Electron beam flue gas treatment

Transcription

1 PlasTEP Summer School and Training Course Warsaw/Szczecin 2011 Andrzej Pawelec Electron beam flue gas treatment Szczecin, 2 August 2011

2 Some history Early phase (Japan, 1970s) Pilot plants phase (Japan, USA, Germany, Poland 1980s, 1990s) Industrial plants phase (China, Poland, late 90s) Recent attempts (China, Bulgaria, Middle East) Present operating plant: EBFGT at Pomorzany Power Station, Poland New facilities under construction

3 Technology basis

4 The idea of EBFGT Conventional process (wet-fgd + SCR) EBFGT

5 Pollutants removed by EB method The method has been designed for simultaneous removal of: SO 2 NO x Also there proceeds removal of other pollutants as: HCl, HF etc. Volatile Organic Hydrocarbons (VOC) Dioxins Mercury Others

6 Electron beam effect on gas Primary radiolysis products 4.43N 100 ev N 2* N( 2 D) N( 2 P) N( 4 S) N N e O 100 ev O 2* O( 1 D) + 2.8O( 3 P) O * O O e H 2 O 0.51H O( 3 P) OH H H 2 O H OH 100 ev H O e CO CO O( 3 P) CO CO C O e ev 1. J.C. Person, D.O. Ham: Radiat. Phys. Chem. 31 (1988) 1 2. H. Matzing: Model studies of flue gas treatment by electron beams, in: Application of isotopes and radiation in conservation of the environment, IAEA-SM-325/186, International Atomic Energy Agency, Vienna 1995, pp

7 Electron beam effect on gas Secondary reactions O( 1 D) + H2O 2OH * N H 2 O * H 3 O + + OH + N 2 O( 3 P) + O 2 + M O 3 + M e - + O 2 + M H 3 O O 2 O - 2 * + M HO 2 + H2 O As a result of these primary and secondary reactions OH *, HO 2 *, O * radicals,o 3 and other oxidizing species are formed, that can oxidize NO, SO 2 and Hg

8 SO x / NO x removal

9 SO 2 removal pathways radiothermal SO 2 + OH* + M HSO 3 + M HSO 3 + O 2 SO 3 + HO 2 * SO 3 + H 2 O H 2 SO 4 thermal H 2 SO 4 + 2NH 3 (NH 4 ) 2 SO 4 SO 2 + 2NH 3 (NH 3 ) 2 SO 2 (NH 3 ) 2 SO O 2, H 2 O 2 (NH 4 ) 2 SO 4 1. H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental Conservation TRCE-JAERI, Takasaki, September/October 1993, A.G. Chmielewski: Nukleonika 45(1) (2000) 31

10 NO x removal pathways NO oxidation NO 2 removal NO + O( 3 P) + M NO 2 + M O( 3 P) + O 2 + M O 3 + M NO + O 3 + M NO 2 + O 2 + M NO + HO 2 * + M NO 2 + OH* +M NO + OH* + M HNO 2 +M HNO 2 + OH* NO 2 + H 2 O NO 2 + OH* + M HNO 3 + M HNO 3 + NH 3 NH 4 NO 3 H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental Conservation TRCE-JAERI, Takasaki, September/October 1993,

11 NO x reduction in the presence of ammonia NO + N( 4 S) N 2 + O NO 2 + N( 4 S) N 2 O + O N( 2 D) + NH 3 NH* + NH 2 * NO + NH 2 * N 2 + H 2 O NO 2 + NH 2 * N 2 O + H 2 O NO + NH* N 2 + OH* NO 2 + NH* N 2 O + OH* H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental Conservation TRCE-JAERI, Takasaki, September/October 1993,

12 Simplified reaction mechanism OH HNO 2 OH O, OH OH NH 3 NO NO 2 HNO 3 NH 4 NO 3 OH O 2, OH H 2 O SO 2 HSO 3 SO 3 H 2 SO 4 NH 3 NH 3 (NH 3 ) 2 SO 2 O 2, H 2 O (NH 4 ) 2 SO 4

13 Reaction mechanisms and sequence of E-beam process

14 NO X removal factors NO x removal depends on such parameters as: Dose (1 kgy = 1kJ/kg) NO x inlet concentration Ammonia concentration (stoichiometry)

15 SO 2 removal factors Main process parameters influencing SO2 removal efficiency : Temperature Humidity Ammonia stoichiometry Dose Other parameters

