CeTiO_x脱硝催化剂的抗硫中毒性能
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摘要
分别以Ce_2(C_2O_4)_3和Ce(SO4)2为Ce前驱体,采用固相球磨法制备了Ce基选择性催化还原(SCR)脱硝催化剂CeTiO_x-A[以Ce_2(C_2O_4)_3为前驱体]和CeTiO_x-B[以Ce(SO4)2为前驱体].将2个催化剂分别在体积分数为0. 15%的SO2的气氛下反应40和60 h,得到高硫条件下SCR反应后的CeTiO_x催化剂,分别记为40CeTiOx-A,60CeTiOx-A,40CeTiOx-B和60CeTiOx-B.考察了反应前后催化剂的NH_3-SCR反应活性.采用X射线衍射(XRD)、X射线荧光光谱(XRF)、比表面积(BET)测试、H2程序升温还原(H2-TPR)、X射线光电子能谱(XPS)、NH_3程序升温脱附(NH_3-TPD)及SO2程序升温脱附(SO2-TPD)等技术对样品进行了表征.结果表明,CeTiO_x-A系列催化剂比CeTiO_x-B系列催化剂具有更高的NH_3-SCR反应活性和更好的抗硫抗水性能.与CeTiO_x-B系列催化剂相比,CeTiO_x-A系列催化剂具有更大的比表面积和孔容,更多的Ce~(3+)和吸附氧(Oα)物种有助于NO的吸附和活化; CeTiO_x-A系统催化剂还具有更多的Lewis强酸性位数量,可以吸附更多的NH_3分子,有利于催化剂上NH_3-SCR反应的进行,提高了CeTiO_x-A系列催化剂的NO转化率.
Ceria-based catalysts( CeTiO_x-A and CeTiO_x-B) were prepared by solid state ball milling method with Ce_2(C_2O_4)_3 and Ce( SO4)2 as precursors,respectively. Then,the prepared ceria-based catalysts were treated in reaction atmosphere consisted of 0. 15% SO2 for 40 and 60 h,respectively. The obtained catalysts were designated as 40 CeTiO_x-A,60 CeTiO_x-A,40 CeTiO_x-B and 60 CeTiO_x-B. The performances of fresh and used catalysts for selective catalytic reduction( SCR) of NO with NH_3 as the reductant were investigated. The catalysts were also characterized using X-ray diffraction( XRD),X-ray fluorescence spectra( XRF),Brunner emmet teller( BET),H2-temperature programmed reduction( H2-TPR),X-ray photoelectron spectra( XPS),NH_3-temperature programmed desorption( NH_3-TPD) and SO2-temperature programmed desorption( SO2-TPD)techniques. The results indicated that the NH_3-SCR activity,SO2 and H2 O resistance over the CeTiO_x-A catalysts were better than over the CeTiO_x-B samples. The reasons for this phenomenon are that CeTiO_x-A catalysts possess larger specific surface area and pore volume than CeTiO_x-B catalysts. Besides,CeTiO_x-A catalysts have plenty of Ce3+and the surface adsorbed oxygen,which would benefit the adsorption and activation of NO. Furthermore,CeTiO_x-A catalysts also have numerous strong Lewis acid sites,which lead to the increasing adsorption of NH_3. Therefore,the NH_3-SCR reaction rate and the NO conversion of CeTiO_x-A catalysts was improved.
Ceria-based catalysts( CeTiO_x-A and CeTiO_x-B) were prepared by solid state ball milling method with Ce_2(C_2O_4)_3 and Ce( SO4)2 as precursors,respectively. Then,the prepared ceria-based catalysts were treated in reaction atmosphere consisted of 0. 15% SO2 for 40 and 60 h,respectively. The obtained catalysts were designated as 40 CeTiO_x-A,60 CeTiO_x-A,40 CeTiO_x-B and 60 CeTiO_x-B. The performances of fresh and used catalysts for selective catalytic reduction( SCR) of NO with NH_3 as the reductant were investigated. The catalysts were also characterized using X-ray diffraction( XRD),X-ray fluorescence spectra( XRF),Brunner emmet teller( BET),H2-temperature programmed reduction( H2-TPR),X-ray photoelectron spectra( XPS),NH_3-temperature programmed desorption( NH_3-TPD) and SO2-temperature programmed desorption( SO2-TPD)techniques. The results indicated that the NH_3-SCR activity,SO2 and H2 O resistance over the CeTiO_x-A catalysts were better than over the CeTiO_x-B samples. The reasons for this phenomenon are that CeTiO_x-A catalysts possess larger specific surface area and pore volume than CeTiO_x-B catalysts. Besides,CeTiO_x-A catalysts have plenty of Ce3+and the surface adsorbed oxygen,which would benefit the adsorption and activation of NO. Furthermore,CeTiO_x-A catalysts also have numerous strong Lewis acid sites,which lead to the increasing adsorption of NH_3. Therefore,the NH_3-SCR reaction rate and the NO conversion of CeTiO_x-A catalysts was improved.
