Super solid-base supported Cu catalysts for hydrogenolysis of glycerol to 1,2-propanediol

doi:10.11949/j.issn.0438-1157.20150646

Abstract

Abstract:

Highly dispersed copper nanoparticles supported on combined alkaline-earth metal oxides MgO-CaO and MgO-SrO were synthesized by impregnation-combustion method and used for hydrogenolysis of glycerol. The nanoparticles were characterized using N₂-adsorption, X-ray diffraction, transmission electronic microscope, temperature-programmed reduction with H₂, dissociative N₂O adsorption and CO₂ temperature-programmed desorption. The results revealed that Cu particles dispersed highly on the surface of Cu/MgO-CaO and Cu/MgO-SrO catalyst. The enhanced alkalinity of Cu/MgO-CaO and Cu/MgO-SrO accelerated the conversion of glycerol compared to Cu/MgO. It was concluded that the activity of Cu-based catalyst increased with its alkalinity.

Key words: biodiesel, glycerol, hydrogenolysis, 1,2-propanediol, solid-base

摘要：

用浸渍-燃烧法制备了固体超强碱MgO-CaO和MgO-SrO负载的高分散铜基催化剂,并将其用于甘油氢解制备1,2-丙二醇的反应。N₂吸附、X射线衍射、透射电子显微镜、H₂程序升温还原和N₂O氧化吸附及CO₂程序升温脱附等表征实验结果显示:Cu粒子均分散于Cu/MgO-CaO(或者Cu/MgO-SrO)催化剂的表面;与Cu/MgO相比,Cu/MgO-CaO和Cu/MgO-SrO具有更强的碱性,可以加速甘油的转化。上述结果表明,甘油氢解反应中铜催化剂的活性随碱性的增强而增加。

关键词: 生物柴油, 甘油, 氢解, 1,2-丙二醇, 固体碱

CLC Number:

TQ028.8

ZHENG Liping, YUAN Zhenle, XIA Shuixin, CHEN Ping, HOU Zhaoyin. Super solid-base supported Cu catalysts for hydrogenolysis of glycerol to 1,2-propanediol[J]. CIESC Journal, 2015, 66(8): 3014-3021.

郑丽萍, 袁振乐, 夏水鑫, 陈平, 侯昭胤. 甘油氢解用固体超强碱负载的铜催化剂[J]. 化工学报, 2015, 66(8): 3014-3021.

