4-14 New para-xylene routes... 4-15 Catalyst for SABIC aromatic alkylation... 4-17 Catalyst activity... 4-17 Toluene methanol ring alkylation to produce p-xylene... 4-18 ExxonMobil para-xylene by methylation... 4-21 Johnson Matthey catalyst contact time... 4-21 5. Exelus styrene monomer technology... 5-1 Process sections... 5-1 Chemistry... 5-1 Main reaction... 5-1 Process chemistry... 5-1 Basis for design and evaluation... 5-2 Process description... 5-3 Section 100 styrene process reaction... 5-4 Section 200 styrene process separation... 5-4 Section 300 styrene process recovery... 5-5 Stream flows... 5-5 Major equipment and utilities summary... 5-7 Process discussion... 5-10 Section 100 styrene process reaction... 5-10 Section 200 styrene process separation... 5-11 Section 300 styrene process recovery... 5-11 Heat-exchanger sizing... 5-11 Product recovery... 5-11 Off-site storage... 5-12 Environmental... 5-12 October 2013 iv 2013 IHS
Contents (continued) Cost estimates... 5-12 Fixed-capital costs... 5-13 Production costs... 5-13 Conclusion... 5-14 6. SABIC para-xylene aromatic alkylation process technology... 6-1 Process sections... 6-1 Chemistry... 6-1 Main reaction... 6-1 Process chemistry... 6-2 Basis for design and evaluation... 6-2 Process description... 6-4 Section 100 SABIC toluene methylation process... 6-4 Section 200 C 9 and xylene separation process... 6-5 Section 300 para-xylene crystallization process... 6-5 Stream flows... 6-6 Major equipment and utilities summary... 6-7 Process discussion... 6-10 Heat-exchanger sizing... 6-11 Product recovery... 6-11 Off-site storage... 6-11 Environmental... 6-11 Cost estimates... 6-12 Fixed-capital costs... 6-12 Production costs... 6-13 Conclusion... 6-13 7. Economic comparisons... 7-1 Introduction... 7-1 Styrene... 7-1 Styrene conventional process summary... 7-1 Summary of main technical aspects... 7-2 Process economics... 7-3 Conclusion... 7-6 para-xylene... 7-7 para-xylene conventional process summary... 7-7 Summary of main technical aspects... 7-8 Process economics... 7-8 Conclusion... 7-11 Appendix A: Patent summary tables... A-1 Appendix B: Design and cost bases... B-1 Appendix C: Cited references... C-1 October 2013 v 2013 IHS
Contents (concluded) Appendix D: Patent references by company... D-1 Appendix E: Process flow diagrams... E-1 October 2013 vi 2013 IHS
Figures 2.1 World styrene producers by shareholder 2012... 2-2 2.2 World styrene supply and demand... 2-2 2.3 ExSyM technology process flow diagram... 2-4 2.4 Exelus process effect of toluene price on styrene product value... 2-6 2.5 Fina/Badger process effect of benzene price on styrene product value... 2-6 2.6 Factors of production new route to styrene by Exelus compared to conventional route by Fina/Badger... 2-7 2.7 SABIC para-xylene block flow diagram... 2-10 2.8 SABIC alkylation process effect of toluene price on para-xylene product value... 2-12 2.9 Mobile STDP process effect of reformate price on para-xylene product value... 2-12 2.10 Factors of production new route to para-xylene by SABIC compared to conventional route by Mobil STDP... 2-13 3.1 World styrene supply and demand... 3-2 3.2 World styrene producers by shareholder 2012... 3-3 3.3 World capacity for styrene... 3-3 3.4 World feedstocks for mixed xylene production... 3-9 3.5 Xylene materials flow... 3-10 4.1 ExSyM styrene block flow diagram... 4-3 4.2 Standard catalyst vs. ExSyM catalyst... 4-4 4.3 Operating vs. capital costs for new vs. conventional styrene process technology... 4-5 4.4 ExSyM process flow diagram... 4-6 4.5 Block flow diagram for production of styrene... 