INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY Warszawa, Poland Electron beam flue gas treatment and effects on volatile organic compounds Andrzej G. Chmielewski Workshop Volatile organic compounds and aerosol removal by means of plasma-based and plasma-assisted technologies Greifswald, 10th September 2010
EB FLUE GAS TREATMENT TECHNOLOGY 1989 LABORATORY INSTALLATION INCT, WARSAW 400 [Nm3/h] 1992 EB TECHNOLOGY IN POLAND FOR SO 2 AND NO X REMOVAL PILOT PLANT EPS Kawęczyn, n. WARSAW 20 000 [Nm3/h] 2002 DEMONSTRATION INDUSTRIAL PLANT EPS Pomorzany in SZCZECIN 270 000 [Nm3/h]
Pilot plant in EPS Kaweczyn
EPS Pomorzany, Szczecin
Plasma inside the reactor in Kaweczyn
The radiolytic yield of primary reactive species 4.43N 2 0.29N 2* + 0.885N( 2 D) + 0.295N( 2 P) + 1.87N( 4 S) + 100 ev 2.27N 2+ + 0.69N + + 2.96e - 5.377O 100 ev 2 0.077O 2* + 2.25O( 1 D) + 2.8O( 3 P) + 0.18O * + 2.07O 2+ + 1.23O + + 3.3e - 7.33H 2 O 100 ev 0.51H 2 + 0.46O( 3 P) + 4.25OH + 4.15H + 1.99 H 2 O + + 0.01H 2+ + 0.57OH + + 0.67H + + 0.06O + + 3.3 e - 7.54CO 100 ev 2 4.72CO + 5.16O( 3 P) + 2.24CO 2+ + 0.51CO + + 0.07C + + 0.21O + + 3.03 e - [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. 115-124
THE POSSIBILITY TO APPLY EB TECHNOLOGY FOR VOCS TREATMENT HAS BEEN INVESTIGATED SINCE LATE 1980S. HYDROCARBONS CxHy ALIPHATIC AROMATIC CHLORINATED HYDROCARBONS CxHyClz ALIPHATIC AROMATIC Pentane CH 3 (CH 2 ) 3 CH 3 Hexane CH 3 (CH 2 ) 4 CH 3 Heptane CH 3 (CH 2 ) 5 CH 3 Benzene C6H6 Toluene C6H5-CH3 Xylene C6H4 (CH3)2 Styrene C6H5-CHCH2 Methylene chloride CH2Cl2 Chloroethylenes: mono-c2h3cl, di-, tri- ClCH:CCl2, Chlorobenzene C6H5Cl tetra- Cl 2 C:CCl 2 ALICYCLIC POLYCYCLIC POLYCYCLIC Cycloxehane CH 2 (CH 2 ) 4 CH 2 Naphthalene C10H8 Chloronaphthalene Cyclohexene CH:CH(CH 2 ) 3 CH 2 Acenaphthene C10H8 Fluoranthene C16H10 OTHER: Aceton, Methanol CH3OH, Buthylacetate, Diphenylether (C 6 H 5 ) 2 O, Phenol C6H5OH
