CuZn/Al2O3催化γ-戊内酯加氢制1,4-戊二醇

doi:10.11944/j.issn.1000-0518.2020.11.200109

摘要/Abstract

摘要： 生物质利用是缓解能源及环境危机的有效途径。本文利用共沉积法制备了一系列CuZn/Al₂O₃催化剂,通过电感耦合等离子光谱(ICP)、X射线粉末衍射(XRD)、透射电子显微镜(TEM)、二氧化碳程序升温脱附(CO₂-TPD)等表征技术对催化剂的结构及性质进行了表征。重点讨论了还原温度对CuZn/Al₂O₃催化γ-戊内酯加氢反应催化性能的影响,研究发现还原温度显著影响催化剂的活性和选择性。高温还原有利于γ-戊内酯加氢生成1,4-戊二醇,440 ℃还原的CuZn/Al₂O₃催化剂对1,4-戊二醇的选择性可高可达98%;而200 ℃还原的催化剂,在相似的转化率下1,4-戊二醇选择性仅为71%。结合催化剂的结构分析,高温有利于ZnO的还原,促使催化剂表面生成新的活性位点,并改变了催化剂表面的酸碱性,促进了1,4-戊二醇的生成。

关键词: Cu基催化剂, 戊内酯, 戊二醇, 还原温度, 碱性位, 选择性

Abstract: Biomass conversion is one of the most effective ways for alleviating the energy and environmental crisis. A series of CuZn/Al₂O₃ catalysts was prepared by co-precipitation method and the structure and properties of the catalysts obtained were characterized by several techniques such as inductively coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM), and CO₂-temperature programmed desorption (TPD). We focused our attention on the effects of reduction temperature on the catalytic performances of CuZn/Al₂O₃ catalysts in γ-valerolactone hydrogenation. It is found that reduction of temperature significantly influences the activity and selectivity of CuZn/Al₂O₃ catalysts, that is, the larger reduction temperature benefits for the formation of 1,4-pentanediol, and a high selectivity of 98% is achieved over the catalyst at 440 ℃, while it is only 71% on the catalyst reduced at 200 ℃. Based on the structure analysis of the catalyst, it is concluded that the high reduction temperature can promote the reduction of ZnO and generate new surface active sites and vary the surface basic-acid properties, thus result in the improvement of 1,4-pentanediol selectivity.

Key words: Cu-based catalysts, valerolactone, pentanediol, reduction temperature, basic sites, selectivity

中图分类号:

O643.3

刘强, 赵振波, 张弨, 赵凤玉. CuZn/Al₂O₃催化γ-戊内酯加氢制1,4-戊二醇[J]. 应用化学, 2020, 37(11): 1285-1292.

LIU Qiang, ZHAO Zhenbo, ZHANG Chao, ZHAO Fengyu. Catalytic Conversion of γ-Valerolactone to 1,4-Pentanediol on CuZn/Al₂O₃ Catalyst[J]. Chinese Journal of Applied Chemistry, 2020, 37(11): 1285-1292.

