锆改性Cu/SiO2催化剂催化3-羟基丙酸甲酯选择性加氢

doi:10.16085/j.issn.1000-6613.2023-0477

摘要/Abstract

摘要：

采用蒸氨法制备了锆（Zr）改性的Cu/SiO₂催化剂，用于3-羟基丙酸甲酯（3-HMP）气相加氢制1,3-丙二醇（1,3-PDO）。采用比表面积及孔分布测试、XRD、ICP-OES、H₂-TPR、NH₃-TPD、CO₂-TPD、FTIR、TG-DTG、HRTEM、XPS和AES等手段对催化剂进行了详细表征，发现Zr物种的加入使得Cu和Zr物种之间发生了强相互作用，产生了较多的层状硅酸铜，在结构方面提高了催化剂的比表面积，降低了铜物种的粒径，促进铜物种的分散，且在电子调控方面提高了Cu⁺的含量，增强了催化剂吸附酰基和甲氧基的能力。与未改性的Cu/SiO₂催化剂相比，在相同反应条件下，Zr掺杂量为0.5%的Cu/SiO₂催化剂表现出更高的催化性能，获得3-羟基丙酸甲酯转化率为96.0%和1,3-丙二醇选择性为84.3%，1,3-PDO的总收率达80.9%。这是目前在高液时空速0.10h^-1的条件下取得的最佳结果。

关键词: 3-羟基丙酸甲酯, 加氢, 1,3-丙二醇, 铜/二氧化硅, Zr改性

Abstract:

A series of the zirconium (Zr)-modified Cu/SiO₂ catalysts were synthesized by ammonia-evaporation method and applied in the gas-phase hydrogenation of methyl 3-hydroxypropionate (3-HMP) to 1,3-propanediol (1,3-PDO). N₂ adsorption-desorption, XRD, ICP-OES, H₂-TPR, NH₃-TPD, CO₂-TPD, FTIR, TG-DTG, HRTEM, XPS and AES techniques were used for detailed characterizations. Introduction of the Zr species results in a strong interactions between the Cu and Zr species, leading to the generation of more copper phyllosilicate, and thus increasing the specific surface area of the catalyst as well as reducing the particle sizes of the copper species. The addition of Zr also made the copper species better be dispersed over the SiO₂ support, increased the Cu⁺ content and enhanced the electronic absorption of the substrate 3-HMP by the acyl and methoxide groups. Compared with the unmodified Cu/SiO₂ catalyst, the Zr-added (0.5%) Cu/SiO₂ catalyst showed better catalytic performance. The conversion of 3-HMP as 96.0% was achieved along with the 1,3-PDO selectivity of 84.3%, Resulting in a total yield of 80.9% for 1,3-PDO. These were the best results obtained currently at a high liquid hourly space velocity (LHSV) of 0.10h^-1.

Key words: methyl 3-hydroxypropionate, hydrogenation, 1,3-propanediol, Cu/SiO₂, Zr modification

中图分类号:

O643.38

李伟杰, 康金灿, 张传明, 林丽娜, 李昌鑫, 朱红平. 锆改性Cu/SiO₂催化剂催化3-羟基丙酸甲酯选择性加氢[J]. 化工进展, 2024, 43(3): 1328-1341.

LI Weijie, KANG Jincan, ZHANG Chuanming, LIN Lina, LI Changxin, ZHU Hongping. Selective hydrogenation of methyl 3-hydroxypropionate over zirconium-modified Cu/SiO₂ catalysts[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1328-1341.

图/表 16

图1 30Cu-nZr/SiO2和30Cu/ZrO2催化剂用于3-羟基丙酸甲酯加氢的催化性能结果（T=160℃，p=6MPa，LHSV=0.10h-1，H2/3-HMP=555）

