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Z.R.Ismagilov , N.V.Shikina, S.A.Yashnik, A.N.Zagoruiko M.A.Kerzhentsev, V.A.Ushakov,

Development of technology of methane combustion on granulated catalysts for environmentally friendly gas turbine power plant. Z.R.Ismagilov , N.V.Shikina, S.A.Yashnik, A.N.Zagoruiko M.A.Kerzhentsev, V.A.Ushakov, S.R.Khairulin, V.A.Sasonov, V.N.Parmon

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Z.R.Ismagilov , N.V.Shikina, S.A.Yashnik, A.N.Zagoruiko M.A.Kerzhentsev, V.A.Ushakov,

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  1. Development of technology of methane combustion on granulated catalysts for environmentally friendly gas turbine power plant Z.R.Ismagilov, N.V.Shikina, S.A.Yashnik, A.N.Zagoruiko M.A.Kerzhentsev, V.A.Ushakov, S.R.Khairulin, V.A.Sasonov, V.N.Parmon Boreskov Institute of Catalysis, Novosibirsk, Russia V.M.Zakharov, B.I.Braynin, G.K.Vedeshkin, E.D.Sverdlov, O.N.Favorski Central Institute of Aviation Motors, Moscow, Russia

  2. The Boreskov Institute of Catalysis (BIC) is one of the largest research centers worldwide specialized in catalysis. The BIC’s R&D activities span the areas from fundamental problems of catalysis to development of new catalysts and catalytic technologies, including catalytic combustion. The Baranov Central Institute of Aviation Motors (CIAM)is leading establishment of the Russia aviation engine - building for provision of world-level basic and applied research, creation of scientific and technological base for development of new "critical" technologies – gasturbine power units. Development advanced environment friendly gas turbine with catalytic combustion chamber

  3. Airplane engines designed at CIAM D-30KP IL-78 (powered by D-30KP) A-50 (powered by D-30KP)

  4. CIAM– the only research organization realizing integral scientific studies and development in the field of aero engines - from fundamental studies of physical processes up design of new engines, certification, as well as scientific support of their operation by reliability and failures. Practically all Soviet (Russian) aircraft engines were created under direct participation of Institute and passed upgrading at CIAM facilities. Large scale engine and turbine testing facilities of CIAM

  5. St-Petersburg Moscow (CIAM) RUSSIA Volgograd Omsk Novosibirsk (BIC) BIC and CIAM in Russia UIC

  6. The goal Development of catalyst and catalytic combustion chamber for small gas turbine power plants for decentralized power supply Approach • Regenerative turbine technology • Low temperarue turbine • Granulated catlyst for stationary turbine loading Key steps • development and study of advanced granulated catalysts with low Pd content, providing minimum emissions of NOx (<5ppm), CO (<5ppm) and HC (5ppm) • modeling of the processes in a catalytic combustor • design of a model catalytic combustion chamber and pilot testing • design and testing of a prototype catalytic combustion chamber

  7. Most active in deep oxidation of methane, CO, unsaturated hydrocarbons For oxidation of methane, MnOx/Al2O3 and hexaaluminates are less active at low temperature than Pd/CeO2-Al2O3catalysts 1. 2. Low light-off temperature Catalysts based on transition metal oxides Catalysts based on noble metals Inexpensive MnLaAl11O19 has high thermal stability The thermal stability of MnOx/Al2O3 catalysts can be increased (up to 1300oC) by doping with La, Mg or Ce oxides Z.R.Ismagilov, Patent RU 2185238(2002) Stable to thermal sintering in the oxidizing environment J.J.Spivey, J.B.Butt Catal. Today. 11 (1992) 465. Pd MnOx MnLaAl11O19 The upper temperaturelimit of their use isabout 800-900°C PdO  Pd R.J.Farrauto, et.al. Appl. Catal. A 81(1992) 227. Very expensive The properties of these two catalyst-types will be used for development of the combined catalytic packagewith reduced Pd content for combustion chamber, Catalysts for high-temperature combustionof hydrocarbon fuel

  8. 1.1. Development of catalyst with low ignition temperature Pd Catalysts supported on -Al2O3 Preparation conditions 1. Type of active component Pd CeO2 2. Loading of active component • CeO2 3 - 12 wt.% • Pd 0.1 - 2 wt.% • H2PdCl4 • Pd(NO3)2 • Pd(CH3COO)2 • Pd(NH3)4(NO3)2 • Pd(NH3)4(Cl3)2 3. Precursor 4. Calcination temperature • 800 оС – 1100оС 5. Characterization XRD • Catalytic activity in methane oxidation • Space velocity: 1000 and 24000 h-1 • Temperature: 200 – 700oC • Feed composition: 1 vol.% in air TPR-H2 X-ray microanalysis

