杨笑,陈长林

• 1:南京工业大学 化工学院 材料化学工程国家重点实验室，江苏 南京 210009

摘要(Abstract)：

用浸渍法制备了磷酸根表面修饰的钨锆复合氧化物载铂催化剂（Pt/PO₄^3--WO₃-ZrO₂）。用NH₃-程序升温脱附（NH₃-TPD）、红外光谱（FT-IR）、X-射线衍射（XRD）、N₂物理吸附-脱附（BET）、H₂-程序升温还原（H₂-TPR）、H₂-脉冲吸附和X射线光电子能谱（XPS）分析等技术对催化剂进行表征。用水热釜考察了钨锆复合氧化物的水热稳定性，固定床反应器考察了催化剂催化甘油氢解制1，3-丙二醇的反应性能。结果表明：引入适量磷酸根可抑制水热处理过程中钨锆复合氧化物单斜相ZrO₂向四方相转变，0.72 PO₄^3--WO₃-ZrO₂样品水热处理前比表面积83 m²·g^-1，水热处理后比表面积86 m²·g^-1，比表面积基本不变，提高了钨锆复合氧化物的水热稳定性。增强了催化剂金属还原性，提高了催化剂H₂吸附量，Pt/PO₄^3--WO₃-ZrO₂催化甘油氢解稳定性较Pt/WO₃-ZrO₂催化剂显著提高。

关键词(KeyWords)： 磷酸根;钨锆复合氧化物;水热稳定性;甘油;氢解;1,3-丙二醇

Abstract:

Keywords:

基金项目(Foundation): 江苏省产学研前瞻性研究项目（BY2015005-08）。

作者(Author): 杨笑,陈长林

DOI: 10.3969/j.issn.1003-9015.2017.06.013

参考文献(References)：

• [1] Pagliaro M, Ciriminna R, Kimura H, et al. From glycerol to value-added products[J]. Angewandte Chemie International Edition, 2007, 46(24):4434-4440.
  [2] Behr A, Eilting J, Irawadi K, et al. Improved utilization of renewable resources:new important derivatives of glycerol[J]. Green Chemistry, 2007, 10(1):13-30.
  [3] Zhu S, Gao X, Zhu Y, et al. SiO₂ promoted Pt/WO_x/ZrO₂ catalysts for the selective hydrogenolysis of glycerol to 1, 3-propanediol[J]. Applied Catalysis B:Environmental, 2014, 158-159:391-399.
  [4] Qin L Z, Song M J, Chen C L. Aqueous-phase deoxygenation of glycerol to 1,3-propanediol over Pt/WO₃/ZrO₂ catalysts in a fixed-bed reactor[J]. Green Chemistry, 2010, 12(8):1466-1472.
  [5] Nakagawa Y, Tamura M, Tomishige K. Catalytic materials for the hydrogenolysis of glycerol to 1,3-propanediol[J]. Journal of Materials Chemistry A, 2014, 2(19):6688-6702.
  [6] García-Fernández S, Gandarias I, Requies J, et al. New approaches to the Pt/WO_x/Al₂O₃ catalytic system behavior for the selective glycerol hydrogenolysis to 1,3-propanediol[J]. Journal of Catalysis, 2015, 323:65-75.
  [7] Kurosaka T, Maruyama H, Naribayashi I, et al. Production of 1,3-propanediol by hydrogenolysis of glycerol catalyzed by Pt/WO₃/ZrO₂[J]. Catalysis Communications, 2008, 9(6):1360-1363.
  [8] Tamura M, Amada Y, Liu S, et al. Promoting effect of Ru on Ir-ReO_x/SiO₂ catalyst in hydrogenolysis of glycerol[J]. Journal of Molecular Catalysis A Chemical, 2014, 388-389:177-187.
  [9] Xiong H, Pham H N, Datye A K. Hydrothermally stable heterogeneous catalysts for conversion of biorenewables[J]. Green Chemistry, 2014, 45(51):4627-4643.
  [10] CHEN Ying (陈英), CHEN Chang-lin (陈长林). Effects of reducing pressure and water for glycerol hydrogenolysis activity of Pt/WO₃/ZrO₂ (还原压力及水对Pt/WO₃/ZrO₂ 催化甘油氢解性能的影响)[J]. Journal of Nanjingtech University (南京工业大学学报), 2013, 35(3):41-45.
  [11] Pagántorres Y J, Gallo J M R, Wang D, et al. Synthesis of highly ordered hydrothermally stable mesoporous niobia catalysts by atomic layer deposition[J]. Acs Catalysis, 2011, 1(10):1234-1245.
  [12] Xiong H, Schwartz T J, Andersen N I, et al. Graphitic-carbon layers on oxides:toward stable heterogeneous catalysts for biomass conversion reactions[J]. Angewandte Chemie International Edition, 2015, 54(27):7939-7943.
  [13] Chen X R, Chen C L, Xu N P, et al. Al-and Ga-promoted WO₃/ZrO₂ strong solid acid catalysts and their catalytic activities in n-butane isomerization[J]. Catalysis Today, 2004, 93(3):129-134.