图2 不同催化剂的稳定性测试（T=160℃，p=6MPa，LHSV=0.10h-1，H2/3-HMP=555）

图3 不同催化剂的红外图谱

表1 不同Zr掺杂量催化剂的组成和结构结果

催化剂	Cu质量分数/%	Zr质量分数/%	比表面积/m²·g^-1	孔径/nm	孔容/cm³·g^-1	Cu粒径^①/nm	Cu粒径^②/nm
30Cu/SiO₂	31.0	0	295.3	6.0	0.43	5.5	5.4
30Cu-0.1Zr/SiO₂	31.0	0.10	311.5	5.7	0.45	5.8	5.8
30Cu-0.25Zr/SiO₂	29.9	0.24	336.3	5.4	0.46	5.7	5.6
30Cu-0.5Zr/SiO₂	30.9	0.50	358.6	5.1	0.46	5.2	4.9
30Cu-1Zr/SiO₂	29.6	0.97	341.6	5.3	0.45	5.5	5.4
30Cu-2Zr/SiO₂	29.5	1.89	326.7	5.7	0.46	5.8	6.1
30Cu/ZrO₂^③	29.3	50.2	19.5	21.0	0.10	18.7	—
ZrO₂	0	75.1	5.8	9.4	0.02	—	—

图4 不同Zr掺杂量催化剂的N2吸脱附等温线和孔径分布曲线

图5 不同Zr掺杂量催化剂的XRD图谱

图6 ZrO2及Cu/ZrO2催化剂的XRD图谱

图7 30Cu-0.5Zr/SiO2和30Cu/SiO2催化剂反应后样品的XRD图谱

图8 不同Zr掺杂量的还原后催化剂的TEM图和30Cu-0.5Zr/SiO2的HRTEM图

图9 反应后的30Cu-0.5Zr/SiO2和30Cu/SiO2催化剂的TEM图和粒径统计分布

图10 不同Zr掺杂量的催化剂的H2-TPR曲线

图11 30Cu/SiO2和30Cu-nZr/SiO2催化剂的酸碱性测试

图12 不同Zr掺杂量的催化剂的XPS图谱

表2 不同Zr掺杂量的催化剂还原后的XPS和Cu LMM XAES反卷积结果

催化剂	XPS结合能/eV		XAES动能/eV		$X C u +$ /%
催化剂	Cu2p_1/2	Cu2p_3/2	Cu⁺	Cu⁰	$X C u +$ /%
30Cu	952.3	932.2	914.0	918.0	38.2
30Cu-0.1Zr	952.3	932.2	914.0	918.0	41.2
30Cu-0.25Zr	952.5	932.4	914.0	918.0	42.2
30Cu-0.5Zr	952.6	932.5	914.0	918.0	49.2
30Cu-1Zr	952.5	932.5	914.0	918.0	45.2
30Cu-2Zr	952.6	932.7	914.0	918.0	44.9
30Cu/ZrO₂	953.0	933.0	914.0	918.0	44.7

表2 不同Zr掺杂量的催化剂还原后的XPS和Cu LMM XAES反卷积结果

催化剂	XPS结合能/eV		XAES动能/eV		$X C u +$ /%
催化剂	Cu2p_1/2	Cu2p_3/2	Cu⁺	Cu⁰	$X C u +$ /%
30Cu	952.3	932.2	914.0	918.0	38.2
30Cu-0.1Zr	952.3	932.2	914.0	918.0	41.2
30Cu-0.25Zr	952.5	932.4	914.0	918.0	42.2
30Cu-0.5Zr	952.6	932.5	914.0	918.0	49.2
30Cu-1Zr	952.5	932.5	914.0	918.0	45.2
30Cu-2Zr	952.6	932.7	914.0	918.0	44.9
30Cu/ZrO₂	953.0	933.0	914.0	918.0	44.7

