5-羟甲基糠醛加氢催化剂的催化性能
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摘要
介绍了负载型5-羟甲基糠醛(HMF)加氢催化剂的制备方法,对所制备的催化剂进行了N_2吸附-脱附等温线、透射电镜、氢氧滴定、吡啶红外等表征,并采用高压反应釜装置对其催化加氢性能进行了评价。比较了Ru、Rh、Pd、Pt 4种贵金属,MoO_3、WO_3、ReO_3 3种助剂,SiO_2、Al_2O_3、Y型分子筛、S-1分子筛、MCM-41介孔材料5种载体对HMF加氢反应催化剂性能的影响,结果表明,以SiO_2为载体负载Pt及助剂MoO_3制得的催化剂性能较好。HMF呋喃环侧链C—C键和C—O键的断裂是引发后续副反应的重要原因,抑制HMF呋喃环侧链C—C键和C—O键的断裂是提高HMF加氢反应目标产物选择性的关键。
Supported catalysts were synthesized for the hydrogenation of 5-hydroxymethylfurfural(HMF). Catalyst preparation methods were introduced, and the obtained catalysts were characterized by multiple methods, such as N_2 adsorption-desorption isotherm, transmission electron microscope, hydrogen and oxygen titration, and Pyridine-adsorbed fourier transform infrared spectroscopy. Catalytic performance of the catalysts was evaluated in a high pressure stirred tank. Effects of four kinds of noble metal(Ru, Rh, Pd, Pt), three kinds of promoter(MoO_3, WO_3, ReO_3) and five kinds of support(SiO_2, Al_2O_3, Y zeolite, S-1 zeolite, MCM-41 mesoporous material) on the performances of catalysts in HMF hydrogenation process were studied. Results show that it is proper to use SiO_2 as the carrier to support Pt and MoO_3 promoter The rupture of C—C and C—O bonds in the side chains of HMF is an important factor to trigger subsequent side reactions. Thus, restraining the rupture favors increasing the selectivity of the target products in HMF hydrogenation reaction.
Supported catalysts were synthesized for the hydrogenation of 5-hydroxymethylfurfural(HMF). Catalyst preparation methods were introduced, and the obtained catalysts were characterized by multiple methods, such as N_2 adsorption-desorption isotherm, transmission electron microscope, hydrogen and oxygen titration, and Pyridine-adsorbed fourier transform infrared spectroscopy. Catalytic performance of the catalysts was evaluated in a high pressure stirred tank. Effects of four kinds of noble metal(Ru, Rh, Pd, Pt), three kinds of promoter(MoO_3, WO_3, ReO_3) and five kinds of support(SiO_2, Al_2O_3, Y zeolite, S-1 zeolite, MCM-41 mesoporous material) on the performances of catalysts in HMF hydrogenation process were studied. Results show that it is proper to use SiO_2 as the carrier to support Pt and MoO_3 promoter The rupture of C—C and C—O bonds in the side chains of HMF is an important factor to trigger subsequent side reactions. Thus, restraining the rupture favors increasing the selectivity of the target products in HMF hydrogenation reaction.
引文
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[14]KARIM K,ZHAO J,RAWLENCE D,et al.Synthesis and characterisation of hexagonal Y(EMT)and cubic Y(FAU)Effect of template and fluoride ions on the zeolite product[J].Microporous Materials,1995,3(6):695-698.
[15]HEITMANN G P,DAHLHOFF G,HLDERICH W F.Catalytically active sites for the Beckmann rearrangement of cyclohexanone oxime toε-caprolactam[J].Journal of Catalysis,1999,186(1):12-19.
[16]BECK J S,VARTULI J C,ROTH W J,et al.A new family of mesoporous molecular sieves prepared with liquid crystal templates[J].Journal of the American Chemical Society,1992,114(27):10834-10843.
[17]CHIA M,PAGN-TORRES Y J,HIBBITTS D,et al.Selective hydrogenolysis of polyols and cyclic ethers over bifunctional surface sites on rhodium-rhenium catalysts[J].Journal of the American Chemical Society,2011,133(32):12675-12689.
