γ-Valerolactone synthesis from levulinic acid hydrogenation over Ni/ZrO2-SiO2 catalyst

doi:10.11949/j.issn.0438-1157.20180027

Abstract

Abstract:

ZrO₂、SiO₂ and ZrO₂-SiO₂ oxide composite supported Ni catalysts with Ni content of 10%(mass) were prepared by incipient impregnation method and characterized by N₂ physical adsorption, NH₃-TPD, H₂-TPR, XRD, TEM. The catalysts were evaluated for liquid phase hydrogenation of levulinic acid. The results showed that levulinic acid was first hydrogenated to 4-hydroxy valeric acid via C=O hydrogenation and γ-valerolactone was then produced by immediate esterification of 4-hydroxy valeric acid. Compared to Ni/ZrO₂ and Ni/SiO₂ catalysts, Ni/ZrO₂-SiO₂ catalyst exhibited highest dispersion of metallic Ni and most surface acid sites. As a result, the Ni/ZrO₂-SiO₂ catalyst demonstrated highest activity for C=O hydrogenation and superior performance for synthesis of γ-valerolactone via levulinic acid hydrogenation. 100% levulinic acid conversion and over 99.9% γ-valerolactone selectivity were achieved under reaction temperature of 200℃ and hydrogen pressure of 4 MPa.

Key words: levulinic acid, γ-valerolactone, catalytic hydrogenation, Ni/ZrO₂-SiO₂

摘要：

分别以ZrO₂、SiO₂及ZrO₂-SiO₂复合氧化物为载体，采用等体积浸渍法制备了Ni含量为10%（质量分数）的催化剂，考察了其催化乙酰丙酸液相加氢性能。采用N₂-物理吸附、NH₃-TPD、H₂-TPR、XRD、TEM等表征手段对催化剂进行了表征。研究结果表明，在所制备的催化剂上，乙酰丙酸先经C=O加氢生成4-羟基戊酸，后者快速脱水酯化为γ-戊内酯。Ni/ZrO₂-SiO₂催化剂较Ni/ZrO₂与Ni/SiO₂催化剂具有高的金属分散度和丰富的表面酸性中心，表现出高的C=O加氢活性以及优异的乙酰丙酸加氢合成γ-戊内酯性能。在反应温度为200℃，氢气压力4 MPa的反应条件下，乙酰丙酸的转化率达到100%，γ-戊内酯的选择性大于99.9%。

关键词: 乙酰丙酸, &gamma, -戊内酯, 催化加氢, Ni/ZrO₂-SiO₂

CLC Number:

O643.36

WANG Jie, ZHANG Yin, GUO Jianjian, ZHAO Lili, ZHAO Yongxiang. γ-Valerolactone synthesis from levulinic acid hydrogenation over Ni/ZrO₂-SiO₂ catalyst[J]. CIESC Journal, 2018, 69(8): 3452-3459.

王杰, 张因, 郭健健, 赵丽丽, 赵永祥. Ni/ZrO₂-SiO₂催化剂催化乙酰丙酸加氢合成γ-戊内酯[J]. 化工学报, 2018, 69(8): 3452-3459.