参考文献

[1] Mosier N,Wywan C,Dale B,et al. Features of Promising Technologies for Pretreatment of Lignocellulosic Biomass[J]. Bioresour Technol,2005,96(6):673-686.
[2] LIN Lu,HE Beihai,SUN Runcang,et al.High Value Chemicals from Lignocellulosic Biomass[J]. Prog Chem,2007,19(Z2):1206-1216(in Chinese) .
林鹿,何北海,孙润仓,等. 木质生物质转化高附加值化学品[J]. 化学进展,2007,19(Z2):1206-1216.
[3] YU Qiang,ZHUANG Xinshu,YUAN Zhenhong,et al. Research Progress on Fuel and Chemicals Production from Lignocellulose Biomass[J]. Chem Ind Eng Proc,2012,31(4):784-791(in Chinese).
余强,庄新姝,袁振宏,等. 木质纤维素类生物质制取燃料及化学品的研究进展[J]. 化工进展,2012,31(4):784-791.
[4] Girisuta B,Janssen L P B M,Heeres H J. Green Chemicals:A Kinetic Study on the Conversion of Glucose to Levulinic Acid[J]. Chem Eng Res Des,2006,84(5):339-349.
[5] Rackemann D W,Doherty W O. The Conversion of Lignocellulosics to Levulinic Acid[J]. Biofuel Bioprod Biorefin,2011,5(2):198-214.
[6] Banerjee B,Singuru R,Kundu S K,et al. Towards Rational Design of Core-Shell Catalytic Nanoreactor with High Performance Catalytic Hydrogenation of Levulinic Acid[J]. Catal Sci Technol,2016,6(13):5102-5115.
[7] Feng H,Li X,Qian H,et al. Efficient and Sustainable Hydrogenation of Levulinic-acid to gamma-Valerolactone in Aqueous Solution over Acid-resistant CePO₄/Co₂P Catalysts[J]. Green Chem,2019,21(7):1743-1756.
[8] Li W,Xie J,Lin H,et al. Highly Efficient Hydrogenation of Biomass-Derived Levulinic Acid to γ-Valerolactone Catalyzed by Iridium Pincer Complexes[J]. Green Chem,2012,14(9):2388-2390.
[9] Mamun O,Saleheen M,Bond J Q,et al. Investigation of Solvent Effects in the Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over Ru Catalysts[J]. J Catal,2019,379:164-179.
[10] Pinto B P,Fortuna A L L,Cardoso C P,et al. Hydrogenation of Levulinic Acid (LA) to γ-Valerolactone (GVL) over Ni-Mo/C Catalysts and Water-Soluble Solvent Systems[J]. Catal Lett,2017,147(3):751-757.
[11] Upare P P,Lee J M,Hwang D W,et al. Selective Hydrogenation of Levulinic Acid to γ-Valerolactone over Carbon-Supported Noble Metal Catalysts[J]. J Ind Eng Chem,2011,17(2):287-292.
[12] Ahn Y C,Han J. Catalytic Production of 1,4-Pentanediol from Corn Stover[J]. Bioresour Technol,2017,245(Pt A):442-448.
[13] Alonso D M,Wettstein S G,Dumesic J A,et al. Gamma-Valerolactone, A Austainable Platform Molecule Derived from Lignocellulosic Biomass[J]. Green Chem,2013,15(3):584-595.
[14] Corbel-demailly L,Ly B K,Minh D P,et al. Heterogeneous Catalytic Hydrogenation of Biobased Levulinic and Succinic Acids in Aqueous Solutions[J]. ChemSusChem,2013,6(12):2388-2395.
[15] Mehdi H,Fabos V,Tuba R,et al. Integration of Homogeneous and Heterogeneous Catalytic Processes for a Multi-step Conversion of Biomass:From Sucrose to Levulinic Acid, γ-Valerolactone, 1,4-Pentanediol, 2-Methyl-tetrahydrofuran, and Alkanes[J]. Top Catal,2008,48(1/2/3/4):49-54.
[16] Pagliaro M,Ciriminna R,Kimura H,et al. From Glycerol to Value-Added Products[J]. Angew Chem Int Ed,2007,46(24):4434-4340.
[17] Climent M J,Corma A,Iborra S, Conversion of Biomass Platform Molecules into Fuel Additives and Liquid Hydrocarbon Fuels[J]. Green Chem,2014,16(2):516-547.