LABORATORY INSTALLATION FOR EB TREATMENT OF FLUE GAS FROM CRUDE OIL COMBUSTION BF REACTION CHAMBER ACTIVATED CARBON BED INLET OUTLET 2 TRAPPING SYSTEMS CONSISTING OF E.G.: CONDENSERS, GAS BULBES, ADSORBENTS, ABSORBERS GM GM FLOW: 5 [m3/h]
LABORATORY EXPERIMENTS ON MODEL MIXTURES LABORATORY FLOW SET-UP (JAEA) Selected compounds CH 2 CH 2 Naphthalene NL Acenaphthene AC Fluoranthene FA Ci = 10 ppmv THE EXPERIMENT LET ESTIMATE: - removal efficiency vs. dose (individual PAHs decomposition rate) - decomposition products (process mechanism)
LABORATORY EXPERIMENTS ON MODEL MIXTURES 1,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0 Co/Ci NL AC 0 1 2 3 4 5 6 7 8 Dose [kgy] Co/Ci ratio vs. dose applied for naphthalene NL and acenaphthene AC (Ci = 10 ppm) BASE GAS COMPOSITION: 6% H 2 O + 10% O 2 + 84% N 2
LABORATORY EXPERIMENTS HOW EB INFLUENCED FLUE GAS COMPOSITION PAHs OH C 10 H 8 C 11 H 10 O C 6 H 6 O C 12 H 8 C 12 H 10 C 9 H 10 O AHs O OH O C 7 H 6 O 2 C 8 H 10 O C 7 H C 8 8 H 10 C 10 H 14 C 8 H 8... CONCENTRATION DECREASE OBSERVED CONCENTRATION INCREASE OBSERVED
LITERATURE BASED LABORATORY EXPERIMENTS OH H OH NO [1] [2] [3] O 2 O 2 NO 2 NO 2 H O H OH OH + HO 2 H NO 2 H OH OH CHOH CH=CHCHO O 2 NO NO 2 OH NO 2 + H 2 O O 2 O HO 2 + CHO CH=CHCHO O NL TRANSFORMATION MECHANISM ANALOGICAL TO ITS ATMOSPHERIC CHEMISTRY
LABORATORY EXPERIMENTS ON MODEL GAS MIXTURES [1] k 1 O2+, O+ C 10 H + 8 [2] k 0,45 3 O 0,55 [2a] [2b] C 10 H 8 O + C 9 H 8 + + CO 0,4 [3] O 0,2 [3a] 0,3 [3b] [3c] C 9 H 8 O + + CO C 9 H 7 O + C 10 H 8 O + 2 [5] O [7] O C 9 H 7 O + 2 + HCO 0,2 [5a] 0,4 [5b] 0,4 [5c] [4] O 0,75 0,05 0,2 [4a] [4b] [4c] C 8 H + 8 + CO C 9 H 7 O + + H C 9 H 8 O + O [6] [6a] [6b] C 7 H + C 7 H + 7 + HCO 8 + CO C 8 H 8 O + + CO C 8 H 7 O 2 + + HCO C 7 H 5 O + + H 3 C 2 O Snow, T. P., Le Page, V., Keheyan, Y., Bierbaum, V.M., (1998) The interstellar chemistry of PAH cations, Nature. Midey, A. J., Williams, S., Arnold, S. T., Dotan, I., Morris, R. A., Viggiano, A. A., (2000) Rate constants and branching ratios for the reactions of various positive ions with naphthalene from 300 to 1400 K, Int. J. Mass Spectr., vol. 195/196.