图13 30Cu-0.5Zr/SiO2和30Cu/SiO2催化剂反应后样品的XPS图谱

图14 反应前后的30Cu-0.5Zr/SiO2和30Cu/SiO2催化剂的TG-DTG曲线

参考文献 63

1	杨金纯, 郭盈. PTT纤维的研究现状与应用前景[J]. 天津纺织科技, 2004, 42(4): 6-10.
	YANG Jinchun, GUO Ying. PTT fibers’ present situation of research and prospect of applications[J]. Tianjin Textile Science & Technology, 2004, 42(4): 6-10.
2	LEE Byeong No, CHEN Byung Soon. Process for preparing 1,3-alkanediol from epoxide derivative: EP1122235[P]. 2002-12-11.
3	朱红平, 赵金波, 洪永顺, 等. 一种有机金属催化剂及使用其制备3-羟基丙酸酯的方法: CN114345414A[P]. 2022-04-15.
	ZHU Hongping, ZHAO Jinbo, HONG Yongshun, et al. A method for preparing 3-hydroxypropionic ester using an organometallic catalyst: CN114345414A[P]. 2022-04-15.
4	赖恩义, 周雨婷, 李伟杰, 等. 3-羟基丙酸甲酯加氢合成1,3-丙二醇反应的热力学计算[J]. 厦门大学学报(自然科学版), 2023, 62(1): 31-38.
	LAI Enyi, ZHOU Yuting, LI Weijie, et al. Thermodynamic calculation of the synthesis of 1,3-propanediol by hydrogenation of methyl 3-hydroxypropionate[J]. Journal of Xiamen University (Natural Science), 2023, 62(1): 31-38.
5	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.
6	ZHENG Jianwei, HUANG Lele, CUI Cunhao, et al. Ambient-pressure synthesis of ethylene glycol catalyzed by C₆₀-buffered Cu/SiO₂ [J]. Science, 2022, 376(6590): 288-292.
7	YANG Wenting, LI Antai, YANG Youwei, et al. Low-temperature hydrogenation of methyl acetate to ethanol over a Manganese-modified Cu/SiO₂ catalyst[J]. Industrial & Engineering Chemistry Research, 2022, 61(32): 11718-11726.
8	FORSCHNER T C, WEIDER P R, SLAUGH L H, et al. Process for preparing 1,3-propanediol from methyl 3 -hydroxypropionate: US6191321[P]. 2001-02-20.
9	FORSCHNER T C, POWELL J B, SLAUGH L H, et al. Process for preparing 1,3-propanediol from methyl 3 -hydroxypropionate: WO0018712[P]. 2000-04-06.
10	李秉鲁, 张银珠, 李正浩, 等. 由3-羟基酯制备1,3 -链烷二醇的方法: CN1355160A[P]. 2002-06-26.
	LEE Byeong No, JANG Eun Joo, LEE Jung Ho. Method for preparation of 1,3-alkamediol by 3-carboxy ester: CN1355160A[P]. 2002-06-26.
11	LEE Byeong No, LEE Jung Ho, JANG Eun Joo, et al. Process for preparing 1,3-alkandiols from 3-hydroxyesters, EP 1211234[P]. 2002-06-05.
12	冯看卡. 3-羟基丙酸甲酯加氢制1,3-丙二醇研究[D]. 青岛: 青岛科技大学, 2008.
	FENG Kanka. Study on the hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol[D]. Qingdao: Qingdao University of Science & Technology, 2008.
13	YING Yuzhou, FENG Kanka, Zhiguo LYU, et al. Study on nano copper-based catalysts for the hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol[J]. Surface Review and Letters, 2009, 16(3): 343-349.
14	巩亚. 3-羟基丙酸甲酯催化加氢制备1,3-丙二醇研究[D]. 上海: 复旦大学, 2012.
	GONG Ya. Study on catalytic hydrogenation of methyl 3-hydroxypropionate to 1,3-propanediol[D]. Shanghai: Fudan University, 2012.
15	赖恩义. 掺杂负载型金属催化剂及其3-HMP催化加氢性能研究[D]. 厦门: 厦门大学, 2021.
	LAI Enyi. Study on catalytic hydrogenation of methyl 3-hydroxypropionate over dopping supported metal catalysts[D]. Xiamen: Xiamen University, 2021.
16	REN Zhiheng, YOUNIS M N, ZHAO Hui, et al. Silver modified Cu/SiO₂ catalyst for the hydrogenation of methyl acetate to ethanol[J]. Chinese Journal of Chemical Engineering, 2020, 28(6): 1612-1622.
17	ZHAO Yujun, SHAN Bin, WANG Yue, et al. An effective CuZn-SiO₂ bimetallic catalyst prepared by hydrolysis precipitation method for the hydrogenation of methyl acetate to ethanol[J]. Industrial & Engineering Chemistry Research, 2018, 57(13): 4526-4534.