[2]ROSATELLA A A,SIMEONOV S P,FRADE R F M,et al.5-Hydroxymethylfurfural(HMF)as a building block platform:Biological properties,synthesis and synthetic applications[J].Green Chemistry,2011,42(32):754-793.
[3]TONG X,MA Y,LI Y.Biomass into chemicals:Conversion of sugars to furan derivatives by catalytic processes[J].Applied Catalysis A General,2010,385(1/2):1-13.
[4]JANG N R,KIM H R,HOU C T,et al.Novel biobased photo-crosslinked polymer networks prepared from vegetable oil and 2,5-furan diacrylate[J].Polymers for Advanced Technologies,2013,24(9):814-818.
[5]GOSWAMI S,DEY S,JANA S.Design and synthesis of a unique ditopic macrocyclic fluorescent receptor containing furan ring as a spacer for the recognition of dicarboxylic acids[J].Tetrahedron,2008,64(27):6358-6363.
[6]MOREAU C,BELGACEM M N,GANDINI A.Recent catalytic advances in the chemistry of substituted furans from carbohydrates and in the ensuing polymers[J].Topics in Catalysis,2004,27(1/2/3/4):11-30.
[7]BUNTARA T,NOEL S,PHUA P H,et al.Caprolactam from renewable resources:Catalytic conversion of 5-hydroxymethylfurfural into caprolactone[J].Angewandte Chemie International Edition,2011,50(31):7083-7087.
[8]TUTEJA J,CHOUDHARY H,NISHIMURA S,et al.Direct synthesis of 1,6-hexanediol from HMF over a heterogeneous Pd/ZrP catalyst using formic acid as hydrogen source[J].Chem Sus Chem,2014,7(1):96-100.
[9]de VRIES J G,TEDDY N,PHUA P H,et al.Preparation of caprolactone,caprolactam,2,5-tetrahydrofuran-dimethanol,1,6-hexanediol or1,2,6-hexanetriol from 5-hydroxymethyl-2-furfuraldehyde:WO 2011149339A1[P].2011-12-01.
[10]NAKAGAWA Y,TOMISHIGE K.Total hydrogenation of furan derivatives over silica-supported Ni-Pd alloy catalyst[J].Catalysis Communications,2010,12(3):154-156.
[11]YAO S,WANG X,JIANG Y,et al.One-step conversion of biomass-derived 5-hydroxymethylfurfural to 1,2,6-hexanetriol over Ni-Co-Al mixed oxide catalysts under mild conditions[J].ACS Sustainable Chemistry&Engineering,2013,2(2):173-180.
[12]GARBER J D,JONES R E,TORLEIF U.Hydrogenation of 5-hydroxy-methyl furfural:CA 696977(A)[P].1963-03-26.
[13]DIAS E L,SHOEMAKER J A W,BOUSSIE T R,et al.Process for production of hexamethylenediamine from carbohydrate-containing materials and intermediates therefor:US 2017144962(A1)[P].2013-07-18.
[14]KARIM K,ZHAO J,RAWLENCE D,et al.Synthesis and characterisation of hexagonal Y(EMT)and cubic Y(FAU)Effect of template and fluoride ions on the zeolite product[J].Microporous Materials,1995,3(6):695-698.
[15]HEITMANN G P,DAHLHOFF G,HLDERICH W F.Catalytically active sites for the Beckmann rearrangement of cyclohexanone oxime toε-caprolactam[J].Journal of Catalysis,1999,186(1):12-19.
[16]BECK J S,VARTULI J C,ROTH W J,et al.A new family of mesoporous molecular sieves prepared with liquid crystal templates[J].Journal of the American Chemical Society,1992,114(27):10834-10843.
[17]CHIA M,PAGN-TORRES Y J,HIBBITTS D,et al.Selective hydrogenolysis of polyols and cyclic ethers over bifunctional surface sites on rhodium-rhenium catalysts[J].Journal of the American Chemical Society,2011,133(32):12675-12689.