4-9 4.6 Fina reactor and catalyst regeneration illustration... 4-11 4.7 Model for para-xylene selectivity in zeolite... 4-15 4.8 SABIC para-xylene block flow diagram... 4-16 4.9 Function of shape-selective zeolite... 4-17 4.10 Relationship of contact time and para-xylene selectivity... 4-22 5.1 Exelus styrene process... E-3 5.2 Exelus styrene monomer technology... E-9 6.1 SABIC para-xylene aromatic alkylation process technology... E-15 7.1 Exelus process effect of toluene price on styrene product value... 7-6 7.2 Fina/Badger process effect of benzene price on styrene product value... 7-6 7.3 SABIC alkylation process effect of toluene price on para-xylene product value... 7-12 7.4 Mobil STDP process effect of reformate price on para-xylene product value... 7-12 October 2013 vii 2013 IHS
Tables 2.1 Styrene capacity by world regions... 2-1 2.2 Styrene production total fixed costs... 2-5 2.3 Styrene production costs... 2-5 2.4 World producers for para-xylene 2012... 2-8 2.5 World supply/demand for para-xylene... 2-9 2.6 para-xylene production total fixed costs... 2-11 2.7 para-xylene production costs... 2-11 3.1 Styrene capacity by world regions... 3-4 3.2 World producing companies for styrene... 3-5 3.3 World consumption of mixed xylenes 2012... 3-11 3.4 Major world producers of xylene isomers... 3-12 4.1 Specifications for a typical polymer-grade SM product... 4-2 4.2 Properties and specifications para-xylene... 4-13 4.3 Process comparison between selective toluene disproportionation and toluene methanol ring alkylation... 4-19 4.4 Economics comparison between selective toluene disproportionation and toluene methanol ring alkylation... 4-20 5.1 Alkylation and by-product reactions... 5-2 5.2 Exelus styrene monomer technology Design bases and assumptions... 5-3 5.3 Exelus styrene monomer technology Stream flows... 5-6 5.4 Exelus styrene monomer technology Major equipment... 5-8 5.5 Exelus styrene monomer technology Utilities summary... 5-10 5.6 Summary of process waste streams... 5-12 5.7 Relation between base capacity and product value... 5-14 5.8 Exelus styrene monomer technology Total capital investment... 5-15 5.9 Exelus styrene monomer technology Capital investment by section... 5-16 5.10 Exelus styrene monomer technology Production costs... 5-17 6.1 Alkylation and by-product reactions... 6-2 6.2 SABIC para-xylene aromatic alkylation process technology Design bases and assumptions... 6-3 6.3 SABIC para-xylene aromatic alkylation process technology Stream flows... 6-6 6.4 SABIC para-xylene aromatic alkylation process technology Major equipment... 6-8 6.5 SABIC para-xylene aromatic alkylation process technology Utilities summary... 6-10 October 2013 viii 2013 IHS
Tables (concluded) 6.6 Summary of process waste streams... 6-12 6.7 Relation between base capacity and product value... 6-13 6.8 SABIC para-xylene aromatic alkylation process technology Total capital investment... 6-14 6.9 SABIC para-xylene aromatic alkylation process technology Capital investment by section... 6-15 6.10 SABIC para-xylene aromatic alkylation process technology Production costs... 6-16 7.1 Exelus and Fina/Badger technical aspects... 7-2 7.2 Styrene production total fixed costs... 7-3 7.3 Styrene production costs... 7-3 7.4 Styrene production Total capital investment... 7-4 7.5 Styrene production Production cost... 7-5 7.6 SABIC and Mobil STDP technical aspects... 7-8 7.7 para-xylene production total fixed costs... 7-8 7.8 para-xylene production costs... 7-9 7.9 para-xylene production Total capital investment... 7-10 7.10 para-xylene production Production cost... 7-11 October 2013 ix 2013 IHS