18	YU Xue, ZHU Wanchun, GAO Shuang, et al. Transformation of ethanol to ethyl acetate over Cu/SiO₂ catalysts modified by ZrO₂ [J]. Chemical Research in Chinese Universities, 2013, 29(5): 986-990.
19	WANG Denghao, ZHANG Chuancai, ZHU Mingyuan, et al. Highly active and stable ZrO₂-SiO₂-supported Cu-catalysts for the hydrogenation of dimethyl oxalate to methyl glycolate[J]. ChemistrySelect, 2017, 2(17): 4823-4829.
20	ZHAO Yujun, ZHANG Huanhuan, XU Yuxi, et al. Interface tuning of Cu⁺/Cu⁰ by zirconia for dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO₂ catalyst[J]. Journal of Energy Chemistry, 2020, 49: 248-256.
21	徐晨阳, 常苏杰, 吴涛, 等. Cu-xZrO₂/SiO₂改性催化剂对醋酸甲酯制乙醇性能的影响[J]. 天然气化工(C1化学与化工), 2020, 45(5): 47-52.
	XU Chenyang, CHANG Sujie, WU Tao, et al. Effect of Cu-xZrO₂/SiO₂ modified catalyst on the performance of methyl acetate to ethanol[J]. Natural Gas Chemical Industry, 2020, 45(5): 47-52.
22	LI Feng, LU Chunshan, LI Xiaonian. The effect of the amount of ammonia on the Cu⁰/Cu⁺ ratio of Cu/SiO₂ catalyst for the hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chinese Chemical Letters, 2014, 25(11): 1461-1465.
23	YIN Anyuan, GUO Xiuying, DAI Weilin, et al. Highly active and selective copper-containing HMS catalyst in the hydrogenation of dimethyl oxalate to ethylene glycol[J]. Applied Catalysis A: General, 2008, 349(1/2): 91-99.
24	ZHAO Yujun, ZHANG Yaqing, WANG Yue, et al. Structure evolution of mesoporous silica supported copper catalyst for dimethyl oxalate hydrogenation[J]. Applied Catalysis A: General, 2017, 539: 59-69.
25	HUANG Zhiwei, CUI Fang, XUE Jingjing, et al. Synthesis and structural characterization of silica dispersed copper nanomaterials with unusual thermal stability prepared by precipitation-gel method[J]. The Journal of Physical Chemistry C, 2010, 114(39): 16104-16113.
26	VAN DER GRIFT C J G, ELBERSE P A, MULDER A, et al. Preparation of silica-supported copper-catalysts by means of deposition-precipitation[J]. Applied Catalysis, 1990, 59(1): 275-289.
27	李竹霞, 钱志刚, 赵秀阁, 等. 草酸二甲酯加氢Cu/SiO₂催化剂前体的研究[J]. 华东理工大学学报(自然科学版), 2004, 30(6): 613-617.
	LI Zhuxia, QIAN Zhigang, ZHAO Xiuge, et al. Research on the precursor of catalyst Cu/SiO₂ for hydrogenation of dimethyl oxalate[J]. Journal of East China University of Science and Technology (Natural Science Edition), 2004, 30(6): 613-617.
28	TOUPANCE T, KERMAREC M, LOUIS C. Metal particle size in silica-supported copper catalysts. Influence of the conditions of preparation and of thermal pretreatments[J]. The Journal of Physical Chemistry B, 2000, 104(5): 965-972.
29	VAN DER GRIFT C J G, WIELERS A F H, JOGH B P J, et al. Effect of the reduction treatment on the structure and reactivity of silica-supported copper particles[J]. Journal of Catalysis, 1991, 131(1): 178-189.
30	JIANG Jiawei, TU Cheng-Chieh, CHEN Chaohuang, et al. Highly selective silica-supported copper catalysts derived from copper phyllosilicates in the hydrogenation of adipic acid to 1,6-hexanediol[J]. ChemCatChem, 2018, 10(23): 5449-5458.
31	杨文龙, 赵玉军, 王胜平, 等. 铜硅催化剂中层状硅酸铜的形成过程[J]. 化学工业与工程, 2016, 33(1): 1-5.
	YANG Wenlong, ZHAO Yujun, WANG Shengping, et al. Formation of copper phyllosilicate in silica supported copper catalyst[J]. Chemical Industry and Engineering, 2016, 33(1): 1-5.
32	谢璇. 醋酸甲酯加氢制乙醇的研究[D]. 上海: 上海师范大学, 2013.
	XIE Xuan. Study on hydrogenation of methyl acetate to ethanol[D]. Shanghai: Shanghai Normal University, 2013.
33	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, 2019, 368, 173-180.
