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Removal of NOx and SOx from the Exhaust of Marine Diesel Engines Using Non-Thermal Plasma Presented by Dr Nada Manivannan CESR Brunel University UK k Contributors : Dr Ornella Gonzini, Professor Wamadeva Balachandran, Dr Radu Beleca and Dr Maysam Abbod ©Centre for Electronic Systems Research

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Contents Why NOx and SOx? Our Project: DEECON Our Research - Non-Thermal plasma Chemistry of NOx and SOx reduction Mass Balance Equations Numerical Modelling Results Real scenario verses Model conclusions ©Centre for Electronic Systems Research

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Why NO x and SO x ? Hazardous gasHealth issues International and National Regulations Sulpher Content Coastal area ©Centre for Electronic Systems Research

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Innovative After-Treatment System for Marine Diesel Engine Emission (DEECON ) EU FP7 2.3m Euro 3 years 8 partners Objectives (Overall) NOx < 2% SO x <2% PM < 1% weight HC < 20% CO < 20% Brunel Project leader – Professor Balachandran NOx and SOx Reduction using Non-Thermal Plasma ©Centre for Electronic Systems Research

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DEECON Consortium Academic Institutes Project management Commercial Companies Associates

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A Typical Two Stroke Engine ©Centre for Electronic Systems Research

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Plasma and Exhaust Gas Exhaust Gas N2, O2, H 2 O, CO2, NO2, NO, SO2, HC, CO and PM Radical and Ions O, OH, O*, O2 +, N, N 2+, H 2 O+,CO2 *, CO2 + Chemical Reactions NO/NO2 -> HNO3 SO 2 - > H 2 SO 4 Treated Gas HNO 3, H 2 SO 4, N 2, O 2, H 2 O, CO 2, NO 2, NO, SO 2, HC, CO and PM Plasma interactions ©Centre for Electronic Systems Research

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Plasma Chemistry – Radical Formation Radical Formation ©Centre for Electronic Systems Research

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Plasma Chemistry – Radical Reactions NO/NO 2 + Radicals SO 2 + OH HSO 3 HSO 3 + O 2 SO 3 + HO 2 SO 3 + H 2 O H 2 SO 4 SO 2 + Radicals R. Atkinson et al, Atmos. Chem. Phys., 4, 1461–1738, 2004 ©Centre for Electronic Systems Research

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Plasma Physics – Mass Balance Equations ©Centre for Electronic Systems Research

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Plasma Physics – Mass Balance Equations..and 10 other equations ©Centre for Electronic Systems Research

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Plasma Physics – Reaction Rates Mean electron energy (1-5eV) Cross section data Electron Energy Distribution Function (EEDF) Radical Reactions (electron impacts) Gas temperature Chemical Reactions Numerical calculation Experimental study/analytical expression ©Centre for Electronic Systems Research

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Modelling – NO x /SO x Reduction Gas concentration matrix Chemical reaction rates Cross section data Gas temperature Gas pressure Residence time Mass balance equation solver – Ordinary differential equations Radical Reaction rate calculation Maxwellian EEDF ©Centre for Electronic Systems Research

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Radical Reaction Rates where, q = charge of electron (C) m e = mass of electron(kg) σ j (ε) = collision cross section of j th collisions as a function of electron energy (m 2 ) f (ε) = Electron Energy Distribution Function (EEDF) m 3 /s The collision cross section data is from: tlse.fr/cross_sec_download.php ©Centre for Electronic Systems Research

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Reactions Rates of Radicals Formation Mean Electron Energy (eV) Reaction Rate (m 3 /s) Our Model using Maxwellian EEDFCOMSOL Boltzman analysis * * Hagelaar et al, Plasma Sources Science and Technology, Vol. 14, pp , 2005 ©Centre for Electronic Systems Research

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Our Model using Maxwellian EEDF COMSOL Boltzman analysis * Mean Electron Energy (eV) Reaction Rate (m 3 /s) Reactions Rates of Radicals Formation * Hagelaar et al, Plasma Sources Science and Technology, Vol. 14, pp , 2005 ©Centre for Electronic Systems Research

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Reactions Rates of Radicals Formation Mean Electron Energy (eV) Reaction Rate (m 3 /s) ©Centre for Electronic Systems Research

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Reaction Rates of Radicals + NO x /SO x Reaction Reaction Rates (k/cm 3 molecule -1 s -1 ) Temp. range (K) Ref O*+H 2 O2OH2.2× a O+NO+MNO 2 +M1.0× (T/300) -1.6 [M] a HNO 2 +OHH 2 O+NO 2 2.5× exp(260/T) a NO+OH+MHNO 2 +M7.4× (T/300) -2.4 [M] a NO 2 +OH+MHNO 3 +M3.3× (T/300) -3.0 [M] a HO+SO 2 +MHSO 3 +M 4.5×10 31 (T /300) 3.9 [M] a HSO 3 + O 2 HO 2 + SO 3 1.3×10 12 exp(330/T ) 1.1×10 13 exp(1200/T )* a SO 3 + H 2 O H 2 SO 4 3.9×10 41 exp(6830/T)[H 2 O] 2 -a N+OHNO+H5.06E b N+NON 2 +O3.11E b N+NON 2 +O3.11E b N+NO 2 N 2 O+O1.21E c ©Centre for Electronic Systems Research a el Atmos. Chem. Phys., 4, 1461–1738, 2004 b el J. Phys. Chem. Ref. Data, 18, 3, 881 – 1097, 1989 c el JPL Publication 97-4, 1 – 266, 1997

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Solving Mass Balance Equations Type of speciesInitial Concentrations % or ppmMolecules/cm -3 Total Gas (M) ×10 19 H2OH2O ×10 18 O2O ×10 18 N2N ×10 19 NO75 vppm1.60×10 15 NO21425 vppm3.05×10 16 SO2600 vppm3.05×10 16 O, O2*, OH, H, N00 Solving ODE s- initial concentrations and residence time two major parameters ODE15s – Matlab model to solve the 13 mass balance equations for a various residence time ©Centre for Electronic Systems Research

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Results – NO x /SO x Reduction Mean Electron Energy = 1eVMean Electron Energy = 2eV ©Centre for Electronic Systems Research

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Results – NO x /SO x Reduction Mean Electron Energy = 3eV 4.9% ©Centre for Electronic Systems Research

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Results – Plasma Volume Mean Electron Energy (eV)ResidentceTime (s) to Reduce Nox/Sox 1% Volume of the Plasma Required [m 3 ] 0.53 × × × × × × × × × × × × × × **N/A ** - [NO2] ~ 4.9% stable after 1.5 × s * - Flow rate = 40liters/s = 0.04m 3 /s a Volume = Flow rate[m3/s]* x Resident Time[s]) ©Centre for Electronic Systems Research

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Results – Plasma Volume ©Centre for Electronic Systems Research

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Summary Non-Thermal Plasma can theoretically eliminate NOx and SOx completely. Mean electron energy is the main parameter in determine the volume of plasma reactions ©Centre for Electronic Systems Research

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Thank YOU! ©Centre for Electronic Systems Research

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