锰铈改性钒钨钛中低温SCR催化剂脱硝及抗水抗硫性能
|
摘要
结合Mn的低温脱硝活性与Ce的储氧能力,将Mn-Ce作为整体改性剂,添加到传统钒钨钛催化剂中,用浸渍法制备了8份样品,以NH_3为还原剂,于管式固定反应器内进行脱硝及抗水抗硫实验,通过NH_3-TPD、H_2-TPR、N_2物理吸附测试、XRD手段对样品进行表征。综合脱硝活性及240℃抗水抗硫测试结果,选出较优的改性催化剂为3V-10W-7.7Mn-4.3Ce/75Ti,其在180~330℃保持脱硝活性95%以上,240℃抗水抗硫活性稳定在80%左右。该样品的比表面积虽然不到67m~2/g,但是Mn O_2与Ce O_2高度分散在Ti O_2表面;7.7%含量的Mn O_2也使催化剂具有大量的强酸位点,能够增强对NH_3的吸附;适当含量的Ce也增强了催化剂的低温氧化还原能力。
Due to the selective catalytic reduction(SCR)activities of Mn at low temperature and the oxygen storage capacity of Ce,Mn and Ce were introduced into V-W/Ti.Eight catalyst samples were prepared by the impregnation method.The experiments of de NO_x and resistance to H_2O and SO_2 for the catalysts were conducted with ammonia gas as the reductant in a fixed-bed stainless steel reactor.The properties of different catalysts were characterized by NH_3-TPD,H_2-TPR,N_2-physisorption,and XRD.The 3V-10W-7.7Mn-4.3Ce/75Ti catalyst sample showed satisfactory performance at 240℃with NO removal efficiency>95%at 180—330℃and 80%remaining in H_2O and SO_2 at 240℃.It possesses substantial strong acid sites that enhances the adsorption capacity for NH_3 due to the 7.7%Mn O_2,and moderate Ce also promotes its low-temperature redox capacity.Mn O_2 and Ce O_2 can highly be dispersed on the surface of Ti O_2 although the BET surface area of 3V-10W-7.7Mn-4.3Ce/75Ti is close to 67m~2/g.
Due to the selective catalytic reduction(SCR)activities of Mn at low temperature and the oxygen storage capacity of Ce,Mn and Ce were introduced into V-W/Ti.Eight catalyst samples were prepared by the impregnation method.The experiments of de NO_x and resistance to H_2O and SO_2 for the catalysts were conducted with ammonia gas as the reductant in a fixed-bed stainless steel reactor.The properties of different catalysts were characterized by NH_3-TPD,H_2-TPR,N_2-physisorption,and XRD.The 3V-10W-7.7Mn-4.3Ce/75Ti catalyst sample showed satisfactory performance at 240℃with NO removal efficiency>95%at 180—330℃and 80%remaining in H_2O and SO_2 at 240℃.It possesses substantial strong acid sites that enhances the adsorption capacity for NH_3 due to the 7.7%Mn O_2,and moderate Ce also promotes its low-temperature redox capacity.Mn O_2 and Ce O_2 can highly be dispersed on the surface of Ti O_2 although the BET surface area of 3V-10W-7.7Mn-4.3Ce/75Ti is close to 67m~2/g.
引文
[1]陈焕章,李宏,李花.负载型Mn-Fe/γ-Al2O3低温脱硝催化剂的性能[J].化工进展,2016,35(4):1107-1112.CHEN H Z,LI H,LI H.Denitration performance of supported Mn-Fe/γ-Al2O3 catalyst at low temperature[J].Chemical Industry and Engineering Progress,2016,35(4):1107-1112.
[2]甘丽娜.低温V2O5-WO3/Ti O2脱硝催化剂开发与应用研究[D].北京:中国科学院大学,2016.GAN L N.Development of V2O5-WO3/Ti O2 catalyst and its application in NH3-SCR of NOx at low temperatures[D].Beijing:University of Chinese Academy of Sciences,2016.
[3]朱崇兵,金保升,李锋,等.蜂窝状V2O5-WO3/Ti O2催化剂脱硝性能研究[J].中国电机工程学报,2007,27(29):45-50.ZHU C B,JIN B S,LI F,et al.Study on de NOx performance of honeycomb V2O5-WO3/Ti O2 catalysts[J].Proceedings of the CSEE,2007,27(29):45-50.
