Integrated processes for converting coal to chemicals and fuels. Maninder Jit Singh Haldor Topsøe

Transcription

1 Integrated processes for converting coal to chemicals and fuels Maninder Jit Singh Haldor Topsøe

2 Converting coal to chemicals and fuels Sulfuric acid SNG Coal Coal gasification Syngas conditioning Ammonia DME Methanol Formaldehyde Gasoline

3 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

4 Process steps in an integrated CTX plant N 2 Air ASU O 2 Steam H 2 S WSA Sulfuric acid Coal Gasifier Syngas Sour shift Acid gas removal Final purification NH 3 synthesis NH 3 product NH 3 Steam CO 2 Urea synthesis Urea product MeOH synthesis MeOH product MeOH DME synthesis DME product

5 Typical Topsoe sour shift section

6 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

7 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

8 What to do with H 2 S? H 2 S Claus plant WSA Plant Sulfur Uses of sulfuric acid Sulfuric acid Sulfuric acid plant

9 What is WSA? Wet gassulfuric Acid A catalytic process for purification of sulfur- containing streams while producing concentrated sulfuric acid Energy Superheated steam (HP Steam) Stack gas Blower S Combustion air H 2 S SO 2 converter RSH BFW Blower Steam Cleaned Air COS drum gasinterbed CS 2 cooler WSA H 2 S gas SO 2 condenser SO 3 H 2 SO Gas Combust 4 cooler or WHB Acid cooler CW Sulfuric Product acid acid

10 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

11 Comparison WSA vs. Claus Production Production figures WSA Claus + TGTU $/t tph $/yr tph $/yr = 0 Sulfuric acid , Sulfur ,974 HP steam ,388, LP steam ,874 Total production value 2,367,903 1,301,848 1,388,964 $ = USD

12 Comparison WSA vs. Claus Consumption Consumption figures WSA Claus + TGTU unit $/unit tph/kwh $/yr tph/kwh $/yr Fuel gas t ,152 Oxygen t ,363 HP steam t ,455 BFW t , ,819 CW t , El. Power kwh , ,213 Total consumption cost 181, ,002 Net production income 2,186, ,846 Sulfuic acid at zero value 1,207,221 $ = USD

13 WSA references Acid production :4 1,140 MTPD 130+ references 30 within gasification Korean Western Power Taean IGCC plant Start-up Oil refining Coking Gasification Metallurgy Viscose Sundry applications Mississippi Power Company Kemper County IGCC plant Start-up Sasol Synfuels (Pty.) Ltd. Secunda, RSA Start-up 2009

14 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

15 Schematic TREMP layout (Topsoe Recycle Energy Efficient Methanation Process) Sulphur guard Bulk methanation Trim methantion Feed Inlet temp. down to 230 C Special features of TREMP Robust process SNG Low operating cost High exit temp., typically 675 C Excellent catalysts

16 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

17 Industrial case Coal to SNG Qinghua SNG plant Two step desulfurization of raw syngas High surface HTZ-5 absorbent Copper-Zinc based ST-101 for final absorption Customer Qinghua, China Start up 2013 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

18 Industrial case Coal to LNG Huineng Coal Chemical Co. Ltd., China SNG to LNG requires high product purity Reached 105% load Services rendered Process and basic design Detailed engineering of high pressure equipment Supply of catalyst Assistance during commissioning and start-up Customer Start up 2014 Huineng Coal Chemical Co.Ltd., China Capacity, SNG 50,000 Nm 3 /h

19 Topsoe synthesis loop S-300 Converter BFW CW Make-up gas Boiler NH 3 (l) Product ammonia

20 Special features of Topsoe ammonia loop Topsoe 3 bed ammonia converter S-300 Converter Well proven radial flow converter with about 50 references Easy to operate BFW CW Highly reliable Boiler Make-up gas NH 3 (l) Product ammonia High efficiency No purge KM ammonia synthesis catalyst High activity Small particles

21 KM 111 New Topsoe ammonia synthesis catalyst Optimized for lower beds Higher NH 3 concentration Lower temperatures Favorable equilibrium S-300 KM1 KM111 KM111

22 Industrial case Coal to ammonia Zhongyan Kunshan Co. Ltd ammonia plant Single S-300 ammonia converter Bayonet u-tube loop boiler Customer Start up 2015 Zhongyan Kunshan, China Services rendered Process and basic design Detailed engineering of high pressure equipment Supply of proprietary equipment and catalyst Assistance during commissioning and start-up Capacity 900 MTPD Ammonia

23 Topsoe methanol synthesis loop

24 MK-151 Topsoe methanol synthesis catalyst The FENCE technology inhibits sintering Cu crystals separated by picket fence of metal oxides Very high activity Long lasting stability Low by-products formation ZnO Cu Al 2 O 3

25 Industrial case Coal to methanol Xianyang methanol plant One step desulfurization of raw syngas Single boiling water methanol reactor Operating at 108% capacity 1% better carbon efficiency compared to design Customer Start up 2010 Capacity Xianyang Shaanxi, China 2000 MTPD 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

26 Industrial case Integrated process Tianfu ammonia and DME plant Single S-300 ammonia converter Single boiling water methanol reactor Single adiabatic DME Product flexibility Services rendered Process and basic design Detailed engineering of high pressure equipment Supply of proprietary equipment and catalyst Assistance during commissioning and start-up Customer Start up 2009 Capacity Tianfu Chemical, China 910 MTPD Ammonia 750 MTPD Methanol 550 MTPD DME

27 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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