铜锌铝催化剂催化脂肪酸甲酯加氢反应研究

摘要研究了铜负载量以及铜锌比对铜锌铝催化剂催化月桂酸甲酯加氢制脂肪醇反应性能的影响规律。结果表明铜锌铝催化剂具有优异的脂肪酸甲酯加氢能力。在5 MPa、190 ℃和空速为2 h^-1条件下,脂肪酸酯转化率和脂肪醇选择性分别高达78.87%和89.14%,远高于Cu/Al₂O₃与Cu/ZnO催化剂。其原因在于锌物种与铜物种相互作用产生的Cu-O-Zn位点提高了Cu⁰的催化活性,获得较高的TOF值 (27.5 h^-1)。同时,铝物种作为结构助剂增加了材料的比表面积并提高了催化剂的稳定性。进一步提高温度到210 ℃时,月桂酸甲酯转化率和月桂醇选择性均可高达99%,表现出较高的催化性能和应用价值。

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	姜峰
	徐云强
	徐艳
	赵玉军

关键词：铜锌铝脂肪酸酯加氢脂肪醇

Abstract： The effect of copper loading and Cu-Zn ratio on the hydrogenation of methyl laurate to fatty alcohol over Cu-Zn-Al catalyst was studied. The results show that Cu-Zn-Al catalyst has excellent hydrogenation activity of fatty acid methyl ester. Under the conditions of 5 MPa, 190 ℃ and 2 h^-1, the conversion of fatty acid ester and selectivity of fatty alcohol are up to 78.87% and 89.14%, respectively, which are much higher than Cu/Al₂O₃ and Cu/ZnO catalysts. The reason is that the Cu-O-Zn site generated by the interaction between zinc species and copper species improves the catalytic activity of Cu⁰, with a high TOF value (27.5 h^-1). Aluminum species as a structural promoter improve the specific surface area and enhances the stability of the catalyst. When the temperature is increased to 210 ℃, the conversion of methyl laurate and the selectivity of lauryl alcohol can be up to 99%, showing high catalytic performance and application value.

Keywords： Cu-Zn-Al fatty acid ester hydrogenation fatty alcohol

Received 2023-02-12;

Corresponding Authors: 赵玉军,教授,E-mail:yujunzhao@tju.edu.cn。 Email: yujunzhao@tju.edu.cn

About author: 姜峰(1975-),男,副教授,现从事化工过程强化方面的研究。

引用本文:

姜峰, 徐云强, 徐艳, 赵玉军.铜锌铝催化剂催化脂肪酸甲酯加氢反应研究[J]. 化学工业与工程, 2024,41(5): 154-163

JIANG Feng, XU Yunqiang, XU Yan, ZHAO Yujun.Study on hydrogenation of fatty acid methyl ester catalyzed by Cu-Zn-Al catalyst[J]. Chemcial Industry and Engineering, 2024,41(5): 154-163