16 Dependence of NO x and SO 2 removal efficiencies on dose

17 VOC/mercury removal

18 The structures of PAHs emitted from coal combustion naphtalene acenaphtene anthracene fluoranthene pyrene benzo(a)pyrene dibenzo(a,h) anthracene

19 PAHs emission at EB pilot plant at EPS Kawęczyn [μg/nm 3 ] PAH name naphtalene n.m acenaphtene C 12 H fluorene n.m phenentrene anthracene C 14 H fluoranthene C 16 H pyrene C 16 H benzo(a)anthracene chrysene benzo(e)pyrene C 20 H benzo(a)pyrene

20 Aromatic VOC decomposition mechanism Positive ions charge transfer reactions Radical neutral particles reactions OH radical reactions M + + RH = M + RH + OH + C 6 H 5 CH 3 = R1 (OH radical addition) C 6 H 5 CH 3 + OH = R2 + H 2 O ( H atom abstraction) Organic radicals reactions R. Atkinson: Chem. Rev. 85 (1985) 69 C 6 H 6 + OH = C 6 H 5 OH + H (H atom elimination) R + O 2 = RO 2 2 RO 2 = 2RO + O 2 RO 2 + NO = RO + NO 2 RO + O 2 = HO 2 + products ( aromatic-cho, -OH) RO aliphatic products

21 Removal efficiency of PAHs(%) PAHs removal efficiency without NH3 NH Acenaphthene Fluorene Phenanthrene fluoranthene Benzo(a)pyrene A. Ostapczuk, A.G. Chmielewski, Y. Sun: Electron beam flue gases treatment as an integrated method of SO 2, NOx and volatile organic compounds (VOC) control. Fifth Inetrnational Symposium and Exhibition on Environmental Contamination in Central and Eastern Europe September 2000, Prague, Czech Republic, p. 227

22 Mercury oxidation First step of removal process Hg o oxidation removal Hg2+ Mercury oxidation proceeds in reaction chamber EPS Pomorzany reaction chamber

23 According to: Does it work? Jo-Chun Kim, Ki-Hyun Kim, Al Armendariz and Mohamad Al-Sheikhly: Electron Beam Irradiation for Mercury Oxidation and Mercury Emissions Control, J. Envir. Engrg. Volume 136, Issue 5, pp (May 2010) At medium energy levels, approximately 98% of gaseous mercury vapor was readily oxidized. Expreriments were performed for following parameters: Hg concentration in gas about 16 µg/m 3 applied doses of E-beam kgy

24 Installation construction

25 The scheme of industrial installation A.G. Chmielewski, E. Iller et al.: Modern Power Systems, (May 2001)

26 History of investment : Feasibility Study 1994 Basic Engineering 1996, technical design Contract with z IAEA, Sumitomo 1996 Contract with Energobudowa (general contractor) 1998 Begin of construction 1 IV 1999 Start-up of the plant X 2000 Routine operation IV2003

27 Main operational data Flue gas flow rate Nm 3 /h Pollutants removal efficiency: 95 % SO 2 70 % NO x Total accelerators power: 1.04 MW Inlet flue gas parameters: temperature C SO 2 concentration mg/nm 3 NO x concentration mg/nm 3 Ammonia water consumption: kg/h By-product yield: kg/h

28 nom nom nom nom nom Main units of the plant AIR COMPRESSORS AMMONIA WATER UNLOADING AND STORAGE STATION M OPWP OPWP t = 250 C M PROCESS WATER M M M M t = 80 C p = 1.3 OWCW III t = 20 C Q= 2100Nm 3 p = 0.8 SPRAY COOLER CISTERN M P2 Z3 PP P1 M Z1 Z2 P3.1 M M P3.2 Ammonia storage and dosing Flue gas conditioning Control and monitoring AMMONIA WATER EVAPORATION COLUMN M Z4 P7.1 M M P7.2 M Reaction unit A1 B1 BY-PRODUCT ELECTROSTATIC PRECIPITATOR WSW M Byproduct collecting and storage M REACTION CHAMBER 1 DC DC SUPPLY NTA1 NTB1 SUPPLY + + M NTA2 NTB2 BY-PRODUCT STORAGE HOUSE AND GRANULATOR A2 B2 M REACTION CHAMBER 2