  9. 1.2. Development of catalyst with high thermal stability Oxide and mixed Catalysts supported on -Al2O3 Preparation conditions 1. Type of active component MnOx and MnLaAl11O19 Pd and MnOx, MnLaAl11O19 2. Loading of active component • MnO2 - 3 -11 wt.% • La2O3 - 5 -22 wt.% • Pd 0.1 - 2 wt.% 3. Precursor • H2PdCl4 • Pd(NO3)2 • Pd(CH3COO)2 • Mn(NO3)3 • Mn(CH3COO)2 4. Calcination temperature • 900 оС – 1100оС • 900 оС – 1100оС 5. Characterization XRD • Catalytic activity in methane oxidation • Space velocity: 1000 and 24000 h-1 • Temperature: 200 – 700oC • Feed composition: 1 vol.% in air TPR-H2 X-ray microanalysis

  10. Properties of granulated catalysts Ring size: Length – 7.5 mm OD– 7.5 mm ID – 2.5 mm

  11. GHSV 1000 h-1 24000 h-1 48000 h-1 Development of catalyst with low ignition temperature 1 vol.% CH4 in air, GHSV The catalyst IC-12-60 based on Pd-CeO2-Al2O3 was selected as a catalyst with low ignition temperature: • the methane ignition temperature on the catalyst is 240С, the combustion products do not contain CO and NOx • the active component is highly dispersed PdO particles which provide high activity at low temperatures This catalyst can be used in the upstream sectionof combustion chamber for initiation of fuel combustion Pd-CeO2-Al2O3

  12. 1.2. Optimization of catalyst with high thermal stability 1 vol.% CH4 in air, 24000 h-1 MnLaAl11O19 Pd/Al2O3 (1200oC) Catalytic activity of Pd-Mn catalyst: Effect of Pd precursor 1.5 %Pd/MnLaAl11O19 (1200oC) Pd precursor Pd(CH3COO)2 Pd(NO3)2 H2PdCl4 • At the same Pd loading (1.5 wt.%) the magnitude of the synergetic effect depends on the palladium precursor: acetate, nitrate or chloropalladic acid. • The Pd loading (0.5 wt.%), Pd precursor (nitrate) and calcination temperature (1000oC) were optimum for Pd-Mn catalysts

  13. 1.2. Optimization of catalyst with high thermal stability 3 vol.% CH4 in air, 10000 h-1 and930oC IC-12-61 360-365oC DT = 100oC IC-12-61, 12-86 ppm IC-12-62 IC-12-62, 0-5 ppm 265-275оC Stability of Mn-La and Pd-Mn-La catalyst at high temperature • The catalysts IC-12-61 containing Mn-La hexaaluminate structure exhibits high stability at high temperatures. • Doping of Mn-La catalyst (IC-12-62) with Pd to 0.5 wt.% allows a decrease of ignition temperature by 100C and reduction of CO content in the reaction products • These catalysts can be used in the downstreamsectionof the combustion chamber for high temperature fuel combustion

  14. 2. Modeling of processes in a catalytic combustor2.1. Calculation of kinetic parameters from experimental data Total rate of methane oxidation k0 – pre-exponential factor of rate constant (s-1), E – activation energy(J/mol), R – absolute gas constant(Jmol-1K-1), Т – reaction temperature (К), – part of free volume in catalyst bed, CCH4 – methane concentration (mole fraction), Р –pressure (atm), Р0 – standard pressure (1 atm). Kinetic parameter of deep methane oxidation

  15. CH4 + air 2.2. Design of catalyst packages in the combustion chamber CH4 + air CH4 + air Combined catalyst packages Uniform catalyst package

  16. 1.5 % CH4 2.0 % CH4 Conversion, % Conversion, % GHSV, h-1 GHSV, h-1 3.6 % CH4 5.0 % CH4 Conversion, % Conversion, % GHSV, h-1 GHSV, h-1 2.2 Modelingof methane combustionprocess onuniformcatalyst package Combustion efficiency as function of methane concentration and GHSV Catalyst package: ICT-12-40 (MnOx-Al2O3) or IC-12-61(Mn-La-Al2O3) (Ссн4- 1.5 - 5.0 vol.%, GHSV - 7000 - 40000 h-1, P – 1 atm) The methane combustion efficiency increases with the increase of the temperature and with methane concentration

