不同方法制备La2O2CO3/ZnO催化乙醇转化的研究：孔结构和表面碱性的影响

虞鸿雁; SHINEunwoo; 门勇

不同方法制备La₂O₂CO₃/ZnO催化乙醇转化的研究：孔结构和表面碱性的影响

虞鸿雁^{1, 2,},
SHINEunwoo²,
门勇^1, ,

1.
上海工程技术大学化学化工学院，上海 201620
2.
韩国蔚山大学化工学院，韩国蔚山 44610

基金项目: 上海市科委部分地方院校能力建设资助项目（18030501100）；State Key Laboratory of Heavy Oil Processing；上海工程技术大学韩国蔚山大学联合培养资助项目

详细信息

作者简介:
虞鸿雁（1993−），女，在读博士生，研究方向为工业催化. E-mail：yuyubobo0908@163.com

通讯作者:
门　勇（1973−），男，教授，博士，研究方向为工业催化. E-mail：men@sues.edu.cn

中图分类号: O643.32
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- 文章访问数: 329
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- 被引次数: 0
出版历程
- 收稿日期: 2020-12-28
- 刊出日期: 2021-09-30

Ethanol conversion over La₂O₂CO₃/ZnO catalysts prepared by two methods: Effect of macroporous structure and basic sites

YU Hongyan^{1, 2
,},
SHIN Eunwoo²,
MEN Yong^{1
, ,}

1.
School of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
2.
Department of Chemical Engineering, University of Ulsan, Ulsan 44610, South Korea

摘要

摘要: 利用共沉淀法和乙二醇燃烧法制备La₂O₂CO₃/ZnO两种催化剂，评价其对生物乙醇脱氢生成乙醛的催化活性，并采用FE−SEM, HR−TEM, FT−IR, XRD, BET，CO₂−TPD等研究手段对催化剂的形貌及表面碱性等物相结构进行表征. 结果表明，制备方法对催化剂形貌以及性能影响十分明显，乙二醇燃烧法形成的大孔结构有助于乙醇的转化，同时产物乙醛的选择性与催化剂表面碱性有关.
- 共沉淀法 /
- 乙二醇燃烧法 /
- 大孔结构 /
- 脱氢反应 /
- 表面碱性
Abstract: In this work, we prepared the La₂O₂CO₃/ZnO catalysts by two different methods-co-precipitation and ethylene glycol combustion method, whose catalytic performance of the dehydrogenation of ethanol to acetaldehyde as well as materials’ properties related to the catalytic behavior through FE−SEM, HR−TEM, FT−IR, XRD, N₂ adsorption/ desorption technique were investigated. The catalyst synthesis method had greatly influenced the morphology and performance, with materials prepared through solution combustion method better in terms of ethanol conversion resulted from the macroporous structure. Characterization results based on CO₂−TPD revealed that catalyst synthesized through co-precipitation or solution combustion method allowed correlation of acetaldehyde selectivity with basicity.
- co-precipitation method /
- solution combustion method /
- macroprosity /
- dehydrogenation /
- surface basicity

HTML全文

图 1 样品的XRD图谱

Figure 1. XRD pattern of samples

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图 2 样品的FTIR图谱

Figure 2. FTIR spectra of samples

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图 3 样品的N₂吸附–解吸等温线

Figure 3. Nitrogen adsorption-desorption isotherms of samples

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图 4 样品的FE−SEM图像

Figure 4. FE−SEM images

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图 5 样品的FE–TEM图像

Figure 5. FE–TEM images of samples

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图 6 CO₂ 程序升温脱附图

Figure 6. CO₂–TPD profiles

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图 7 La₂O₂CO₃ / ZnO对乙醇的催化转化活性图

Figure 7. Catalytic performance diagrams of La₂O₂CO₃ / ZnO on bio-ethanol

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图 8 La₂O₂CO₃ / ZnO对乙醇的催化反应机理示意图

Figure 8. Schematic of catalytic mechanism of La₂O₂CO₃ / ZnO on ethanol

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参考文献(29)

