Flue Gas Treatment using Industrial EB Accelerators - Status and Challenges Andrzej G. Chmielewski Institute of Nuclear Chemistry and Technology, Warsaw, Poland NICSTAR-2018 NAARRI INTERNATIONAL CONFERENCE Advanced Applications of Radiation Technology March 05 -07, 2018 Hotel Courtyard by Marriott, Mumbai, India TANGO 2

Fossil fuels

Environmental impact

Wet FGD + SCR

Electron beam

radiothermal SO2 + OH* + M  HSO3 + M HSO3 + O2  SO3 + HO2* SO3 + H2O  H2SO4 H2SO4 + 2NH3  (NH4)2SO4 thermal SO2 + 2NH3  (NH3)2SO2 (NH3)2SO2 --> (NH4)2SO4 1. H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental Conservation TRCE-JAERI, Takasaki, September/October 1993, 99-104 2. A.G. Chmielewski: Nukleonika 45(1) (2000) 31

NO oxidation NO + O(3P) + M  NO2 + M O(3P) + O2 + M  O3 + M NO + O3 + M  NO2 + O2 + M NO + HO2* + M  NO2 + OH* +M NO + OH* + M  HNO2 +M HNO2 + OH*  NO2 + H2O NO2 removal NO2 + OH* + M  HNO3 + M HNO3 + NH3  NH4NO3 H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental Conservation TRCE-JAERI, Takasaki, September/October 1993, 99-104

NO + N(4S)  N2 + O NO2 + N(4S)  N2O + O N(2D) + NH3  NH* + NH2* NO + NH2*  N2 + H2O NO2 + NH2*  N2O + H2O NO + NH*  N2 + OH* NO2 + NH*  N2O + OH* H. Namba: Materials of UNDP(IAEA)RCA Regional Training Course on Radiation Technology for Environmental Conservation TRCE-JAERI, Takasaki, September/October 1993, 99-104

EPS Kawęczyn

EPS Pomorzany

EPS Pomorzany

Results

NPK Fertilizer

Pilot plant, China

The IEB-FGC Lab INET, Tsinghua University

Flue Gas Cleaning Plant in Changdu, China

Pilot Plant in Maritsa East 2 Thermal Plant

BULGARIA

Oil fired boiler

General view of the pilot plant 1- stack of F 1001 boiler 7 - bag filter 2- boiler F1001 8 - insulated duct part 3-flue gas duct 9 - cyclone 4-control room 10 - ammonia storage and injection unit 5-humidification unit 11 - EB mobile unit 6-pilot plant stack

Pilot plant process units inlet to process vessel, 5. ID fan EB-TECH mobile unit, 6. stack cyclone, cartridge filter

Process vessel

EB mobile unit (EBTECH)

Monitoring system

Limits for heavy metals content in NPK fertilizer 41 39 300 17 420 As Cd Cr Co Pb Hg Ni Zn Remarks <0.02 <0.01 0.43 0.03 1.01 <0.03 63.5 18.3 averaged values for byproducts collected by cartridge bag filter 0.24 0.09 1.61 0.54 1.41 22.80 1476 byproducts collected by ESP Limits for heavy metals content in NPK fertilizer 41 39 300 17 420 2800 US EPA CFR40 Part. 503 75 20 150 500 5 180 1350 Canadian Fertilizer Act (1996) 50 140 2 Polish standard 32.2 276.8 12.9 17.8 72.3 mean values of heavy metals concentrations in fertilizers marketed Contents of heavy metals (mg/kg) in the byproduct and limits for heavy metals content in the NPK fertilizer established in some countries

CARGO SHIPS

Flow process and typical exhaust gas composition for 2-stroke diesel engine

A Hybrid SOx scrubbing system , operating in closed loop

SCR + FGD systems integration

The general scheme of the electron beam interaction with the flue gas

NO + O(3P) + M → NO2 + M (M is a third inert body in the reaction system) O(3P) + O2 + M → O3 + M NO + O3 + M → NO2 + O2 + M NO + HO2∙ + M → NO2 + ∙OH + M SO2 + ∙OH + M → ∙HSO3 + M ∙HSO3 + O2 → SO3 + HO2∙ NO2 + ∙OH + M → HNO3 + M SO3 + H2O → H2SO4 Main reactions

EB +SWS+ OX block diagram 1)inlet to the installation, 2) inlet gas parameters, 3) heat exchanger (outlet temperature 70-90o C), 4) process chamber, 5) accelerator, 6) accelerator’s shelter, 7) wet simple spray tower scrubber, 8) demister, 9) outlet gas parameters (of scrubber), 10) process water (fresh), 11) NaClO2, 12) Michaelis buffer Na2HPO4 and KH2PO4 , 13) seawater, 14) NaCl solution, 15) fresh water, 16) centrifugal separator, 17) sludge tank, 18) post-reaction water tank, 19) monitoring system of post-reaction water, 20) sewage or sea, 21) exhaust fan, 22) stack 23) recirculation (optional) EB +SWS+ OX block diagram

The comparison of the NOX removal efficiency between technology using electron beam only, hybrid technology, where electron beam was coupled with wet scrubber and hybrid technology, where electron beam was coupled with wet scrubber as well as with NaClO2 and buffer (the inlet SO2 concentration was 700 ppm and NO was 1000 ppm), where : EB – Irradiation of gases with electron beam from accelerator, SWS – Sea water scrubber, buffer – Michelis buffer Hybrid technology

Conceptual scheme of the installation using EB technology for SOx and NOx removal as applied onboard, water closed or hybrid system

Electron accelerator with linear cathode

PAH treatment naphtalene acenaphtene anthracene fluoranthene pyrene benzo(a)pyrene dibenzo(a,h) anthracene PAH treatment

VOC treatment (exp.vs.modeling) Toluene, benzene over 50 kinetic equations in each case;SOx, NOx in presence of VOC

MUNICIPAL WASTE INCINERATION JAERI, Takasaki, Japan Electron accelerator & Irradiation vessel Flue gas out Stack Electron accelerator House for test Irradiation vessel Self-shielded type and Curtain beams 300 keV max. and 40 mA max.

EB/Catalyst Konkuk , ROK Acceleration of Electron Irradiation of Electron Activation of Catalyst & Oxidation of by-Products VOC Removal by Radical Reaction N2, O2, H2O, etc. e- OH , N , H , HO2 , O radicals VOC CO2 , O3 , By-products VOC Decomposition by EB Oxidation by Catalyst radical Surface Activation Surface Reforming Oxidation of by-products & VOC Catalyst O3 43

Conclusions EBFGT is the most advanced technology for simultaneous SOx and NOx removal Feasibility of the technology has been demonstrated for coal fired plant in the full industrial scale Feasibility of the technology has been demonstrated for oil fired boiler in pilot industrial scale The process can be applied for diesel engine flue gas treatment at cargo ships (laboratory tests) The process can be applied for VOC and PAH treatment (laboratory and industrial pilot tests) The process can be applied for mercury emission control (laboratory tests)

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