Công nghệ khí hóa than

CÔNG NGHỆ KHÍ HÓA THAN PGS.TS. Văn Đình Sơn Thọ Bộ môn Công nghệ hữu cơ – hóa dầu Khoa Công nghệ Hóa học Đại học Bách Khoa Hà Nội Email : thovds-petrochem@mail.hut.edu.vn thovds@yahoo.com Tel : 097.360.4372 Key Technology : Gasification Gasification with Oxygen C + 1/2 O2 CO Combustion with Oxygen C + O2 CO2 Gasification with Carbon Dioxide C + CO2 2CO Gasification with Steam C + H2O CO + H2 Gasification with Hydrogen C + 2H2 CH4 Water-Gas Shift CO + H2O H2 + CO2 Methanation CO + 3H2 CH4 + H2O Feedstock Oxygen Steam Gasifier Gas Composition (Vol %) H2 25 - 30 CO 30 - 60 CO2 5 - 15 H2O 2 - 30 CH4 0 - 5 H2S 0.2 - 1 COS 0 - 0.1 N2 0.5 - 4 Ar 0.2 - 1 NH3 + HCN 0 -0.3 Ash/Slag/PM Heating value 250 Btu/scf (1/4 of natural gas) C, H, O, N, S, Cl, Ash What is Gasification Carbon Ash Sulfur Nitrogen Hydrogen Water 1. Oxidant : Air ·Excess O2 2. Product : CO2, H2O Ash 3 Pollutant : SOx, NOx 4. Application ·Power plant (Steam turbine) Combustion Gasification 1. Oxidant : O2 ·Excess fuel 2. Product : CO, H2 Slag 3 Pollutant : H2S, NH3 4. Application · Power plant (Combined cycle) · Chemical production : Methanol, Dimethyl Ether · Fuel production : Liquid Fuel : Substitute Natural Gas : Hydrogen Combustion & Gasification Products 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 0.1 0.7 1.3 1.9 2.5 3.1 O2/Coal (Moisture ash free basis) M o le f ra c ti o n ( % ) CH4 H2S SO2 H2 C CO CO2 H2O O2 Gasification Zone Combustion Zone Complete combustion condition The Case of Coal  Low cost  Abundant (domestic) resources  Energy security  Clean coal is not an oxymoron  High and volatile crude oil, natural gas prices How has Gasification been Used?  A New but old technology  Making “town gas” from coal  First practical use of town gas in modern times was for street lighting in America and Europe  The first public street lighting with gas took place in Pall Mall, London on January 28, 1807  Baltimore, Maryland began the first commercial gas lighting of residences, streets, and businesses in 1816  Manufactured gas plants – prior to discovery and use of natural gas How has Gasification been Used?  Used during World War II to convert coal into transportation fuels (Fischer – Tropsch) Used extensively in the last 50+ years to convert coal and heavy oil into hydrogen – for the production of ammonia/urea fertilizer Chemical industry (1960’s) Refinery industry (1980’s) Global power industry (Today) Syngas Compositions 0 10 20 30 40 50 60 70 Mo v in g d r y a s h Mo v in g sla g g in g Mo v in g sla g g in g Fl u id K RW Fl u id t r a n sp o r t En tra in ed si ng le sl u r ry En tra in ed si ng le d ry En tra in ed tw o slu rry En tra in ed tw o slu rry En tra in ed tw o d r y H2 C O C H4 C O 2 N2 M o le f ra c ti o n ( % ) GE Energy (formerly Texaco process)  Coal-water slurry feed  Oxygen-blown  Refractory-lined gasifier  Good for bituminous coal, pet coke, or blends of pet coke with low-rank coals  GE Energy provides gasification technology  GE Power provides combined cycle plant  EPC alliance with Bechtel for guarantees on total IGCC plant ConocoPhillips (E-Gas process) Coal-water slurry feed Oxygen-blown Refractory-lined gasifier Good for a wide range of coals, from pet coke to PRB, and blends ConocoPhillips provides gasification technology and process guarantee Project specific EPC and combined cycle supplier alliances Shell Dry feed (coal is crushed and dried and then fed into gasifier) Oxygen-blown Waterwall in gasifier Good for wide variety of feedstocks, from pet coke to PRB Shell provides gasification technology Alliance with Black & Veatch and Uhde for engineering How has Gasification been Used? How has Gasification been Used?  Methanol : CO+2H2 → CH3OH (for Methanol)  Dimethyl Ether : 3CO + 3H2 → CH3OCH3+CO2 (for Demethyl-Ether)  Fischer-Tropsch : nCO + 2nH2 → (-CH2-)n + nH2O (for diesel and naphtha)  Combustion : CO + H2 + O2 → CO2 + H2O (for Fuel)  Water Gas Shift : CO + H2O → CO2 + H2 (for hydrogen and CO2 recovery)  Methanation : CO + 3H2 → CH4 + H2O (for Substitute Natural Gas) Coal Gasification CO, H2 Shift reaction Synthesis H2 Methanation Diesel fuel DME Methanol Syngas CO2 Substitute Natural Gas IGCC (Integrated Gasification Combined Cycle) IGFC (Integrated Gasification Fuel Cell) Cumulative Worldwide Gasification Capacity and Growth Gasification by Primary Feedstock Gasification by Product Schematic of a Generic IGCC Power Plant Coal Oxygen Water Gasifier Slag Particulate Removal Other Chemical Products Activated Charcoal Bed Sulfur Removal Sulfur Acid Pure Sulfur Solids & Co-Products Air Generator Electricity Compressor