CuFe-SAPO-34分子筛的结构和催化性能研究
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摘要
采用一步水热合成法,通过调变初始凝胶中的硅铁比,制备系列铜铁含量不同的CuFe-SAPO-34催化剂用于NH_3选择性催化还原NO_x反应(NH_3-SCR),并采用ICP、 XRD、 SEM、 BET、 H_2-TPR等方法对其结构进行表征.结果表明, CuFe-SAPO-34催化剂具有典型的CHA结构, Cu和Fe均处于分子筛载体的离子交换位.当初始凝胶SiO_2/Fe_2O_3=10时, Cu_(2.5)Fe_(3.1)-SAPO-34催化剂具有最大的比表面积和孔容.掺杂适量的Fe,可提高活性物种Cu~(2+)的比例及其氧化还原性能,显著降低Cu物种的聚集程度. NH_3-SCR反应结果表明, Cu_(2.5)Fe_(3.1)-SAPO-34催化剂具有最宽的反应温度窗口.与Cu-SAPO-34相比, Fe的掺杂显著提高了其高温段的催化活性和低温抗水能力,提高了Cu-CHA催化剂在实际应用中的稳定性.
CuFe-SAPO-34 catalysts were prepared by one-pot hydrothermal synthesized method in this study. The physiochemical structure was characterized by ICP, XRD, SEM, BET and H_2-TPR. The performance in selective catalytic reduction of NO_x with NH_3(NH_3-SCR) were carried out. The CuFe-SAPO-34 catalyst with typical CHA structure and different content of Cu and Fe could be obtained through the adjustment of the addition of Fe in the initial gel. When the ratio of SiO_2/Fe_2O_3 was 10, the obtained Cu_(2.5)Fe_(3.1)-SAPO-34 showed higher specific area and pore volume with more active sites and less accumulation of Cu species. The results of NH_3-SCR reaction indicated that the obtained Cu_(2.5)Fe_(3.1)-SAPO-34 catalyst showed the widest reaction temperature window. Compared with Cu-SAPO-34 catalyst, Cu_(2.5)Fe_(3.1)-SAPO-34 showed better NH_3-SCR performance, especially in middle and high temperature range. The results of H_2O resistance in low temperature range also revealed that the addition of Fe was beneficial for the enhancement of the stability of Cu-CHA catalyst.
CuFe-SAPO-34 catalysts were prepared by one-pot hydrothermal synthesized method in this study. The physiochemical structure was characterized by ICP, XRD, SEM, BET and H_2-TPR. The performance in selective catalytic reduction of NO_x with NH_3(NH_3-SCR) were carried out. The CuFe-SAPO-34 catalyst with typical CHA structure and different content of Cu and Fe could be obtained through the adjustment of the addition of Fe in the initial gel. When the ratio of SiO_2/Fe_2O_3 was 10, the obtained Cu_(2.5)Fe_(3.1)-SAPO-34 showed higher specific area and pore volume with more active sites and less accumulation of Cu species. The results of NH_3-SCR reaction indicated that the obtained Cu_(2.5)Fe_(3.1)-SAPO-34 catalyst showed the widest reaction temperature window. Compared with Cu-SAPO-34 catalyst, Cu_(2.5)Fe_(3.1)-SAPO-34 showed better NH_3-SCR performance, especially in middle and high temperature range. The results of H_2O resistance in low temperature range also revealed that the addition of Fe was beneficial for the enhancement of the stability of Cu-CHA catalyst.
引文
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[20] Cao Y,Zou S,Lan L,et al.Promotional effect of Ce on Cu-SAPO-34 monolith catalyst for selective catalytic reduction of NOx with ammonia[J].J Mol Catal A:Chem,2015,398:304-311.
[21] Niu C,Shi X,Liu K,et al.A novel one-pot synthesized CuCe-SAPO-34 catalyst with high NH3-SCR activity and H2O resistance[J].Catal Commun,2016,81:20-23.
[22] Dou Sheng-ping(窦生平),Zhao Wei(赵炜),Zhang Kai(张凯),et al.Catalytic performance research of Nd-doped V2O5/TiO2 for low temperature selective reduction of NOx with NH3 (Nd 掺杂V2O5/TiO2低温NH3选择性催化还原NOx性能研究) [J].J Mol Catal(China) (分子催化),2019,33(1):50-57.
[23] Yu Rui(喻瑞),Zhao Zhen-chao(赵侦超),Zhang Zhen-yu(张振宇),et al.Effects of Pt modification and reaction atmosphere on the catalytic performances of Cu/Al-rich beta zeolite in selective catalytic reduction of NO by NH3 (Pt修饰和反应气氛对富铝Cu-Beta分子筛NH3-SCR反应性能的影响) [J].J Mol Catal(China) (分子催化),2016,30(5):428-434.