EB AS MULTICOMPONENT PURIFICATION TECHNOLOGY FOR FOSSIL FUEL COMBUSTION SO2, NOx AND VOCs REMOVAL. THE KEY ORGANIC COMPOUNDS INVESTIGATED BY INCT POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) Naphtalene Acenaphtene Antracene Fluoranthene C10H8 C12H10 C14H10 C16H10 Pyrene C16H10 Benzo(a)pyrene C20H12 Dibenzo(a,h) anthracene C22H14
POLYCYCLIC AROMATIC HYDROCARBONS WHY? PAHs EMISSION LEGISLATION AND REGULATIONS: Due to PAHs carcinogenicity*, they are subject to emission controls specified in annex III to the 1998 Protocol on Persistent Organic Pollutants (UNECE POPs). Some European countries applies own PAHs emission limits: benzo[a]pyrene is controlled in many of them Sweden - fluoranthene emission limited up to [2ng/m 3 ] Switzerland naphthalene up to 100 [mg/m 3 ]. IN POLAND OVER 90% OF ENERGY IS GENERATED BY COAL COMBUSTION PROCESS. * The epidemiological studies suggest an association between lung cancer and exposure to PAHs. EB.AIR/WG.1/2002/14, UNECE (http://www.unece.org/env/documents/2002/eb/wg1/eb.air.wg.1.2002.14.e.pdf
EB PILOT PLANT AT COAL-FIRED POWER STATION KAWĘCZYN ESP 200 000 Nm3/h 20 000 Nm3/h H2O Inlet sampling point Accelerators NH3 Irradiation chamber EP Outlet sampling point NH4NO3 & (NH4)2 SO4
ANALYTICAL PROCEDURE: GM COMBUSTION GASES ICE XAD2 - resin Activated carbon PRE-CONCENTRATION SORBENTS (XAD-2, ACTIVATED CARBON) EXTRACTION BY ETHERE SAMPLING SYSTEM Usually at least 200 dm3 minimum should be pumped through with the flow rate 100 dm3/h ETHERE EXTRACT EXTRACTION BY TOLUENE TOLUENE EXTRACT SEPARATION ORGANIC POLLUTANTS GAS CHROMATOGRAPHY, GC/FID POLYAROMATIC HYDROCARBONS (PAHs)
acenaphthylene acenaphthene fluorene phenanthrene anthracene fluoranthene pyrene benzo[a]anthracene chrysene benzo[bk]fluoranthene benzo[a]pyrene dibenzo[ah]anthracene benzo[ghi]perylene RESULTS PAH Ci Co naphthalene 0,000 0,000 acenaphthylene 0,000 0,184 2,000 Concentration [ g/nm³] acenaphthene 0,000 0,011 1,500 fluorene 0,000 0,073 phenanthrene 0,046 0,636 1,000 anthracene 0,043 0,509 fluoranthene 0,374 1,433 0,500 pyrene 0,049 0,071 benzo[a]anthracene 2,305 1,253 0,000 chrysene 0,856 0,433 benzo[bk]fluoranthene 0,102 0,244 benzo[a]pyrene 0,210 0,073 dibenzo[ah]anthracene 1,203 0,118 benzo[ghi]perylene 0,938 0,133 TOTAL 6,534 5,269 inlet outlet
RESULTS [ g/nm³] 2 4 Fused benzene rings 3 5-1- 0,000 0,500 1,000 1,500 2,000 NL ACL ACL FL PHE AN FA PY BaA CHR BbkFA BeP BaP P DBahA BghiP inlet outlet 0,000 1,000 2,000 3,000 4,000 5,000 6,000 NL ACL ACL FL PHE AN FA PY BaA CHR BbkFA BeP BaP P DBahA BghiP [ g/nm³] -3-0,000 0,500 1,000 1,500 2,000 2,500 3,000 NL ACL ACL FL PHE AN FA PY BaA CHR BbkFA BeP BaP P DBahA BghiP -4-0,000 0,500 1,000 1,500 2,000 NL ACL ACL FL PHE AN FA PY BaA CHR BbkFA BeP BaP P DBahA BghiP