[1]	GONZALEZ-GARCIA S, LOU L, MOREIRA M T, et al. Life cycle assessment of hemp hurds use in second generation ethanol production[J] . Biomass & Bioenergy,2012,36:268 − 279.
[2]	JOHN R P, ANISHA G S, NAMPOOTHIRI K M, et al. Micro and macroalgal biomass: A renewable source for bioethanol[J] . Bioresource Technology,2011,102(1):186 − 193. doi: 10.1016/j.biortech.2010.06.139
[3]	GHASEMZADEH K, JALILNEJAD E, BASILE A. 3-Production of bioalcohol and biomethane[J] . Bioenergy Systems for the Future,2017:61 − 86.
[4]	PAMPARARO G, GARBARINO G, RIANI P, et al. A study of ethanol dehydrogenation to acetaldehyde over supported copper catalysts: catalytic activity, deactivation and regeneration[J] . Applied Catalysis A: General,2020, 602:117710.
[5]	MOSTROU S, SIPŐCZ T, NAGL A, et al. Catalytic oxidation of aqueous bioethanol: An efficient upgrade from batch to flow[J] . Reaction Chemistry & Engineering,2018,3(5):781 − 789.
[6]	HAGEMEYER H J. Kirk-Othmer Encyclopedia of Chemical Technology[M]. 5th Edition. Hoboken: John Wiley & Sons, 2002: 564 − 575.
[7]	GUAN Y, HENSEN E J M. Ethanol dehydrogenation by gold catalysts: The effect of the gold particle size and the presence of oxygen[J] . Applied Catalysis A: General,2009,361(1/2):49 − 56.
[8]	CHANG F W, YANG H C, ROSELIN L S, et al. Ethanol dehydrogenation over copper catalysts on rice husk ash prepared by ion exchange[J] . Applied Catalysis A General,2006,304:30 − 39. doi: 10.1016/j.apcata.2006.02.017
[9]	LI S X, MEN Y, WANG J G, et al. Morphological control of inverted MgO-SiO₂ composite catalysts for efficient conversion of ethanol to 1, 3-butadiene[J] . Applied Catalysis A General,2019,577:1 − 9. doi: 10.1016/j.apcata.2019.03.007
[10]	WANG X F, MEN Y, WANG J G, et al. The influence of zinc loadings on the selectivity control of bio-ethanol transformation over MgO-SiO₂ catalysts[J]. Applied Catalysis A: General, 2020, 598: 117565. DOI: 10.1016/j.apcata.2020.117565
[11]	SATO A G, VOLANTI D P, FREITAS I, et al. Site-selective ethanol conversion over supported copper catalysts[J] . Catalysis Communications,2012,26:122 − 126. doi: 10.1016/j.catcom.2012.05.008
[12]	FREITAS I C, DAMYANOVA S, OLIVEIRA D C, et al. Effect of Cu content on the surface and catalytic properties of Cu/ZrO₂ catalyst for ethanol dehydrogenation[J] . Journal of Molecular Catalysis A: Chemical,2014,381(1):26 − 37.
[13]	DEWILDE J F, CZOPINSKI C J, BHAN A. Ethanol dehydration and dehydrogenation on γ-Al₂O₃: Mechanism of acetaldehyde formation[J] . ACS Catalysis,2014,4(12):4425 − 4433. doi: 10.1021/cs501239x
[14]	SKINNER M J, MICHOR E L, FAN W, et al. Ethanol dehydration to ethylene in a stratified autothermal millisecond reactor[J] . ChemSusChem,2011,4(8):1151 − 1156. doi: 10.1002/cssc.201100026
[15]	AUTTHANIT C, JONGSOMJIT B. Production of Ethylene through Ethanol Dehydration on SBA-15 Catalysts Synthesized by Sol-gel and One-step Hydrothermal Methods[J] . Journal of oleo science,2018,67(2):235 − 243. doi: 10.5650/jos.ess17167
