燃煤电厂宽温催化剂的开发与应用示范
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摘要
国家能源集团电力装机2.26亿kW,其中火电总装机1.75亿kW,占全国的15.8%。目前,1.35亿kW机组实现超低排放,脱硝催化剂总填装量约20万m~3,集团在我国电力污染物控制领域开拓创新,走在前列。随着2016年火电机组适应电网深度调峰的深入,传统商业SCR脱硝催化剂(温度窗口为300℃～450℃)已不能满足日益严格的环保排放要求。为实现燃煤电厂全负荷运行时NO_x排放达标,针对可在260℃～420℃范围内长时间运行的宽温脱硝催化剂进行研究。通过研究低温反应机理进行了催化剂配方设计,并通过组分优化和成型工艺调整,开发了可匹配传统脱硝催化剂的生产工艺,制备了一系列不同配方的3×3孔蜂窝脱硝催化剂,通过性能评价发现0.6-MoV/W-TiO_2具有合适的孔结构和表面酸性,表现出最好的宽温脱硝活性和较低的SO_2/SO_3氧化率。将该催化剂配方进行工业级放大,完成了多温区新型脱硝催化剂产品试制,成品率达100%,可实现中低温高效脱硝。该催化剂已在江油电厂32号机组侧线反应器完成2000h长周期低负荷中试运行,测试温度为260℃～300℃。在测试工况下,脱硝效率达到90%,SO_2/SO_3氧化率和氨逃逸符合国家标准,脱硝系统运行稳定,效果良好。
The China Energy Group installed 226 million kilowatts of electricity, of which the total installed capacity of thermal power generation was 175 million kilowatts, accounting for 15.8% of the country. The China Energy Group is pioneering innovation in the field of power pollutant control in China. At present, 135 million kilowatt units have achieved ultra-low emission, with the total filling capacity of SCR catalysts of 200000m~3. With deepening of thermal power units adapt to the deep peak-shaving of the power grid since 2016, the traditional commercial SCR catalysts(temperature window of 300℃～450℃) cannot meet the increasingly strict requirements of pollution emission. In order to achieve the standard of NO_x emission during full-load operation of coal-fired power plants, the SCR atalysts in the wide temperature range which can be operated for a long time in the temperature range of 260℃ to 420℃ are researched. The formulation of SCR catalysts were designed according to the mechanism of low temperature reaction. The production process adapted to the traditional SCR catalysts was developed through the optimization of components and the adjustment of the molding process. A series of 3×3 honeycomb denitration catalysts with different Mo/V molar ratio have been prepared. Through the characterization and performance evaluation tests, it was found that 0.6-MoV/W-TiO_2 had suitable pore structure and surface acidity, showing the best wide-temperature NH_3-SCR activity and lower SO_2/SO_3 oxidation rate.The industrial grade trial productions of novel SCR catalysts with multi-temperature zone were completed, which can realize high efficiency denitrification at medium and low temperature.The proportion of finished product of the SCR catalysts was 100%. The catalyst has been operated under low-load operation for 2000 h long period in the side-line reactor of Jiangyou Power Plant NO.32 unit. The test temperature range was 260-300℃. Under the test conditions, the NO_x conversion reached to 90%, the SO_2/SO_3 oxidation rate and ammonia escape met the national standards. The denitration system ran stably with good effect.
The China Energy Group installed 226 million kilowatts of electricity, of which the total installed capacity of thermal power generation was 175 million kilowatts, accounting for 15.8% of the country. The China Energy Group is pioneering innovation in the field of power pollutant control in China. At present, 135 million kilowatt units have achieved ultra-low emission, with the total filling capacity of SCR catalysts of 200000m~3. With deepening of thermal power units adapt to the deep peak-shaving of the power grid since 2016, the traditional commercial SCR catalysts(temperature window of 300℃～450℃) cannot meet the increasingly strict requirements of pollution emission. In order to achieve the standard of NO_x emission during full-load operation of coal-fired power plants, the SCR atalysts in the wide temperature range which can be operated for a long time in the temperature range of 260℃ to 420℃ are researched. The formulation of SCR catalysts were designed according to the mechanism of low temperature reaction. The production process adapted to the traditional SCR catalysts was developed through the optimization of components and the adjustment of the molding process. A series of 3×3 honeycomb denitration catalysts with different Mo/V molar ratio have been prepared. Through the characterization and performance evaluation tests, it was found that 0.6-MoV/W-TiO_2 had suitable pore structure and surface acidity, showing the best wide-temperature NH_3-SCR activity and lower SO_2/SO_3 oxidation rate.The industrial grade trial productions of novel SCR catalysts with multi-temperature zone were completed, which can realize high efficiency denitrification at medium and low temperature.The proportion of finished product of the SCR catalysts was 100%. The catalyst has been operated under low-load operation for 2000 h long period in the side-line reactor of Jiangyou Power Plant NO.32 unit. The test temperature range was 260-300℃. Under the test conditions, the NO_x conversion reached to 90%, the SO_2/SO_3 oxidation rate and ammonia escape met the national standards. The denitration system ran stably with good effect.
