Indirect Coal Liquefaction Better Solution to Clean Energy System Yong-Wang Li, Director, Chief Scientist State Key Laboratory of Coal Conversion Institute of Coal Chemistry Chinese Academy of Sciences Taiyuan 030001
Clean Energy system 2005 First Car Fueled by 100% F-T Super Clean Diesel EU III / 2.0L diesel engine Volks Wagen CADDY SDI 2.0 Economic fuel consumption ~5.0 L /100 km Cetane No. > 70 Extremely low S and N EU IV emission limit
Main points Energy status in China CTL solution CTL development in China Future development Summary
Energy status in China Coal Reserves Oil 700 600 500 400 300 200 100 Gas 0 Million tons A B C 2000 2005 2010 2020 Year Production in China 2020: 200 million tons/a Demands: A: 610 million tons/a B: 560 million tons/a C: 450 million tons/a Coal as major primary energy Oil insufficiency for the growing demands Solutions needed for sustainable development Gap: 250-410 million tons/a
CTL Solution Coal Organic wastes Biomass Syngas production Syngas Purification Synthesis Highly Integrated System Power Generation CO 2 control NOW Electricity Liquid fuels Naphtha & Chemicals Hydrogen FUTURE CTL pointing to the sustainable solutions on the basis of GAIFICATION Less limited life span of CTL initialized production system
CTL Solution Fischer-Tropsch Synthesis Commercial scale operation SASOL HTFT gas-solid solid fluidized bed iron light fractions LTFT slurry phase /fixed bed iron and cobalt heavy fractions SHELL SMDS Fixed bed cobalt Technology in China: pilot plant proven iron (main) cobalt (in development) HFPT LFPT slurry phase-low temperature <250 o C heavy fractions slurry phase high high temperature 270-290 290 o C diesel range high
CTL Development In China CTL in China: Brief history 1950-1962 1962 First BASF FTS technology Cobalt catalyst at normal pressure 74(X13ton) fixed bed reactors 30000ton Hydrocarbons/ a The plant was removed due to oil field discovery in 1960s in China
CTL Development In China -1979-1989: 1989: Development of iron catalysts Fixed bed reactor up to single tube tests. Slurry phase test in laboratory
CTL Development In China -1990-1993: 1993: 40 b /d demonstration plant test Fixed bed reactor with about 2000 tubes 1) Desulfurization was not adequate 2) Extremely low oil price
CTL Development In China New enhanced development initialized in 1997 Fischer-Tropsch synthesis in slurry phase
CTL Development In China FTS catalyst group Engineering group Fundamental Syncrude workingup
CTL Development In China FTS catalyst research and development - Iron based ICC-I I (heavy fraction) 230-250 250 o C, slurry phase - Iron based ICC-II II (lighter fraction) 260-280 280 o C, slurry phase - Cobalt based ICC-III III 220 o C~240 o C, slurry phase, fixed bed 100 96 92 SPU W 80 100 FSCP 70 Transmission (%) 96 100 96 100 96 100 96 100 98 100 FM SE FM SD FM SC FM SB Conversion/Selectivity (%) 60 50 40 30 20 10 CO con. H 2 con. CO+H 2 con. CH 4 sel. C 5 + sel. C 2 -C 4 = sel. 96 FM SA 92-1 0-5 0 5 1 0 V e lo c ity (m m /s, re la tiv e to α -F e ) 0 1000 2000 3000 4000 5000 Time on stream (h)
CTL Development In China Process development and integration analysis - Simulation of Fischer-Tropsch loop for different catalyst systems - Hydrodynamics of slurry phase FT reactors and related - Pilot plant design & operation - Large scale slurry reactor design (4 m~ 8 m)
CTL Development In China Syncrude workup technology - New hydrogenation catalysts for hydrogenating FTS crudes - Cracking of FTS wax (new route) - Oligmerization of light olefins - Separation engineering
CTL Development In China Engineering fundamental - CFD calculation of three phase reactors - Quantum calculations on catalytic mechanism - Thermodymic data - Kinetics and reactor modeling