Combustion Chamber Heat Recovery Steam Generator Steam Water Exhaust Stack Heated Water Cooling Water Condenser Generator Electricity Electricity Synthesis gas (CO, H2) Moisture Combustibles Ash Operating IGCC Projects Conventional Coal Power Plant IGCC Efficiency Efficiency ↑ CO2/kwh ↓ Pollutants Emission Traditional PC Retrofit Older PC With Scrubber & SCR (using low- S Coal) Advanced PC/SCPC/CFB IGCC with MDEA Absorber IGCC with Rectisol & SCR NGCC With SCR NOx SO2 Particulates Type of Power Plant lb /M M B T U Where has IGCC Been Used? Cool Water IGCC Demonstration Project Daggett, CA  First demonstration of IGCC in the U.S.  1984-89  110 MW size  Texaco gasifier and GE combined cycle  1,150 TPD Utah coal  Co-funded by Southern California Edison, Texaco, GE & EPRI  Considerable information provided for development of full-scale plant Wabash River Generating Station Start-up July 1995 ConocoPhillips (formerly Destec) E-Gas gasifier 2,500 TPD coal and/or pet coke DOE Clean Coal Technology Program : repowering of existing unit Power generation  Combustion turbine: 192 MW  Steam turbine: 104 MW  Internal load: 34 MW  Net output: 262 MW Wabash River Generating Station : process Wabash River Clean Coal Project A Case Study for Cleaner Air Polk Power Station Start-up July 1996 GE Energy (formerly Texaco) gasifier  2,500 TPD coal/pet coke blend  DOE Clean Coal Technology Program : new plant  Power generation  Combustion turbine: 192 MW  Steam turbine: 120 MW  Internal load: 60 MW  Net output: 252 MW Polk Power Station : process SASOL Located in South Africa Started up in 1955 Lurgi gasifiers (97) Fischer-Tropsch process converts syngas to liquid fuels Now processes 90,000 tons coal/day into 160,000 barrels/day of transportation fuels Dakota Gasification Company Great Plains Synfuels Plant  Beulah, North Dakota  Part of Basin Electric Power Cooperative  Started up in 1984  Converts 16,000 tons/day of North Dakota lignite to:  Synthetic natural gas  Fertilizers  Chemicals  CO2: pressurized and piped 205 miles to Saskatchewan and sold for use in enhanced oil recovery by EnCana and Apache Canada Eastman Chemical - Kingsport, Tennessee  “Coal-to-Chemicals” Facility  Started up in 1983  Originally part of Eastman Kodak  Texaco gasifiers  Gasifies 1,200 TPD Central Appalachian medium sulfur coal  Sulfur compounds and ash are removed from the syngas  Syngas is used to make methanol, acetic acid, acetic anhydride, methyl acetate Coal to Substitute Natural Gas  CO + 3 H2 → CH4 + H2O  Condition : 200~300℃ : Ni based catalyst  CO + H2O→ CO2 + H2  Condition : 200~400℃ : Co-Mo based catalyst H2/CO : 0.5~0.7 Coal to Hydrogen  CO + H2O→ CO2 + H2  Condition : 200~400℃ : Co-Mo based catalyst Coal to Liquid Fuel Upgrading FT synthesis Transportation Fuel H2  nCO + (2n+1) H2 → H-(CH2)-H + H2O  Condition : 250~450℃ : Ni or Fe based catalyst  CO + 2H2 → CH3OH  Condition : 230~270℃ : Cu/ZnO based catalyst  3CO + 3H2 → CH3OCH3+CO2  Condition : 230~270℃ : Cu/ZnO + Al2O3 based catalyst Waste Gasification with Gas Engine Capacity 70 Ton/Day, 2 trains (Japan, Mutsu) Waste composition Combustibles : 45.2 % Ash : 7.0% Moisture : 47.8% Gas engine efficiency 35~36% Net Efficiency 19% Emission Dioxin : 0.0023 ng-TEQ/Nm3 Particulates : < 2mg/Nm3 SOx : 11 ppm HCl : 0.4 ppm NOx : 10ppm Waste Gasification with Fuel Cell Fuel cell capacity 300 kW (Japan ) Feedstock/ syngas cleaning waste + low temperature wet scrubbing Fuel cell MCFC Power Fuel cell : 336 kW, Turbine : 22kW Efficiency 54 % Waste Gasification with Methanol Production Gasifier British Gas Lurgi slagging gasifier (Germany, Schwarze Pumpe ) Capacity 30 Ton/h Product Methanol : 120,000Ton/h Power : 35MW The Challenges  High capital cost  Reliability concerns  Financing issues  Economies of scale  Market risks Co-fed, Co-production Source : Driving Clean Coal Forward, Peter de Wit, Shell Gas & Power 300 MW IGCC Demonstration Plant in KOREA  Project schedule 2006. 12 2007 2008 2009 2010 2011 2012 2013 2014.11 Design Construction Operation & Optimization 30 Ton/Day pilot plant development Project Target : Thermal efficiency > 42% (HHV basis) : NOX < 30 ppm, SOX : < 15 ppm Doosan Heavy Industries and Construction Korea Western Power Korea Electric Power research Institute Korea Electric Power research Institute Conclusions  Global demand for Gasification is increasing  Chemicals/SNG (Substitute Natural Gas)  Transportation liquids  IGCC (Integrated Gasification Combined Cycle)  Gasification plant developers are facing more challenges  Global materials and labor cost increases  Carbon capture and storage Thank you for your attention