[24] Zhao Kun(赵堃),Han Wei-liang(韩维亮),Zhang Guo-dong(张国栋),et al.Review of metal oxide catalysts for diesel exhaust purification (柴油车SCR脱硝金属氧化物催化剂研究进展) [J].J Mol Catal(China) (分子催化),2015,29(5):494-504.
[25] Tang Nan(唐南),Huang Yan(黄妍),Li Yuan-yuan(李元元),et al.Low temperature selective catalytic reduction of NO with NH3 over Fe-Mn catalysts prepared by hydrothermal method (水热法制备铁锰催化剂脱硝性能及抗水抗硫性能研究) [J].J Mol Catal(China) (分子催化),2018,32(3):240-248.
[26] Fang Qi-long(方祺隆),Zhu Bao-zhong(朱宝忠),Sun Yun-lan(孙运兰),et al.Study on the performance of low temperature De-NOx based on Mn-Fe/Al2O3 catalysts (Mn-Fe/Al2O3催化剂的低温脱硝性能研究) [J].J Mol Catal(China) (分子催化),2018,32(4):305-314.
[27] Gao Rui-rui(高蕊蕊),Lou Xiao-rong(娄晓荣),Bai Wen-jun(白文君),et al.Influence of preparation technology on the activities of Mn-Fe/ZSM-5 catalysts for selective catalytic reduction of NO with NH3 (制备工艺对Mn-Fe/ZSM-5催化剂在NH3选择催化还原NO反应中催化性能的影响) [J].J Mol Catal(China) (分子催化),2015,29(6):563-574.
[28] Yang X,Wu Z,Moses-Debusk M,et al.Heterometal incorporation in metal-exchanged zeolites enables low-temperature catalytic activity of NOx reduction[J].J Phys Chem C,2012,116(44):23322-23331.
[29] Zhang R,Li Y,Zhen T.Ammonia selective catalytic reduction of NO over Fe/Cu-SSZ-13[J].RSC Adv,2014,4:52130-52139.
[30] Liu X,Li Y,Zhang R.Ammonia selective catalytic reduction of NO over Ce-Fe/Cu-SSZ-13 catalysts[J].RSC Adv,2015,5:85453-85459.
[31] Ren L,Zhu L,Yang C,et al.Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH3[J].Chem Commun(Camb),2011,47(35):9789-9791.
[32] Gao F,Kollár M,Kukkadapu R K,et al.Fe/SSZ-13 as an NH3-SCR catalyst:A reaction kinetics and FTIR/M?ssbauer spectroscopic study[J].Appl Catal B:Environ,2015,164:407-419.
[33] Wang J,Yu T,Wang X,et al.The influence of silicon on the catalytic properties of Cu/SAPO-34 for NOx reduction by ammonia-SCR [J].Appl Catal B:Environ,2012,127:137-147.
[34] Kispersky V F,Kropf A J,Ribeiro F H,et al.Low absorption vitreous carbon reactors for operando XAS:a case study on Cu/Zeolites for selective catalytic reduction of NOx by NH3[J].Phys Chem Chem Phys,2012,14(7):2229-2238.
[35] Xue J,Wang X,Qi G,et al.Characterization of copper species over Cu/SAPO-34 in selective catalytic reduction of NOx with ammonia:Relationships between active Cu sites and de-NOx performance at low temperature[J].J Catal,2013,297:56-64.
[36] Xie L,Liu F,Ren L,et al.Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NO with NH3[J].Environ Sci & Technol,2014,48(1):566-572.
[37] Zhang R,Li Y,Zhen T.Ammonia selective catalytic reduction of NO over Fe/Cu-SSZ-13[J].RSC Adv,2014,4:52130-52139.
[38] Wang L,Li W,Qi G,et al.Location and nature of Cu species in Cu/SAPO-34 for selective catalytic reduction of NO with NH3[J].J Catal,2012,289:21-29.
[2] Sun Y,Jiang Q,Wang Z,et al.Investigation of the sources and evolution processes of severe haze pollution in Beijing in January 2013[J].J Geophys Res:Atmos,2014,119(7):4380-4398.
[3] He H,Wang Y,Ma Q,et al.Mineral dust and NOx promote the conversion of SO2 to sulfate in heavy pollution days[J].Sci Rep,2014,4:4172.
