Al掺杂的Cu/SBA-15催化剂用于己二酸二甲酯加氢合成1,6-己二醇

doi:10.16085/j.issn.1000-6613.2022-0584

摘要/Abstract

摘要：

作为一种重要的有机合成原料，1,6-己二醇（HDO）的工业化生产主要通过己二酸二甲酯（DMA）加氢反应来实现，而理性设计开发相应的Cu基催化剂是提高HDO产率的关键。本文采用Al掺杂的介孔分子筛SBA-15为载体制备得到了一系列CuAl _x /SBA-15催化剂，探究了使用该催化剂用于DMA加氢反应合成HDO的催化性能和催化机理，并对反应条件进行了优化。研究结果表明：CuAl₅/SBA-15催化剂能够增加催化剂的路易斯酸酸量，提高Cu⁺/Cu⁰的比例，从而提升DMA加氢反应的选择性，同时Al的掺杂也能减少Cu活性组分的团聚，从而增强催化剂的稳定性。当反应温度为240℃、反应压力为6MPa、反应时间为6h时，HDO的反应产率达到最大，为87.05%；重复使用CuAl₅/SBA-15催化剂36h后，HDO的反应产率能够维持在86.01%左右。本文的研究结果对设计Cu基催化剂用于酯加氢反应具有一定的借鉴意义。

关键词: 催化剂, 分子筛, 加氢, 反应, 优化

Abstract:

The industrial production of 1,6-hexanediol (HDO) is by the hydrogenation of dimethyl adipate (DMA). The rational design and development of the Cu-based catalysts is of great importance to improve the yield of HDO. In this work, a series of CuAl _x /SBA-15 catalysts on Al-doped mesoporous molecular sieve SBA-15 were prepared. The catalytic performance and mechanism of the catalysts were investigated, and the reaction conditions were also optimized. The results showed that the CuAl₅/SBA-15 catalyst increased the amount of Lewis acid in the catalyst matrix and improved the Cu⁺/Cu⁰ ratio, thus enhancing the selectivity of the DMA hydrogenation reaction. Besides, the doping of Al reduced the agglomeration of Cu active species, and therefore, improved the stability of the catalyst. The yield of HDO reached the maximum of 87.05% under the reaction conditions of 240℃, 6MPa, and 6h. After the CuAl₅/SBA-15 catalyst was recycled for 36h, the yield of HDO maintained at about 86.01%, implying great stability of catalyst. In summary, the results of this study provided reference for the design of Cu-based catalysts for ester hydrogenation reactions.

Key words: catalyst, molecular sieves, hydrogenation, reaction, optimization

中图分类号:

TQ225.2

刘书林, 杨娜, 张龙飞, 孙永利, 姜斌, 肖晓明, 澹台晓伟, 张吕鸿. Al掺杂的Cu/SBA-15催化剂用于己二酸二甲酯加氢合成1,6-己二醇[J]. 化工进展, 2023, 42(1): 289-296.

LIU Shulin, YANG Na, ZHANG Longfei, SUN Yongli, JIANG Bin, XIAO Xiaoming, TANTAI Xiaowei, ZHANG Lyuhong. Al-doped Cu/SBA-15 catalysts for the hydrogenation of dimethyl adipate to 1,6-hexanediol[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 289-296.

图/表 13

表1 催化剂的结构特性

催化剂名称	Cu质量分数/%	Al质量分数/%	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
Cu/SBA-15	24.18	0	450.91	0.51	4.35
CuAl_2.5/SBA-15	24.48	2.57	423.01	0.50	4.26
CuAl₅/SBA-15	24.76	4.86	399.12	0.42	3.87
CuAl_7.5/SBA-15	24.53	7.48	391.00	0.43	4.35