  17. 1000 1 / h 40000 1/h h Temperature, oC h Methane conversion, % Beds border Beds border Relative bed height Relative bed height 2.3. Modelingof methane combustionprocess oncombined catalyst package Temperature profile in the catalyst bed and methane conversion profile as function of GHSV Catalyst package: IC-12-60 (Pd-Ce-Al2O3)- 20 mm + IC-12-61(Mn-La-Al2O3)-180 mm • The temperature growth in catalyst bed and the methane conversion growth are higher in IC-12-60 catalyst bed than in IC-12-61 catalyst bed

  18. 20 / 180 mm 40 / 160 mm Methane conversion, % Methane conversion, % 10000 h-1 40000 h-1 60000 h-1 10000 h-1 40000 h-1 60000 h-1 Bed height, m Bed height, m 2.3. Modelingof methane combustionprocess oncombined catalyst package Effect of ratio of heights of IC-12-60 andIC-12-62 catalyst beds and GHSV on methane conversion Catalytic package: IC-12-60 (2%Pd-Ce-Al2O3)+ IC-12-62 (0.5%Pd-Mn-La-Al2O3) Inlet temperature - 450ºС,Inlet methane concentration - 1.5 vol.%, pressure – 1 atm • The methane combustion takes place mainly in IC-12-60 catalyst bed • This tendency becomes stronger with the decreasing space velocity and the increasing of the height of IC-12-60 catalyst bed

  19. CCH4 1.5 vol. %, P – 1 atm IC-12-60 / IC-12-61 40 / 160 mm 30 / 170 mm 20 / 180 mm CCH4 3.6 vol. %, P – 1 atm IC-12-60 / IC-12-61 20 / 180 mm 2.3. Modelingof methane combustionprocess oncombined catalyst package Combustion efficiency as function of ratio between height of the catalyst bed and GHSV Catalyst package: IC-12-60 (Pd-Ce-Al2O3) + IC-12-61(Mn-La-Al2O3) The methane combustion efficiency increases with the increase of the height of IC-12-60 catalyst bed and with methane concentration

  20. Residual methane content, ppm Maximum catalyst temperature, oC GHSV , 1/h GHSV , 1/h 2.3 Modelingof methane combustionprocess oncombined catalyst package Effect of height ratio of IC-12-60/IC-12-62 catalyst beds on parameters of methane combustion Catalytic package: IK-12-60 (2%Pd-Ce-Al2O3)+ IK-12-62 (0.5%Pd-Mn-La-Al2O3) Inlet temperature - 450ºС,Inlet methane concentration - 1.5% vol., pressure – 1 atm The methane combustion efficiency and temperature in catalyst bed increase with the increase of the height of IC-12-60 catalyst bed

  21. Pressure drop, atm GHSV, 1/h GHSV, 1/h 2.3. Modelingof methane combustionprocess oncombined catalyst package Effect of shape and size of catalyst granules on parameters of methane combustion process Catalyst package: IC-12-60 (2%Pd-Ce-Al2O3)-20 mm+ IC-12-62 (0.5%Pd-Mn-La-Al2O3)-180 mm Inlet temperature - 450ºС, inlet methane concentration - 1.5% vol., pressure – 1 atm Granule shape - ring Methane conversion Methane conversion The methane combustion efficiency and the pressure drop in catalyst bed increase with the decrease of the granule size

  22. CH4 + air 3. Design of catalyst packages in the combustion chamber CH4 + air CH4 + air Combined catalyst packages Uniform catalyst package

  23. CH4+air Т=1200K Т<1000K 3. Design of catalyst packages in the combustion chamber Schematic view of two-step methane oxidation in catalytic combustion chamber Catalytic activity in methane conversion Pd-Ce-Al2O3-catalyst «ignition region» Pd-catalyst with low light-off temperature -240ºС initiatesmethaneoxidation andprovides outlet temperature sufficient to start methane combustion on the oxide catalyst Mn-La-Al2O3-catalyst:  - initial; □- after 30 h;○ - 50 h; ▲ - 100 h testing at 930oC «high temperature region» thermostable oxide catalyst, Mn-La-Al2O3,provides stable methane combustion at high temperatures

  24. 4. Tests in a model catalytic combustion chamber Scheme of the model catalytic combustion chamber (BIC) Fuel/Air mixture Thermocouples Sampling pipes Reaction products