[4] Wang Y,Yao L,Wang L,et al.Mechanism for the formation of the January 2013 heavy haze pollution episode over central and eastern China[J].Sci Chin-Earth Sci,2013,57(1):14-25.
[5] Xie Li-juan (谢利娟),Shi Xiao-yan (石晓燕),Liu Fu-dong (刘福东),et al.Selective catalytic reduction of NO from diesel engine with NH3 over zeolites catalysts with chabazite (菱沸石在柴油车尾气NOx催化净化中的应用) [J].Prog Chem(化学进展),2016,28(12):1860-1869.
[6] He Hong (贺泓) ,Wang Xin-ming (王新明),Wang Yue-si (王跃思),et al.Formation mechanism and control strategies of haze in china (大气灰霾追因与控制) [J].Bull Chin Acad Sci(中国科学院院刊),2013,28(3):344-352.
[7] Johnson T V.Review of diesel emissions and control[J].Inter J Engineer Res,2009,10(5):275-285.
[8] Peng Zhao-liang (彭兆亮),Yu Hua-feng (俞华峰),Chen Ying (陈影),et al.Effect of HF on the properties of in situ synthesized Cu-SSZ-13 /cordierite catalyst and the removal of NOx (HF对Cu-SSZ-13 /堇青石的原位合成及脱除NOx的影响) [J].Environ Chem(环境化学),2015,34(4):627-636.
[9] Kwak J H,Tonkyn R G,Kim D H,et al.Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3[J].J Catal,2010,275(2):187-190.
[10] Fickel D W,D’ Addio E,Lauterbach J A,et al.The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites[J].Appl Catal B:Environ,2011,102(3/4):441-448.
[11] Su Qian (苏潜),Huang Yan (黄妍),Zhang Ying (张颖),et al.Effects of copper sources on selective catalytic reduction of NO with NH3 of Cu-SAPO-34 (铜源对Cu-SAPO-34氨催化还原NO性能的影响) [J].J Mol Catal(China) (分子催化),2016,30(2):151-158.
[12] Ye Q,Wang L,Yang R T.Activity,propene poisoning resistance and hydrothermal stability of copper exchanged chabazite-like zeolite catalysts for SCR of NO with ammonia in comparison to Cu-ZSM-5[J].Appl Catal A:Gener,2012,427/428(1):24-34.
[13] Wang D,Jangjou Y,Liu Y,et al.A comparison of hydrothermal aging effects on NH3-SCR of NOx over Cu-SSZ-13 and Cu-SAPO-34 catalysts[J].Appl Catal B:Environ,2015,165:438-445.
[14] Li Heng-yu(李恒宇),Bai Jie(白杰),Wang Jun-zhong(王俊忠),et al.Ullmann-type coupling reactions catalyzed by SAPO-34 supported copper nanoparticles (SAPO-34 分子筛载铜催化剂催化 Ullmann 偶联反应) [J].J Mol Catal(China) (分子催化),2016,30(4):317-323.
[15] Niu C,Shi X,Liu F,et al.High hydrothermal stability of Cu-SAPO-34 catalysts for the NH3-SCR of NOx[J].Chem Engineer J,2016,294:254-263.
[16] Fan S,Xue J,Yu T,et al.The effect of synthesis methods on Cu species and active sites over Cu/SAPO-34 for NH3-SCR reaction[J].Catal Sci & Technol,2013,3(9):2357-2364.
[17] Leistner K,Olsson L.Deactivation of Cu/SAPO-34 during low-temperature NH3-SCR[J].Appl Catal B:Environ,2015,165:192-199.
[18] Wang J,Fan D,Yu T,et al.Improvement of low-temperature hydrothermal stability of Cu/SAPO-34 catalysts by Cu2+ species[J].J Catal,2015,322:84-90.
[19] Dong X,Wang J,Zhao H,et al.The promotion effect of CeOx on Cu-SAPO-34 catalyst for selective catalytic reduction of NOx with ammonia[J].Catal Today,2015,258:28-34.
[20] Cao Y,Zou S,Lan L,et al.Promotional effect of Ce on Cu-SAPO-34 monolith catalyst for selective catalytic reduction of NOx with ammonia[J].J Mol Catal A:Chem,2015,398:304-311.
[21] Niu C,Shi X,Liu K,et al.A novel one-pot synthesized CuCe-SAPO-34 catalyst with high NH3-SCR activity and H2O resistance[J].Catal Commun,2016,81:20-23.