HOW EB INFLUENCES OVERALL TOXICITY OF FLUE GAS? - SO2 and NOx removed - PAHs in some cases incresed concentration observed after irradiation COMPARISION OF OVERALL TOXICITY OF FLUE GAS (BASED ON PAHs) AT INLET AND OUTLET OF IRRADIATION VESSEL TEQ = c i TEF i TEQ - overall toxicity c i - PAH concentration [ g/nm 3 ] TEF i - PAH Toxic Equivalency Factor
TOXIC EQUIVALENCY FACTOR TEF* PAH TOXICITY EQUIVALENT FACTOR EPA Chu&Chen Nisbet&LaGoy naphtalene C 10 H 8 0,001 acenaphthylene C 12 H 8 0,000 acenaphthene C 12 H 10 0,000 0,001 fluorene C 13 H 10 0,000 0,001 phenanthrene C 14 H 10 0,001 anthracene C 14 H 10 0,000 0,010 fluoranthene C 16 H 10 0,000 0,001 pyrene C 16 H 10 0,000 0,001 benzo(a)anthracene C 18 H 12 0,100 0,013 0,100 chrysene C 18 H 12 1,000 0,001 0,010 benzo(bk)fluoranthene C 20 H 12 0,100 0,080 0,100 benzo(a)pyrene C 20 H 12 1,000 1,000 1,000 benzo(e)pyrene C 20 H 12 perylene C 20 H 12 dibenzo(ah)anthracene C 22 H 14 1,0909 0,690 5,000 benzo(ghi)perylene C 22 H 12 0,000 0,010 * TEF of individual PAHs have been determine in different bioassays on the base of their carcinogenic potencies
OVERALL TOXICITY - RESULTS OVERALL TOXICITY RESULTS BASED ON TEF EPA TEQ 6 5 4 3 SERIE 3 Inlet outlet inlet outlet PAH TEF EPA [ g/nm 3 c i c o [ g/nm 3 ] c i TEF C o TEF acenaphthene 0,0000 0,000 0,011 0,000 0,000 fluorene 0,0000 0,000 0,073 0,000 0,000 anthracene 0,0000 0,043 0,509 0,000 0,000 fluoranthene 0,0000 0,374 1,433 0,000 0,000 pyrene 0,0000 0,049 0,071 0,000 0,000 benzo[a]anthracene 0,1000 2,305 1,253 0,230 0,125 chrysene 1,0000 0,856 0,433 0,856 0,433 benzo[bk]fluoranthene 0,1000 0,102 0,244 0,010 0,024 benzo[a]pyrene 1,0000 0,210 0,073 0,210 0,073 dibenzo[ah]anthracene 1,0909 1,203 0,118 1,313 0,128 benzo[ghi]perylene 0,0000 0,938 0,133 0,000 0,000 TOTAL c 0 6,534 c k 5,269 TEQ 0 2,619 TEQ k 0,785 2 1 0 1 2 3 4 serie TEQinlet TEQoutlet
(TEQi-TEQo)/TEQi RELATIVE DECRESE OF OVERALL TOXICITY TEQi TEQo - inlet flue gas overall toxicity - outlet flue gas overall toxicity E TEQ = (TEQi-TEQo)/TEQi 1,00 0,90 0,80 0,70 0,60 0,50 0,40 0,30 0,20 0,10 0,00 1 2 3 4 serie EPA Chu&Chen Nisbet&LaGoy
12:48 13:54 14:08 16:10 17:58 18:24 18:40 19:58 20:20 21:45 22:36 00:10 01:40 Flow rate [Nm3/h] Concentration [mg/nm3] PAHs ADSORPTION ON THE BY-PRODUCT SURFACE MEASUREMENT OF AMOUNT OF PAHs ADSORBED : 1. Collected by-product samples analysed PAHs concentration determined [ gpah /kg BP] 2. By-product concentration in flue gas measured continously average concentration for PAHs sampling calculated [mg/nm³] PAH PAH in by product [ g/kg] Serie 