不同方法制备的Cu/SiO2催化剂对己二酸二甲酯加氢制1,6-己二醇的影响

doi:10.3969/j.issn.2095-2198.2023.03.003

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分别采用沉积沉淀法、溶胶凝胶法和蒸氨法制备Cu/SiO₂催化剂.利用N₂吸附-脱附、N₂O滴定、XRD、FT-IR、H₂-TPR和NH₃-TPD对催化剂的物理化学性质进行表征，并考察其己二酸二甲酯加氢合成1,6-己二醇的性能.结果表明：虽然溶胶凝胶法和蒸氨法因层状硅酸铜的存在具有较高的铜分散度和表面酸性等性质，但受制于较小孔径结构，反而是传统的沉积沉淀法制备的Cu/SiO₂催化剂因较大的孔径具有更高的反应活性.在反应温度200 ℃、反应压力50 MPa、液时空速0.6 h^-1和n(氢)/n(酯)=175的条件下该催化剂可稳定运行50 h，己二酸二甲酯的转化率可达99.8%，1，6-己二醇的选择性可达98.2%.

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关键词: 己二酸二甲酯；1')" href="#">

己二酸二甲酯；1 6-己二醇；酯加氢；Cu/SiO₂催化剂；制备方法

Abstract:

Cu/SiO₂ catalysts were prepared by deposition precipitation,sol-gel and ammonia evaporation method,respectively.The physicochemical structure properties of the catalyst were characterized by N₂ adsorption-desorption,N₂O titration,XRD,FT-IR,H₂-TPR and NH₃-TPD,and the performance of hydrogenation of dimethyl adipate (DMA) to 1,6-hexanediol (HDO) was investigated.The results showed that although the sol-gel and ammonia evaporation method had high copper dispersion and surface acidity due to the the presence of copper phyllosilicate structure,they are restricted by the smaller pore structure.Instead,the Cu/SiO₂ catalyst prepared by the traditional deposition precipitation method had higher reaction activitydue to the larger pore.Under the conditions of reaction temperature 200 ℃,reaction pressure of 50 MPa,liquid hourly space velocity of 0.6 h^-1and molar ratio of H₂ to ester of 175,the reaction could be run stably for 50 h.The conversion rate of dimethyl adipate can reach 99.8%,and the 1,6-hexanediol selectivity can reach 98.2%.

Key words: dimethyl ')" href="#">

dimethyl adipate 1,6-hexanediol ester hydrogenation Cu/SiO2 catalyst preparation methods

出版日期: 2023-06-30 发布日期: 2024-03-11 整期出版日期: 2023-06-30

ZTFLH:

O0643.38

基金资助: 辽宁省兴辽英才青年拔尖项目（XLYC1907029）；辽宁省教育厅项目(LJKZ0439,LJKQ2021068)；沈阳化工大学“优青”托举计划项目(2019YQ001)；辽宁省科技厅创新能力提升联合基金项目（2021-NLTS-12-01）

通讯作者: 刘蝈蝈

作者简介: 王英斌（1996—），男，辽宁铁岭人，硕士研究生在读，主要从事酯类化合物催化加氢催化剂开发的研究.

引用本文:

王英斌1, 2, 王康军1, 2, 刘蝈蝈1, 2, 宋雨莹1, 2, 秦王昕1, 2, 张亚芳1.

不同方法制备的Cu/SiO₂催化剂对己二酸二甲酯加氢制1,6-己二醇的影响 [J]. 沈阳化工大学学报, 2023, 37(3): 208-217.
WANG Yingbin1, 2, WANG Kangjun1, 2, LIU Guoguo1, 2, SONG Yuying1, 2, QIN Wangxin1, 2, ZHANG Yafang1.

Effect of Cu/SiO₂Catalysts Prepared by Different Methods on Hydrogenation of Dimethyl Adipate to 1,6-Dexadiol . Journal of Shenyang University of Chemical Technology, 2023, 37(3): 208-217.

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https://xuebao.syuct.edu.cn/CN/10.3969/j.issn.2095-2198.2023.03.003 或 https://xuebao.syuct.edu.cn/CN/Y2023/V37/I3/208

［1］TU C C,TSOU Y J,TO T D,et al.Phyllosilicates-Derived CuNi/SiO₂ Catalysts in the Selective Hydrogenation of Adipic Acid to 1,6-Hexandiol［J］.ACS Sustainable Chemistry & Engineering,2019,7 (21):17872-17881.

［2］王新龙,王晓东,雷小楠,等.1,6-己二醇制备工艺进展［J］.石油化工,2019,48(5):513-521.

［3］TUREK T,TRIMM D L,CANT N W.The Catalytic Hydrogenolysis of Esters to Alcohols［J］.Catalysis Reviews-Science and Engineering,1994,36(4):645-683.

［4］JIANG H B,JIANG H J,SU K,et al.A Ru-Sn-Co/AlO(OH) as a Highly Efficient Catalyst for Hydrogenation of Dimethyl Adipate to 1,6-Hexanodiol in Aqueous Phase［J］.Applied Catalysis A:General,2012,447/448:164-170.

［5］POSPELOVA V,AUBRECHT J,KIKHTYANIN O,et al.CuZn Catalysts Superior to Adkins Catalysts for Dimethyl Adipate Hydrogenolysis［J］.ChemCatChem,2019,11(8):2169-2178.