29 Control, monitoring and data management system E-beam flue gas treatment process Flue gas T 0, w 0, s 0, C 0SO2, C 0NOx water compressed air steam Cooling and humidification waste water T 1, w 1, s 1, C 0SO2, C 0NOx Ammonia storage ammonia Mixing T 1, w 1, s 1, a 0, C 0SO2, C 0NOx electric energy Reaction T 2, w 1, s 2, a 1, C 1SO2, C 1NOx electric energy Filtration T 2, w 1, s 3, a 1, C 1SO2, C 1NOx electric energy Transportation and storage of by-product electric energy Compression of purified flue gas electric energy Granulation or packaging T 2, w 1, s 3, a 1, C 1SO2, C 1NOx electric energy Loading and transportation

30 Cooling and humidification process 1. Cooling column with dry bottom 2. Cooling column with water recirculation

31 Cooling and humidification process 3. Cooling in ducts

32 EPS Pomorzany gas cooling tower

33 1. Liquid ammonia Ammonia supply system

34 2. Ammonia water Ammonia supply system

35 EPS Pomorzany ammonia water tank

36 EPS Pomorzany - accelerator

37 Accelerator vs. kinescope

38 Reaction unit power suppliers water cooling system windows cooling system X-radiation shielding ventilation system

39 EPS Pomorzany process vessel

40 Accelerator and reaction chamber Zasilanie katody Zasilacz DC Katoda Tuba przyspieszająca Elektrody przyspieszające Cewki odchylania Skaner Pompa próżniowa Powietrze chłodzące folie

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42 Dose deposition in reactor Arbitral units

43 Different reactor construction variants Variant 1 Variant 2 Variant 3 Variant 4

44 Velocity field Variant 1 Variant 4

45 The obtained results

46 Filtration Electrostatic precipitator Bag filter Wet gravel bed filter Venturi scrubber

47 EPS Pomorzany - ESP

48 By-product storage EPS Pomorzany byproduct storage building

49 Control and monitoring system Control room at EPS Pomorzany

50 Removal [%] The obtained results The dependence of SO 2 and NO x removal efficiency on dose SO NOx ,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5 9,0 9,5 10,0 Dose [kgy]

51 Removal [mg/nm 3 ] The obtained results The dependence of SO 2 removal on temperature Temperature [ C]

52 Removal [mg/nm 3 ] The obtained results The dependence of SO 2 and NO x removal on ammonia stoichiometry SO2 400 NOx ,00 40,00 50,00 60,00 70,00 80,00 90,00 100,00 Ammonia stoichiometry [%]

53 Removal [%] The obtained results The dependence of SO 2 removal efficiency on ammonia injection mode ,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,00 Ammonia mass fraction sprayed into cooling tower

54 The byproduct

55 NPK fertilizers made of by-product

56 The by-product by-product composition: (NH 4 ) 2 SO % NH 4 NO % NH 4 Cl 10-20% moisture 0,4-1% water insoluble parts 0,5-2% by-product yield: up to 300 kg/h

57 By-product heavy metals concentrations [ppm] Metal Pb Cd Hg As Pilot plant EPS Kawęczyn < Max. allowable (Polish standards)

58 Economy Emission control method Investment cost (USD/kW e ) Annual operational cost (USD/MW e ) Wet flue gas desulphurisation Selective catalytic reduction Wet FGD + SCR Electron beam FGT EBFGT (low NOx removal)

59 Strong points of technology Simultaneous removal of SO 2 and NO x, multipollution control system High removal efficiency High flexibility of installation Dry process Wasteless process, usable byproduct Simple facility construction Easy retrofitting Economical competitiveness

60 Potential applications of EBFGT technology Power plants (hard coal, oil, lignite combustion) - Asia, Middle East, developing countries Refineries (oil combustion) Waste incinerators (VOC, dioxins) Ore sintering plants, (high SO 2 content) Chemical processes (multipollutant emission control) Others

61 Final remarks 1. Electron Beam flue gas treatment process has been implemented in power industry. Due to the installed beam power (over 1 MW), plant constructed in EPS Pomorzany is the biggest radiation processing facility ever built. 2. High efficiency of pollutants removal has been achieved. 3. The technology is competitive to conventional ones from removal efficiency and economical points of views. 4. With the agricultural use of the by-product the method becomes waste free and environmental friendly. 5. There are possibilities for the process application for PAH emission control e.g. at municipal waste incineration plant.

62 Thank You for Your Attention