[16]	LA-SALVIA N, LOVON-QUINTANA JJ, VALENCA GP. Vapor-Phase Catalytic Conversion of Ethanol into 1, 3-Butadiene on Cr-Ba/MCM-41 Catalysts[J] . Brazilian Journal of Chemical Engineering,2015,32(2):489 − 500. doi: 10.1590/0104-6632.20150322s00003039
[17]	DING D G, LU W B, XIONG Y, et al. Facile synthesis of La₂O₂CO₃ nanoparticle films and Its CO₂ sensing properties and mechanisms[J] . Applied Surface Science,2017,426 (31):725 − 733. doi: 10.1016/j.apsusc.2017.07.126
[18]	PARK C Y, NGUYEN-PHU H, SHIN E W. Glycerol carbonation with CO₂ and La₂O₂CO₃/ZnO catalysts prepared by two different methods: Preferred reaction route depending on crystalline structure[J] . Molecular Catalysis,2017,435:99 − 109. doi: 10.1016/j.mcat.2017.03.025
[19]	LI H G, GAO D Z, GAO P, et al. The synthesis of glycerol carbonate from glycerol and CO₂ over La₂O₂CO₃-ZnO catalysts[J] . Catalysis Science & Technology,2013,3:2801 − 2814.
[20]	LI H, Xi J, Lei L, et al. Synthesis of glycerol carbonate by direct carbonylation of glycerol with CO₂ over solid catalysts derived from Zn/Al/La and Zn/Al/La/M (M = Li, Mg and Zr) hydrotalcites[J] . Catalysis Science & Technology,2015,5:989 − 996.
[21]	JIN L, ZHANG Y, DOMBROWSKI J P, et al. ZnO/La₂O₂CO₃ layered composite: A new heterogeneous catalyst for the efficient ultra-fast microwave biofuel production[J] . Applied Catalysis B Environmental,2011,103(1/2):200 − 205. doi: 10.1016/j.apcatb.2011.01.027
[22]	ZHANG G, ZHAO Z, LIU J, et al. Macroporous perovskite-type complex oxide catalysts of La_{1– x}K_xCo_{1– y}Fe_yO₃ for diesel soot combustion[J] . Journal of Rare Earths,2009,27(6):955 − 960. doi: 10.1016/S1002-0721(08)60369-5
[23]	YU H Y, MEN Y, SHIN E W. Structural properties of disordered macroporous La₂O₂CO₃/ZnO materials prepared by a solution combustion method[J] . Korean Journal of Chemical Engineering,2019,36(4):522 − 528. doi: 10.1007/s11814-019-0239-5
[24]	IRUSTA S, CORNAGLIA L M, LOM BA RDO E A. Effects of rhodium and platinum on the reactivity of lanthanum phases[J] . Materials Chemistry & Physics,2004,86(2/3):440 − 447.
[25]	TURCOTTE R P, SAWYER J O, EYRING L R. On the rare earth dioxymonocarbonates and their decomposition[J] . Inorganic Chemistry,1969,8(2):238 − 246. doi: 10.1021/ic50072a012
[26]	LEVAN T, CHE M, TATIBOUET J M, et al. Infrared study of the formation and stability of La₂O₂CO₃ during the oxidative coupling of methane on La₂O₃[J] . Journal of Catalysis,1993,142(1):18 − 26. doi: 10.1006/jcat.1993.1185
[27]	NI J, CHEN L, LIN J, et al. High performance of Mg-La mixed oxides supported Ni catalysts for dry reforming of methane: The effect of crystal structure[J] . International Journal of Hydrogen Energy,2013,38(31):13631 − 13642. doi: 10.1016/j.ijhydene.2013.08.041
[28]	PAKHARE D, SCHWARTZ V, ABDELSAYED V, et al. Kinetic and mechanistic study of dry (CO₂) reforming of methane over ROOH-substituted La₂Zr₂O₇ pyrochlores[J] . Journal of Catalysis,2014,316:78 − 92. doi: 10.1016/j.jcat.2014.04.023
[29]	KVISLE S, AGUERO A, SNEEDEN R. Transformation of ethanol into 1, 3-butadiene over magnesium oxide/silica catalysts[J] . Applied Catalysis,1988,43(1):117 − 131. doi: 10.1016/S0166-9834(00)80905-7