[18] Lange J P,Price R,Ayoub P M,et al. Valeric Biofuels:A Platform of Cellulosic Transportation Fuels[J]. Angew Chem Int Ed,2010,49(26):4479-4483.
[19] Obregon I,Gandarias I,Al-shaal M G,et al. The Role of the Hydrogen Source on the Selective Production of γ-Valerolactone and 2-Methyltetrahydrofuran from Levulinic Acid[J]. ChemSusChem,2016,9(17):2488-2495.
[20] Pace V,Hoyos D P,Castoldi L,et al. 2-Methyltetrahydrofuran (2-MeTHF):A Biomass-Derived Solvent with Broad Application in Organic Chemistry[J]. ChemSusChem,2012,5(8):1369-1379.
[21] Sun D,Saito T,Yamada Y,et al. Hydrogenation of γ-Valerolactone to 1,4-Pentanediol in a Continuous Flow Reactor[J]. Appl Catal A,2017,542:289-295.
[22] Zhai X J,Li C,Di X,et al. Preparation of Cu/MgO Catalysts for γ-Valerolactone Hydrogenation to 1,4-Pentanediol by MOCVD[J]. J Fuel Chem Technol,2017,45(5):537-546.
[23] Du X,Bi Q,Liu Y,et al. Tunable Copper-Catalyzed Chemoselective Hydrogenolysis of Biomass-Derived γ-Valerolactone into 1,4-Pentanediol or 2-Methyltetrahydrofuran[J]. Green Chem,2012,14(4):935-939.
[24] Obregon I,Gandarias I,Ocio A,et al. Structure-Activity Relationships of Ni-Cu/Al₂O₃ Catalysts for γ-Valerolactone Conversion to 2-Methyltetrahydrofuran[J]. Appl Catal B,2017,210:328-341.
[25] Li M,Li G,Li N,et al. Aqueous Phase Hydrogenation of Levulinic Acid to 1,4-Pentanediol[J]. Chem Commun,2014,50(12):1414-1416.
[26] Wu J,Gao G,Sun P,et al. Synergetic Catalysis of Bimetallic CuCo Nanocomposites for Selective Hydrogenation of Bioderived Esters[J]. ACS Catal,2017,7(11):7890-7901.
[27]Xie Z,Chen B,Wu H,et al. Highly Efficient Hydrogenation of Levulinic Acid into 2-Methyltetrahydrofuran over Ni-Cu/Al₂O₃-ZrO₂ Bifunctional Catalysts[J]. Green Chem,2019,21(3):606-613.
[28] Xu Q,Li X,Pan T,et al. Supported Copper Catalysts for Highly Efficient Hydrogenation of Biomass-Derived Levulinic Acid and γ-Valerolactone[J]. Green Chem,2016,18(5):1287-1294.
[29] Kanai Y,Watanabe T,Fujitani T,et al. Evidence for the Mmigration of ZnO_x in a Cu/ZnO Methanol Synthesis Catalyst[J]. Catal Lett,1994,27(1/2/3/4):67-78.
[30] Kuld S,Conradsen C,Moses P G,et al. Quantification of Zinc Atoms in a Surface Alloy on Copper in an Industrial-Type Methanol Synthesis Catalyst[J]. Angew Chem Int Ed,2014,53(23):5941-5945.
[31] Kuld S,Thorhauge M,Falsig H,et al. Quantifying the Promotion of Cu Catalysts by ZnO for Mmethanol Synthesis[J]. Science,2016,352(6288):969-974.
[32] Tisseraud C,Comminges C,Belin T,et al. The Cu-ZnO Synergy in Methanol Synthesis from CO₂, Part 2:Origin of the Methanol and CO Selectivities Explained by Experimental Studies and a Sphere Contact Quantification Model in Randomly Packed Binary Mixtures on Cu-ZnO Coprecipitate Catalysts[J]. J Catal,2015,330:533-544.
[33] Valant A L,Comminges C,Tisseraud C,et al. The Cu-ZnO Synergy in Methanol Synthesis from CO₂, Part 1:Origin of Active Site Explained by Experimental Studies and a Sphere Contact Quantification Model on Cu+ZnO Mechanical Mixtures[J]. J Catal,2015,324:41-49.

CuZn/Al₂O₃催化γ-戊内酯加氢制1,4-戊二醇

Catalytic Conversion of γ-Valerolactone to 1,4-Pentanediol on CuZn/Al₂O₃ Catalyst

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