表面改性未焙烧TS-1固载金催化丙烯氢氧环氧化反应性能研究

doi:10.11949/0438-1157.20210255

摘要/Abstract

摘要：

采用四丙基氢氧化铵（TPAOH）溶液对未焙烧钛硅分子筛TS-1（TS-1-B）进行二次晶化改性，以尿素为沉淀剂通过沉积-沉淀法制备改性和非改性的TS-1-B固载Au纳米催化剂，对比研究这两种催化剂丙烯氢氧环氧化反应性能的差异，阐明二次晶化改性对TS-1-B表面结构及催化行为的影响。结果表明：二次晶化改性提高了TS-1-B结晶度，降低了缺陷位硅羟基数量；改性的TS-1-B表面疏水性的提高有助于抑制产物环氧丙烷（PO）在羟基位点上吸附，其固载的金催化剂表现出显著提高的稳定性和活性。此外，对该催化剂的动力学行为也进行了研究，并计算了主/副产物生成活化能。

关键词: 催化, 环氧丙烷, 丙烯环氧化, 稳定性, 改性, 动力学

Abstract:

Developing highly efficient stable Au-Ti bifunctional catalysts is scientific and technological challenge for direct propylene epoxidation with H₂ and O₂. This work describes a novel strategy of employing tetrapropylammonium hydroxide (TPAOH) to modify uncalcined titanium silicalite-1 (TS-1-B) by secondary crystallization. Urea is used as the precipitation agent to immobilize gold nanoparticles onto the modified TS-1-B by deposition-precipitation method, aiming at allowing high gold capture efficiency as well as avoiding the introduction of residual alkaline cations to the catalyst. Compared with the reference Au/TS-1-B catalyst, the nano-gold particles immobilized on the modified TS-1 delivers significantly enhanced stability (> 36 h), propylene oxide (PO) formation rate (about 120 g/(h·kg)), PO selectivity (about 92.1%) and hydrogen efficiency (about 33.3%). The Fourier transform infrared spectroscopy (FT-IR) spectra demonstrates that the strength of the hydrogen-bonded silanols and trapped water in the TS-1-B decreased remarkably after secondary crystallization, indicating that the hydrophobic of TS-1-B is increased, which can be responsible for the improved stability and activity of the modified TS-1-B immobilized nano-gold catalyst. Moreover, the analysis of kinetic characteristic demonstrates that the propylene conversion and PO formation rate increase with increasing reaction temperature, while the PO selectivity and hydrogen efficiency decrease monotonously, and the apparent activation energies of by-products are much higher than the PO, indicating that higher reaction temperature favours the formation of by-products. In addition, the kinetic behavior of the catalyst was also studied, and the activation energy for the formation of main/by-products was calculated.

Key words: catalysis, propylene oxide, propylene epoxidation, stability, modification, kinetics

中图分类号:

TQ 203.2

张志华, 杜威, 段学志, 周兴贵. 表面改性未焙烧TS-1固载金催化丙烯氢氧环氧化反应性能研究[J]. 化工学报, 2021, 72(7): 3613-3625.

ZHANG Zhihua, DU Wei, DUAN Xuezhi, ZHOU Xinggui. Au nanoparticles immobilized on surface modified TS-1-B as high-efficiency bifunctional catalyst for propylene epoxidation with H₂and O₂[J]. CIESC Journal, 2021, 72(7): 3613-3625.

