王广建,孟凡飞,赵强,孙兴源,邴连成,王芳

• 1:青岛科技大学 化工学院，山东 青岛 266042

摘要(Abstract)：

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SnO_x物种之间存在较强的相互作用，导致SnO_x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。

关键词(KeyWords)： Silicalite-1;镁改性;Pt-Sn;异丁烷脱氢

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金（21506107）；煤与绿色化工高效利用国家重点实验室开放课题（2017-k17，2017-k23）。

作者(Author): 王广建,孟凡飞,赵强,孙兴源,邴连成,王芳

DOI: 10.3969/j.issn.1003-9015.2019.01.014

参考文献(References)：

• [1] 李丽, 阎子锋. 异丁烷脱氢催化剂的研究[J]. 化学进展, 2005, 17(4):651-659. LI L, YAN Z F. Review of catalytic dehydrogenation of isobutene[J]. Progress In Chemistry, 2005, 17(4):651-659.
  [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 VO_x/γ-Al₂O₃ and VO_x/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 dehydrogenation Ⅲ. 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.