ZrO_2改性SAPO-34负载Ru催化加氢解聚褐煤模型化合物的研究

• 1:西北大学化工学院

• 2:西北大学城市与环境学院

ZrO_(2)改性SAPO-34负载Ru催化加氢解聚褐煤模型化合物的研究.pdf

摘要(Abstract)：

采用无溶剂法合成SAPO-34分子筛，然后使用浸渍法制备金属氧化物改性复合载体MO_x-SAPO-34,并在此基础上合成双功能催化剂Ru/MO_x-SAPO-34.利用X-射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、吡啶吸附红外光谱(Py-IR)、氨气-程序升温脱附(NH_3-TPD)及其他手段对催化剂进行了结构和酸性表征.以一系列含C-O键的化合物作为褐煤的模型化合物，考察不同金属氧化物改性的催化剂Ru/MO_x-SAPO-34加氢解聚C-O键的反应活性.结果表明，经具有丰富Lewis酸ZrO_2改性所得到的双功能催化剂Ru/ZrO_2-SAPO-34表现出更优异的加氢解聚C-O键性能.
A series of composite supports MO_x-SAPO-34 were prepared by impregnating metal oxides onto SAPO-34 molecular sieve, which was synthesized by solvent-free method. And on this basis, bifunctional catalysts Ru/MO_x-SAPO-34 were fabricated. X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM), pyridine adsorption infrared spectroscopy(Py-IR), ammonia-temperature-programmed desorption(NH_3-TPD) and other methods were used to characterize the structure and acidity of the prepared catalysts. Using several C-O linkage containing lignite-related model compounds as probe molecules, the reactivity of Ru/MO_x-SAPO-34 for catalytic hydrogenolysis of C-O linkages was investigated. The results reveal that Ru/ZrO_2-SAPO-34, a bifunctional catalyst modified by Lewis acid-riched ZrO_2, presented outstanding catalytic performance for hydrogenolysis of C-O linkage.

关键词(KeyWords)：加氢解聚;褐煤;金属氧化物;C-O键;模型化合物
hydrogenolysis;lignite;metallic oxide;C-O linkage;model compound

基金项目(Foundation):国家自然科学基金(21875186);; 陕西省自然科学基础研究计划(2019JM-259);; 陕西省科学技术厅工业攻关基金资助项目(2014K10-10)

作者(Authors):杜青攀;冀红顺;陈博;刁智俊;张娟;赵思佳;
Du Qingpan;Ji Hongshun;Chen Bo;Diao Zhijun;Zhang Juan;Zhao Sijia;School of Chemical Engineering,Northwest University;College of Urban and Environment Science,Northwest University;

DOI:10.16366/j.cnki.1000-2367.2023.04.008

参考文献(References)：

• [1] WANG L Y,XU Y L,JIANG S G,et al.Imidazolium based ionic liquids affecting functional groups and oxidation properties of bituminous coal[J].Safety Science,2012,50(7):1528-1534.

• [2] CONG X S,ZONG Z M,LI M,et al.Enrichment and identification of cyclized hopanoids from Shengli lignite[J].Fuel Processing Technology,2015,134:399-403.

• [3] JIANG W,CAO J P,ZHU C,et al.Selective cleavage of lignin-derived diphenyl ether C-O bond over weakly acidic Ni/Nb2O5 catalyst[J].Fuel,2021,295:120635.

• [4] XIN Y Y,ZHENG Z X,LUO Z C,et al.The influence of pore structures and Lewis acid sites on selective hydrogenolysis of guaiacol to benzene over Ru/TS-1[J].Green Energy & Environment,2022,7(5):1014-1023.

• [5] SHAO Y,XIA Q N,DONG L,et al.Selective production of arenes via direct lignin upgrading over a niobium-based catalyst[J].Nature Communications,2017,8:16104.

• [6] CHEN B,LI L,DIAO Z J,et al.Catalytic hydrogenolysis of diphenyl ether over Ru supported on amorphous silicon-aluminum-TiO2[J].Journal of Fuel Chemistry and Technology,2022,50(5):621-627.

• [7] DIAO Z J,HUANG L Q,CHEN B,et al.Amorphous Ni-Ru bimetallic phosphide composites as efficient catalysts for the hydrogenolysis of diphenyl ether and lignin[J].Fuel,2022,324:124489.

• [8] LI R,SHAHBAZI A,WANG L J,et al.Graphite encapsulated molybdenum carbide core/shell nanocomposite for highly selective conversion of guaiacol to phenolic compounds in methanol[J].Applied Catalysis A:General,2016,528:123-130.

• [9] CAO Y L,WANG J W,LI Q F,et al.Hydrolytic hydrogenation of cellulose over Ni-WO3/SBA-15 catalysts[J].Journal of Fuel Chemistry and Technology,2013,41(8):943-949.

• [10] TAI Z J,ZHANG J Y,WANG A Q,et al.Temperature-controlled phase-transfer catalysis for ethylene glycol production from cellulose[J].Chemical Communications,2012,48(56):7052-7054.

• [11] TONG M L,GAPU CHIZEMA L,CHANG X N,et al.Tandem catalysis over tailored ZnO-ZrO2/MnSAPO-34 composite catalyst for enhanced light olefins selectivity in CO2 hydrogenation[J].Microporous and Mesoporous Materials,2021,320:111105.