引文
[1]刘庆航,晏乃强,瞿赞,等.钒基催化剂中低温SCR脱硝性能研究 [J].环境科学与技术, 2017, 40(9):116-123.
[2]郑长乐.脱硝催化剂再生技术研究进展[J].电力科技与环保,2019,35(1):10-12.
[3]王宝冬,何发泉,林德海等. 燃煤电厂脱硝催化剂失活与再生技术研究[A]. 中国环境科学学会.2016中国环境科学学会学术年会论文集(第三卷)[C].中国环境科学学会: 中国环境科学学会, 2016.
[4]王继华.SCR、SNCR和SNCR/SCR烟气脱硝技术应用及比较[J].电力科技与环保,2018,34(5):35-36.
[5]王学涛,胡海鹏,张兴宇,等.Cu/HZSM-5催化剂低温SCR脱硝实验研究 [J].中国电机工程学报, 2018, 38(20):6029-6036.
[6]中国电力设备管理协会研究室.全国火电亏损面超半:路在何方 [J].电力设备管理, 2018(12):14-18.
[7]赵炜.F-S改性V2O5/TiO2低温NH3还原NO及抗毒性能研究 [J].电力科技与环保, 2018, 34(3):11-14.
[8]Mosrati J, Atia H, Eckelt R, et al. Nb-Modified Ce/Ti Oxide Catalyst for the Selective Catalytic Reduction of NO with NH3 at Low Temperature [J]. Catalysts (2073-4344), 2018, 8(5):1-16.
[9]Huang N, Geng Y, Xiong S, et al. The promotion effect of ceria on high vanadia loading NH3-SCR catalysts [J]. Catalysis Communications, 2019(121): 84-88.
[10]Zhang G, Han W, Zhao H, et al. Solvothermal synthesis of well-designed ceria-tin-titanium catalysts with enhanced catalytic performance for wide temperature NH3-SCR reaction [J]. Applied Catalysis B: Environmental, 2018(226):117-126.
[11]Xu T, Wu X, Gao Y, et al. Comparative study on sulfur poisoning of V2O5-Sb2O3/TiO2 and V2O5-WO3/TiO2 monolithic catalysts for low-temperature NH3-SCR [J]. Catalysis Communications, 2017(93): 33-36.
[12]Fang D, He F, Liu X, et al. Low temperature NH3-SCR of NO over an unexpected Mn-based catalyst: Promotional effect of Mg doping [J]. Applied Surface Science, 2018 (427): 45-55.
[13]Huang J, Huang H, Jiang H, et al. The promotional role of Nd on Mn/TiO2 catalyst for the low-temperature NH3 SCR of NOx [EB/OL]. Catalysis Today, 2018, https://www.sciencedirect.com/science/article/pii/S0920586118310526.
[14]Phil H H, Reddy M P, Kumar P A, et al. SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures [J]. Applied Catalysis B: Environmental, 2008, 78(3-4): 301-308.
[15]Jin R, Liu Y, Wu Z, et al. Low-temperature selective catalytic reduction of NO with NH3 over Mn Ce oxides supported on TiO2 and Al2O3: A comparative study. Chemosphere. 2010, 78(9): 1160-1166.
