CÔNG NGHỆ KHÍ HÓA THAN PGS.TS Văn Đình Sơn Thọ Bộ môn Công nghệ hữu – 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 Feedstock C, H, O, N, S, Cl, Ash Oxygen 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 Steam Water-Gas Shift CO + H2O H2 + CO2 Methanation CO + 3H2 CH4 + H2O Gasifier Gas Composition (Vol %) H2 CO CO2 H2O CH4 25 - 30 30 - 60 - 15 - 30 0-5 H2S 0.2 - COS - 0.1 N2 0.5 - Ar 0.2 - NH3 + HCN -0.3 Ash/Slag/PM Heating value 250 Btu/scf (1/4 of natural gas) What is Gasification Combustion Oxidant : Air ·Excess O2 Product : CO2, H2O Ash Pollutant : SOx, NOx Application ·Power plant (Steam turbine) Gasification Carbon Ash Sulfur Nitrogen Hydrogen Water Oxidant : O2 ·Excess fuel Product : CO, H2 Slag Pollutant : H2S, NH3 Application · Power plant (Combined cycle) · Chemical production : Methanol, Dimethyl Ether · Fuel production : Liquid Fuel : Substitute Natural Gas : Hydrogen Combustion & Gasification Products Complete combustion condition H2S CH4 Gasification Zone SO2 Combustion Zone 100% O2 90% H2O Mole fraction (%) 80% H2 70% 60% 50% C CO2 40% 30% CO 20% 10% 0% 0.1 0.7 1.3 1.9 O2/Coal (Moisture ash free basis) 2.5 3.1 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 H2 CO C H4 CO2 N2 70 Mole fraction (%) 60 50 40 30 20 10 t g g ry ry RW or in in r ry r ry rry d d K p g g u u u l l l s o e y g g s s s gl la la dr an tw u id o o e l l s s r n i t w w F g g d s t t g g id d in in d d si n ne v in i u e v v e e l o a F r in in in M ed Mo Mo nt ra in t t t E a tr En En En En as h 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 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 H2/CO : 0.5~0.7  CO + H2O→ CO2 + H2  Condition : 200~400℃ : Co-Mo based catalyst  CO + H2 → CH4 + H2O  Condition : 200~300℃ : Ni based catalyst Coal to Hydrogen  CO + H2O→ CO2 + H2  Condition : 200~400℃ : Co-Mo based catalyst Coal to Liquid Fuel Transportation Fuel FT synthesis Upgrading H2  3CO + 3H2 → CH3OCH3+CO2  Condition : 230~270℃ : Cu/ZnO + Al2O3 based catalyst  CO + 2H2 → CH3OH  Condition : 230~270℃ : Cu/ZnO based catalyst  nCO + (2n+1) H2 → H-(CH2)-H + H2O  Condition : 250~450℃ : Ni or Fe based catalyst Waste Gasification with Gas Engine Capacity 70 Ton/Day, 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 Feedstock/ syngas cleaning Fuel cell Power Efficiency 300 kW (Japan ) waste + low temperature wet scrubbing MCFC Fuel cell : 336 kW, Turbine : 22kW 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 Doosan Heavy Industries and Construction Construction Korea Western Power Operation & Optimization Korea Electric Power research Institute 30 Ton/Day pilot plant development Korea Electric Power research Institute Project Target : Thermal efficiency > 42% (HHV basis) : NOX < 30 ppm, SOX : < 15 ppm 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 [...]... Gasification been Used? How has Gasification been Used?  Methanol : CO+2H2 → CH3OH (for Methanol)  Combustion : CO + H2 + O2 → CO2 + H2O (for Fuel)  Dimethyl Ether : 3CO + 3H2 → CH3OCH3+CO2 (for Demethyl-Ether)  Water Gas Shift : CO + H2O → CO2 + H2 (for hydrogen and CO2 recovery)  Fischer-Tropsch : nCO + 2nH2 → (-CH2-)n + nH2O (for diesel and naphtha)  Methanation : CO + 3H2 → CH4 + H2O (for Substitute... CH4 + H2O (for Substitute Natural Gas) Syngas IGCC (Integrated Gasification Combined Cycle) IGFC (Integrated Gasification Fuel Cell) CO2 Coal Gasification CO, H2 H2 Shift reaction Methanation Diesel fuel Synthesis DME Methanol Substitute Natural Gas Cumulative Worldwide Gasification Capacity and Growth Gasification by Primary Feedstock Gasification by Product Schematic of a Generic IGCC Power Plant... 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 H2/CO : 0.5~0.7  CO + H2O→ CO2 + H2  Condition : 200~400℃ : Co-Mo based catalyst  CO + 3 H2 → CH4 + H2O  Condition ... engineering How has Gasification been Used? How has Gasification been Used?  Methanol : CO+2H2 → CH3OH (for Methanol)  Combustion : CO + H2 + O2 → CO2 + H2O (for Fuel)  Dimethyl Ether : 3CO... (Integrated Gasification Fuel Cell) CO2 Coal Gasification CO, H2 H2 Shift reaction Methanation Diesel fuel Synthesis DME Methanol Substitute Natural Gas Cumulative Worldwide Gasification Capacity and... 22kW 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