乙醇制高级醇有序介孔氧化铝负载铜基催化剂研究

doi:10.11949/0438-1157.20221517

摘要/Abstract

摘要：

为了实现乙醇向高级醇的高效转化，以蒸发诱导自组装法合成的有序介孔氧化铝(ordered mesoporous alumina，OMA)为载体制备了系列Cu-La₂O₃/OMA催化剂，并深入研究了其在乙醇制高级醇反应中的构效关系。在533 K、3 MPa、LHSV=2 ml/(g cat·h)、V(N₂)/V(EtOH)=250∶1的反应条件下，最佳的Cu-La₂O₃/OMA(973)催化剂表现出高达55.5%的乙醇转化率和40.1%的高级醇收率，并且在200 h的连续反应中展现出优异的稳定性。OMA载体表面高度分散的Cu和La₂O₃活性组分协同OMA载体提供了大量的金属和酸碱中心，同时其较大的介孔孔径有利于降低反应物及产物分子在催化剂孔道中的扩散阻力，从而使得Cu-La₂O₃/OMA催化剂表现出较高的活性及高级醇选择性。此外，OMA载体表面五配位Al³⁺通过Cu-O-Al键对Cu活性物种的锚定作用是催化剂具有良好稳定性的重要原因。

关键词: 有序介孔氧化铝, Cu基催化剂, 乙醇, 高级醇

Abstract:

In order to realize highly efficient conversion of ethanol to higher alcohols, a series of Cu-La₂O₃/OMA catalysts were prepared on the basis of ordered mesoporous alumina (OMA) synthesized by evaporation-induced self-assembly method, and their structure-activity relationships in higher alcohol synthesis reaction were studied in depth. The optimal Cu-La₂O₃/OMA (973) catalyst exhibited up to 55.5% ethanol conversion and 40.1% yield of higher alcohols under the reaction conditions of 533 K, 3 MPa, LHSV=2 ml/(g cat·h) and V(N₂)/V(EtOH)=250∶1. Moreover, it showed excellent stability in 200 h on-stream evaluation. The highly dispersed Cu and La₂O₃active components and OMA support afforded large amounts of metal and acid-base sites while OMA support also provided mesoporous channels with larger pore size to reduce the diffusion resistance of the reactants and products, thus resulting in higher ethanol conversion and selectivity to higher alcohols. Additionally, the penta-coordinated Al³⁺ on the surface of OMA anchored the Cu active species by formation of Cu-O-Al bonds, thus enhancing the stability of the Cu-based catalysts.

Key words: ordered mesoporous alumina, Cu-based catalysts, ethanol, higher alcohols

中图分类号:

O 643.3

何金峰, 李秀珍, 寇建耀, 陶庭杰, 余灿, 刘欢, 陈永元, 赵豪健, 江大好, 李小年. 乙醇制高级醇有序介孔氧化铝负载铜基催化剂研究[J]. 化工学报, 2023, 74(3): 1082-1091.

Jinfeng HE, Xiuzhen LI, Jianyao KOU, Tingjie TAO, Can YU, Huan LIU, Yongyuan CHEN, Haojian ZHAO, Dahao JIANG, Xiaonian LI. Ethanol upgrading to higher alcohols over ordered mesoporous alumina supported Cu-based catalysts[J]. CIESC Journal, 2023, 74(3): 1082-1091.

图/表 12

图1 不同温度焙烧的OMA载体的N2物理吸附脱附等温线及孔径分布

Fig.1 N2 physical adsorption-desorption isotherms curves and pore size distribution of OMA supports with different calcination temperatures

表1 不同温度焙烧的OMA载体的结构性质

Table 1 Structural properties of OMA supports calcined at different temperatures

Calcination temperature/K	Specific surface area/(m²/g)	Pore volume/ (cm³/g)	Average pore size/nm
723	321.91	1.10	13.17
773	322.16	1.14	13.83
873	314.37	1.05	13.63
973	254.40	1.06	14.93
1073	269.11	0.85	11.82
1273	103.37	0.67	21.92
723^①	241.70	0.43	6.82