[16]Lee K J, Kumar P A, Maqbool M S, et al. Ceria added Sb-V2O5/TiO2 catalysts for low temperature NH3 SCR: Physico-chemical properties and catalytic activity [J]. Applied Catalysis B: Environmental, 2013(142): 705-717.
[17]Lee M, Ye B, Jeong B, et al. Reduced graphene oxide supported V2O5-WO3-TiO2 catalysts for selective catalytic reduction of NOx [J]. Korean Journal of Chemical Engineering, 2018, 35(10): 1988-1993.
[18]Putluru S S R, Jensen A D, Riisager A, et al. Heteropoly acid promoted V2O5/TiO2 catalysts for NO abatement with ammonia in alkali containing flue gases [J]. Catalysis Science & Technology, 2011, 1(4): 631-637.
[19]Ma D Z, Li J, Yin D, et al. Denitrification Activities of Mo-V-Ti Catalysts Prepared by Dipping Method at Low Temperature[C]//Materials Science Forum. Trans Tech Publications, 2018(913): 900-906.
[20]周惠, 黄华存, 董文华,等. SiO2掺杂对V2O5-WO3/TiO2脱硝催化性能的影响 [J].环境工程学报, 2017, 11(8):4677-4684.
[21]Zhao X, Huang L, Li H, et al. Highly dispersed V2O5/TiO2 modified with transition metals (Cu, Fe, Mn, Co) as efficient catalysts for the selective reduction of NO with NH3[J]. Chinese Journal of Catalysis, 2015, 36(11): 1886-1899.
[22]方祺隆, 朱宝忠, 孙运兰, 等. Mn-Fe/Al2O3催化剂的低温脱硝性能研究 [J].分子催化, 2018, 32(4):305-314.
[23]Srnak T Z, Dumesic J A, Clausen B S, et al. Temperature-programmed desorption/reaction and in situ spectroscopic studies of vanadia/titania for catalytic reduction of nitric oxide[J]. Journal of Catalysis, 1992, 135(1): 246-262.
[24]Mhamdi M, Khaddar-Zine S, Ghorbel A. Influence of the cobalt salt precursors on the cobalt speciation and catalytic properties of H-ZSM-5 modified with cobalt by solid-state ion exchange reaction. Applied Catalysis A: General. 2009, 357(1): 42-50.
[25]郑方栋, 李文华, 赵敏, 等.全负荷脱硝氨逃逸率与SO3转化率的变化 [J].中国电机工程学报, 2017, 37(9):2607-2614.
[26]Kwon D W, Park K H, Hong S C. Enhancement of SCR activity and SO2 resistance on VOx/TiO2 catalyst by addition of molybdenum[J]. Chemical Engineering Journal, 2016(284): 315-324.
[2]郑长乐.脱硝催化剂再生技术研究进展[J].电力科技与环保,2019,35(1):10-12.
[3]王宝冬,何发泉,林德海等. 燃煤电厂脱硝催化剂失活与再生技术研究[A]. 中国环境科学学会.2016中国环境科学学会学术年会论文集(第三卷)[C].中国环境科学学会: 中国环境科学学会, 2016.
[4]王继华.SCR、SNCR和SNCR/SCR烟气脱硝技术应用及比较[J].电力科技与环保,2018,34(5):35-36.
[5]王学涛,胡海鹏,张兴宇,等.Cu/HZSM-5催化剂低温SCR脱硝实验研究 [J].中国电机工程学报, 2018, 38(20):6029-6036.
[6]中国电力设备管理协会研究室.全国火电亏损面超半:路在何方 [J].电力设备管理, 2018(12):14-18.
[7]赵炜.F-S改性V2O5/TiO2低温NH3还原NO及抗毒性能研究 [J].电力科技与环保, 2018, 34(3):11-14.
[8]Mosrati J, Atia H, Eckelt R, et al. Nb-Modified Ce/Ti Oxide Catalyst for the Selective Catalytic Reduction of NO with NH3 at Low Temperature [J]. Catalysts (2073-4344), 2018, 8(5):1-16.
[9]Huang N, Geng Y, Xiong S, et al. The promotion effect of ceria on high vanadia loading NH3-SCR catalysts [J]. Catalysis Communications, 2019(121): 84-88.