References 30

[1]	ALONSO D M, WETTSTEIN S G, DUMESIC J A. Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass[J]. Green Chemistry, 2013, 15(3):584-595.
[2]	HORVATH I T, MEHDI H, FABOS V, et al. Valerolactone-a sustainable liquid for energy and carbon-based chemicals[J]. Green Chemistry, 2008, 10(2):238-242.
[3]	WEINGARTEN R, CONNER W C, HUBER G W. Production of levulinic acid from cellulose by hydrothermal decomposition combined with aqueous phase dehydration with a solid acid catalyst[J]. Energy & Environmental Science, 2012, 5(6):7559-7574.
[4]	ABDELRAHMAN O A, HEYDEN A, BOND J Q. Analysis of kinetics and reaction pathways in the aqueous-phase hydrogenation of levulinic acid to form γ-valerolactone over Ru/C[J]. ACS Catalysis, 2014, 4(4):1171-1181.
[5]	WRIGHT W R, PALKOVITS R. Development of heterogeneous catalysts for the conversion of levulinic acid to gamma-valerolactone[J]. ChemSusChem, 2012, 5(9):1657-1667.
[6]	MANZER L E. Catalytic synthesis of a-methylene-g-valerolactone:a biomass-derived acrylic monomer[J]. Applied Catalysis A:General, 2004, 272:249-256.
[7]	UPARE P P, LEE J M, HWANG D W, et al. Selective hydrogenation of levulinic acid to g-valerolactone over carbon-supported noble metal catalysts[J]. Journal of Industrial and Engineering Chemistry, 2011, 17(2):287-292.
[8]	AL-SHAAL M G, WRIGHT W R H, PALKOVITS R. Exploring the ruthenium catalysed synthesis of g-valerolactone in alcohols and utilisation of mild solvent-free reaction conditions[J]. Green Chemistry, 2012, 14(5):1260-1263.
[9]	DU X L, HE L, ZHAO S, et al. Hydrogen-independent reductive transformation of carbohydrate biomass into gamma-valerolactone and pyrrolidone derivatives with supported gold catalysts[J]. Angew Chem. Int. Ed. Eng., 2011, 50(34):7815-7819.
[10]	YAN K, LAFLEUR T, WU G, et al. Highly selective production of value-added g-valerolactone from biomass-derived levulinic acid using the robust Pd nanoparticles[J]. Applied Catalysis A:General, 2013, 468:52-58.
[11]	SHIMIZU K I, KANNO S, KON K. Hydrogenation of levulinic acid to g-valerolactone by Ni and MoOx co-loaded carbon catalysts[J]. Green Chemistry, 2014, 16(8):3899-3903.
[12]	JONES D R, IQBAL S, ISHIKAWA S, et al. The conversion of levulinic acid into g-valerolactone using Cu-ZrO2catalysts[J]. Catal. Sci. Technol., 2016, 6(15):6022-6030.
[13]	SUN D, OHKUBO A, ASAMI K, et al. Vapor-phase hydrogenation of levulinic acid and methyl levulinate to g-valerolactone over non-noble metal-based catalysts[J]. Molecular Catalysis, 2017, 437:105-113.
[14]	OBREG N I, CORRO E, IZQUIERDO U, et al. Levulinic acid hydrogenolysis on Al2O3-based Ni-Cu bimetallic catalysts[J]. Chinese Journal of Catalysis, 2014, 35(5):656-662.
[15]	CHRISTIAN R V, HORACE D B, HIXON R M. Derivatives of g-valerolactone, 1, 4-pentanedioland1, 4-di-(b-cyanoethoxy)-pentane[J]. Journal of the American Chemical Society, 1947, 69:1961-1963.
