Pd-Cu/Fe_3O_4@C催化1,4-丁炔二醇选择性加氢的研究
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摘要
1,4-丁烯二醇是一种高经济价值的精细化学品,1,4-丁炔二醇选择性加氢是制备1,4-丁烯二醇的有效途径。本文采用浸渍法制备了双金属磁性催化剂Pd-Cu/Fe_3O_4@C,利用X射线衍射(XRD)、X射线光电子能谱(XPS)及透射电子显微镜(TEM)等技术手段对催化剂进行了表征,考察了Pd/Cu物质的量比、反应温度、H2压力、反应时间和催化剂用量等因素对催化剂性能的影响。结果表明,在Pd/Cu物质的量之比1∶1、催化剂/底物为1∶90000、反应温度为50℃、H_2压力为4MPa、时间为25min的条件下,1,4-丁炔二醇选择性加氢的转化率和选择性分别达到了95.2%和98.3%。该催化剂不仅具有高催化活性和选择性,而且易与反应产物实现磁性分离,为该过程的工业化应用奠定了基础。
1,4-butene glycol is a kind of high commercial valuefine chemical.The effective way of preparing 1,4-butylene glycol is the selective hydrogenation of 1,4-butylene glycol.The double metal magnetic catalyst Pd-Cu/Fe_3O_4@C was prepared by impregnation method and the catalyst was characterized by some technical approaches such as X ray diffraction(XRD),X ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM)and so on.The influence catalyst performance effects of Pd/Cu molar ratio,reaction temperature,H_2 pressure,reaction time and catalyst dosage were investigated.Under the optimized conditions(Pd/Cu=1∶1,substrate/catalyst=1/90 000,50℃,4 MPa,and 25 min),the conversion and the selectivity of hydrogenation of 1,4-butynediol could reached 95.2%and 98.3%,respectively.The catalyst not only had high catalytic activity and selectivity,but also easy to achieve magnetic separation with the reaction product,laying the foundation for the industrial application of the process.
1,4-butene glycol is a kind of high commercial valuefine chemical.The effective way of preparing 1,4-butylene glycol is the selective hydrogenation of 1,4-butylene glycol.The double metal magnetic catalyst Pd-Cu/Fe_3O_4@C was prepared by impregnation method and the catalyst was characterized by some technical approaches such as X ray diffraction(XRD),X ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM)and so on.The influence catalyst performance effects of Pd/Cu molar ratio,reaction temperature,H_2 pressure,reaction time and catalyst dosage were investigated.Under the optimized conditions(Pd/Cu=1∶1,substrate/catalyst=1/90 000,50℃,4 MPa,and 25 min),the conversion and the selectivity of hydrogenation of 1,4-butynediol could reached 95.2%and 98.3%,respectively.The catalyst not only had high catalytic activity and selectivity,but also easy to achieve magnetic separation with the reaction product,laying the foundation for the industrial application of the process.
引文
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[2]Guo Z,Xiao C,Maligalganesh R V,et al.Pt nanoclusters confined within metal-organic framework cavities for chemoselective cinnamaldehyde hydrogenation[J].Acs Catal,2014,4(5):1 340-1 348.
[3]Shen L,Wu W,Liang R,et al.Highly dispersed palladium nanoparticles anchored on UiO-66(NH2)metalorganic framework as a reusable and dual functional visible-light-driven photocatalyst.[J].Nanoscale,2013,5(19):9 374-9 382.
[4]Kardanpour R,Tangestaninejad S,Mirkhani V,et al.Highly dispersed palladium nanoparticles supported on amino functionalized metal-organic frameworks as an efficient and reusable catalyst for Suzuki cross-coupling reaction[J].J Organomet Chem,2014,761(4):127-133.
[5]Li C,Zhang M,Di X,et al.One-step synthesis of Pt@ZIF-8catalyst for the selective hydrogenation of 1,4-butynediol to 1,4-butenediol[J].Chin J Cat,2016,37(9):1 555-1 561.
[6]Zhang M,Yang Y,Li C,et al.PVP-Pd@ZIF-8as highly efficient and stable catalysts for selective hydrogenation of 1,4-butynediol[J].Cat Sci Technol,2014,4(2):329-332.
[7]Song S,Li K,Pan J,et al.Achieving the trade-off between selectivity and activity in semihydrogenation of alkynes by fabrication of(asymmetrical Pd@Ag core)@(CeO2Shell)nanocatalysts via autoredox reaction[J].Adv Maters,2017,29(8):1-6.
[8]Naoki Toshima,Rei Ito,Toru Matsushita,et al.Trimetallic nanoparticleshaving a Au-core structure[J].Catal Today,2007,122(3-4):239-244.
[9]Telkar M M,Rode C V,Rane V H,et al.Influence of alkali metal doping on selectivity behaviour of platinum catalysts for hydrogenation of 2-butyne-1,4-diol[J].Catal Commun,2005,6(11):725-730.
[10]Chaudhari R V,Parande M G,Ramachandran P A,et al.Hydrogenation of butynediol to cis-butenediol catalyzed by Pd-Zn-CaCO3:reaction kinetics and modeling of a batch slurry reactor[J].Aiche J,1985,31(11):1891-1 903.
[11]Liu Y,Liu X,Feng Q,et al.Intermetallic nix my(M=Ga and Sn)nanocrystals:a non-precious metal catalyst for semi-hydrogenation of alkynes[J].Adv Mater,2016,28(23):4747-4754.
[12]李霞,胡玉方,刘德蓉,等.Ru-Cu/Fe3O4-TiO2催化剂上甘油氢解制备1,2-丙二醇的研究[J].化学研究与应用,2016,28(5):629-635.
[13]Gustafson B L,Wehner P S.XPS and XRD studies of supported Pd-Cu bimetallics[J].Appl Surf Sci,1991,52(4):261-270.
[14]冯娟,李兴华,邓霞,等.核-壳结构Fe3O4@C磁性纳米颗粒的制备及其结构表征[J].电子显微学报,2012,31(5):406-410.
[15]王沾祺,周志明,张锐,等.Pd-Cu/γ-Al2O3催化苯乙炔选择性加氢反应[J].物理化学学报,2014(12):2 315-2322.
[16]Mane R B,Rode C V.Simultaneous glycerol dehydration and in situ hydrogenolysis over Cu-Al oxide under an inert atmosphere[J].Green Chem,2012,14(10):2780-2 789.
[17]林欣燕,马静静,周雪梅.高效催化Suzuki偶联反应的催化剂——石墨烯负载纳米Pd-Cu合金纳米复合材料[J].合成化学研究,2013,1(2):5-9.
[18]Veldurthi S,Shin C H,Joo O S,et al.Promotional effects of Cu on Pt/Al2O3,and Pd/Al2O3,catalysts during n-butane dehydrogenation[J].Catal Today,2012,185(1):88-93.
[19]Miyazawa T,Kusunoki Y,Kunimori K,et al.glycerol Conversion in aqueous solution under hydrogen over Ru/C+An ion-exchange resin and its reaction mechanism[J].J Catal,2006,240(2):213-221.
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