引文
[1] Dunn J. P.,Koppula P. R.,Stenger H. G.,Wachs I. E.,Appl. Catal. B:Environ.,1998,19,103—117
[2] Dunn J. P.,Stenger H. G. Jr.,Wachs I. E.,J. Catal.,1999,181,233—243
[3] Yates M.,Martin J. A.,Martin-Luengo M. A.,Suarez S.,Suarez J.,Catal. Today,2005,107/108,120—125
[4] Koebel M.,Elsener M.,Kleemann M.,Catal. Today,2000,59,335—345
[5] Qu R. Y.,Gao X.,Cen K. F.,Li J. H.,Appl. Catal. B:Environ.,2013,142/143,290—297
[6] Ma Z.,Weng D.,Wu X. D.,Si Z. C.,Wang B.,Catal. Commun.,2012,27,97—100
[7] Li X. L.,Li Y. H.,Deng S. S.,Rong T. A.,Catal. Commun.,2013,40,47—50
[8] Sun X. L.,He H.,Su Y. C.,Yan J. F.,Song L. Y.,Qiu W. G.,Chem. J. Chinese Universities,2017,38(5),814—822(孙向丽,何洪,苏垚超,闫京芳,宋丽云,邱文革.高等学校化学学报,2017,38(5),814—822)
[9] Gao X.,Jiang Y.,Fu Y. C.,Zhong Y.,Luo Z. Y.,Cen K. F.,Catal. Commun.,2010,11,465—469
[10] Zhang Q. L.,Song Z. X.,Ning P.,Liu X.,Li H.,Gu J. J.,Catal. Commun.,2015,59,170—174
[11] Gao S.,Wang P. L.,Chen X. B.,Wang H. Q.,Wu Z. B.,Liu Y.,Weng X. L.,Catal. Commun.,2014,43,223—226
[12] Zhang L.,Zou W. X.,Ma K. L.,Cao Y.,Xiong Y.,Wu S. G.,Tang C. J.,Gao F.,Dong L.,J. Phys. Chem. C.,2015,119,1155—1163
[13] Yan J. F.,Qiu W. G.,Song L. Y.,Chen Y.,Su Y. C.,Bai G. M.,Zhang G. Z.,He H.,Chem. Commun.,2017,53,1321—1324
[14] Song L. Y.,Zhan Z. C.,Liu X. J.,He H.,Qiu W. G.,Zi X. H.,Chinese J. Catal.,2014,35(7),1030—1035(宋丽云,展宗城,刘晓军,何洪,邱文革,訾学红.催化学报,2014,35(7),1030—1035)
[15] Chao J. D.,He H.,Song L. Y.,Fang Y. J.,Liang Q. M.,Zhang G. G.,Qiu W. G.,Zhang R.,Chem. J. Chinese Universities,2015,36(3),523—530(晁晶迪,何洪,宋丽云,房玉娇,梁全明,张桂臻,邱文革,张然.高等学校化学学报,2015,36(3),523—530)
[16] Casanova M.,Rocchini E.,Trovarelli A.,Schermanz K.,Begsteiger I.,J. Alloys. Compd.,2006,408/412,1108—1112
[17] Guo X. Y.,Bartholomew C.,Hecker W.,Baxter L. L.,Appl. Catal. B:Environ.,2009,92,30—40
[18] Sheng Z. Y.,Hu Y. F.,Xue J. M.,Wang X. M.,Liao W. P.,J. Rare. Earth.,2012,30,676—682
[19] Arakawa K.,Matsuda S.,Kinoshita H.,Appl. Surf. Sci..,1997,121(1),382—386
[20] Liu F. D.,Asakura K.,He H.,Shan W. P.,Shi X. Y.,Zhang C. B.,Appl. Catal. B:Environ.,2011,103,369—377
[21] Waqif M.,Bazin P.,Saur O.,Lavalley J. C.,Blanchard G.,Touret O.,Appl. Catal. B:Environ.,1997,11,193—205
[22] Yang S. J.,Guo Y. F.,Chang H. Z.,Ma L.,Peng Y.,Qu Z.,Yan N. Q.,Wang C. Z.,Li J. H.,Appl. Catal. B:Environ.,2013,136/137,19—28
[23] Zhang L.,Li L. L.,Cao Y.,Yao X. J.,Ge C. Y.,Gao F.,Deng Y.,Tang C. J.,Dong L.,Appl. Catal. B:Environ.,2015,165,589—598
