Mg改性Silicalite-1分子筛负载Pt-Sn催化剂对异丁烷脱氢性能的影响?
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摘要
利用等体积浸渍法制备不同镁含量的Mg-Silicalite-1 (Mg-SC-1)分子筛,以该分子筛为载体负载Pt-Sn双金属组分催化异丁烷脱氢反应,采用固定床连续反应器评价催化剂性能,并利用X-射线粉末衍射(XRD)、N2吸附-脱附、程序升温还原(H2-TPR)、扫描电镜(SEM)和碳含量分析等方法研究不同MgO含量的Pt-Sn/Mg-SC-1催化剂的催化性能。实验结果表明,添加w(MgO)=7%到SC-1载体,再负载Pt-Sn组分制备的催化剂异丁烷脱氢效果较好,相比于以纯硅SC-1分子筛为载体的催化剂具有高的反应稳定性和活性。而且经Mg改性后的SC-1载体与助剂SnOx物种之间存在较强的相互作用,导致SnOx物种不易被还原,并促进Pt粒子的分散度。在反应12 h后含w(MgO)=7%的Pt-Sn/Mg-SC-1催化剂仍保留较多的活性Pt粒子。
Pt-Sn/Mg-SC-1 catalysts with different magnesium contents were prepared by sequential incipient wetness impregnation, which were evaluated in a micro fixed bed continuous reactor for isobutane dehydrogenation. X-ray powder diffraction(XRD), N2 adsorption-desorption, temperature programmed reduction(H2-TPR), scanning electron microscopy(SEM) and carbon content analysis were used to study the catalytic performance of the Pt-Sn/Mg-SC-1 catalysts. The experimental results indicate that the Pt-Sn/Mg-SC-1 catalyst with w(MgO) = 7% exhibits excellent dehydrogenation performance. The characterization results reveal that the interaction between Mg-SC-1 and SnOx species is enhanced, and the SnOx species are not easily reduced, which is beneficial to the dispersion of Pt particles. Moreover, the Pt-Sn/Mg-SC-1 catalysts with w(MgO) = 7% has more active Pt particles than other catalysts after 12 h reaction.
Pt-Sn/Mg-SC-1 catalysts with different magnesium contents were prepared by sequential incipient wetness impregnation, which were evaluated in a micro fixed bed continuous reactor for isobutane dehydrogenation. X-ray powder diffraction(XRD), N2 adsorption-desorption, temperature programmed reduction(H2-TPR), scanning electron microscopy(SEM) and carbon content analysis were used to study the catalytic performance of the Pt-Sn/Mg-SC-1 catalysts. The experimental results indicate that the Pt-Sn/Mg-SC-1 catalyst with w(MgO) = 7% exhibits excellent dehydrogenation performance. The characterization results reveal that the interaction between Mg-SC-1 and SnOx species is enhanced, and the SnOx species are not easily reduced, which is beneficial to the dispersion of Pt particles. Moreover, the Pt-Sn/Mg-SC-1 catalysts with w(MgO) = 7% has more active Pt particles than other catalysts after 12 h reaction.
引文
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[24]ZHU Q,WANG G,LIU J,et al.Effect of Sn on isobutane dehydrogenation performance of Ni/SiO2 catalyst:adsorption modes and adsorption energies of isobutane and isobutene[J].ACS Applied Materials&Interfaces,2017,9(36):30711-30721.
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[26]罗沙,吴楠,周波,等.氧化铝载体对Pt-Sn-K/γ-Al2O3催化剂上异丁烷脱氢性能的影响[J].燃料化学学报,2013,41(12):1481-1486.LUO S,WU N,ZHOU B,et al.Effect of alumina support on the performance of Pt-Sn-K/γ-Al2O3 catalyst in the dehydrogenation of isobutane[J].Journal of Fuel Chemistry and Technology,2013,41(12):1481-1486.
[27]徐禄禄,赵侦超,赵蓉蓉,等.镁改性HZSM-5分子筛催化乙烯制丙烯的影响[J].物理化学学报,2018,35(1):92-100.XU L L,ZHAO Z C,ZHAO R R,et al.Effects of magnesium modification on the catalytic performances of HZSM-5 zeolite for the conversion of ethene to propene[J].Acta Physico-Chimica Sinica,2018,35(1):92-100.