[22] Dou Sheng-ping(窦生平),Zhao Wei(赵炜),Zhang Kai(张凯),et al.Catalytic performance research of Nd-doped V2O5/TiO2 for low temperature selective reduction of NOx with NH3 (Nd 掺杂V2O5/TiO2低温NH3选择性催化还原NOx性能研究) [J].J Mol Catal(China) (分子催化),2019,33(1):50-57.
[23] Yu Rui(喻瑞),Zhao Zhen-chao(赵侦超),Zhang Zhen-yu(张振宇),et al.Effects of Pt modification and reaction atmosphere on the catalytic performances of Cu/Al-rich beta zeolite in selective catalytic reduction of NO by NH3 (Pt修饰和反应气氛对富铝Cu-Beta分子筛NH3-SCR反应性能的影响) [J].J Mol Catal(China) (分子催化),2016,30(5):428-434.
[24] Zhao Kun(赵堃),Han Wei-liang(韩维亮),Zhang Guo-dong(张国栋),et al.Review of metal oxide catalysts for diesel exhaust purification (柴油车SCR脱硝金属氧化物催化剂研究进展) [J].J Mol Catal(China) (分子催化),2015,29(5):494-504.
[25] Tang Nan(唐南),Huang Yan(黄妍),Li Yuan-yuan(李元元),et al.Low temperature selective catalytic reduction of NO with NH3 over Fe-Mn catalysts prepared by hydrothermal method (水热法制备铁锰催化剂脱硝性能及抗水抗硫性能研究) [J].J Mol Catal(China) (分子催化),2018,32(3):240-248.
[26] Fang Qi-long(方祺隆),Zhu Bao-zhong(朱宝忠),Sun Yun-lan(孙运兰),et al.Study on the performance of low temperature De-NOx based on Mn-Fe/Al2O3 catalysts (Mn-Fe/Al2O3催化剂的低温脱硝性能研究) [J].J Mol Catal(China) (分子催化),2018,32(4):305-314.
[27] Gao Rui-rui(高蕊蕊),Lou Xiao-rong(娄晓荣),Bai Wen-jun(白文君),et al.Influence of preparation technology on the activities of Mn-Fe/ZSM-5 catalysts for selective catalytic reduction of NO with NH3 (制备工艺对Mn-Fe/ZSM-5催化剂在NH3选择催化还原NO反应中催化性能的影响) [J].J Mol Catal(China) (分子催化),2015,29(6):563-574.
[28] Yang X,Wu Z,Moses-Debusk M,et al.Heterometal incorporation in metal-exchanged zeolites enables low-temperature catalytic activity of NOx reduction[J].J Phys Chem C,2012,116(44):23322-23331.
[29] Zhang R,Li Y,Zhen T.Ammonia selective catalytic reduction of NO over Fe/Cu-SSZ-13[J].RSC Adv,2014,4:52130-52139.
[30] Liu X,Li Y,Zhang R.Ammonia selective catalytic reduction of NO over Ce-Fe/Cu-SSZ-13 catalysts[J].RSC Adv,2015,5:85453-85459.
[31] Ren L,Zhu L,Yang C,et al.Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NOx by NH3[J].Chem Commun(Camb),2011,47(35):9789-9791.
[32] Gao F,Kollár M,Kukkadapu R K,et al.Fe/SSZ-13 as an NH3-SCR catalyst:A reaction kinetics and FTIR/M?ssbauer spectroscopic study[J].Appl Catal B:Environ,2015,164:407-419.
[33] Wang J,Yu T,Wang X,et al.The influence of silicon on the catalytic properties of Cu/SAPO-34 for NOx reduction by ammonia-SCR [J].Appl Catal B:Environ,2012,127:137-147.
[34] Kispersky V F,Kropf A J,Ribeiro F H,et al.Low absorption vitreous carbon reactors for operando XAS:a case study on Cu/Zeolites for selective catalytic reduction of NOx by NH3[J].Phys Chem Chem Phys,2012,14(7):2229-2238.
[35] Xue J,Wang X,Qi G,et al.Characterization of copper species over Cu/SAPO-34 in selective catalytic reduction of NOx with ammonia:Relationships between active Cu sites and de-NOx performance at low temperature[J].J Catal,2013,297:56-64.
[36] Xie L,Liu F,Ren L,et al.Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NO with NH3[J].Environ Sci & Technol,2014,48(1):566-572.
[37] Zhang R,Li Y,Zhen T.Ammonia selective catalytic reduction of NO over Fe/Cu-SSZ-13[J].RSC Adv,2014,4:52130-52139.
[38] Wang L,Li W,Qi G,et al.Location and nature of Cu species in Cu/SAPO-34 for selective catalytic reduction of NO with NH3[J].J Catal,2012,289:21-29.
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