[16]	HENGST K, SCHUBERT M, CARVALHO H W P, et al. Synthesis of g-valerolactone by hydrogenation of levulinic acid over supported nickel catalysts[J]. Applied Catalysis A:General, 2015, 502:18-26.
[17]	MOHAN V, VENKATESHWARLU V, PRAMOD C V, et al. Vapour phase hydrocyclisation of levulinic acid to g-valerolactone over supported Ni catalysts[J]. Catal. Sci. Technol., 2014, 4(5):1253-1259.
[18]	MOHAN V, RAGHAVENDRA C, PRAMOD C V, et al. Ni/H-ZSM-5 as a promising catalyst for vapour phase hydrogenation of levulinic acid at atmospheric pressure[J]. RSC Advances, 2014, 4(19):9660-9668.
[19]	HENGNE A M, RODE C V. Cu-ZrO2 nanocomposite catalyst for selective hydrogenation of levulinic acid and its ester to g-valerolactone[J]. Green Chemistry, 2012, 14(4):1064-1072.
[20]	GAO C G, ZHAO Y X, LIU D S. Liquid phase hydrogenation of maleic anhydride over nickel catalyst supported on ZrO2-SiO2 composite aerogels[J]. Catalysis Letters, 2007, 118(1/2):50-54.
[21]	ZHANG Y, PAN L, GAO C, et al. Synthesis of ZrO2-SiO2 mixed oxide by alcohol-aqueous heating method[J]. Journal of Sol-Gel Science and Technology, 2011, 58(2):572-579.
[22]	MILLER J B, RANKIN S E, KO E I. Strategies in controlling the homogeneity of zirconia-silica aerogels:effect of preparation on textural and catalytic properties[J]. Journal of Catalysis, 1994, 148(2):673-682.
[23]	ANDERSON J, FERGUSSON C, RODRIGUEZRAMOS I, et al. Influence of Si/Zr ratio on the formation of surface acidity in silica-zirconia aerogels[J]. Journal of Catalysis, 2000, 192(2):344-354.
[24]	MEYER C I, REGENHARDT S A, BERTONE M E, et al. Gas-phase maleic anhydride hydrogenation over Ni/SiO2-Al2O3 catalysts:effect of metal loading[J]. Catalysis Letters, 2013, 143(10):1067-1073.
[25]	刘迎新, 陈吉祥, 张继炎. Ni/SiO2催化剂上间二硝基苯液相加氢制间苯二胺[J]. 催化学报, 2003, 24(3):224-228. LIU Y X, CHEN J X, ZHANG J Y. Liquid-phase hydrogenation of m-dinitrobenzene to m-phenylenediamine over silica-supported nickel catalyst[J]. Chinese Journal of Catalysis, 2003, 24(3):224-228.
[26]	SEO J G, YOUN M H, SONG I K. Effect of SiO2-ZrO2 supports prepared by a grafting method on hydrogen production by steam reforming of liquefied natural gas over Ni/SiO2-ZrO2 catalysts[J]. Journal of Power Sources, 2007, 168(1):251-257.
[27]	JING Q, ZHENG X. Combined catalytic partial oxidation and CO2 reforming of methane over ZrO2-modified Ni/SiO2 catalysts using fluidized-bed reactor[J]. Energy, 2006, 31(12):2184-2192.
[28]	AGUILAR D H, TORRES-GONZALEZ L C, TORRES-MARTINEZ L M, et al. A study of the crystallization of ZrO2 in the sol-gel system:ZrO2-SiO2[J]. Journal of Solid State Chemistry, 2001, 158(2):349-357.
[29]	SUDHAKAR M, KUMAR V V, NARESH G, et al. Vapor phase hydrogenation of aqueous levulinic acid over hydroxyapatite supported metal (M=Pd, Pt, Ru, Cu, Ni) catalysts[J]. Applied Catalysis B:Environmental, 2016, 180:113-120.
[30]	GALLETTI A M R, ANTONETTI C, DE LUISE V, et al. A sustainable process for the production of g-valerolactone by hydrogenation of biomass-derived levulinic acid[J]. Green Chemistry, 2012, 14(3):688-694.