[4]李晨露,唐晓龙,易红宏,等.Mn基低温SCR催化剂的抗H2O、抗SO2研究进展[J].化工进展,2017,36(3):934-943.LI C L,TANG X L,YI H H,et al.Review on manganese based catalysts resistant to H2O and SO2 for SCR reduction at low temperature[J].Chemical Industry and Engineering Progress,2017,36(3):934-943.
[5]耿春香,刘文蓉,柴倩倩,等.Mn-Ce/Ti O2低温脱硝催化剂的性能[J].化工进展,2012,31(6):1353-1356.GENG C X,LIU W R,CHAI Q Q,et al.Study on the denitration characteristics of Mn-Ce/Ti O2 catalyst at low temperature[J].Chemical Industry and Engineering Progress,2012,31(6):1353-1356.
[6]JIN R,LIU Y,WU Z,et al.Relationship between SO2 poisoning effects and reaction temperature for selective catalytic reduction of NO over Mn-Ce/Ti O2 catalyst[J].Catalysis Today,2010,153(3/4):84-89.
[7]张呈祥.Mn-Ce/Al2O3低温SCR脱硝催化剂抗SO2中毒性能研究[D].大连:大连理工大学,2015.ZHANG C X.Study on SO2 resistance of Mn-Ce/Al2O3 for low-temperature selective catalytic reduction of NOx[D].Dalian:Dalian University of Technology,2015.
[8]张晓鹏.基于Mn/Ce-Zr O2催化剂的低温NH3-SCR脱硝性能研究[D].天津:南开大学,2013.ZHANG X P.Research of Mn/Ce-Zr O2 for selective catalytic reduction of NOx with NH3 at low temperature[D].Tianjin:Nankai University,2013.
[9]沈伯雄,吴姁徐,马宏卿,等.Mn-Ce/Ti-Zr-柱撑膨润土催化剂低温选择性催化还原法脱硝[J].化工环保,2012,32(6):552-556.SHEN B X,WU X X,MA H Q,et al.NO removal by low-temperature selective catalytic reduction on Mn-Ce/Ti-Zr-OPILC catalyst[J].Environmental Protection of Chemical Industry,2012,32(6):552-556.
[10]ZHU L,ZHONG Z,YANG H,et al.Effect of Mo O3 on vanadium based catalysts for the selective catalytic reduction of NOx with NH3at low temperature[J].Journal of Environmental Sciences,2017,56:169-179.
[11]王幸宜.催化剂表征[M].上海:华东理工大学出版社,2008.WANG X Y.Catalyst characterization[M].Shanghai:East China University of Science and Technology Press,2008.
[12]邹鹏.钒钛SCR烟气脱硝催化剂改性研究[D].济南:山东大学,2012.ZHOU P.Study on modification of V2O5/Ti O2 catalyst in SCR flue gas denitrification[D].Jinan:Shandong University,2012.
[13]ZHU L,ZHONG Z,YANG H,et al.De NOx performance and characteristic study for transition metals doped iron based catalysts[J].Korean Journal of Chemical Engineering,2017,34(4):1229-1237.
[14]TAE S P,SOON K J,AND S H H,et al.Selective catalytic reduction of nitrogen oxides with NH3 over natural manganese ore at low temperature[J].Ind.Eng.Chem.Res,2001,40(21):4491-4495.
[15]BESSELMANN S,FREITAG C,HINRICHSEN O,et al.Temperature-programmed reduction and oxidation experiments with V2O5/Ti O2 catalysts[J].Physical Chemistry Chemical Physics,2001,3(21):4633-4638.
[16]KIJLSTRA W S,BIERVLIET M,POELS E K,et al.Deactivation by SO2 of Mn Ox/Al2O3 catalysts used for the selective catalytic reduction of NO with NH3 at low temperatures[J].Applied Catalysis B:Environmental,1998,16(4):327-337.
[17]PICASSO G,GUTIéRREZ M,PINA M P,et al.Preparation and characterization of Ce-Zr and Ce-Mn based oxides for n-hexane combustion:application to catalytic membrane reactors[J].Chemical Engineering Journal,2007,126(2):119-130.
[18]杨剑,孙健,赵东.铈掺杂量对钒基SCR催化剂结构及性能的影响[J].功能材料,2015,46(18):18033-18036.YANG J,SUN J,ZHAO D.Inference of SCR catalyst microstructure and de-NO property over different amount of cerium doped[J].Journal of Functional Materials,2015,46(18):18033-18036.
