锡负载量对PtSn/Al_2O_3催化丙烷脱氢性能的影响
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摘要
采用羰基合成-浸渍法制备了不同Pt/Sn摩尔比(3∶1,1∶1,1∶2和1∶3)的PtSn/Al_2O_3催化剂,利用N2吸附-脱附实验、X射线衍射(XRD)、透射电子显微镜(TEM)、吡啶吸附红外光谱(Py-IR)和热重-差热分析(TG-DTA)等手段对其进行了表征,研究了Sn负载量对PtSn/Al_2O_3的结构性质及催化丙烷脱氢性能的影响.结果表明,制备的PtSn/Al_2O_3具有较高的丙烯选择性和稳定性.当Pt/Sn摩尔比为3∶1和1∶1时,铂和锡在催化剂上主要以Pt3Sn和PtSn合金形式存在,合金的形成明显改善了催化剂的脱氢性能,可抑制金属颗粒的高温烧结;当Pt/Sn摩尔比为1∶2和1∶3时,铂主要以金属形式存在.随着Sn负载量的增加,催化剂上L酸性位逐渐减少,丙烷转化率降低,丙烯选择性增加,同时促使反应积炭从金属表面向载体迁移,改善了催化剂的稳定性.
PtSn/Al_2O_3 catalysts with different Pt/Sn molar ratios( 3 ∶ 1,1 ∶ 1,1 ∶ 2 and 1 ∶ 3) were prepared by carbonylation-impregnation method. The catalysts were characterized by means of nitrogen adsorptiondesorption,X-ray diffraction( XRD),transmission electron microscopy( TEM),infrared spectra of pyridine adsorption( Py-IR),and thermogravimetric-differential thermal analysis( TG-DTA). The effect of Sn loading on the catalytic properties of PtSn/Al_2O_3 in the propane dehydrogenation was studied. The results showed that the PtSn/Al_2O_3 catalyst had high propylene selectivity and catalytic stability. Platinum and tin were mainly in the form of Pt3 Sn and PtSn alloys with Pt/Sn ratios of 3 ∶ 1 and 1 ∶ 1. With the formation of the alloy,the dehydrogenation performance of the catalyst was improved significantly,and the high temperature sintering of metal particles was effectively suppressed. When the Pt/Sn ratio was 1 ∶ 2 and 1 ∶ 3,the metallic Pt was mainly resulted. With the increase of Sn loading,the Lewis acid sites on the catalyst gradually decreased,and the propylene selectivity increased associated with the propane conversion decreased. At the same time,the addition of Sn promoted the migration of carbon deposition from the metal surface to support,and improved the stability of the catalyst.
PtSn/Al_2O_3 catalysts with different Pt/Sn molar ratios( 3 ∶ 1,1 ∶ 1,1 ∶ 2 and 1 ∶ 3) were prepared by carbonylation-impregnation method. The catalysts were characterized by means of nitrogen adsorptiondesorption,X-ray diffraction( XRD),transmission electron microscopy( TEM),infrared spectra of pyridine adsorption( Py-IR),and thermogravimetric-differential thermal analysis( TG-DTA). The effect of Sn loading on the catalytic properties of PtSn/Al_2O_3 in the propane dehydrogenation was studied. The results showed that the PtSn/Al_2O_3 catalyst had high propylene selectivity and catalytic stability. Platinum and tin were mainly in the form of Pt3 Sn and PtSn alloys with Pt/Sn ratios of 3 ∶ 1 and 1 ∶ 1. With the formation of the alloy,the dehydrogenation performance of the catalyst was improved significantly,and the high temperature sintering of metal particles was effectively suppressed. When the Pt/Sn ratio was 1 ∶ 2 and 1 ∶ 3,the metallic Pt was mainly resulted. With the increase of Sn loading,the Lewis acid sites on the catalyst gradually decreased,and the propylene selectivity increased associated with the propane conversion decreased. At the same time,the addition of Sn promoted the migration of carbon deposition from the metal surface to support,and improved the stability of the catalyst.