图/表 2

参考文献 43

1	宋钊宁, 冯翔, 刘熠斌, 等. 丙烯直接气相临氢环氧化催化剂结构调控和催化剂构-效关系研究进展[J]. 化学进展, 2016, 28(12): 1762-1773.
	Song Z N, Feng X, Liu Y B, et al. Advances in manipulation of catalyst structure and relationship of structure-performance for direct propene epoxidation with H₂ and O₂[J]. Progress in Chemistry, 2016, 28(12): 1762-1773.
2	Huang J H, Haruta M. Gas-phase propene epoxidation over coinage metal catalysts[J]. Research on Chemical Intermediates, 2012, 38(1): 1-24.
3	Sinha A K, Seelan S, Tsubota S, et al. Catalysis by gold nanoparticles: epoxidation of propene[J]. Topics in Catalysis, 2004, 29(3/4): 95-102.
4	Qi C X. The production of propylene oxide over nanometer Au catalysts in the presence of H₂ and O₂[J]. Gold Bulletin, 2008, 41(3): 224-234.
5	原宇航, 吴魏, 周兴贵, 等. 金催化剂在丙烯气相直接环氧化反应中的应用[J]. 化学反应工程与工艺, 2005, 21(4): 353-359.
	Yuan Y H, Wu W, Zhou X G, et al. Application of gold supported catalysts in gas-phase direct epoxidation of propylene[J]. Chemical Reaction Engineering and Technology, 2005, 21(4): 353-359.
6	Uphade B S, Tsubota S, Hayashi T, et al. Selective oxidation of propylene to propylene oxide or propionaldehyde over Au supported on titanosilicates in the presence of H₂ and O₂[J]. Chemistry Letters, 1998, 27(12): 1277-1278.
7	Bravo-Suárez J J, Bando K K, Lu J Q, et al. Transient technique for identification of true reaction intermediates: hydroperoxide species in propylene epoxidation on gold/titanosilicate catalysts by X-ray absorption fine structure spectroscopy[J]. The Journal of Physical Chemistry C, 2008, 112(4): 1115-1123.
8	Chowdhury B, Bravo-Suárez J J, Mimura N, et al. In situ UV-Vis and EPR study on the formation of hydroperoxide species during direct gas phase propylene epoxidation over Au/Ti-SiO₂ catalyst[J]. The Journal of Physical Chemistry B, 2006, 110(46): 22995-22999.
9	Lu J Q, Zhang X M, Bravo-Suárez J J, et al. Kinetics of propylene epoxidation using H₂ and O₂ over a gold/mesoporous titanosilicate catalyst[J]. Catalysis Today, 2007, 123(1/2/3/4): 189-197.
10	Yap N, Andres R P, Delgass W N. Reactivity and stability of Au in and on TS-1 for epoxidation of propylene with H₂ and O₂[J]. Journal of Catalysis, 2004, 226(1): 156-170.
11	Sinha A K, Seelan S, Akita T, et al. Vapor-phase epoxidation of propene over Au/Ti-MCM-41 catalysts: influence of Ti content and Au content[J]. Catalysis Letters, 2003, 85(3/4): 223-228.
12	Sacaliuc-Parvulescu E, Friedrich H, Palkovits R, et al. Understanding the effect of postsynthesis ammonium treatment on the catalytic activity of Au/Ti-SBA-15 catalysts for the oxidation of propene[J]. Journal of Catalysis, 2008, 259(1): 43-53.
13	Uphade B S, Akita T, Nakamura T, et al. Vapor-phase epoxidation of propene using H₂ and O₂ over Au/Ti-MCM-48[J]. Journal of Catalysis, 2002, 209(2): 331-340.
14	Lu J Q, Zhang X M, Bravo-Suárez J J, et al. Direct propylene epoxidation over barium-promoted Au/Ti-TUD catalysts with H₂ and O₂: effect of Au particle size[J]. Journal of Catalysis, 2007, 250(2): 350-359.
15	Sinha A K, Seelan S, Tsubota S, et al. A three-dimensional mesoporous titanosilicate support for gold nanoparticles: vapor-phase epoxidation of propene with high conversion[J]. Angewandte Chemie International Edition, 2004, 43(12): 1546-1548.
16	Jin F, Wu Y X, Liu S W, et al. Effect of Ti incorporated MWW supports on Au loading and catalytic performance for direct propylene epoxidation[J]. Catalysis Today, 2016, 264: 98-108.