［6］POSPELOVA V,AUBRECHT J,PACULTOVA K,et al.Does the Structure of CuZn Hydroxycarbonate Precursors Affect the Intrinsic Hydrogenolysis Activity of CuZn Catalysts?［J］.Catalysis Science & Technology,2020,10(10):3303-3314.

［7］KIKHTYANIN O,POSPELOVA V,AUBRECHT J,et al.Effect of Calcination Atmosphere and Temperature on the Hydrogenolysis Activity and Selectivity of Copper-Zinc Catalysts［J］.Catalysts,2018,8(10):446.

［8］CHEN Z,ZHU G S,WU Y,et al.The Promotion Effect of Transition Metals on Water-Tolerant Performance of Cu/SiO₂ Catalysts in Hydrogenation Reaction［J］.ChemistrySelect,2019,4(48):14063-14068.

［9］CHEN Z,CHEN J G.Comparative Study of the Effect of Water on Cu/SiO₂ Catalysts Prepared by Different Methods:Structure,Hydrogenation Performance and the Promotion of Reduction Cu⁺ to Cu⁰［J］.ChemistrySelect,2020,5(34):10781-10786.

［10］DONG X H,MA X G,XU H Y,et al.Comparative Study of Silica-Supported Copper Catalysts Prepared by Different Methods:Formation and Transition of Copper Phyllosilicate［J］.Catalysis Science & Technology,2016,6(12):4151-4158.

［11］HE L M,CHEN X C,MA J S,et al.Characterization and Catalytic Performance of Sol-Gel Derived Cu/SiO₂Catalysts for Hydrogenolysis of Diethyl Oxalate to Ethylene Glycol［J］.Journal of Sol-Gel Science and Technology,2010,55(3):285-292.

［12］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.

［13］王峰,吴静,王康军.糠醛加氢Cu/SiO₂催化剂成型及性能研究［J］.沈阳化工大学学报,2012,26(3):210-214.

［14］CHEN L F,GUO P J,QIAO M H,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.

［15］ZHANG H W,TAN H R,JAENICKE S,et al.Highly Efficient and Robust Cu Catalyst for Non-Oxidative Dehydrogenation of Ethanol to Acetaldehyde and Hydrogen［J］.Journal of Catalysis,2020,389:19-28.

［16］WU L B,LI B L,ZHAO C.Direct Synthesis of Hydrogen and Dimethoxylmethane from Methanol on Copper/Silica Catalysts with Optimal Cu⁺/Cu⁰ Sites［J］.Chem Cat Chem,2018,10(5):1140-1147.

［17］BIAN Z F,ZHONG W Q,YU Y,et al.Cu/SiO₂ Derived from Copper Phyllosilicate for Low-Temperature Water-Gas Shift Reaction:Role of Cu⁺Sites［J］.Industrial Journal of Hydrogen Energy,2020,45(51):27078-27088.

［18］CHEN C Q,REN H J,HE Y Y,et al.Unraveling the Role of Cu⁰ and Cu⁺ Sites in Cu/SiO₂ Catalysts for Water-Gas Shift Reaction［J］.Chem Cat Chem,2020,12(18):4672-4679.

［19］刘红磊,张晓宇,张雅静,等.Zn、Al改性Cu/SiO₂催化剂及其对草酸二甲酯加氢合成乙二醇催化性能的影响［J］.沈阳化工大学学报,2014,28(1):15-19.

［20］FIGUEIREDO F C A,JORDA~O E,CARVALHO W A.Adipic Ester Hydrogenation Catalyzed by Platinum Supported in Alumina,Titania and Pillared Clays［J］.Applied Catalysis A:General,2008,351(2):259-266.

［21］DONG F,DING G Q,ZHENG H Y,et al.Highly Dispersed Cu Nanoparticles as an Efficient Catalyst for the Synthesis of the Biofuel 2-Methylfuran［J］.Catalysis Science & Technology,2016,6(3):767-779.

［22］DONG F,ZHU Y L,ZHENG HY,et al.Cr-Free Cu-Catalysts for the Selective Hydrogenation of Biomass-Derived Furfural to 2-Methylfuran:the Synergistic Effect of Metal and Acid Sites［J］.Journal of Molecular Catalysis A:Chemical,2015,398:140-148.

［23］NIE R F,LEI H,PAN S Y,et al.Core-Shell Structured CuO-ZnO@H-ZSM-5 Catalysts for CO Hydrogenation to Dimethyl Ether［J］.Fuel,2012,96:419-425.

［24］ZHAO Y J,GUO Z Y,ZHANG H J,et al.Ordered Mesoporous CuZn/HPS Catalysts for the Chemoselective Hydrogenation of Dimethyl Adipate to 1,6-Hexanediol［J］.Chemistry Letters,2017,46(8):1079-1082.

［25］ZHAO Y J,GUO Z Y,ZHANG H J,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］徐晓清,刘仲能,涂云宝,等.锰、锆对铜锌铝催化剂结构的影响及其对己二酸二甲酯加氢制备1,6-己二醇的催化性能［J］.工业催化,2018,26(6):57-63.

［27］DOS SANTOS S M,SILVA A M,JORDA~O E,et al.Performance of RuSn Catalysts Supported on Different Oxides in the Selective Hydrogenation of Dimethyl Adipate［J］.Catalysis Today,2005,107-108:250-257.

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