引文
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[2] Sheintuch M.,Nekhamkina O.,Chem. Eng. J.,2018,347,900—912
[3] Ren Y. J.,Hua W. M.,Yue Y. H.,Gao Z.,Chem. J. Chinese Universities,2009,30(6),1162—1167(任英杰,华伟明,乐英红,高滋.高等学校化学学报,2009,30(6),1162—1167)
[4] Yang M. L.,Zhu J.,Zhu Y. A.,Sui Z. J.,Yu Y. D.,Zhou X. G.,Chen D.,J. Mol. Catal. A:Chem.,2014,395,329—336
[5] Jesper J. H. B. S.,Javier R. M.,Eduardo S. J.,Bert M. W.,Chem. Rev.,2014,114,10613—10653
[6] Siri G. J.,Ramallo-López J. M.,Casella M. L.,Fierro J. L. G.,Requejo F. G.,Ferretti O. A.,Appl. Catal. A:Gen.,2005,278,239—249
[7] Yu C. L.,Xu H. Y.,Ge Q. J.,Li W. Z.,Chem. J. Chinese Universities,2006,27(8),1492—1495(余长林,徐恒泳,葛庆杰,李文钊.高等学校化学学报,2006,27(8),1492—1495)
[8] Lee M. H.,Nagaraja B. M.,Lee K. Y.,Jung K. D.,Catal. Today,2014,232,53—62
[9] Uemura Y.,Inada Y.,Bando K. K.,Sasaki T.,Kamiuchi N.,Eguchi K.,Yagishita A.,Nomura M.,Tada M.,Iwasawa Y.,J. Phys.Chem. C,2011,115,5823—5833
[10] Kappenstein C.,Guérin M.,Lázár K.,Matusek K. Paál Z.,J. Chem. Soc. Faraday Trans.,1998,94(16),2463—2473
[11] Vu B. K.,Song M. B.,Ahn I. Y.,Suh Y. W.,Suh D. J.,Kim W.,Koh H. L.,Choi Y. G.,Shin E. W.,Appl. Catal. A:Gen.,2011,400(1),25—33
[12] Llorca J.,Homs N.,Fierro J. G.,Sales J.,Piscina P. R. D. L.,J. Catal.,1997,166(1),44—52
[13] Kwak D. H.,Lee Y. W.,Han S. B.,Hwang E. T.,Park H. C.,Kim M. C.,Park K. W.,J. Power Sources,2015,275,557—562
[14] Yang M. L.,Density Functional Study of Propane Dehydrogenation on Pt Catalyst,East China University of Science and Technology,Shanghai,2012(杨明磊. Pt催化剂上丙烷脱氢反应机理的密度泛函理论研究,上海:华东理工大学,2012)
[15] Yang M. L.,Zhu Y. A.,Fan C.,Sui Z. J., Chen D., Zhou X. G., Phys. Chem. Chem. Phys.,2011,13(8),3257—3267
[16] Yang M. L.,Zhu Y. A.,Zhou X. G.,Sui Z. J.,Chen D.,ACS Catal.,2012,2(6),1247—1258
[17] Sing K. S. W.,Everett D. H.,Haul R.A.W.,Moscou L.,Pierotti R. A.,Rouquerol J.,Siemieniewska T.,Pure and Appl. Chem.,1985,57(4),603—619
[18] Liu X.,Lang W. Z.,Long L. L.,Hu C. L.,Chu L. F.,Guo Y. J.,Chem. Eng. J.,2014,247,183—192
[19] Fang P.,He M.,Xie Y. L.,Luo M. F.,Spectros. Spect. Anal.,2006,26(11),2039—3042(方萍,何迈,谢云龙,罗梦飞.光谱学与光谱分析,2006,26(11),2039—3042)
[20] Paál Z.,Wootsch A.,Teschner D.,Lázár K.,SajóI. E.,Gy9rffy N.,Weinberg G.,Appl. Catal. A:Gen.,2011,391,377—385
[21] Ma A. Z.,Scientia Sinica Chimica,2014,44(1),25—39(马爱增.中国科学:化学,2014,44(1),25—39)
[22] Sun Y. N.,Tao L.,You T.,Shan H.,Chem. Eng. J.,2014,244(10),145—151
[23] Jeon S.,Park Y. M.,Park J.,Saravanan K.,Jeong H. K.,Bae J. W.,Appl. Catal. A:Gen.,2018,551,49—62
[24] Yu C. L.,Xu H. Y.,Ge Q. J.,Li W. Z.,J. Mol. Catal. A:Chem.,2007,266,80—87
[25] Yu C. L.,The Study of Supported Platinum Catalysts and Catalytic Process for Propane Dehydrogenation,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,2007(余长林.丙烷脱氢铂催化剂与反应性能的研究,大连:中国科学院大连化学物理研究所,2007)
[26] Larsson M.,Hultén M.,Blekkan E. A.,Andersson B.,J. Catal.,1996,164(1),44—53
[27] Li Q.,The Kinetics of Propane Dehydrogenation and Coke Formation Over Pt Catalysts,East China University of Science and Technology,Shanghai,2012(李庆. Pt催化剂上丙烷脱氢反应与结焦,上海:华东理工大学,2012)
[28] Sokolov S.,Stoyanova M.,Rodemerck U.,Linke D.,Kondratenko E. V.,J. Catal.,2012,293(9),67—75
[29] Bai L. Y.,Zhou Y. M.,Zhang Y. W.,Liu H.,Sheng X. L.,Ind. Eng. Chem. Res.,2009,48,9885—9891
[30] Zhang H. J.,Wang S.,Gao W. Y.,Wan H.,Gao J.,Journal of Fuel Chemistry and Technology,2017,45(9),1130—1136(张海娟,王申,高文艺,万海,高杰.燃料化学学报,2017,45(9),1130—1136)
[31] Srihiranpullop S.,Praserthdam P.,Mongkhonsi T.,Korean J. Chem. Eng.,2000,17(5),548—552
[32] Fiedorow R. M. J.,Wanke S. E.,J. Catal.,1976,43(1),34—42
[33] Yarusov I. B.,Zatolookina E. V.,Shitova N. V.,Belyi A. S.,Ostrovskii N. M.,Catal. Today,1992,13,655—658