1 Serie 2 Serie 3 Naphthalene n.m. n.m. n.m. Acenaphthylene n.m. 2,276 n.m. Acenaphthene n.m. n.m. n.m. Fluorene n.m. n.m. n.m. Fenanthrene 0,684 0,896 n.m. Anthracene 0,094 0,125 0,095 Fluoranthene 3,329 n.m. 1,035 Pyrene n.m. n.m. n.m. Benz(a)anthracene n.m. 2,178 n.m. Chrysene n.m. 1,114 0,821 Benzo(b+k)fluoranthene n.m. 0,484 0,084 Benzo(e)pyrene 1,925 0,458 1,092 Benzo(a)pyrene 2,029 1,177 0,711 Perylene 0,677 0,792 0,534 Dibenzo(a,h)anthracene n.m. 1,210 0,092 Benzo(ghi)perylene n.m. 0,400 1,678 8,738 11,110 6,142 10 500 9 500 8 500 7 500 6 500 5 500 Flue gas flow rate and by-product concentration during PAHs sampling in EB experiment (Serie 2) 1500 1400 1300 1200 1100 1000 900 800 700 600 time
PAHs ADSORBED ON THE BY-PRODUCT SURFACE Serie Average by-product concentration c p [mg/nm 3 ] PAHs concentration in by-product M PAH [ g/kgbp] PAHs removed from flue gas [ g/ Nm 3 ] PAHs adsorbed In by-product [ g/ Nm 3 ] 1 500,51 8,738 1,255 0,0044 2 1119,27 11,110 5,388 0,0125 3 295,23 6,142 1,402 0,002 PAHs ADSORPTION PLAYS MINOR ROLE IN THE WHOLE REMOVAL PROCESS (LESS THAN 1% REMOVED)
Reason for Cl-VOCs treatment Principle for destruction Cl-VOCs using EB technology examples for Cl-VOCs treatment in lab scale Dioxins removal
Reason for Cl-VOCs treatment most Cl-VOCs have adverse effect on human s healthy, they can cause ozone depletion in stratosphere and ozone formation in troposphere, recent studies show that some Cl-VOCs (aromatic compounds) are suspected as precusor for dioxin s formation PhCl + OH = PhOH + Cl (1) PhOH + PhCl = HCl + PhOPh (2) Ph: benzene ring
Principle for Cl-VOCs removal using EB technology Active species formed from radiolysis of base gas react with Cl-VOCs (reactions of 5 big groups) and cause Cl- VOCs destruction
Main Reactions 1. positive ions-neutral reactions 2. negative ions-neutral reactions 3. ionic recombination reactions 4. radical-radical reactions 5. radical-neutral reactions
Rate constants of OH radicals with different dioxins (298K, 1atm) Compound Rate constant ( 10-12 cm 3.s - 1,4-dioxane 1 ) 11 dibenzo-p-dioxin 11-18 1-chlorodibenzo-p-dioxin 3.1-6.3 2,7-dichlorodibenzo-pdioxin 3.4-5.8 1,2,3,4-tetrachlorodibenzop-dioxin 0.47-1.6 Dibenzofuran 2.9-4.2 2,8-dichlorodibenzofuran 1.8-2.5
Set-up for 1,4-DCB irradiation with EB
Example of lab scale experiment Flow meter Mixer Ventilation Pump Air Air GC Reactor 1,4-DCB Setup for preparation of model gas containing 1,4-DCB
Removal efficiency(%) 1,1-, cis- & trans-dce decomposition vs. dose under EB-irradiation (C0: 900~1000ppm) 100 80 60 1,1-DCE trans-dce Cis-DCE 40 20 0 0 5 10 15 20 25 30 35 40 Dose(kGy)