[10]Zhang G, Han W, Zhao H, et al. Solvothermal synthesis of well-designed ceria-tin-titanium catalysts with enhanced catalytic performance for wide temperature NH3-SCR reaction [J]. Applied Catalysis B: Environmental, 2018(226):117-126.
[11]Xu T, Wu X, Gao Y, et al. Comparative study on sulfur poisoning of V2O5-Sb2O3/TiO2 and V2O5-WO3/TiO2 monolithic catalysts for low-temperature NH3-SCR [J]. Catalysis Communications, 2017(93): 33-36.
[12]Fang D, He F, Liu X, et al. Low temperature NH3-SCR of NO over an unexpected Mn-based catalyst: Promotional effect of Mg doping [J]. Applied Surface Science, 2018 (427): 45-55.
[13]Huang J, Huang H, Jiang H, et al. The promotional role of Nd on Mn/TiO2 catalyst for the low-temperature NH3 SCR of NOx [EB/OL]. Catalysis Today, 2018, https://www.sciencedirect.com/science/article/pii/S0920586118310526.
[14]Phil H H, Reddy M P, Kumar P A, et al. SO2 resistant antimony promoted V2O5/TiO2 catalyst for NH3-SCR of NOx at low temperatures [J]. Applied Catalysis B: Environmental, 2008, 78(3-4): 301-308.
[15]Jin R, Liu Y, Wu Z, et al. Low-temperature selective catalytic reduction of NO with NH3 over Mn Ce oxides supported on TiO2 and Al2O3: A comparative study. Chemosphere. 2010, 78(9): 1160-1166.
[16]Lee K J, Kumar P A, Maqbool M S, et al. Ceria added Sb-V2O5/TiO2 catalysts for low temperature NH3 SCR: Physico-chemical properties and catalytic activity [J]. Applied Catalysis B: Environmental, 2013(142): 705-717.
[17]Lee M, Ye B, Jeong B, et al. Reduced graphene oxide supported V2O5-WO3-TiO2 catalysts for selective catalytic reduction of NOx [J]. Korean Journal of Chemical Engineering, 2018, 35(10): 1988-1993.
[18]Putluru S S R, Jensen A D, Riisager A, et al. Heteropoly acid promoted V2O5/TiO2 catalysts for NO abatement with ammonia in alkali containing flue gases [J]. Catalysis Science & Technology, 2011, 1(4): 631-637.
[19]Ma D Z, Li J, Yin D, et al. Denitrification Activities of Mo-V-Ti Catalysts Prepared by Dipping Method at Low Temperature[C]//Materials Science Forum. Trans Tech Publications, 2018(913): 900-906.
[20]周惠, 黄华存, 董文华,等. SiO2掺杂对V2O5-WO3/TiO2脱硝催化性能的影响 [J].环境工程学报, 2017, 11(8):4677-4684.
[21]Zhao X, Huang L, Li H, et al. Highly dispersed V2O5/TiO2 modified with transition metals (Cu, Fe, Mn, Co) as efficient catalysts for the selective reduction of NO with NH3[J]. Chinese Journal of Catalysis, 2015, 36(11): 1886-1899.
[22]方祺隆, 朱宝忠, 孙运兰, 等. Mn-Fe/Al2O3催化剂的低温脱硝性能研究 [J].分子催化, 2018, 32(4):305-314.
[23]Srnak T Z, Dumesic J A, Clausen B S, et al. Temperature-programmed desorption/reaction and in situ spectroscopic studies of vanadia/titania for catalytic reduction of nitric oxide[J]. Journal of Catalysis, 1992, 135(1): 246-262.
[24]Mhamdi M, Khaddar-Zine S, Ghorbel A. Influence of the cobalt salt precursors on the cobalt speciation and catalytic properties of H-ZSM-5 modified with cobalt by solid-state ion exchange reaction. Applied Catalysis A: General. 2009, 357(1): 42-50.
[25]郑方栋, 李文华, 赵敏, 等.全负荷脱硝氨逃逸率与SO3转化率的变化 [J].中国电机工程学报, 2017, 37(9):2607-2614.
[26]Kwon D W, Park K H, Hong S C. Enhancement of SCR activity and SO2 resistance on VOx/TiO2 catalyst by addition of molybdenum[J]. Chemical Engineering Journal, 2016(284): 315-324.