34	KIM Dohyung, RESASCO J, YU Yi, et al. Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold-copper bimetallic nanoparticles[J]. Nature Communications, 2014, 5(1): 4948.
35	ZHAO Yujun, LI Siming, WANG Yue, et al. Efficient tuning of surface copper species of Cu/SiO₂ catalyst for hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chemical Engineering Journal, 2017, 313: 759-768.
36	YAO Dawei, WANG Yue, LI Ying, et al. A high-performance nanoreactor for carbon-oxygen bond hydrogenation reactions achieved by the morphology of nanotube-assembled hollow spheres[J]. ACS Catalysis, 2018, 8(2): 1218-1226.
37	WANG, Yue, LIAO Junyu, ZHANG Jian, et al. Hydrogenation of methyl acetate to ethanol by Cu/ZnO catalyst encapsulated in SBA-15[J]. AIChE Journal, 2017, 63(7): 2839-2849.
38	XU Yuxi, KONG Lingxin, HUANG Huijiang, et al. Promotional effect of indium on Cu/SiO₂ catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol[J]. Catalysis Science & Technology, 2021, 11(20): 6854-6865.
39	刘淑芝, 徐培强, 李瑞达. 助剂La对Ni/γ-Al₂O₃催化剂加氢性能的影响[J]. 青岛科技大学学报(自然科学版), 2016, 37(4): 388-391.
	LIU Shuzhi, XU Peiqiang, LI Ruida. Effect of La on Ni/γ-Al₂O₃ catalyst in benzene hydrogenation[J]. Journal of Qingdao University of Science and Technology (Natural Science Edition), 2016, 37(4): 388-391.
40	HUANG Ying, ARIGA H, ZHENG Xinlei, et al. Silver-modulated SiO₂-supported copper catalysts for selective hydrogenation of dimethyl oxalate to ethylene glycol[J]. Journal of Catalysis, 2013, 307: 74-83.
41	MARCHI A J, FIERRO J L G, SANTAMARÍA J, et al. Dehydrogenation of isopropylic alcohol on a Cu/SiO₂ catalyst: A study of the activity evolution and reactivation of the catalyst[J]. Applied Catalysis A: General, 1996, 142(2): 375-386.
42	CHEN Liangfeng, GUO Pingjun, QIAO Minghua, et al. Cu/SiO₂ catalysts prepared by the ammonia-evaporation method: Texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol[J]. Journal of Catalysis, 2008, 257(1): 172-180.
43	RESENDE K A, TELES C A, JACOBS Gary, et al. Hydrodeoxygenation of phenol over zirconia supported Pd bimetallic catalysts. The effect of second metal on catalyst performance[J]. Applied Catalysis B: Environmental, 2018, 232: 213-231.
44	ZHENG Xinlei, LIN Haiqiang, ZHENG Jianwei, et al. Lanthanum oxide-modified Cu/SiO₂ as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol[J]. ACS Catalysis, 2013, 3(12): 2738-2749.
45	SHAO Yuewen, SUN Kai, LI Qingyin, et al. Copper-based catalysts with tunable acidic and basic sites for the selective conversion of levulinic acid/ester to γ-valerolactone or 1,4-pentanediol[J]. Green Chemistry, 2019, 21(16): 4499-4511.
46	ZHU Yifeng, ZHU Yulei, DING Guoqiang, et al. Highly selective synthesis of ethylene glycol and ethanol via hydrogenation of dimethyl oxalate on Cu catalysts: Influence of support[J]. Applied Catalysis A: General, 2013, 468: 296-304.
47	CHEN Zhen, LIU Qian, GUO Lei, et al. The promoting mechanism of in situ Zr doping on the hydrothermal stability of Fe-SSZ-13 catalyst for NH₃-SCR reaction[J]. Applied Catalysis B: Environmental, 2021, 286: 119816.
48	BACHILLER-BAEZA B, RODRIGUEZ-RAMOS I, GUERRERO-RUIZ A. Interaction of carbon dioxide with the surface of zirconia polymorphs[J]. Langmuir, 1998, 14(13): 3556-3564.