图2 不同温度焙烧OMA载体的XRD谱图

Fig.2 XRD patterns of OMA supports with different calcination temperatures

图3 不同温度焙烧所得OMA载体的HRTEM图像

Fig.3 HRTEM images of OMA supports calcined at different temperatures

图4 OMA前体的TG、DTG以及DSC曲线

Fig.4 TG, DTG, and DSC curves of OMA precursor

图5 反应前后Cu-La2O3/OMA(x)催化剂的XRD谱图

Fig.5 XRD patterns of Cu-La2O3/OMA(x) catalysts before and after reaction

图6 反应12 h后催化剂的HRTEM、HAADF-STEM和对应EDX成像图片

Fig.6 HRTEM, HAADF-STEM, and corresponding EDX mapping images of catalysts after 12 h reaction

图7 不同催化剂的27Al NMR谱图

Fig.7 27Al NMR spectra of various catalysts

图8 Cu-La2O3/OMA(x)催化剂的NH3-TPD和CO2-TPD谱图

Fig.8 NH3-TPD and CO2-TPD profiles of Cu-La2O3/OMA(x) catalysts

表2 Cu-La2O3/OMA（x）催化剂的酸碱性质

Table 2 Acid-base properties of Cu-La2O3/OMA（x） catalysts

Catalysts	Acidity distribution/ (mmol/g)		Total acidity/ (mmol/g)	Basicity distribution/ (mmol/g)		Total basicity/ (mmol/g)
Catalysts	Weak	Strong	Total acidity/ (mmol/g)	Weak	Strong	Total basicity/ (mmol/g)
Cu-La₂O₃/OMA(773)	0.569	0.841	1.410	0.032	0.174	0.206
Cu-La₂O₃/OMA(973)	0.381	1.374	1.755	0.095	0.066	0.161
Cu-La₂O₃/OMA(1273)	0.115	0.380	0.495	0.059	0.135	0.194

表3 Cu-La2O3/OMA‍(x)催化剂在乙醇制高级醇反应中的催化性能

Table 3 Catalytic performance of Cu-La2O3/OMA‍(x) catalysts for ethanol upgrading to higher alcohols

Catalysts	Conversion/%	Selectivity/%						S_T^③/%	Y_T^④/%
Catalysts	Conversion/%	Acetaldehyde	Butyradehyde	Ethyl acetate	n-Butanol	C₆—C₈ alcohols^①	Others^②	S_T^③/%	Y_T^④/%
Cu-La₂O₃/OMA(723)	26.6	4.4	4.4	11.7	52.8	13.9	12.8	66.7	17.7
Cu-La₂O₃/OMA(773)	30.8	2.3	4.4	10.4	54.8	15.5	12.6	70.3	21.7
Cu-La₂O₃/OMA(873)	37.2	2.1	5.0	9.1	53.0	17.7	13.0	70.7	26.3
Cu-La₂O₃/OMA(973)	55.5	2.7	5.3	6.5	46.4	25.9	13.2	72.3	40.1
Cu-La₂O₃/OMA(1073)	53.8	1.9	4.9	11.2	44.9	18.3	18.8	63.2	34.0
Cu-La₂O₃/OMA(1273)	38.7	3.7	11.4	24.5	34.8	4.3	21.4	39.1	15.1
Cu-La₂O₃/γ-Al₂O₃	42.2	2.9	8.0	19.4	44.3	5.8	19.6	50.1	21.1