[19]ZHAO H,BENNICI S,SHEN J,et al.Surface and catalytic properties of V2O5-Ti O2/SO42-catalysts for the oxidation of methanol prepared by various methods[J].Journal of Molecular Catalysis A:Chemical,2009,309(1/2):28-34.
[20]PAN S,LUO H,LI L,et al.H2O and SO2 deactivation mechanism of Mn Ox/MWCNTs for low-temperature SCR of NOx with NH3[J].Journal of Molecular Catalysis A:Chemical,2013,377:154-161.
[21]ZHU Z,LIU Z,NIU H,et al.Promoting effect of SO2 on activated carbon-supported vanadia catalyst for NO reduction by NH3 at low temperatures[J].Journal of Catalysis,1999,187(1):245-248.
[22]LIU F,HE H.Selective catalytic reduction of NO with NH3 over manganese substituted iron titanate catalyst:reaction mechanism and H2O/SO2 inhibition mechanism study[J].Catalysis Today,2010,153(3/4):70-76.
[23]JING W,GUO Q,HOU Y,et al.Catalytic role of vanadium(Ⅴ)sulfate on activated carbon for SO2 oxidation and NH3-SCR of NO at low temperatures[J].Catalysis Communications,2014,56:23-26.
[24]LIANG X,LI J,LIN Q,et al.Synthesis and characterization of mesoporous Mn/Al-SBA-15 and its catalytic activity for NO reduction with ammonia[J].Catalysis Communications,2007,8(12):1901-1904.
[25]SMIRNIOTIS P G,PENA D A,UPHADE B S.Chem Inform abstract:low-temperature selective catalytic reduction(SCR)of NO with NH3 by using Mn,Cr,and Cu oxides supported on hombikat Ti O2[J].Cheminform,2001,40(13):2479-2482.
[2]甘丽娜.低温V2O5-WO3/Ti O2脱硝催化剂开发与应用研究[D].北京:中国科学院大学,2016.GAN L N.Development of V2O5-WO3/Ti O2 catalyst and its application in NH3-SCR of NOx at low temperatures[D].Beijing:University of Chinese Academy of Sciences,2016.
[3]朱崇兵,金保升,李锋,等.蜂窝状V2O5-WO3/Ti O2催化剂脱硝性能研究[J].中国电机工程学报,2007,27(29):45-50.ZHU C B,JIN B S,LI F,et al.Study on de NOx performance of honeycomb V2O5-WO3/Ti O2 catalysts[J].Proceedings of the CSEE,2007,27(29):45-50.
[4]李晨露,唐晓龙,易红宏,等.Mn基低温SCR催化剂的抗H2O、抗SO2研究进展[J].化工进展,2017,36(3):934-943.LI C L,TANG X L,YI H H,et al.Review on manganese based catalysts resistant to H2O and SO2 for SCR reduction at low temperature[J].Chemical Industry and Engineering Progress,2017,36(3):934-943.
[5]耿春香,刘文蓉,柴倩倩,等.Mn-Ce/Ti O2低温脱硝催化剂的性能[J].化工进展,2012,31(6):1353-1356.GENG C X,LIU W R,CHAI Q Q,et al.Study on the denitration characteristics of Mn-Ce/Ti O2 catalyst at low temperature[J].Chemical Industry and Engineering Progress,2012,31(6):1353-1356.
[6]JIN R,LIU Y,WU Z,et al.Relationship between SO2 poisoning effects and reaction temperature for selective catalytic reduction of NO over Mn-Ce/Ti O2 catalyst[J].Catalysis Today,2010,153(3/4):84-89.
[7]张呈祥.Mn-Ce/Al2O3低温SCR脱硝催化剂抗SO2中毒性能研究[D].大连:大连理工大学,2015.ZHANG C X.Study on SO2 resistance of Mn-Ce/Al2O3 for low-temperature selective catalytic reduction of NOx[D].Dalian:Dalian University of Technology,2015.
[8]张晓鹏.基于Mn/Ce-Zr O2催化剂的低温NH3-SCR脱硝性能研究[D].天津:南开大学,2013.ZHANG X P.Research of Mn/Ce-Zr O2 for selective catalytic reduction of NOx with NH3 at low temperature[D].Tianjin:Nankai University,2013.