[28]邱安定,范以宁.添加锡组分对Pt/ZSM-5催化剂丙烷脱氢反应性能的影响[J].燃料化学学报,2008,36(5):637-640.QIU A D,FAN Y N.Effect of addition of tin on the catalytic properties of Pt/ZSM-5 catalyst in propane dehydrogenation[J].Journal of Fuel Chemistry and Technology,2008,36(5):637-640.
[2]姜冬宇,吴文海,吴省,等.低碳烷烃脱氢Pt系催化剂的研究进展[J].化学世界,2014,55(6):373-378.JIANG D Y,WU W H,WU S,et al.Research progress of Pt-based catalysts for dehydrogenation of low hydrocarbons[J].Chemical World,2014,55(6):373-378.
[3]郭秋双,蔡奇,孙彦民,等.低碳烷烃脱氢催化剂的研究进展[J].无机盐工业,2016,48(8):11-15.GUO Q S,CAI Q,SUN Y M,et al.Research progress of low carbon alkane dehydrogenation catalyst[J].Inorganic Chemical Industry,2016,48(8):11-15.
[4]MIGUEL S R D,BOCANEGRA S A,VILELLA I M J,et al.Characterization and catalytic performance of PtSn catalysts supported on Al2O3 and Na-doped Al2O3 in n-butane dehydrogenation[J].Catalysis Letters,2007,119(1):5-15.
[5]ZHAO S,XU B,YU L,et al.Catalytic dehydrogenation of propane to propylene over highly active PtSnNa/γ-Al2O3 catalyst[J].Chinese Chemical Letters,2018,29(3):475-478.
[6]蔡奇,杨玉旺,吴同旭,等.载体处理方式对PtSnK/Al2O3催化剂异丁烷脱氢性能的影响[J].石油化工,2017,46(3):289-293.CAI Q,YANG Y W,WU T X,et al.Influences of support treatment on the catalytic properties of PtSnK/Al2O3 for isobutane dehydrogenation[J].Petrochemical Technology,2017,46(3):289-293.
[7]REDEKOP E A,GALVITA V V,POELMAN H,et al.Delivering a modifying element to metal nanoparticles via support:Pt-Ga alloying during the reduction of Pt/Mg(Al,Ga)Ox catalysts and its effects on propane dehydrogenation[J].ACS Catalysis,2014,4(6):1812-1824.
[8]DONG A,WANG K,ZHU S,et al.Facile preparation of PtSn-La/Al2O3 catalyst with large pore size and its improved catalytic performance for isobutane dehydrogenation[J].Fuel Processing Technology,2017,158:218-225.
[9]VU B K,SONG M B,AHN I Y,et al.Propane dehydrogenation over Pt-Sn/rare-earth-doped Al2O3:influence of La,Ce,or Y on the formation and stability of Pt-Sn alloys[J].Catalysis Today,2011,164(1):214-220.
[10]LIU G,LIU J,HE N,et al.Silicalite-1 zeolite acidification by zinc modification and its catalytic properties for isobutane conversion[J].RSC Advances,2018,8(33):18663-18671.
[11]CHENG M,ZHAO H,YANG J,et al.The catalytic dehydrogenation of isobutane and the stability enhancement over Fe incorporated SBA-15[J].Microporous&Mesoporous Materials,2018,266:117-125.
[12]EHIRO T,ITAGAKI A,MISU H,et al.Oxidative dehydrogenation of isobutane to isobutene on metal-doped MCM-41 catalysts[J].Journal of Chemical Engineering of Japan,2016,49(2):136-143.
[13]ZHOU H L,GONG J J,XU B L,et al.PtSnNa/SUZ-4:An efficient catalyst for propane dehydrogenation[J].Catalysis,2017,38(3):529-536.
[14]WEGENER E C,WU Z,TSENG H T,et al.Structure and reactivity of Pt-In intermetallic alloy nanoparticles:highly selective catalysts for ethane dehydrogenation[J].Catalysis Today,2018,299:146-153.
[15]王康,朱士贞,董安华,等.PtSnLa/Ca-Al2O3作为异丁烷脱氢催化剂的研究[J].天津大学学报,2017,50(10):1105-1110.WANG K,ZHU S Z,DONG A H,et al.PtSnLa/Ca-Al2O3 as catalysts for isobutane dehydrogenation[J].Journal of Tianjin University,2017,50(10):1105-1110.