• [12] ZHONG M,ZHAI J,XU Y,et al.Catalytic cracking of coal-tar model compounds over ZrO2/Al2O3 and Ni-Ce/Al2O3 catalysts under steam atmosphere[J].Fuel,2020,263:116763.

• [13] HUANG Y,WANG L,SONG Z N,et al.Growth of high-quality,thickness-reduced zeolite membranes towards N2/CH4 separation using high-aspect-ratio seeds[J].Angewandte Chemie,2015,127(37):10993-10997.

• [14] ZHANG X,WANG R J,YANG X X,et al.Comparison of four catalysts in the catalytic dehydration of ethanol to ethylene[J].Microporous and Mesoporous Materials,2008,116(1/2/3):210-215.

• [15] SINGH A K,KONDAMUDI K,YADAV R,et al.Uniform mesoporous silicoaluminophosphate derived by vapor phase treatment:its catalytic and kinetic studies in hydroisomerization of 1-octene[J].The Journal of Physical Chemistry C,2014,118(48):27961-27972.

• [16] VARZANEH A Z,TOWFIGHI J,MOHAMADALIZADEH A.Comparative study of naphtha cracking over SAPO-34 and HZSM-5:effects of cerium and zirconium on the catalytic performance[J].Journal of Analytical and Applied Pyrolysis,2014,107:165-173.

• [17] YU L M,ZHONG Q,ZHANG S L.Research of copper contained SAPO-34 zeolite for NH3-SCR DeNOx by solvent-free synthesis with Cu-TEPA[J].Microporous and Mesoporous Materials,2016,234:303-309.

• [18] LI X F,SHEN B J,XU C M.Interaction of titanium and iron oxide with ZSM-5 to tune the catalytic cracking of hydrocarbons[J].Applied Catalysis A:General,2010,375(2):222-229.

• [19] ZHOU H P,SHEN Y,XI J Y,et al.ZrO2-nanoparticle-modified graphite felt:bifunctional effects on vanadium flow batteries[J].ACS Applied Materials & Interfaces,2016,8(24):15369-15378.

• [20] LI X C,GUO T Y,XIA Q N,et al.One-pot catalytic transformation of lignocellulosic biomass into alkylcyclohexanes and polyols[J].ACS Sustainable Chemistry & Engineering,2018,6(3):4390-4399.

• [21] LIANG T Y,CHEN J L,QIN Z F,et al.Conversion of methanol to olefins over H-ZSM-5 zeolite:reaction pathway is related to the framework aluminum siting[J].ACS Catalysis,2016,6(11):7311-7325.

• [22] RAHIMI N,KARIMZADEH R.Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins:a review[J].Applied Catalysis A:General,2011,398(1/2):1-17.

• [23] KOKURYO S,TAMURA K,MIYAKE K,et al.Zr-doped SAPO-34 with enhanced Lewis acidity[J].New Journal of Chemistry,2022,46(8):3838-3843.

• [24] YAO G,WU G J,DAI W L,et al.Hydrodeoxygenation of lignin-derived phenolic compounds over bi-functional Ru/H-Beta under mild conditions[J].Fuel,2015,150:175-183.

• [25] 赵国利，王少军，凌凤香，等.γ-Al2O3表面结构的红外光谱研究[J].当代化工，2012,41(7):661-663.ZHAO G L,WANG S J,LING F X,et al.Infrared spectroscopic study of the surface of γ-alumina[J].Contemporary Chemical Industry,2012,41(7):661-663.

• [26] SEDIGHI M,MOHAMMADI M.CO2 hydrogenation to light olefins over Cu-CeO2/SAPO-34 catalysts:product distribution and optimization[J].Journal of CO2 Utilization,2020,35:236-244.

• [27] YANG M,CUI H T,DANG Q,et al.Preparation and characterization of nano Cr/H-ZSM-5 catalysts for the oxidative dehydrogenation of ethane[J].Applied Mechanics and Materials,2012,174/175/176/177:672-675.

• [28] AMMAR M,CAO Y,HE P,et al.An efficient green route for hexamethylene-1,6-diisocyanate synthesis by thermal decomposition of hexamethylene-1,6-dicarbamate over Co3O4/ZSM-5 catalyst:an indirect utilization of CO2[J].Chinese Journal of Chemical Engineering,2017,25(12):1760-1770.

• [29] LIU J G,HE Y R,YAN L L,et al.Nano-ZrO2 as hydrogenation phase in bi-functional catalyst for syngas aromatization[J].Fuel,2020,263:116803.

• [30] ZHOU Y W,JIANG Y X,QIN Z Z,et al.Influence of Zr,Ce,and La on Co3O4 catalyst for CO2 methanation at low temperature[J].Chinese Journal of Chemical Engineering,2018,26(4):768-774.

• [31] HE J Y,ZHAO C,MEI D H,et al.Mechanisms of selective cleavage of C-O bonds in di-aryl ethers in aqueous phase[J].Journal of Catalysis,2014,309:280-290.

• [32] LI L,FAN H J,HU H Q.A theoretical study on bond dissociation enthalpies of coal based model compounds[J].Fuel,2015,153:70-77.