49	ZHANG Yanfei, ZHONG Liangshu, WANG Hui, et al. Catalytic performance of spray-dried Cu/ZnO/Al₂O₃/ZrO₂ catalysts for slurry methanol synthesis from CO₂ hydrogenation[J]. Journal of CO₂ Utilization, 2016, 15: 72-82.
50	PAVEL O D, TICHIT D, I-C MARCU. Acido-basic and catalytic properties of transition-metal containing Mg-Al hydrotalcites and their corresponding mixed oxides[J]. Applied Clay Science, 2012, 61: 52-58.
51	WU Xuemei, TAN Minghui, XU Bing, et al. Tuning the crystallite size of monoclinic ZrO₂ to reveal critical roles of surface defects on m-ZrO₂ catalyst for direct synthesis of isobutene from syngas[J]. Chinese Journal of Chemical Engineering, 2021, 35: 211-219.
52	LU Jinzhao, YANG Lijun, XU Bolian, et al. Promotion effects of nitrogen doping into carbon nanotubes on supported iron Fischer-Tropsch catalysts for lower olefins[J]. ACS Catalysis, 2014, 4(2): 613-621.
53	CUI Guoqing, MENG Xiaoyu, ZHANG Xi, et al. Low-temperature hydrogenation of dimethyl oxalate to ethylene glycol via ternary synergistic catalysis of Cu and acid-base sites[J]. Applied Catalysis B: Environmental, 2019, 248: 394-404.
54	WANG Sheng, FANG Yue, HUANG Zhen, et al. The effects of the crystalline phase of zirconia on C—O activation and C—C coupling in converting syngas into aromatics[J]. Catalysts, 2020, 10(2): 262.
55	HUANG Jingjing, DING Tong, MA Kui, et al. Modification of Cu/SiO₂ catalysts by La₂O₃ to quantitatively tune Cu⁺-Cu⁰ dual sites with improved catalytic activities and stabilities for dimethyl ether steam reforming[J]. ChemCatChem, 2018, 10(17): 3862-3871.
56	ZHU Yifeng, KONG Xiao, CAO Dongbo, et al. The rise of calcination temperature enhances the performance of Cu catalysts: Contributions of support[J]. ACS Catalysis, 2014, 4(10): 3675-3681.
57	XI Yushan, WANG Yue, YAO Dawei, et al. Impact of the oxygen vacancies on copper electronic state and activity of Cu-based catalysts in the hydrogenation of methyl acetate to ethanol[J]. ChemCatChem, 2019, 11(11): 2607-2614.
58	AI Peipei, TAN Minghui, YAMANE N, et al. Synergistic effect of a boron-doped carbon-nanotube-supported Cu catalyst for selective hydrogenation of dimethyl oxalate to ethanol[J]. Chemistry—A European Journal, 2017, 23(34): 8252-8261.
59	GONG Xiaoxiao, WANG Meiling, FANG Huihuang, et al. Copper nanoparticles socketed in situ into copper phyllosilicate nanotubes with enhanced performance for chemoselective hydrogenation of esters[J]. Chemical Communications, 2017, 53(51): 6933-6936.
60	YUE Hairong, ZHAO Yujun, ZHAO Shuo, et al. A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions[J]. Nature Communications, 2013, 4(1): 2339.
61	WANG Zhiqiao, XU Zhongning, PENG Siyan, et al. High-performance and long-lived Cu/SiO₂ nanocatalyst for CO₂ hydrogenation[J]. ACS Catalysis, 2015, 5(7): 4255-4259.
62	MEYER C I, MARCHI A J, MONZON A, et al. Deactivation and regeneration of Cu/SiO₂ catalyst in the hydrogenation of maleic anhydride. Kinetic modeling[J]. Applied Catalysis A: General, 2009, 367(1/2): 122-129.
63	ZHAO Yujun, KONG Lingxin, XU Yuxi, et al. Deactivation mechanism of Cu/SiO₂ catalysts in the synthesis of ethylene glycol via methyl glycolate hydrogenation[J]. Industrial & Engineering Chemistry Research, 2020, 59(27): 12381-12388.

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锆改性Cu/SiO₂催化剂催化3-羟基丙酸甲酯选择性加氢

Selective hydrogenation of methyl 3-hydroxypropionate over zirconium-modified Cu/SiO₂ catalysts

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