1,1-DCE(molecules.cm-3) Main species contribute to 903.8ppm 1,1-DCE decomposition under EB-irradiation 1.00E+18 1.00E+16 1.00E+14 1.00E+12 1.00E+10 1.00E+08 1.00E+06 1.00E+04 1.00E+02 Cl e O2- OH O2+ H2O3+ O N2+ 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00 1.00E+02 Dose(kGy)
Mechanism of 1,1-DCE decomposition under EB-irradiation CH 2 CCl 2 R1 Cl R48b H2 O,CH 2 CCl 2 + CH 2 (OH)CCl 2 R29 CH 2 (OH)CCl2(O 2 ) CH 2 ClCCl 2 R9 CH 2 ClCCl 2 (O 2 ) R10,R11 HCHO,CCl 2 R49 OCl,COCl CH 2 CCl, Cl- COCl, HCHO M+ Cl CH 2 CCl 2+,CH 2 CCl - 2 CH 2 CCl 2, R30,R31 R12a CH 2 ClCCl2(O) R12b R18/R19 R34,R35,R36 CH 2 (OH)CCl 2 (O) CH 2 ClCOCl,Cl COCl 2, CH 2 Cl CO, Cl HCO, H 2 O / HCl / H 2 O 2 R32 R13,R14 R39 R22 R37 CH 2 OH, COCl 2 R33 HO 2, HCHO R58 H 2 O 2 H 2 O/HCl, CHClCOCl R15 COClCHCl(O 2 ) R16 COClCHCl(O) CO, Cl 2 - R54~R57 Cl 2 CH 2 ClO 2 R23,R24 CH 2 ClO R25 HCOCl, HO 2 CO, HO 2 H, CO 2 R38 R17 COCl, HCOCl
Concn. (ppm) 100 80 1,4-DCB/air mixture vs. dose in EB-irradiation 32 ppm 52.7ppm 68.5 ppm 90 ppm 60 40 20 0 0 10 20 30 40 50 60 Dose (kgy)
Removal efficiency (%) 100 80 1,4-DCB decomposition in different gas mixtures N2 air 1%NO-99%N2 60 40 20 0 0 10 20 30 40 50 60 Dose(kGy)
molecules/cm3 Kinetic reactions along time scale contributing to 1,4-DCB degradation in air mixture under EB irradiation(1,4-dcb = 90.0 ppm, H2O = 170.0 ppm) 1.E+15 1.E+14 1.E+13 1.E+12 1.E+11 1.E+10 OH M+ e M- Cl NO3 1.E+09 1.E+08 1.00E-08 1.00E-06 1.00E-04 1.00E-02 1.00E+00 1.00E+02 Time(s)
1,4-DCB/air decomposition under EB-irradiation Total irradiation time (s.) Dose (kgy) Main Species 10-8 ~ 10-4 4.8E-9 ~ 4.8E-5 e, M -, M + 10-3 ~ 10-2 4.8E-4 ~ 4.8E-3 OH 0.1 4.8E-2 M +, OH 1.0 0.48 Cl, NO3 10 ~ 100 4.83 ~ 48.3 OH, NO3
Schema of reaction pathways of 1,4-DCB decomposition and products formation C 6 H 4 Cl 2 M + M - OH Cl NO 3 A +, C 6 H 4 Cl + O 2 - A, O 3 - A, A - C 6 H 4 Cl(OH), Cl HCl, C 6 H 3 Cl 2 C 6 H 3 Cl 2, HNO 3 R128-129 R349 O 2 A 11+, A 12 + HO 2, C 6 H 4 Cl C 6 H 3 Cl 2 O 2 R149-157 M - R347 O 2 - Cl R343 C 4 H 3 C 2 HCl, C 6 H 4 Cl, others H 2 O 2 C 6 H 4 Cl(O 2- ) C 6 H 4 Cl 2 C 4 H 2 O 2 Cl, HC CCl O 2 M + R344 C 2 H, HCO C 4 H 3 Cl C 6 H 4 Cl CO, C 2 HCl, HCO NO 2 O 2 O 2 HCCO, O HCO, COCl C 2 HCl 2 HCONO 2 H O 2 CH 2 CO CH 2 CO CO CO 2 CO, Cl COCl 2, HCO CH 3 COCONO 2 R336 CO, CH 2 Cl CO 2 Cl 2
Conc. (mg/m3) Conc. of 1-chloronaphthalene vs. dose under EB-irradiation (for 1-chloronaphthalene, 1 mg/m 3 = 0.15ppm V/V) 40 12,08(mg/m3) 30,15(mg/m3) 30 20 10 0 0 10 20 30 40 50 60 Dose(kGy)
Present control technology for VOC (dioxin) emission and treatment Optimize combustion process Adsorption Plasma (EB) treatment
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