阮厚航,吕喜蕾,王立新,吕秀阳

• 1:浙江大学生物质化工教育部重点实验室
• 2:浙江大学化学工程与生物工程学院

摘要(Abstract)：

糠醇是重要的有机化工原料,用途广泛。现行糠醛催化加氢制备糠醇的技术存在氢耗大、成本高等缺点。本文提出了一种在近临界异丙醇中,Cu-Pd/Al_2O_3催化糠醛转移氢化制备糠醇的方法。采用共沉淀法制备了不同Cu、Pd负载量的Cu-Pd/Al_2O_3催化剂,并进行了XRD、氮气吸脱附表征。考察了催化剂中Cu-Pd的负载量、催化剂用量、糠醛浓度、反应温度和反应时间对反应的影响。结果表明:18%Cu-2%Pd/Al_2O_3双金属催化剂对糠醛催化转移氢化反应效果最好;在18%Cu-2%Pd/Al_2O_3催化剂作用下,反应温度为190℃、反应时间为3h时,糠醛转化率为100%、糠醇收率达到86.4%;催化剂重复使用四次后依然保持良好的活性。本文提出的方法具有非临氢、糠醇收率高、催化剂重复使用性能好等优点。

关键词(KeyWords)： 糠醛;糠醇;双金属催化剂;催化转移氢化

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金(21476204,21676243);; 浙江省自然科学基金重点项目(LZ14B060002);; 中央高校基本科研业务费专项资金

作者(Author): 阮厚航,吕喜蕾,王立新,吕秀阳

参考文献(References)：

• [1]Mamman A S,Lee J M,Kim Y C,et al.Furfural:Hemicellulose/xylose-derived biochemical[J].Biofuels,Bioproducts and Biorefining,2008,2(5):438-454.
• [2]XU Xiu-xiu(徐秀秀),LüXi-lei(吕喜蕾),FU Jie(傅杰),et al.Catalytic decomposition of furfural residue with dilute sulfuric acid to produce levulinic acid in high temperature liquid water(高温液态水中稀硫酸催化糠醛渣降解制备乙酰丙酸)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2015,29(6):1377-1382.
• [3]Nagaraja BM,Padmasri AH,Raju BD,et al.Vapor phase selective hydrogenation of furfural to furfuryl alcohol over Cu–Mg O coprecipitated catalysts[J].Journal of Molecular Catalysis A:Chemical,2007,265(1):90-97.
• [4]Sharma RV,Das U,Sammynaiken R,et al.Liquid phase chemo-selective catalytic hydrogenation of furfural to furfuryl alcohol[J].Applied Catalysis A:General,2013,454:127-136.
• [5]LI Dian-qing(李殿卿),ZHU Zhuo-qun(朱卓群),WANG Fu-rong(王福荣).Measurement of model parameters for furfuryl alcohol hydrogenation reaction with impulse-response technique(脉冲-应答技术测定糠醇加氢反应的模型参数)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),1993,7(3):262-266.
• [6]CAO Xiao-xia(曹晓霞),XIANG Yi-zhi(项益智),LU Chun-shan(卢春山),et al.In-situ reduction of furfural to furfuryl alcohol with hydrogen derived from aqueous-phase reforming of methanol(甲醇水相重整制氢原位还原糠醛制备糠醇)[J].Rare Metal Materials and Engineering(稀有金属材料与工程),2010,39(Supplement 2):516-520.
• [7]Xu Y,Qiu S,Long J,et al.In situ hydrogenation of furfural with additives over a RANEY Ni catalyst[J].RSC Advances,2015,5(111):91190-91195.
• [8]Dong J,Zhu MM,Zhang GS,et al.Highly selective supported gold catalyst for CO-driven reduction of furfural in aqueous media[J].Chinese Journal of Catalysis,2016,37(10):1669-1675.
• [9]Panagiotopoulou P,Martin N,Vlachos D G.Effect of hydrogen donor on liquid phase catalytic transfer hydrogenation of furfural over a Ru/Ru O2/C catalyst[J].Journal of Molecular Catalysis A:Chemical,2014,392:223-228.
• [10]Panagiotopoulou P,Martin N,Vlachos D G.Liquid-phase catalytic transfer hydrogenation of furfural over homogeneous lewis acid–Ru/C catalysts[J].Chem Sus Chem,2015,8(12):2046-2054.
• [11]Kannapu HPR,Mullen C A,Elkasabi Y,et al.Catalytic transfer hydrogenation for stabilization of bio-oil oxygenates:Reduction of p-cresol and furfural over bimetallic Ni–Cu catalysts using isopropanol[J].Fuel Processing Technology,2015,137:220-228.
• [12]Scholz D,Aellig C,Hermans I.Catalytic transfer hydrogenation/hydrogenolysis for reductive upgrading of furfural and 5-(hydroxymethyl)furfural[J].Chem Sus Chem,2014,7(1):268-275.
• [13]Villaverde MM,Garetto TF,Marchi A J.Liquid-phase transfer hydrogenation of furfural to furfuryl alcohol on Cu–Mg–Al catalysts[J].Catalysis Communications,2015,58:6-10.
• [14]Biradar N S,Hengne A M,Sakate S S,et al.Single pot transfer hydrogenation and aldolization of furfural over metal oxide catalysts[J].Catalysis Letters,2016,146(8):1611-1619.
• [15]Li J,Liu J L,Zhou H J,et al.Catalytic transfer hydrogenation of furfural to furfuryl alcohol over nitrogen-doped carbon-supported iron catalysts[J].Chem Sus Chem,2016,9(11):1339-1347.
• [16]Li H,He J,Riisager A,et al.Acid-base bifunctional zirconium N-alkyltriphosphate nanohybrid for hydrogen transfer of biomass-derived carboxides[J].ACS Catalysis,2016,6(11):7722-7727.
• [17]Sanchez-Escribano V,Arrighi L,Riani P,et al.Characterization of Pd-Cu alloy nanoparticles onγ-Al2O3-supported catalysts[J].Langmuir,2006,22(22):9214-9219.
• [18]Lodziana Z,N?rskov J K.Adsorption of Cu and Pd onα-Al2O3(0001)surfaces with different stoichiometries[J].Journal of Chemical Physics,2001,115(24):11261-11267.
• [19]Wang H,Chen L,Lv Y,et al.H2 dissociation on gamma-Al2O3 supported Cu/Pd atoms:A DFT investigation[J].Applied Surface Science,2014,290:154-160.
• [20]Feng F,Ye J,Cheng Z,et al.Cu-Pd/gamma-Al2O3 catalyzed the coupling of multi-step reactions:direct synthesis of benzimidazole derivatives[J].RSC Advances,2016,6(76):72750-72755.