17	Lee W S, Cem Akatay M, Stach E A, et al. Reproducible preparation of Au/TS-1 with high reaction rate for gas phase epoxidation of propylene[J]. Journal of Catalysis, 2012, 287: 178-189.
18	Feng X, Duan X Z, Qian G, et al. Au nanoparticles deposited on the external surfaces of TS-1: enhanced stability and activity for direct propylene epoxidation with H₂ and O₂[J]. Applied Catalysis B: Environmental, 2014, 150/151: 396-401.
19	Wu L Z, Zhao S F, Lin L F, et al. In-depth understanding of acid catalysis of solvolysis of propene oxide over titanosilicates and titanosilicate/H₂O₂ systems[J]. Journal of Catalysis, 2016, 337: 248-259.
20	Mul G, Zwijnenburg A, van der Linden B, et al. Stability and selectivity of Au/TiO₂ and Au/TiO₂/SiO₂ catalysts in propene epoxidation: an in situ FT-IR study[J]. Journal of Catalysis, 2001, 201(1): 128-137.
21	Chowdhury B, Bravo-Suárez J J, Daté M, et al. Trimethylamine as a gas-phase promoter: highly efficient epoxidation of propylene over supported gold catalysts[J]. Angewandte Chemie International Edition, 2006, 45(3): 412-415.
22	Sinha A K, Seelan S, Akita T, et al. Vapor phase propylene epoxidation over Au/Ti-MCM-41 catalysts prepared by different Ti incorporation modes[J]. Applied Catalysis A: General, 2003, 240(1/2): 243-252.
23	Liu Y W, Zhang X M, Suo J S. Gold supported on nitrogen-incorporated TS-1 for gas-phase epoxidation of propylene[J]. Chinese Journal of Catalysis, 2013, 34(2): 336-340.
24	Lee W S, Cem Akatay M, Stach E A, et al. Enhanced reaction rate for gas-phase epoxidation of propylene using H₂ and O₂ by Cs promotion of Au/TS-1[J]. Journal of Catalysis, 2013, 308: 98-113.
25	Lu X N, Zhao G F, Lu Y. Propylene epoxidation with O₂and H₂: a high-performance Au/TS-1 catalyst prepared via a deposition-precipitation method using urea[J]. Catalysis Science & Technology, 2013, 3(11): 2906-2909.
26	Song W C, Zuo Y, Xiong G, et al. Transformation of SiO₂ in titanium silicalite-1/SiO₂ extrudates during tetrapropylammonium hydroxide treatment and improvement of catalytic properties for propylene epoxidation[J]. Chemical Engineering Journal, 2014, 253: 464-471.
27	Wu L Z, Deng X J, Zhao S F, et al. Synthesis of a highly active oxidation catalyst with improved distribution of titanium coordination states[J]. Chemical Communications, 2016, 52(56): 8679-8682.
28	Wang J, Chen Z, Yu Y, et al. Hollow core–shell structured TS-1@S-1 as an efficient catalyst for alkene epoxidation[J]. RSC Advances, 2019, 9(65): 37801-37808.
29	Xu H, Tian W W, Xu L P, et al. Crossed intergrowth triggered TS-2 microsphere: formation mechanism, modification and catalytic performance[J]. Chinese Journal of Catalysis, 2020, 41(7): 1109-1117.
30	Zhang Z H, Zhao X, Wang G, et al. Uncalcined TS-2 immobilized Au nanoparticles as a bifunctional catalyst to boost direct propylene epoxidation with H₂ and O₂[J]. AIChE Journal, 2020, 66(2): e16815.
31	Feng X, Duan X Z, Yang J, et al. Au/uncalcined TS-1 catalysts for direct propene epoxidation with H₂ and O₂: effects of Si/Ti molar ratio and Au loading[J]. Chemical Engineering Journal, 2015, 278: 234-239.
32	Zhan G W, Du M M, Sun D H, et al. Vapor-phase propylene epoxidation with H₂/O₂ over bioreduction Au/TS-1 catalysts: synthesis, characterization, and optimization[J]. Industrial & Engineering Chemistry Research, 2011, 50(15): 9019-9026.
