氯的脱除对丙烷脱氢PtSnNa/Al_2O_3催化剂结构的影响
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摘要
考察了氯的脱除对丙烷脱氢铂锡催化剂结构和反应性能的影响,并采用XRD、N_2吸脱附、TPR、NH_3-TPD、TEM和Raman等方法进行表征。结果表明,氯的脱除温度显著影响催化剂的酸性、孔体积、比表面积、孔径和Pt颗粒尺寸。随着处理温度的提高,催化剂酸性、比表面积、孔体积都呈现下降的趋势,平均孔径增加,Pt颗粒的烧结程度加剧。随着处理温度的增加,催化剂初活性逐渐降低,丙烯选择性增加,稳定性出现先增加后降低趋势。研究表明,氯的较佳的脱除温度为540℃,催化剂具有很好的脱氢性能和稳定性,收率最高。
The effect of chlorine elimination on the catalytic performance and structure of PtSnNa/Al_2O_3 catalyst for propane dehydrogenation was studied. The catalysts were characterized by XRD, N_2 adsorption-desorption, TPR, NH_3-TPD, TEM and Raman spectroscopy, respectively. The results showed that the chlorine elimination temperature affected the properties of the catalysts greatly, such as acidity, specific surface area, pore volume, mean pore diameter and the size of Pt particle. With the increase of the treatment temperature, the acidity the specific surface area and pore volume of the catalyst,dramatically decreased, whereas the mean pore diameter increased. Meantime, the extent of Pt sintering was aggravated. At higher treatment temperature, the catalyst has lower initial activity and higher propylene selectivity. But the stability increased firstly and then decreased with the raising of treatment temperature. The highest yield of propylene was obtained with the treatment temperature of 540 ℃, and the PtSnNa/Al_2O_3 catalyst exhibited the best performance of propane dehydrogenation and stability.
The effect of chlorine elimination on the catalytic performance and structure of PtSnNa/Al_2O_3 catalyst for propane dehydrogenation was studied. The catalysts were characterized by XRD, N_2 adsorption-desorption, TPR, NH_3-TPD, TEM and Raman spectroscopy, respectively. The results showed that the chlorine elimination temperature affected the properties of the catalysts greatly, such as acidity, specific surface area, pore volume, mean pore diameter and the size of Pt particle. With the increase of the treatment temperature, the acidity the specific surface area and pore volume of the catalyst,dramatically decreased, whereas the mean pore diameter increased. Meantime, the extent of Pt sintering was aggravated. At higher treatment temperature, the catalyst has lower initial activity and higher propylene selectivity. But the stability increased firstly and then decreased with the raising of treatment temperature. The highest yield of propylene was obtained with the treatment temperature of 540 ℃, and the PtSnNa/Al_2O_3 catalyst exhibited the best performance of propane dehydrogenation and stability.
引文
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[18]李庆,隋志军,朱贻安,等.Pt催化丙烷脱氢过程中结焦反应的粒径效应与Sn的作用[J].化工学报,2013,64(2):525-531.LI Qing,SUI Zhijun,ZHU Yian,et al.Formation of coke on Pt catalysts during propane dehydrogenation:effect of Pt particle size and Sn addition[J].CIESC Journal,2013,64(2):525-531.
[2]DOMENICO S,IVANO M.Dehydrogenation of paraffins:synergies between catalystdesign and reactor engineering[J].Catalysis Today,2006,111(1):133-139.
[3]TALLMAN M J,KLAVERS R R.North American olefin producers riding the shale gas wave[J].Hydrocarbon Process,2013,4:37-40.
[4]张海娟,高杰,张浩楠,等.低碳烷烃深加工制烯烃技术的研究进展[J].石油化工,2016,45(12):1411-1418.ZHANG Haijuan,GAO Jie,ZHANG Haonan,et al.Progresses in processes and catalysts for dehydrogenation of light paraffins to olefins[J].Petrochemical Technology,2016,45(12):1411-1418.
[5]SAQER S M,KONDARIDES D I,VERYKIOS X E.Catalytic activity of supported platinum and metal oxide catalysts for toluene oxidation[J].Topics in Catalysis,2009,52(5):517-527.
[6]ZANGENEH T F,TAEBA A,GHOLIVANDC K,et al.The effect of mixed HCl-KCl competitive adsorbate on Pt adsorptionand catalytic properties of Pt-Sn/Al2O3 catalysts in propane dehydrogenation[J].Applied Surface Science,2015,357(7):172-178.
[7]LIU J,LIU C,MA A,et al.Effects of Al2O3 phase and Cl component on dehydrogenation of propane[J].Applied Surface Science,2016,368:233-240.
[8]ARTEAGA G J,ANDERSON J A,ROCHESTER C H.Effects of catalyst regeneration with and without chlorine on heptane reforming reactions over Pt/Al2O3 and Pt-Sn/Al2O3[J].Journal of Catalysis,1999,187(1):219-229.
[9]ZHANG Y,ZHOU Y,LIU H,et al.Influence of the different dechlorination time on catalytic performances of Pt Sn Na/ZSM-5catalyst for propane dehydrogenation[J].Fuel Processing Technology,2009,90(12):1524-1531.
[10]COTTRIGHT D,LEVIN E,DUMESIC A.Kinetic studies of isobutane dehydrogenation and ispbutene over Pt-Sn-based catalysts[J].Industrial&Engineering Chemistry Research,1986,37(8):1717-1723.
[11]GRACIA F J,MILLER J T,KROPF A J,et al.Kinetics,FTIR,and controlled atmosphere exafs study of the effect of chlorine on Pt-supported catalysts during oxidation reactions[J].Journal of Catalysis,2002,209(2):341-354.
[12]PAULIS M,PEYRARD H,MONTES M.Influence of chlorine on the activity and stability of Pt/Al2O3 catalysts in the complete oxidation of toluene[J].Journal of Catalysis,2001,199(1):30-40.
[13]KAMIUCHI N,TAGUCHI K,MATSUI T,et al.Sintering and redispersion of platinum catalysts supported on tin oxide[J].Applied Catalysis B,2009,89(1/2):65-72.
[14]DUMONT M,CHOLLON G,DOURGES M A,et al.Chemical,microstructural and thermal analyses of a naphthalene-derived mesophase pitch[J].Carbon,2002,40(9):1475-1486.
[15]BAO K V,SONG M B,AHN I Y,et al.Location and structure of coke generated over Pt-Sn/Al2O3 in propane dehydrogenation[J].Journal of Industrial and Engineering Chemistry,2011,17(1):71-76.
[16]张海娟,王申,高文艺,等.丙烷脱氢Pt Sn/Al2O3催化剂积炭行为研究[J].燃料化学学报,2017,45(9):1131-1136.ZHANG Haijuan,WANG Shen,GAO Wenyi,et al.Study of deactivated catalyst structure on Pt Sn/Al2O3 propane dehydrogenation catalyst[J].Journal of Fuel Chemistry and Technology,2017,45(9):1131-1136.
[17]KUMAR M S,CHEN D,WALMSLEY J C,et al.Dehydrogenation of propane over Pt-SBA-15:effect of Pt particle size[J].Catalysis Communications,2008,9(5):747-750.
[18]李庆,隋志军,朱贻安,等.Pt催化丙烷脱氢过程中结焦反应的粒径效应与Sn的作用[J].化工学报,2013,64(2):525-531.LI Qing,SUI Zhijun,ZHU Yian,et al.Formation of coke on Pt catalysts during propane dehydrogenation:effect of Pt particle size and Sn addition[J].CIESC Journal,2013,64(2):525-531.
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