CTL Development In China Pilot plant 2001-2004 2004 - Two types catalysts have been tested - Slurry phase reaction engineering well proved: reactor & related d process - Product working-up proved - Design package accomplished for the demonstration plant (3500 b/d) Demonstration plant (Synfuels( China+industries) - Iron catalyst + slurry phase reactor (~ 5.5m) - Dry fed entrained flow gasification (2 GSP ) - Diesel 70% Naphtha 18% LPG 12% - Possible IGCC scheme is considered (If governmental support got) - Efficiency ~ 43% Commercial action (Industries+government( Industries+government) - Two trains 3.2 million ton/year Shenhua Ningmei - Sasol technology (tendency) - 2006-2007 2007 initializing
Preliminary results of the CTL diesel Index Co-Mo Mo-S Hy. Co-Mo Mo-S S Cr Ni Hy Density kg/l 0.7684 0.7782 0.7664 Viscosity mm2/s, 20 o C 3.172 3.957 3.276 Initi.. boiling point o C 154 138 150 Final boiling point o C 370 385 350 Flash point o C 64 66 74 Centane No. 74.1-80.1 66 >78-90 Total aromatics % 0.4 0.7 0 Poly aromatics % 0 0 0 Olefin % 0.5 0 0 Sulfur ppm <4 <5 <0.5 CFPP o C -3-34 -2 Oxidation stability - - <0.3 mg/100ml Acidity 5.39 - <0.2mg KOH /100ml
CTL Future Development High selective catalysts development - Narrowing to middle distillates - Working at high temperature (280 o C) but in slurry phase - Optimizing factors affecting efficiency Reactor & processes - Enhancing reaction heat recovery ( 15% energy of syngas ) - Pressure up to 45 bars to increase single train productivity - Process integration optimization (co-production evaluation) - Water saving and treatment technologies New technology for syncrude up-grading - S free catalyst for hydrogenation & cracking - Light fraction utilization - New route for fuel production - Chemicals from syncrudes
CTL Future Development: Co-production (2) (1) Steam MP 50 tons 4.911 ton ST coal Oxygen 681375 Nm 3 88.942 ton ST coal Coal 1000 tons 6500 kcal/kg 928.571 ST coal Electricity Steam (HP, MP,LP) (3) (7) (5) Electricity Steam (HP-MP) Electricity 30000 KWh 1200 tons 446412.827 KWh 9.9 ton ST coal 117.857 ton ST coal 147.316 ton ST coal (4) Syngas 1965125 Nm 3 Syngas 800.087 ton ST coal production (6) F-T synthesis Product upgrading Tail gas (9) (8) 66.565 ton ST coal (10) Steam (LP-MP) 1883 tons 184.925 ton ST coal Efficiency Oil 43-45% FTS thermal: 78-80%; CTL thermal: 63-65% Gasification thermal: 90% Oil products 342.341 tons 528.183 ton ST coal Energy points: Air separation & other unrecoverable: 15~25%. Recoverable: hot gas recovery 10%; tail gas 5.6%; reaction heat 15%.
Co-generation an introduction Electricity Efficiency (2) (1) Steam MP 50 tons 4.911 ton ST coal Oxygen 681375 Nm 3 88.942 ton ST coal Coal 1000 tons 6500 kcal/kg 928.571 ST coal Steam (HP, MP,LP) (3) (7) (5) Electricity Steam (HP-MP) 30000 KWh 1200 tons 9.9 ton ST coal 117.857 ton ST coal (4) Syngas 1965125 Nm 3 Syngas 800.087 ton ST coal production (6) F-T Product upgrading Electricity 446412.827 KWh 147.316 ton ST coal Steam (LP-MP) 1883 tons 184.925 ton ST coal (10) Oil_electricity 52-54% FTS thermal: 78-80%; CTL thermal: 63-65% Gasification thermal: 90% Oil products 342.341 tons 528.183 ton ST coal (8) (9) Tai gas 66.565 ton ST coal (11) Steam 1200 tons (HP-MP) 1883 tons (LP) (12) IGCC Electricity 2898036 MJ 99.1 ton ST coal Simple Co-production scheme can optimize the energy flows into valuable products
Summary CTL in whole has been well proved by large scale production and d is an important and practical option for China s s future liquid fuel supply. CTL route will bring us to a sustainable way in using our available able sources via syngas. CTL technology in China is approaching matured and will play important roles in the growing market. The super-clean diesel produced via CTL route will largely impose great benefits from environment improvement. Co-production solutions should be seriously considered.
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