33	Feng X, Sheng N, Liu Y B, et al. Simultaneously enhanced stability and selectivity for propene epoxidation with H₂ and O₂ on Au catalysts supported on nano-crystalline mesoporous TS-1[J]. ACS Catalysis, 2017, 7(4): 2668-2675.
34	Qi C X, Akita T, Okumura M, et al. Effect of surface chemical properties and texture of mesoporous titanosilicates on direct vapor-phase epoxidation of propylene over Au catalysts at high reaction temperature[J]. Applied Catalysis A: General, 2003, 253(1): 75-89.
35	Kanungo S, Keshri K S, Hensen E J M, et al. Direct epoxidation of propene on silylated Au-Ti catalysts: a study on silylation procedures and the effect on propane formation[J]. Catalysis Science & Technology, 2018, 8(12): 3052-3059.
36	Kanungo S, Keshri K S, van Hoof A J F, et al. Silylation enhances the performance of Au/Ti-SiO₂ catalysts in direct epoxidation of propene using H₂ and O₂[J]. Journal of Catalysis, 2016, 344: 434-444.
37	Sheng N, Liu Z K, Song Z N, et al. Enhanced stability for propene epoxidation with H₂ and O₂ over wormhole-like hierarchical TS-1 supported Au nanocatalyst[J]. Chemical Engineering Journal, 2019, 377: 119954.
38	Lu J Q, Zhang X M, Bravo-Suárez J J, et al. Effect of composition and promoters in Au/TS-1 catalysts for direct propylene epoxidation using H₂ and O₂[J]. Catalysis Today, 2009, 147(3/4): 186-195.
39	Nijhuis T A, Visser T, Weckhuysen B M. The role of gold in gold-titania epoxidation catalysts[J]. Angewandte Chemie, 2005, 117(7): 1139-1142.
40	Wang G, Cao Y Q, Zhang Z H, et al. Surface engineering and kinetics behaviors of Au/uncalcined TS-1 catalysts for propylene epoxidation with H₂ and O₂[J]. Industrial & Engineering Chemistry Research, 2019, 58(37): 17300-17307.
41	Du M M, Huang J L, Sun D H, et al. Propylene epoxidation over biogenic Au/TS-1 catalysts by Cinnamomum camphora extract in the presence of H₂ and O₂[J]. Applied Surface Science, 2016, 366: 292-298.
42	Feng X, Chen D, Zhou X G. Thermal stability of TPA template and size-dependent selectivity of uncalcined TS-1 supported Au catalyst for propene epoxidation with H₂ and O₂[J]. RSC Advances, 2016, 6(50): 44050-44056.
43	Lee W S, Cem Akatay M, Stach E A, et al. Gas-phase epoxidation of propylene in the presence of H₂ and O₂ over small gold ensembles in uncalcined TS-1[J]. Journal of Catalysis, 2014, 313: 104-112.

[1]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[2]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[3]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[4]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[5]	江河, 袁俊飞, 王林, 邢谷雨. 均流腔结构对微细通道内相变流动特性影响的实验研究[J]. 化工学报, 2023, 74(S1): 235-244.
[6]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[7]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[8]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[9]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[10]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[11]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[12]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[13]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[14]	杨越, 张丹, 郑巨淦, 涂茂萍, 杨庆忠. NaCl水溶液喷射闪蒸-掺混蒸发的实验研究[J]. 化工学报, 2023, 74(8): 3279-3291.
[15]	孟令玎, 崇汝青, 孙菲雪, 孟子晖, 刘文芳. 改性聚乙烯膜和氧化硅固定化碳酸酐酶[J]. 化工学报, 2023, 74(8): 3472-3484.