[9]沈伯雄,吴姁徐,马宏卿,等.Mn-Ce/Ti-Zr-柱撑膨润土催化剂低温选择性催化还原法脱硝[J].化工环保,2012,32(6):552-556.SHEN B X,WU X X,MA H Q,et al.NO removal by low-temperature selective catalytic reduction on Mn-Ce/Ti-Zr-OPILC catalyst[J].Environmental Protection of Chemical Industry,2012,32(6):552-556.
[10]ZHU L,ZHONG Z,YANG H,et al.Effect of Mo O3 on vanadium based catalysts for the selective catalytic reduction of NOx with NH3at low temperature[J].Journal of Environmental Sciences,2017,56:169-179.
[11]王幸宜.催化剂表征[M].上海:华东理工大学出版社,2008.WANG X Y.Catalyst characterization[M].Shanghai:East China University of Science and Technology Press,2008.
[12]邹鹏.钒钛SCR烟气脱硝催化剂改性研究[D].济南:山东大学,2012.ZHOU P.Study on modification of V2O5/Ti O2 catalyst in SCR flue gas denitrification[D].Jinan:Shandong University,2012.
[13]ZHU L,ZHONG Z,YANG H,et al.De NOx performance and characteristic study for transition metals doped iron based catalysts[J].Korean Journal of Chemical Engineering,2017,34(4):1229-1237.
[14]TAE S P,SOON K J,AND S H H,et al.Selective catalytic reduction of nitrogen oxides with NH3 over natural manganese ore at low temperature[J].Ind.Eng.Chem.Res,2001,40(21):4491-4495.
[15]BESSELMANN S,FREITAG C,HINRICHSEN O,et al.Temperature-programmed reduction and oxidation experiments with V2O5/Ti O2 catalysts[J].Physical Chemistry Chemical Physics,2001,3(21):4633-4638.
[16]KIJLSTRA W S,BIERVLIET M,POELS E K,et al.Deactivation by SO2 of Mn Ox/Al2O3 catalysts used for the selective catalytic reduction of NO with NH3 at low temperatures[J].Applied Catalysis B:Environmental,1998,16(4):327-337.
[17]PICASSO G,GUTIéRREZ M,PINA M P,et al.Preparation and characterization of Ce-Zr and Ce-Mn based oxides for n-hexane combustion:application to catalytic membrane reactors[J].Chemical Engineering Journal,2007,126(2):119-130.
[18]杨剑,孙健,赵东.铈掺杂量对钒基SCR催化剂结构及性能的影响[J].功能材料,2015,46(18):18033-18036.YANG J,SUN J,ZHAO D.Inference of SCR catalyst microstructure and de-NO property over different amount of cerium doped[J].Journal of Functional Materials,2015,46(18):18033-18036.
[19]ZHAO H,BENNICI S,SHEN J,et al.Surface and catalytic properties of V2O5-Ti O2/SO42-catalysts for the oxidation of methanol prepared by various methods[J].Journal of Molecular Catalysis A:Chemical,2009,309(1/2):28-34.
[20]PAN S,LUO H,LI L,et al.H2O and SO2 deactivation mechanism of Mn Ox/MWCNTs for low-temperature SCR of NOx with NH3[J].Journal of Molecular Catalysis A:Chemical,2013,377:154-161.
[21]ZHU Z,LIU Z,NIU H,et al.Promoting effect of SO2 on activated carbon-supported vanadia catalyst for NO reduction by NH3 at low temperatures[J].Journal of Catalysis,1999,187(1):245-248.
[22]LIU F,HE H.Selective catalytic reduction of NO with NH3 over manganese substituted iron titanate catalyst:reaction mechanism and H2O/SO2 inhibition mechanism study[J].Catalysis Today,2010,153(3/4):70-76.
[23]JING W,GUO Q,HOU Y,et al.Catalytic role of vanadium(Ⅴ)sulfate on activated carbon for SO2 oxidation and NH3-SCR of NO at low temperatures[J].Catalysis Communications,2014,56:23-26.
[24]LIANG X,LI J,LIN Q,et al.Synthesis and characterization of mesoporous Mn/Al-SBA-15 and its catalytic activity for NO reduction with ammonia[J].Catalysis Communications,2007,8(12):1901-1904.
[25]SMIRNIOTIS P G,PENA D A,UPHADE B S.Chem Inform abstract:low-temperature selective catalytic reduction(SCR)of NO with NH3 by using Mn,Cr,and Cu oxides supported on hombikat Ti O2[J].Cheminform,2001,40(13):2479-2482.