References 35

[1]	Ma F, Hanna M A. Biodiesel production: a review [J]. Bioresour. Technol., 1999, 70: 1-15.
[2]	Kouzu M, Tsunomori M, Yamanaka S, Hidaka J. Solid base catalysis of calcium oxide for a reaction to convert vegetable oil into biodiesel [J]. Adv. Powder Technol., 2010, 21: 488-494.
[3]	King F, Kelly G J. Combined solid base/hydrogenation catalysts for industrial condensation reaction [J]. Catal. Today, 2002, 73: 75-81.
[4]	Kabashima H, Tsuji H, Hattori H. Michael addition of methyl crotonate over solid base catalysts [J]. Appl. Catal. A, 1997, 165: 319-325.
[5]	Yuan Z L, Wu P, Gao J, Lu X Y, Hou Z Y. Pt/solid-base: a predominant catalyst for glycerol hydrogenolysis in a base-free aqueous solution [J]. Catal. Lett., 2009, 130: 261-265.
[6]	Yuan Z L, Wang J H, Wang L N, Xie W H, Chen P, Hou Z Y. Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts [J]. Bioresour. Technol., 2010, 101: 7088-7092.
[7]	Yuan Z L, Wang L N, Wang J H, Xia S H, Chen P, Hou Z Y. Hydrogenolysis of glycerol over homogenously dispersed copper on solid base catalysts [J]. Appl. Catal. B, 2011, 101: 431-440.
[8]	Xia S X, Yuan Z L, Wang L N, Chen P, Hou Z Y. Hydrogenolysis of glycerol on bimetallic Pd-Cu/solid-base catalysts prepared via layered double hydroxides precursors [J]. Appl. Catal. A, 2011, 403: 173-182.
[9]	Xia S X, Du W C, Zheng L P, Chen P, Hou Z Y. A thermally stable and easily recycled core-shell Fe2O3@CuMgAl catalyst for hydrogenolysis of glycerol [J]. Catal. Sci. Technol., 2014, 4: 912-916.
[10]	Xia S X, Zheng L P, Nie R F, Chen P, Lou H, Hou Z Y. Trivalent metal ions M3+ in M0.02Cu0.4Mg5.6Al1.98(OH)16CO3 layered double hydroxide as catalyst precursors for the hydrogenolysis of glycerol [J]. Chin. J. Catal., 2013, 34: 986-992.
[11]	Xia S, Zheng L P, Wang L N, Chen P, Hou Z Y. Hydrogen-free synthesis of 1,2-propanediol from glycerol over Cu-Mg-Al catalysts [J]. RSC Adv., 2013, 3: 16569-16576.
[12]	Ma L, He D H. Influence of catalyst pretreatment on catalytic properties and performances of Ru-Re/SiO2 in glycerol hydrogenolysis to propanediols [J]. Catal. Today, 2010, 149: 148-156.
[13]	Zhu S H, Gao X Q, Zhu Y L, Zhu Y F, Xiang X M, Hu C X, Li Y W. Alkaline metals modified Pt-H4SiW12O40/ZrO2 catalysts for the selective hydrogenolysis of glycerol to 1,3-propanediol [J]. Appl. Catal. B, 2013, 140/141: 60-67.
[14]	Li Y M, Liu H M, Ma L, He D H. Glycerol hydrogenolysis to propanediols over supported Pd-Re catalysts [J]. RSC Adv., 2014, 4: 5503-5512.
[15]	Niu L, Wei R P, Yang H, Li X, Jiang F, Xiao G M. Hydrogenolysis of glycerol to propanediols over Cu-MgO/USY catalyst [J]. Chin. J. Catal., 2013, 34: 2230-2235.
[16]	Gao J, Liang D, Chen P, Hou Z Y, Zheng X M. Oxidation of glycerol with oxygen in a base-free aqueous solution over Pt/AC and Pt/MWNTs catalysts [J]. Catal. Lett., 2009, 130: 185-191.
[17]	Liang D, Gao J, Wang J H, Chen P, Hou Z Y, Zheng X M. Selective oxidation of glycerol in a base-free aqueous solution over different sized Pt catalysts [J]. Catal. Commun., 2009, 10: 1586-1590.
[18]	Liang D, Gao J, Sun H, Chen P, Hou Z Y, Zheng X M. Selective oxidation of glycerol with oxygen in a base-free aqueous solution over MWNTs supported Pt catalysts [J]. Appl. Catal. B, 2011, 106: 423-432.
[19]	Nie R, Liang D, Shen L, Gao J, Chen P, Hou Z Y. Selective oxidation of glycerol with oxygen in base-free solution over MWCNTs supported PtSb alloy nanoparticles [J]. Appl. Catal. B, 2012, 127: 212-220.
[20]	Zhang M Y, Nie R F, Wang L N, Shi J J, Du W C, Hou Z Y. Selective oxidation of glycerol over carbon nanofibers supported Pt catalysts in a base-free aqueous solution [J]. Catal. Commun., 2015, 59: 5-9.
[21]	Gandarias I, Arias P L, Requies J, EI Doukkali M, Güemez M B. Liquid-phase glycerol hydrogenolysis to 1,2-propanediol under nitrogen pressure using 2-propanol as hydrogen source [J]. J. Catal., 2011, 282: 237-247.
[22]	Zhu S H, Gao X Q, Zhu Y L, Fan W B, Wang J G, Li Y W. A highly efficient and robust Cu/SiO2 catalyst prepared by the ammonia evaporation hydrothermal method for glycerol hydrogenolysis to 1,2-propanediol [J]. Catal. Sci. Technol., 2015, 5: 1169-1180.
[23]	Hu J Y, Liu X Y, Fan Y Q, Xie S H, Pei Y, Qiao M H, Fan K, Zhang X, Zong B. Physically mixed ZnO and skeletal NiMo for one-pot reforming-hydrogenolysis of glycerol to 1,2-propanediol [J]. Chin. J. Catal., 2013, 34: 1020-1026.
[24]	Feng J, Fu H Y, Wang J B, Li R X, Chen H, Li X J. Hydrogenolysis of glycerol to glycols over ruthenium catalysts: effect of support and catalyst reduction temperature [J]. Catal. Commun., 2008, 9: 1458-1464.
[25]	Maris E P, Davis R J. Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts [J]. J. Catal., 2007, 249: 328-337.
[26]	Lahr D G, Shanks B H. Effect of sulfur and temperature on ruthenium-catalyzed glycerol hydrogenolysis to glycols [J]. J. Catal., 2005, 232: 386-394.
[27]	Runeberg J, Baiker A, Kijenski J. Copper catalyzed amination of ethylene glycol [J]. Appl. Catal., 1985, 17: 309-319.
[28]	Huang Z W, Cui F, Kang H X, Chen J, Zhang X Z, Xia C G. Highly dispersed silica-supported copper nanoparticles prepared by precipitation-gel method: a simple but efficient and stable catalyst for glycerol hydrogenolysis [J]. Chem. Mater., 2008, 20: 5090-5099.
[29]	Huang Z W, Cui F, Kang H X, Chen J, Xia C G. Characterization and catalytic properties of the CuO/SiO2 catalysts prepared by precipitation-gel method in the hydrogenolysis of glycerol to 1,2-propanediol: effect of residual sodium [J]. Appl. Catal. A, 2009, 366: 288-298.
[30]	Wang S, Liu H C. Selective hydrogenolysis of glycerol to propylene glycol on Cu-ZnO catalysts [J]. Catal. Lett., 2007, 117: 62-67.
[31]	Gandarias I, Arias P L, Requies J, Güemez M B, Fierro J L G. Hydrogenolysis of glycerol to propanediols over a Pt/ASA catalyst: the role of acid and metal sites on product selectivity and the reaction mechanism [J]. Appl. Catal. B, 2010, 97: 248-256.
[32]	Wang S, Zhang Y C, Liu H C. Selective hydrogenolysis of glycerol to propylene glycol on Cu-ZnO composite catalysts: structural requirements and reaction mechanism [J]. Chem.-Asi. J., 2010, 5: 1100-1111.
[33]	Anderson J A, Márquez-Alvarez C, López-Munõz M J, Rodríguez-Ramos I, Guerrero-Ruiz A. Reduction of NOx in C3H6/air mixtures over Cu/Al2O3 catalysts[J]. Appl. Catal. B, 1997, 14(3/4): 189-202.
[34]	Carniti P, Gervasini A, Modica V H, Ravasio N. Catalytic selective reduction of NO with ethylene over a series of copper catalysts on amorphous silicas [J]. Appl. Catal. B, 2000, 28: 175-185.
[35]	Suh Y-W, Moon S-H, Rhee H-K. Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2 [J]. Catal. Today, 2000, 63: 447-452.