[16]WEE L H,WANG Z,TOSHEVA L,et al.Silicalite films with preferred orientation[J].Microporous&Mesoporous Materials,2008,116(1-3):22-27.
[17]陈红丽,丁键,王一萌.具有多级孔道结构、高水热稳定性的含氧化镁Silicalite-1分子筛的合成[J].物理化学学报,2013,29(5):1035-1040.CHEN H L,DING J,WANG Y M.Synthesis of hierarchical MgO-containing silicalite-1 zeolites with high hydrothermal stability[J].Acta Physico-Chimica Siniva,2013,29(5):1035-1040.
[18]ZHANG Y W,ZHOU Y M,QIU A D,et al.Propane dehydrogenation on PtSn/ZSM-5 catalyst:effect of tin as a promoter[J].Catalysis Communications,2006,7(11):860-866.
[19]黄丽华,杨利利,许波连,等.PtSn/Al2O3/MCM-41催化剂的丙烷脱氢催化性能[J].物理化学学报,2008,24(7):1297-1301.HUANG L H,YANG L L,XU B L,et al.Catalytic properties of PtSn/Al2O3/MCM-41 catalysts for propane dehydrogenation[J].Acta Physico-Chimica Siniva,2008,24(7):1297-1301.
[20]ZHANG Y,ZHOU Y,SHI J,et al.Comparative study of bimetallic Pt-Sn catalysts supported on different supports for propane dehydrogenation[J].Journal of Molecular Catalysis A Chemical,2014,381(1):138-147.
[21]SHEN L L,XIA K,LANG W Z,et al.The effects of calcination temperature of support on PtIn/Mg(Al)O catalysts for propane dehydrogenation reaction[J].Chemical Engineering Journal,2017,324:336-346.
[22]ROSTOM S,LASA H I D.Propane oxidative dehydrogenation using consecutive feed injections and fluidizable VOx/γ-Al2O3 and VOx/ZrO2-γ-Al2O3 catalysts[J].Industrial&Engineering Chemistry Research,2017,56(45):13109-13124.
[23]李春义,王国玮.丙烷/异丁烷脱氢Pt系催化剂的研究进展Ⅲ.Pt的存在形态、颗粒大小与脱氢性能[J].石油技术与应用,2017,35(3):171-176.LI C Y,WANG G W.Pt-based catalysts for propane/isobutane dehydrogenationⅢ.Existing state and particle size of Pt[J].Petrochemical Technology&Application,2017,35(3):171-176.
[24]ZHU Q,WANG G,LIU J,et al.Effect of Sn on isobutane dehydrogenation performance of Ni/SiO2 catalyst:adsorption modes and adsorption energies of isobutane and isobutene[J].ACS Applied Materials&Interfaces,2017,9(36):30711-30721.
[25]JIANG F,ZENG L,LI S,et al.Propane dehydrogenation over Pt/TiO2-Al2O3 Catalysts[J].ACS Catalysis,2014,5(1):438-447.
[26]罗沙,吴楠,周波,等.氧化铝载体对Pt-Sn-K/γ-Al2O3催化剂上异丁烷脱氢性能的影响[J].燃料化学学报,2013,41(12):1481-1486.LUO S,WU N,ZHOU B,et al.Effect of alumina support on the performance of Pt-Sn-K/γ-Al2O3 catalyst in the dehydrogenation of isobutane[J].Journal of Fuel Chemistry and Technology,2013,41(12):1481-1486.
[27]徐禄禄,赵侦超,赵蓉蓉,等.镁改性HZSM-5分子筛催化乙烯制丙烯的影响[J].物理化学学报,2018,35(1):92-100.XU L L,ZHAO Z C,ZHAO R R,et al.Effects of magnesium modification on the catalytic performances of HZSM-5 zeolite for the conversion of ethene to propene[J].Acta Physico-Chimica Sinica,2018,35(1):92-100.
[28]邱安定,范以宁.添加锡组分对Pt/ZSM-5催化剂丙烷脱氢反应性能的影响[J].燃料化学学报,2008,36(5):637-640.QIU A D,FAN Y N.Effect of addition of tin on the catalytic properties of Pt/ZSM-5 catalyst in propane dehydrogenation[J].Journal of Fuel Chemistry and Technology,2008,36(5):637-640.