γ-Valerolactone synthesis from levulinic acid hydrogenation over Ni/ZrO₂-SiO₂ catalyst

Ni/ZrO₂-SiO₂催化剂催化乙酰丙酸加氢合成γ-戊内酯

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 30

Related Articles 15

Recommended Articles 0

Metrics

Comments

[1]	Lihui WANG, Huan LIU, Heyu LI, Xiaobing ZHENG, Yanjun JIANG, Jing GAO. Preparation and application of core-shell hydrophobic magnetic dendritic fibrous organosilica immobilized lipase [J]. CIESC Journal, 2021, 72(9): 4861-4871.
[2]	Yin ZHANG, Jianjian GUO, Huanjie REN, Juan CHENG, Haitao LI, Jianbing WU, Yongxiang ZHAO. Effect of intercalation anions on catalytic performance of hydrotalcite-like precursor Ni-Al₂O₃ catalyst for levulinic acid hydrogenation [J]. CIESC Journal, 2020, 71(8): 3614-3624.
[3]	Qian ZHANG, Yanhua WANG. Selective hydrogenation of α, β-unsaturated aldehydes and ketones over thermo regulated phase-separable Ir nano catalyst [J]. CIESC Journal, 2019, 70(9): 3396-3403.
[4]	Jiacheng TU, Le SANG, Ning AI, Jianhong XU, Jisong ZHANG. Research progress of continuous hydrogenation in organic synthesis [J]. CIESC Journal, 2019, 70(10): 3859-3868.
[5]	LI Chenyang, FENG Miao, CUI Haifeng, CAO Guiping, LÜ Hui, CHEN Rongqi. Preparation of carbon nanotube catalyst on structure-modified cordierite monolith for polystyrene hydrogenation [J]. CIESC Journal, 2017, 68(7): 2746-2754.
[6]	CHEN Lungang, LIU Yong, DING Mingyue, ZHANG Xinghua, LI Yuping, ZHANG Qi, WANG Tiejun, MA Longlong. Removal of oxygenates in aqueous phase product of F-T process by catalytic hydrogenation over Ru catalyst [J]. CIESC Journal, 2014, 65(11): 4347-4355.
[7]	JIANG Nan1，XIE Nan1，QI Wei1，2，3，SU Rongxin1，2，3，HE Zhimin1，2，3. Process intensification of levulinic acid from glucose using sulfuric acid as catalyst [J]. Chemical Industry and Engineering Progree, 2014, 33(11): 2888-2893.
[8]	SUN Meijuan1，HUANG Xiaodian1，GUAN Qingqing1，ZHANG Chunyun2，CHAI Xinsheng2，TIAN Senlin1，NING Ping1，GU Junjie1. Degradation behavior of phenol though catalytic hydrogenation in supercritical ethanol [J]. Chemical Industry and Engineering Progree, 2014, 33(07): 1902-1907.
[9]	GAO Xueyi，WU Yanwei，WANG Kebing. Preparation of levulinic acid from hydrolysis of Salix psammophila catalyzed by acid and its separation and purification [J]. Chemical Industry and Engineering Progree, 2014, 33(01): 242-246.
[10]	SUN Hongzhi，WANG Qian，SONG Mingxiu，Abudoulajiang ? Nasi’er，WANG Fuyan，ZHU Weiqun. Progress in the chemical utilization of carbon dioxide [J]. Chemical Industry and Engineering Progree, 2013, 32(07): 1666-1672.
[11]	LIU Tao，LI Lijun，HUANG Wenyi，LIU Liu. Solid superacid catalyst SO42?/ Kaolin for preparation of levulinic acid [J]. Chemical Industry and Engineering Progree, 2013, 32(06): 1300-1306.
[12]	DENG Li1，LIAO Bing1，GUO Qingxiang2. Recent progress in selective catalytic conversion of cellulose into key platform molecules [J]. Chemical Industry and Engineering Progree, 2013, 32(02): 245-254.
[13]	ZENG Shanshan, LIN Lu, LIU Di, PENG Lincai. Catalytic conversion of glucose to levulinic acid by solid heteropolyacid salts [J]. CIESC Journal, 2012, 63(12): 3875-3881.
[14]	ZHANG Junhua1，GUO Haiguang1，HUAN Changyong1，JIANG Li2，SHEN Qiang1. Preparation of 4,4'-diaminostilbene-2,2'-disulfonic acid by Pt/C catalytic hydrogenation [J]. Chemical Industry and Engineering Progree, 2012, 31(09): 2070-2074.
[15]	LIU Tao，LI Lijun，LIU Liu，LI Guo，LI Wei，QIN Gui. Solid superacid catalyst S2O82―/ZrO2-TiO2- Al 2O3 for preparation of levulinic acid [J]. Chemical Industry and Engineering Progree, 2012, 31(09): 1975-1979.