[24] Chen Y. X.,Jiang Y.,Li W. Z.,Jin R. C.,Tang S. Z.,Hu W. B.,Catal. Today,1999,50,39—47
[25] Wu Z. B.,Jin R. B.,Wang H. Q.,Liu Y.,Catal. Commun.,2009,10,935—939
[26] Karami A.,Salehi V.,J. Catal.,2012,292,32—43
[27] Ferrizz R. M.,Gorte R. J.,Vohs J. M.,Catal. Lett.,2002,82,123—129
[28] Hino M.,Kurashige M.,Matsuhashi H.,Arata K.,Thermochim. Acta,2006,441,35—41
[29] Shinde V. M.,Madras G.,Appl. Catal. B:Environ.,2013,138/139,51—61
[30] Rodriguez J. A.,Jirsak T.,Freitag A.,Hanson J. C.,Larese J. Z.,Chaturvedi S.,Catal. Lett.,1999,62,113—119
[31] Boaro M.,Leitenburg C. D.,Dolcetti G.,Trovarelli A.,Graziani M.,Top. Catal.,2001,16/17,229—306
[32] Chen L.,Li J. H.,Ge M. F.,Zhu R. H.,Catal. Today,2010,153,77—83
[33] Yao X. J.,Zhang L.,Li L. L.,Liu L. C.,Cao Y.,Dong X.,Gao F.,Deng Y.,Tang C. J.,Chen Z.,Dong L.,Chen Y.,Appl. Catal.B:Environ.,2014,150/151,315—329
[34] Zhang R.,Zhong Q.,Zhao W.,Yu L. M.,Qu H. X.,Appl. Surf. Sci.,2014,289,237—244
[35] Guo R. T.,Zhou Y.,Pan W. G.,Hong J. N.,Zhen W. L.,Jin Q.,Ding C. G.,Guo S. Y.,J. Ind. Eng. Chem.,2013,19,2022—2025
[36] Xu T. F.,Wu X. D.,Liu X. S.,Cao L.,Lin Q. W.,Weng D.,J. Environ. Sci.,2016,57,110—117
[37] Zhu M. H.,Lai J. K.,Tumuluri U.,Wu Z. L.,Wachs I. E.,J. Am. Chem. Soc.,2017,139,44,15624—15627
[2] Dunn J. P.,Stenger H. G. Jr.,Wachs I. E.,J. Catal.,1999,181,233—243
[3] Yates M.,Martin J. A.,Martin-Luengo M. A.,Suarez S.,Suarez J.,Catal. Today,2005,107/108,120—125
[4] Koebel M.,Elsener M.,Kleemann M.,Catal. Today,2000,59,335—345
[5] Qu R. Y.,Gao X.,Cen K. F.,Li J. H.,Appl. Catal. B:Environ.,2013,142/143,290—297
[6] Ma Z.,Weng D.,Wu X. D.,Si Z. C.,Wang B.,Catal. Commun.,2012,27,97—100
[7] Li X. L.,Li Y. H.,Deng S. S.,Rong T. A.,Catal. Commun.,2013,40,47—50
[8] Sun X. L.,He H.,Su Y. C.,Yan J. F.,Song L. Y.,Qiu W. G.,Chem. J. Chinese Universities,2017,38(5),814—822(孙向丽,何洪,苏垚超,闫京芳,宋丽云,邱文革.高等学校化学学报,2017,38(5),814—822)
[9] Gao X.,Jiang Y.,Fu Y. C.,Zhong Y.,Luo Z. Y.,Cen K. F.,Catal. Commun.,2010,11,465—469
[10] Zhang Q. L.,Song Z. X.,Ning P.,Liu X.,Li H.,Gu J. J.,Catal. Commun.,2015,59,170—174
[11] Gao S.,Wang P. L.,Chen X. B.,Wang H. Q.,Wu Z. B.,Liu Y.,Weng X. L.,Catal. Commun.,2014,43,223—226
[12] Zhang L.,Zou W. X.,Ma K. L.,Cao Y.,Xiong Y.,Wu S. G.,Tang C. J.,Gao F.,Dong L.,J. Phys. Chem. C.,2015,119,1155—1163
[13] Yan J. F.,Qiu W. G.,Song L. Y.,Chen Y.,Su Y. C.,Bai G. M.,Zhang G. Z.,He H.,Chem. Commun.,2017,53,1321—1324