图1 氮气吸附-脱附等温线

图2 孔径分布曲线

图3 CuAl x /SBA-15催化剂的红外谱图

图4 催化剂的XRD衍射图

图5 Cu/SBA-15与CuAl5/SBA-15催化剂的化学吸附图

图6 Cu/SBA-15与CuAl5/SBA-15催化剂的Cu 2p XPS图

图7 Cu/SBA-15与CuAl5/SBA-15催化剂的Cu LMM 俄歇能谱图

图8 己二酸二甲酯加氢制1, 6-己二醇反应路径图

图9 不同Al掺杂量催化剂的加氢性能图

图10 不同反应条件下CuAl5/SBA-15催化剂的加氢性能

图11 催化剂的加氢机理图

图12 Cu/SBA-15和CuAl5/SBA-15催化剂的循环性能

参考文献 21

1	丁璟, 赵俊琦, 程时标, 等. 生物基1,6-己二醇的研究进展[J]. 化工进展, 2015, 34(12): 4209-4213.
	DING Jing, ZHAO Junqi, CHENG Shibiao, et al. Advances in production of biobased 1,6-HDO[J]. Chemical Industry and Engineering Progress, 2015, 34(12): 4209-4213.
2	张峻炜, 宋怀俊. 脂肪酸酯催化加氢制醇研究进展[J]. 化工进展, 2009, 28(S1): 54-57.
	ZHANG Junwei, SONG Huaijun. The progress in the formation of alcohol from catalytic hydrogenation of fatty acid ester[J]. Chemical Industry and Engineering Progress, 2009, 28(S1): 54-57.
3	GONG Jinlong, YUE Hairong, ZHAO Yujun, et al. Synthesis of ethanol via syngas on Cu/SiO₂ catalysts with balanced Cu⁰-Cu⁺ sites[J]. Journal of the American Chemical Society, 2012, 134(34): 13922-13925.
4	YAO Yaqi, WU Xiaoqian, GUTIÉRREZ Oliver Y, et al. Roles of Cu⁺ and Cu⁰ sites in liquid-phase hydrogenation of esters on core-shell CuZn _x @C catalysts[J]. Applied Catalysis B: Environmental, 2020, 267: 118698.
5	WANG Meilin, YAO Dawei, LI Antai, et al. Enhanced selectivity and stability of Cu/SiO₂ catalysts for dimethyl oxalate hydrogenation to ethylene glycol by using silane coupling agents for surface modification[J]. Industrial & Engineering Chemistry Research, 2020, 59(20): 9414-9422.
6	吴佳佳, 鲁树亮, 田保亮. 复合雷尼铜催化剂在乙酸酯加氢中的应用[J]. 化工进展, 2020, 39(2): 533-538.
	WU Jiajia, LU Shuliang, TIAN Baoliang. Application of raney Cu composite catalysts in the hydrogenation of ethyl acetate[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 533-538.
7	AUBRECHT Jaroslav, POSPELOVA Violetta, KIKHTYANIN Oleg, et al. Do metal-oxide promoters of Cu hydrogenolysis catalysts affect the Cu intrinsic activity?[J]. Applied Catalysis A: General, 2020, 608: 117889.
8	ZHAO Yujun, GUO Ziyuan, ZHANG Haojie, et al. Hydrogenation of diesters on copper catalyst anchored on ordered hierarchical porous silica: pore size effect[J]. Journal of Catalysis, 2018, 357: 223-237.
9	YUAN Peng, LIU Zhongyi, ZHANG Wanqing, et al. Cu-Zn/Al₂O₃ catalyst for the hydrogenation of esters to alcohols[J]. Chinese Journal of Catalysis, 2010, 31(7): 769-775.
10	赵玉军, 赵硕, 王博, 等. 草酸酯加氢铜基催化剂关键技术与理论研究进展[J]. 化工进展, 2013, 32(4): 721-731.
	ZHAO Yujun, ZHAO Shuo, WANG Bo, et al. Technical and theoretical advances in copper-based catalysts for oxalate hydrogenation[J]. Chemical Industry and Engineering Progress, 2013, 32(4): 721-731.
11	SHU Guoqiang, MA Kui, TANG Siyang, et al. Highly selective hydrogenation of diesters to ethylene glycol and ethanol on aluminum-promoted CuAl/SiO₂ catalysts[J]. Catalysis Today, 2021, 368: 173-180.
12	ZHANG Shaoyan, FAN Guoli, LI Feng. Lewis-base-promoted copper-based catalyst for highly efficient hydrogenation of dimethyl 1,4-cyclohexane dicarboxylate[J]. Green Chemistry, 2013, 15(9): 2389-2393.
13	NEELI Chinna Krishna Prasad, NARANI Anand, MARELLA Ravi Kumar, et al. Selective benzylic oxidation of alkylaromatics over Cu/SBA-15 catalysts under solvent-free conditions[J]. Catalysis Communications, 2013, 39: 5-9.
14	KUMARAVEL Sakthivel, THIRIPURANTHAGAN Sivakumar, DURAI Mani, et al. Catalytic transfer hydrogenation of biomass-derived levulinic acid to γ-valerolactone over Sn/Al-SBA-15 catalysts[J]. New Journal of Chemistry, 2020, 44(20): 8209-8222.
15	HUANG Huijiang, WANG Bo, WANG Yue, et al. Partial hydrogenation of dimethyl oxalate on Cu/SiO₂ catalyst modified by sodium silicate[J]. Catalysis Today, 2020, 358: 68-73.
16	WU Jun, GAO Guang, LI Yong, et al. Highly chemoselective hydrogenation of lactone to diol over efficient copper-based bifunctional nanocatalysts[J]. Applied Catalysis B: Environmental, 2019, 245: 251-261.
17	LI Jun, YANG Chengwu, ZHANG Qian, et al. Effects of Fe addition on the structure and catalytic performance of mesoporous Mn/Al-SBA-15 catalysts for the reduction of NO with ammonia[J]. Catalysis Communications, 2015, 62: 24-28.
18	HU Qi, FAN Guoli, YANG Lan, et al. Aluminum-doped zirconia-supported copper nanocatalysts: surface synergistic catalytic effects in the gas-phase hydrogenation of esters[J]. ChemCatChem, 2014, 6(12): 3501-3510.
19	WANG Weichao, WANG Hui, ZHANG Jingwei, et al. Determining roles of Cu⁰ in the chemosynthesis of diols via condensed diester hydrogenation on Cu/SiO₂ catalyst[J]. ChemCatChem, 2020, 12(15): 3849-3852.
20	KIKHTYANIN Oleg, AUBRECHT Jaroslav, POSPELOVA Violetta, et al. On the origin of the transesterification reaction route during dimethyl adipate hydrogenolysis[J]. Applied Catalysis A: General, 2020, 606: 117825.
21	FONTANA J, VIGNADO C, JORDAO E, et al. Evaluation of some supports to RuSn catalysts applied to dimethyl adipate hydrogenation[J]. Catalysis Today, 2011, 172(1): 27-33.

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