[1] SÁNCHEZ M A, TORRES G C, MAZZIERI V A, et al. Selective hydrogenation of fatty acids and methyl esters of fatty acids to obtain fatty alcohols-A review[J]. Journal of Chemical Technology & Biotechnology, 2017, 92(1): 27-42
[2] BEHR A, WESTFECHTEL A, PÉREZ GOMES J. Catalytic processes for the technical use of natural fats and oils[J]. Chemical Engineering & Technology, 2008, 31(5): 700-714
[3] SÁNCHEZ M A, MAZZIERI V A, VICERICH M A, et al. Influence of the support material on the activity and selectivity of Ru-Sn-B catalysts for the selective hydrogenation of methyl oleate[J]. Industrial & Engineering Chemistry Research, 2015, 54(27): 6845-6854
[4] 耿尧辰, 赵玉军, 王胜平, 等. 热稳定性增强的铈改性Cu/SiO₂催化剂及在草酸酯加氢制乙二醇反应中的应用[J]. 化学工业与工程, 2015, 32(6): 1-612, 12 GENG Yaochen, ZHAO Yujun, WANG Shengping, et al. Ceria-modified Cu/SiO₂ catalyst with enhanced thermal stability and its application in hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chemical Industry and Engineering, 2015, 32(6): 1-612, 12(in Chinese)
[5] YAO Y, WU X, CHEN B, et al. Copper-based catalysts confined in carbon nanocage reactors for condensed ester hydrogenation: Tuning copper species by confined SiO₂ and methanol resistance[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(48): 16270-16280
[6] CHURCH J M, ABDEL-GELIL M A. Catalytic hydrogenation of methyl laurate to lauryl alcohol[J]. Industrial & Engineering Chemistry, 1957, 49(5): 813-817
[7] ZHAO Y, WU X, ZHOU J, et al. MOF-derived Cu@C catalyst for the liquid-phase hydrogenation of esters[J]. Chemistry Letters, 2018, 47(7): 883-886
[8] WANG Y, ZHAO Y, LV J, et al. Facile synthesis of Cu@CeO₂ and its catalytic behavior for the hydrogenation of methyl acetate to ethanol[J]. ChemCatChem, 2017, 9(12): 2085-2090
[9] YAO Y, WU X, GUTIÉRREZ O 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
[10] 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(in Chinese)
[11] WEN C, LI F, CUI Y, et al. Investigation of the structural evolution and catalytic performance of the CuZnAl catalysts in the hydrogenation of dimethyl oxalate to ethylene glycol[J]. Catalysis Today, 2014, 233: 117-126
[12] 廖俊宇, 赵玉军, 王胜平, 等. 载体极化率对乙酸甲酯加氢Cu/ZnO催化剂的作用机制研究[J]. 化学工业与工程, 2017, 34(6):11-17 LIAO Junyu, ZHAO Yujun, WANG Shengping, et al. Roles of the support polarity ratio on Cu/ZnO catalysts for methyl acetate hydrogenation[J]. Chemical Industry and Engineering, 2017, 34(6): 11-17(in Chinese)
[13] HE L, CHENG H, LIANG G, et al. Effect of structure of CuO/ZnO/Al₂O₃ composites on catalytic performance for hydrogenation of fatty acid ester[J]. Applied Catalysis A: General, 2013, 452: 88-93
[14] HUANG H, CAO G, FAN C, et al. Effect of water on Cu/Zn catalyst for hydrogenation of fatty methyl ester to fatty alcohol[J]. Korean Journal of Chemical Engineering, 2009, 26(6): 1574-1579
[15] YUAN P, LIU Z, ZHANG W, et al. Cu-Zn/Al₂O₃ catalyst for the hydrogenation of esters to alcohols[J]. Chinese Journal of Catalysis, 2010, 31(7): 769-775
[16] SHAO Y, SUN K, LI Q, 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
[17] SINGH R, TRIPATHI K, PANT K K, et al. Unravelling synergetic interaction over tandem Cu-ZnO-ZrO₂/hierarchical ZSM5 catalyst for CO₂ hydrogenation to methanol and DME[J]. Fuel, 2022, 318: 123641
[18] LIU Q, ZHAO Z, ARAI M, et al. Transformation of γ-valerolactone into 1,4-pentanediol and 2-methyltetrahydrofuran over Zn-promoted Cu/Al₂O₃ catalysts[J]. Catal Sci Technol, 2020, 10(13): 4412-4423
[19] TISSERAUD C, COMMINGES C, BELIN T, et al. The Cu-ZnO synergy in methanol synthesis from CO₂, Part 2: Origin of the methanol and CO selectivities explained by experimental studies and a sphere contact quantification model in randomly packed binary mixtures on Cu-ZnO coprecipitate catalysts[J]. Journal of Catalysis, 2015, 330: 533-544
[20] NGUYEN HOANG T T, TSAI D H. Low-temperature methanol synthesis via (CO₂+CO) combined hydrogenation using Cu-ZnO/Al₂O₃ hybrid nanoparticle cluster[J]. Applied Catalysis A: General, 2022, 645: 118844
[21] HAN C, ZHANG H, LI C, et al. The regulation of Cu-ZnO interface by Cu-Zn bimetallic metal organic framework-templated strategy for enhanced CO₂ hydrogenation to methanol[J]. Applied Catalysis A: General, 2022, 643: 118805
[22] YU J, CHEN G, GUO Q, et al. Ultrasmall bimetallic Cu/ZnO_x nanoparticles encapsulated in UiO-66 by deposition-precipitation method for CO₂ hydrogenation to methanol[J]. Fuel, 2022, 324: 124694
[23] YAO D, WANG Y, LI Y, 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
[24] CHEN L, GUO P, QIAO M, 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
[25] ZHAO Y, GUO Z, ZHANG H, 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
[26] CHARY K V R, SAGAR G V, SRIKANTH C S, et al. Characterization and catalytic functionalities of copper oxide catalysts supported on zirconia[J]. The Journal of Physical Chemistry B, 2007, 111(3): 543-550
[27] JIA P, LIU Y, YANG R, et al. Insight into the structural sensitivity of CuZnAl catalysts for CO hydrogenation to alcohols[J]. Fuel, 2022, 323: 124265
[28] KANAI Y, WATANABE T, FUJITANI T, et al. Evidence for the migration of ZnO_x in a Cu/ZnO methanol synthesis catalyst[J]. Catalysis Letters, 1994, 27(1): 67-78
[29] WU L, LI L, LI B, et al. Selective conversion of coconut oil to fatty alcohols in methanol over a hydrothermally prepared Cu/SiO₂ catalyst without extraneous hydrogen[J]. Chemical Communications, 2017, 53(45): 6152-6155
[30] HUANG H, WANG S, WANG S, et al. Deactivation mechanism of Cu/Zn catalyst poisoned by organic chlorides in hydrogenation of fatty methyl ester to fatty alcohol[J]. Catalysis Letters, 2010, 134(3): 351-357
[31] REN D, WAN X, JIN F, et al. Selective hydrogenation of levulinate esters to 1, 4-pentanediol using a ternary skeletal CuAlZn catalyst[J]. Green Chemistry, 2016, 18(22): 5999-6003