[14] Song L. Y.,Zhan Z. C.,Liu X. J.,He H.,Qiu W. G.,Zi X. H.,Chinese J. Catal.,2014,35(7),1030—1035(宋丽云,展宗城,刘晓军,何洪,邱文革,訾学红.催化学报,2014,35(7),1030—1035)
[15] Chao J. D.,He H.,Song L. Y.,Fang Y. J.,Liang Q. M.,Zhang G. G.,Qiu W. G.,Zhang R.,Chem. J. Chinese Universities,2015,36(3),523—530(晁晶迪,何洪,宋丽云,房玉娇,梁全明,张桂臻,邱文革,张然.高等学校化学学报,2015,36(3),523—530)
[16] Casanova M.,Rocchini E.,Trovarelli A.,Schermanz K.,Begsteiger I.,J. Alloys. Compd.,2006,408/412,1108—1112
[17] Guo X. Y.,Bartholomew C.,Hecker W.,Baxter L. L.,Appl. Catal. B:Environ.,2009,92,30—40
[18] Sheng Z. Y.,Hu Y. F.,Xue J. M.,Wang X. M.,Liao W. P.,J. Rare. Earth.,2012,30,676—682
[19] Arakawa K.,Matsuda S.,Kinoshita H.,Appl. Surf. Sci..,1997,121(1),382—386
[20] Liu F. D.,Asakura K.,He H.,Shan W. P.,Shi X. Y.,Zhang C. B.,Appl. Catal. B:Environ.,2011,103,369—377
[21] Waqif M.,Bazin P.,Saur O.,Lavalley J. C.,Blanchard G.,Touret O.,Appl. Catal. B:Environ.,1997,11,193—205
[22] Yang S. J.,Guo Y. F.,Chang H. Z.,Ma L.,Peng Y.,Qu Z.,Yan N. Q.,Wang C. Z.,Li J. H.,Appl. Catal. B:Environ.,2013,136/137,19—28
[23] Zhang L.,Li L. L.,Cao Y.,Yao X. J.,Ge C. Y.,Gao F.,Deng Y.,Tang C. J.,Dong L.,Appl. Catal. B:Environ.,2015,165,589—598
[24] Chen Y. X.,Jiang Y.,Li W. Z.,Jin R. C.,Tang S. Z.,Hu W. B.,Catal. Today,1999,50,39—47
[25] Wu Z. B.,Jin R. B.,Wang H. Q.,Liu Y.,Catal. Commun.,2009,10,935—939
[26] Karami A.,Salehi V.,J. Catal.,2012,292,32—43
[27] Ferrizz R. M.,Gorte R. J.,Vohs J. M.,Catal. Lett.,2002,82,123—129
[28] Hino M.,Kurashige M.,Matsuhashi H.,Arata K.,Thermochim. Acta,2006,441,35—41
[29] Shinde V. M.,Madras G.,Appl. Catal. B:Environ.,2013,138/139,51—61
[30] Rodriguez J. A.,Jirsak T.,Freitag A.,Hanson J. C.,Larese J. Z.,Chaturvedi S.,Catal. Lett.,1999,62,113—119
[31] Boaro M.,Leitenburg C. D.,Dolcetti G.,Trovarelli A.,Graziani M.,Top. Catal.,2001,16/17,229—306
[32] Chen L.,Li J. H.,Ge M. F.,Zhu R. H.,Catal. Today,2010,153,77—83
[33] Yao X. J.,Zhang L.,Li L. L.,Liu L. C.,Cao Y.,Dong X.,Gao F.,Deng Y.,Tang C. J.,Chen Z.,Dong L.,Chen Y.,Appl. Catal.B:Environ.,2014,150/151,315—329
[34] Zhang R.,Zhong Q.,Zhao W.,Yu L. M.,Qu H. X.,Appl. Surf. Sci.,2014,289,237—244
[35] Guo R. T.,Zhou Y.,Pan W. G.,Hong J. N.,Zhen W. L.,Jin Q.,Ding C. G.,Guo S. Y.,J. Ind. Eng. Chem.,2013,19,2022—2025
[36] Xu T. F.,Wu X. D.,Liu X. S.,Cao L.,Lin Q. W.,Weng D.,J. Environ. Sci.,2016,57,110—117
[37] Zhu M. H.,Lai J. K.,Tumuluri U.,Wu Z. L.,Wachs I. E.,J. Am. Chem. Soc.,2017,139,44,15624—15627
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