Integrated processes for converting coal to chemicals and fuels Maninder J it Singh Haldor Topsøe
Converting coal to chemicals and fuels Sulfuric acid SNG Coal Coal Syngas Ammonia DME gasification conditioning Methanol Formaldehyde Gasoline
Integrated production Maximize utilization of H 2 and CO 2 • Combined production • Hydrogen, TREMP TM • Ammonia, urea, methanol • TIGAS • Minimizing sulfur emissions • Sulfur removal unit • Commercial grade sulfuric acid • Integrated steam system • Overall benefit on energy efficiency
Process steps in an integrated CTX plant N 2 Air Sulfuric acid ASU WSA™ Steam H 2 S O 2 Syngas Coal NH 3 NH 3 product Acid gas Final Gasifier Sour shift synthesis removal purification NH 3 Steam Urea product CO 2 Urea synthesis MeOH product MeOH synthesis MeOH DME DME product synthesis
Typical Topsoe sour shift section
Features of sour shift catalyst SSK-10 • Active at low temperatures • Allows high CO conversion at low steam/dry gas • High selectivity at low steam to dry gas ratio • Methanation reaction is limited • Proprietary kinetics for the CH 4 formation • Sour shift can be designed for minimum S/DG ratio • No risk of temperature run away • Specialised guard catalyst • Dust protection • Carbonyl protection
Sulfur removal downstream the sour shift • Both H 2 S and COS will typically be present • Sour shift will hydrolyze the COS to equilibrium • Methanol plants with by-pass across the shift section • Possibility to install hydrolysis reactor on the by-pass stream • CKA-3 catalyst from Topsoe • Selective hydrolysis of COS to equilibrium • No change in the H 2 /CO ratio • HTZ-31 promoted absorbent from Topsoe • Remove equilibrium COS before the synthesis units
What to do with H 2 S? H 2 S Sulfur Claus plant WSA Plant Sulfuric acid plant Sulfuric acid Uses of sulfuric acid
What is WSA? W et gas S ulfuric A cid A catalytic process for purification of sulfur- containing streams while producing concentrated sulfuric acid Energy Superheated steam Stack gas (HP Steam) Blower Combustion air S H 2 S SO 2 converter Blower BFW RSH Cleaned Steam Air drum COS gas Interbed cooler CS 2 WSA SO 2 H 2 S gas condenser SO 3 Gas H 2 SO 4 Combust cooler or WHB Acid cooler CW Sulfuric Product acid acid
Value addition by WSA! CAPEX & Environment: • More than 99.9% of the sulfur content can be recovered • Without need of tail gas treatment unit • Simple lay-out • Relatively few components and small plot space gives low investment OPEX: • Excellent heat management • Producing large amount of valuable HP superheated steam • Sulfur is recovered as concentrated sulfuric acid of commercial grade • Valuable product of extensive use in India • Ease of operation • High plant availability (no fouling S-condensers/catalyst or HC and NH 3 feed issues) • No waste products or chemicals added • Minimal impact on OSBL utilities
Comparison WSA vs. Claus Production Production figures WSA Claus + TGTU $/t tph $/yr tph $/yr = 0 Sulfuric acid 32 3.56 978,939 - - Sulfur 100 - - 1.16 999,974 HP steam 17 9.50 1,388,965 - - LP steam 13 - - 2.70 301,874 Total production value 2,367,903 1,301,848 $ = USD 1,388,964
Comparison WSA vs. Claus Consumption Consumption figures WSA Claus + TGTU tph/kWh tph/kWh unit $/unit $/yr $/yr Fuel gas t 130 - - 0.23 257,152 Oxygen t 47 - - 0.56 226,363 HP steam t 17 - - 1.33 194,455 BFW t 0.34 11.2 32,750 3.70 10,819 CW t 0.03 30.8 7,947 - - El. Power kWh 0.08 205 141,047 400 275,213 Total consumption cost 181,744 964,002 Net production income 2,186,160 337,846 $ = USD Sulfuic acid at zero value 1,207,221
WSA references Acid production :4 – 1,140 MTPD 130+ references 30 within gasification Korean Western Power Taean IGCC plant Start-up 2015 1 1 2 3 11 13 5 24 18 1 26 8 12 16 1 14 20 8 5 2 15 25 4 1 6 29 4 14 31 3 5 2 7 7 17 4 4 2 4 10 8 9 2 9 10 12 28 14 30 35 23 11 19 24 16 30 2 24 17 31 19 17 8 29 18 23 12 33 37 6 20 11 26 3 3 4 22 38 11 3 27 7 28 8 5 25 25 18 13 10 19 6 21 16 15 26 32 5 29 28 20 21 13 9 6 15 7 6 27 Oil refining 9 1 5 22 23 6 Coking 13 21 Sasol Synfuels (Pty.) Ltd. Gasification 12 10 7 14 Secunda, RSA Metallurgy 34 3 9 Start-up 2009 36 Viscose Mississippi Power Company Sundry applications Kemper County IGCC plant Start-up 2015
