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Theme 4. Industrial environmental issues Flue gas purification processes. Schedule for Theme 4. Monday 25/11, 08.15 -- 10.00 ( DC:Lhö ): Lecture on “Flue Gas Cleaning” (Hans) Tuesday 26/11, 10.15 -- 12.00 (Hall C): Lecture on “Gas-Liquid Reactions” (Hans)
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Theme 4 Industrial environmental issues Flue gas purification processes
Schedule for Theme 4 • Monday 25/11, 08.15 -- 10.00 (DC:Lhö): • Lecture on “Flue Gas Cleaning” (Hans) • Tuesday 26/11, 10.15 -- 12.00 (Hall C): • Lecture on “Gas-Liquid Reactions” (Hans) • Wednesday 27/11, 08.15 -- 10.00 (Hall C): • Lecture on “Absorber design” (Hans) • Wednesday 27/11, 13.15 -- 16.00 (Seminar room L): • Exercises demonstrated on whiteboard(Hans) • Note: Disregard Tasks 4.1 and 4.2 • Presentation of compulsory task 4 (Anders) • Thursday 28/11, 10.15 -- 12.00 (Seminar room L): • Try yourself, examination 2008 + exercise 4.5 (Hans) • Friday 30/11, 13.15 -- 15.00 (Seminar room M): • Work with compulsory task (Anders)
Hand-outs for Theme 4 • PPT material on Flue gas cleaning • Absorption with chemical reaction • PPT material • Gas-Liquid Reactions (mini-compendium) • Absorber Design (mini-compendium) • Solutions to exercises • Text description of compulsory task 4
Flue gas cleaning Removal of gaseous and particulate polutants from flue gases generated by stationary combustion plants • Coal or oil fired power plants • Gas turbines • Soda boilers • Biomass fired heating plants • Waste fired combustion plants Flue gas cleaning is only one of generic technologies for emissions control
Proclamation in 1276 ”Whosoever shall be found guilty of burning coal, shall suffer the loss of his head” King Edward I
Generic problems • Combustion plants are not classified as traditional process industry • Flue gas cleaning plants are based on technology emerged from the process industry • Utility companies require simple technology, the process industry uses complex technology but cheap feed-stocks • The utility industry requires 25 years of capital depreciation, the process industry 10 years at the most
Flue gas content • Inert components • Nitrogen, water and oxygen • Toxic components • Fly ash, trace metals, hydrocarbons, dioxines and POM • Acidic species • Sulfur oxides (SO2, SO3), nitrogen oxides (NO, NO2) and halogen acids (HCl, HF, HBr) • Greenhouse gases • Carbon dioxide (CO2) and laughing gas (N2O)
Feed-stocks and products • Principle: Pollutant + Reagent Product • Problem • Cost of reagent • Secondary pollutants • Alternatives: • Reagent • Throwaway • Useful by-product • Becomes inert • Recycled • No reagent • Pollutant • Throwaway • Useful by-product • Becomes inert
Residual products • Waste-water • Solid waste • Sludge • By-products Residual products might contain • Ash • Sulfur species • Nitrogen species • Chlorides • Heavy metals • Traces of organics
Removal of particulates PRINCIPAL SOURCES OF PARTICULATES • Ashes from the fuel Minerals, un-combusted, trace elements • Bottom ash • Fly ash • Reagents and products Calcium compounds, etc. • Generic removal principles • Cyclones • Wet scrubbers/Absorption towers • Electrostatic precipitators • Baghouse filters
Trace metals Content of trace metals in waste product from desulfurization process based on spray drying. Major constituents are calcium sulfite and fly ash.
Flue-gas desulfurization • The Wellman-Lord Process • Sulfuric acid, elemental sulfur or sulfur dioxide • The Walter Process • Ammonium sulfate • The activated coke • Sulfuric acid • Spray-Dry Scrubbing (Wet-Dry Scrubbing) • Dry calcium sulfite • Dry injection • Mixed product containing calcium sulfite • Wet FGD • Gypsum or sludge of calcium sulfite
Spray-Dry Scubbing • Spray-drying of a lime slurry Ca(OH)2 + SO2F CaSO3 + H2O
Wet Flue Gas desulfurization Process Typical Process schematic
Wet Flue-Gas Desulfurization (WFGD) • The process is based on a slurry of slaked lime • Ca(OH)2 + SO2 CaSO3 + H2O • or • Limestone • CaCO3 + SO2 CaSO3 + CO2 • Oxidation may occur • CaSO3 + ½ O2 CaSO4 • Limestone is a mineral that has to be ground, lime is obtained by calcination (heat requirement) of limestone and slaked by the use of water • CaCO3CaO + CO2 • CaO + H2O Ca(OH)2 Presently, the cost determines how reagent is selected!!!!
Schematic reaction mechanism • Absorption step • SO2 + H2O HSO3- + H+ • H+ + SO32- HSO3- • Limestone dissolution • CaCO3 + 2H+ Ca2+ + H2O + CO2 • Oxidation • SO32- + ½ O2 SO42- • Precipitation • Ca2+ + SO32- CaSO3 • Ca2+ + SO42- CaSO4
Important design considerations • Oxidation or not? • Natural oxidation • Forced oxidation • Inhibited oxidation • Important parameters • Removal efficiency • Scrubber design • Limestone grinding • Process chemistry and pH • Additives • Scaling (incrust formation) • Scrubber design • Process chemistry and pH • Degree of oxidation • Corrosion • pH • Materials of construction • Chloride content • Cost • Scrubber size • Energy consumption
Additives and auxillaries • Additives • Adipic acid • Magnesium ion • Thiosulfate or elemental sulfur • Sodium salts • Auxillary equipment • Pre-quencher • Demister/Mist eliminator • Reheater • Grinder • Sludge treater • Thickener • Filter system
Flue Gas Denitrification • Nitogen oxides coinsist of 95% NO and 5% NO2 from combustion processes. Fluidized beds might generate some N2O • The generic problem: NO has a low solubility and is not very reactive. • Wet methods • Potasium permanganate • Sodium chlorite • Iron- EDTA • Oxidation-Absorption • Pre-oxidation of NO to NO2 using ozone or chlorine dioxid • Dry processes • The cupper oxide process • Alkalized alumina • Electron beam • Selective non-catalytic oxidation • Selective catalytic oxidation
Carbon capture • Pressure swing adsorption • Scrubbing with water • Chilled ammonia absorption • Absorption in aqueous amine systems • Leading system: MDEA and Piperazine • CO2 + A*H2O HCO3- + AH+