  25. T inlet ICT-12-40, 580oC IC-12-61, 600oC IC-12-62, 575oC 4. Testing of uniformcatalytic packagein the model catalytic combustor GHSV - 15000 h-1,  - 6.8-7.0, CH4 – 1.5 vol.% GHSV - 1000 h-1, CH4 – 1.5 vol.% 80-120 hours of testing Fresh – close symbol Spent – open symbol • The Mn-La catalyst which contains hexaaluminate structure exhibits higher stability at high temperatures than MnOx-Al2O3 catalyst • Doping of Mn-La catalyst with palladium to 0.5 wt.% allows an increase of methane combustion efficiency (from 99.3 to 99.5%) and a decrease of inlet temperature (from 600 to 575oC)

  26. 4. Testing of combined catalytic packagein the model catalytic combustor GHSV - 15000 h-1,  - 6.8-7.0, CH4 – 1.5 vol.% Catalyst and T inlet ICT-12-62, 580oC IC-12-62, ring+sphere, 580oC IC-12-61 (ring)+ IC-12-62(sphere), 575oC Catalyst package formed by two beds of catalysts of the same chemical composition: the upstream bed of large rings and the downstream bed of smaller beads (with different void volumes)allows a considerable increase of combustion efficiency

  27. T inlet ICT-12-61, 600oC IC-12-60+IC12-61, ring, 580oC IC-12-60, IC-12-61 (ring)+ IC-12-62(sphere), 470oC 4. Testing of combined catalytic packagein amodel catalytic combustor GHSV - 15000 h-1,  - 6.8-7.0, CH4 – 1.5 vol.% • Composing the catalyst package by three catalysts with different chemical compositions and different shapes: • IC-12-60 (ring) with low ignition temperature • IC-12-61 (ring) with high thermal stability • IC-12-62 (sphere) smaller granules and high activity • allowed us to achieve high combustion efficiency at a low inlet temperature 470оС

  28. Combustion Products Sampling Air + CH4 4. Tests in a model catalytic combustion chamber Scheme of the model catalytic combustion chamber (CIAM) 1 – catalytic combustion chamber 2 – thermal shield 3 – air electric heater 4 – compensating lattice 5 – electric heater 6 – «guard» electric heater 7 – thermal protection of frame 8 – mixer 9 – hot probe

  29. 4. Testing of combined catalytic packagein the model catalytic combustion chamber Design ofcatalytic combustion chamber Catalyst bed height – 300 mm Combination of beds: IC-12-60 (Pd-Ce-Al2O3) - 20mm Inert material – 20 mm IC-12-61 (Mn-La-Al2O3) - 260mm Reaction CH4 + 2O2 = CO2 + 2H2O Temperature profile through catalyst bed(=6.68-10) Outlet concentrations ofCH, CO, NOx (=6.68-10) Tinlet – 840 K Gair – 4.5 g/s The layer of inert material acts as a heat shield. At differrent methane concentrations and low air/fuel eqivalence ratio ( = 6.7), thePd-catalyst is not overheated above 1000К ( 730ºС ) Concentrations of emissions at the outlet of the catalytic combustion chamber are NOx 0-1 ppm; CO < 4 ppm; CH <10 ppm

  30. Methane 5. Testing of the prototype catalytic combustion chamber Schematic view and main characteristics of the prototype catalytic combustor for a 125 kW gas turbine

  31. Photos of the prototype catalytic combustor for a 125 kW gas turbine

  32. 5. Testing of the prototype catalytic combustion chamber Design of catalytic combustion chamber Catalyst: ICT-12-40 (Mn-Al2O3) Catalyst bed height– 450 mm Catalyst bed volume– 87dm3 Granule shape - ring Granule size - 7.5 x 7.5 x 2.5 mm Test conditions Temperature at the combustor inlet 850 K Pressure at the combustor inlet 5 atm Air flow velocity at the combustor inlet 830g/s (2310 nm3/h) Methane flow velocity in the preheating chamber 0-0.9g/s (0-4.5 nm3/h) Methane flow velocity in the combustor 6,9-7.5g/s (34.8-37.5 nm3/h) GHSV 19000 - 31200 h-1

  33. 5. Testing of the prototype catalytic combustion chamber Results of the tests of the prototype catalytic combustor

  34. CO, NO concentration, ppm CH4 concentration, ppm 5 – 6 ppm CO 18-20 ppm CH4 0 ppm NOx Time duration, s Time duration, s 5. Testing of the prototype catalytic combustion chamber СО, NOxand CH4 concentrations (ppm) at the outlet of the catalytic combustion chamber

  35. 5. Testing of the modifiedprototype catalytic combustion chamber

  36. THANK YOU FOR YOUR ATTENTION First Snow in Novosibirsk. October 2007 (the same we had this year on 17 September 2008) 36

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