Uncoupling India from LNG import - by utilisation of national coal resources for SNG • India is the fourth largest LNG importer in the world • Imports are expected to rise ~30% in 2015 • National coal reserves and pet coke is the key
Schematic TREMP™layout (Topsoe Recycle Energy Efficient Methanation Process) Sulphur guard Bulk methanation Trim methantion Inlet temp. down to 230°C Feed Special features of TREMP™ • Robust process • Low operating cost SNG • Excellent catalysts High exit temp., typically 675°C
MCR catalyst developed for Topsoe TREMP™ methanation • MCR Catalyst – the heart of the TREMP ™unit • High thermal stability, demonstrated up to 800°C • Active at low temperature (300°C) • High resistance to carbon formation • High mechanical strength • The catalyst is delivered prereduced
Industrial case – Coal to SNG Customer Qinghua, China • Qinghua SNG plant • Two step desulfurization of raw syngas Start up 2013 • High surface HTZ-5 absorbent • Copper-Zinc based ST-101 for final absorption Capacity, SNG 172,000 Nm 3 /h • Services rendered • Process and basic design • Detailed engineering of high pressure equipment • Supply of catalyst • Assistance during commissioning and start-up
Industrial case – Coal to LNG Huineng Coal Huineng Coal Chemical Co. Ltd. , China Customer Chemical Co.Ltd., China • SNG to LNG requires high product purity • Reached 105% load Start up 2014 • Services rendered 50,000 Nm 3 /h Capacity, SNG • Process and basic design • Detailed engineering of high pressure equipment • Supply of catalyst • Assistance during commissioning and start-up
Topsoe synthesis loop S-300 Converter BFW CW Boiler NH 3 (l) Product ammonia Make-up gas
Special features of Topsoe ammonia loop S-300 • Topsoe 3 bed ammonia converter Converter • Well proven radial flow converter with about 50 references BFW CW • Easy to operate Boiler NH 3 (l) • Highly reliable Product ammonia Make-up gas • High efficiency • No purge • KM ammonia synthesis catalyst • High activity • Small particles
KM 111 – New Topsoe ammonia synthesis catalyst S-300 • Optimized for lower beds • Higher NH 3 concentration KM1 • Lower temperatures • Favorable equilibrium KM 111 KM 111
Industrial case – Coal to ammonia • Zhongyan Kunshan Co. Ltd ammonia plant Zhongyan Customer Kunshan, China • Single S-300 ammonia converter • Bayonet u-tube loop boiler Start up 2015 900 MTPD • Services rendered Capacity Ammonia • Process and basic design • Detailed engineering of high pressure equipment • Supply of proprietary equipment and catalyst • Assistance during commissioning and start-up
Topsoe methanol synthesis loop
MK-151 Topsoe methanol synthesis catalyst ZnO Cu Al 2 O 3 • The FENCE™technology inhibits sintering • Cu crystals separated by picket fence of metal oxides • Very high activity • Long lasting stability • Low by-products formation
Industrial case – Coal to methanol • Xianyang methanol plant Xianyang Customer Shaanxi, China • One step desulfurization of raw syngas • Single boiling water methanol reactor Start up 2010 • Operating at 108% capacity 2000 MTPD • 1% better carbon efficiency compared to design Capacity Methanol • Services rendered • Process and basic design • Detailed engineering of high pressure equipment • Supply of proprietary equipment and catalyst • Assistance during commissioning and start-up
Industrial case – Integrated process • Tianfu ammonia and DME plant Tianfu Chemical, Customer China • Single S-300 ammonia converter • Single boiling water methanol reactor Start up 2009 • Single adiabatic DME • 910 MTPD • Product flexibility Ammonia • 750 MTPD Capacity • Services rendered Methanol • Process and basic design • 550 MTPD • Detailed engineering of high pressure equipment DME • Supply of proprietary equipment and catalyst • Assistance during commissioning and start-up
Conclusion • Coal can be used to produce a variety of products • Added value to the plant owner • Integration of the process units creates synergies • Improves overall energy efficiency • Economy of scale • Product diversity
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