图9 Cu-La2O3/OMA(973)催化剂的稳定性评价

Fig.9 Stability evaluation of Cu-La2O3/OMA(973) catalyst

参考文献 34

1	Ribeiro B E. Beyond commonplace biofuels: social aspects of ethanol[J]. Energy Policy, 2013, 57: 355-362.
2	Britto Júnior R F, Martins C A. Emission analysis of a diesel engine operating in diesel-ethanol dual-fuel mode[J]. Fuel, 2015, 148: 191-201.
3	Nanthagopal K, Ashok B, Saravanan B, et al. An assessment on the effects of 1-pentanol and 1-butanol as additives with Calophyllum Inophyllum biodiesel[J]. Energy Conversion and Management, 2018, 158: 70-80.
4	Atmanli A, Yilmaz N. A comparative analysis of n-butanol/diesel and 1-pentanol/diesel blends in a compression ignition engine[J]. Fuel, 2018, 234: 161-169.
5	Kozlowski J T, Davis R J. Heterogeneous catalysts for the guerbet coupling of alcohols[J]. ACS Catalysis, 2013, 3(7): 1588-1600.
6	Jordison T L, Lira C T, Miller D J. Condensed-phase ethanol conversion to higher alcohols[J]. Industrial & Engineering Chemistry Research, 2015, 54(44): 10991-11000.
7	Wu X Y, Fang G Q, Tong Y Q, et al. Catalytic upgrading of ethanol to n-butanol: progress in catalyst development[J]. ChemSusChem, 2018, 11(1): 71-85.
8	Marcu I C, Tichit D, Fajula F, et al. Catalytic valorization of bioethanol over Cu-Mg-Al mixed oxide catalysts[J]. Catalysis Today, 2009, 147(3/4): 231-238.
9	Carvalho D L, de Avillez R R, Rodrigues M T, et al. Mg and Al mixed oxides and the synthesis of n-butanol from ethanol[J]. Applied Catalysis A: General, 2012, 415/416: 96-100.
10	Birky T W, Kozlowski J T, Davis R J. Isotopic transient analysis of the ethanol coupling reaction over magnesia[J]. Journal of Catalysis, 2013, 298: 130-137.
11	Yang C, Meng Z Y. Bimolecular condensation of ethanol to 1-butanol catalyzed by alkali cation zeolites[J]. Journal of Catalysis, 1993, 142(1): 37-44.
12	Ogo S, Onda A, Yanagisawa K. Selective synthesis of 1-butanol from ethanol over strontium phosphate hydroxyapatite catalysts[J]. Applied Catalysis A: General, 2011, 402(1/2): 188-195.
13	Earley J H, Bourne R A, Watson M J, et al. Continuous catalytic upgrading of ethanol to n-butanol and >C₄ products over Cu/CeO₂ catalysts in supercritical CO₂ [J]. Green Chemistry, 2015, 17(5): 3018-3025.
14	Jiang D H, Wu X Y, Mao J, et al. Continuous catalytic upgrading of ethanol to n-butanol over Cu-CeO₂/AC catalysts[J]. Chemical Communications, 2016, 52(95): 13749-13752.
15	Jiang D H, Fang G Q, Tong Y Q, et al. Multifunctional Pd@UiO-66 catalysts for continuous catalytic upgrading of ethanol to n-butanol[J]. ACS Catalysis, 2018, 8(12): 11973-11978.
16	Riittonen T, Toukoniitty E, Madnani D K, et al. One-pot liquid-phase catalytic conversion of ethanol to 1-butanol over aluminium oxide—the effect of the active metal on the selectivity[J]. Catalysts, 2012, 2(1): 68-84.
17	Davda R R, Shabaker J W, Huber G W, et al. A review of catalytic issues and process conditions for renewable hydrogen and alkanes by aqueous-phase reforming of oxygenated hydrocarbons over supported metal catalysts[J]. Applied Catalysis B: Environmental, 2005, 56(1/2): 171-186.
18	Pang J F, Zheng M Y, He L, et al. Upgrading ethanol to n-butanol over highly dispersed Ni-MgAlO catalysts[J]. Journal of Catalysis, 2016, 344: 184-193.
19	Wang Z N, Yin M, Pang J F, et al. Active and stable Cu doped NiMgAlO catalysts for upgrading ethanol to n-butanol[J]. Journal of Energy Chemistry, 2022, 72: 306-317.
20	Yun Y S, Park D S, Yi J. Effect of nickel on catalytic behaviour of bimetallic Cu-Ni catalyst supported on mesoporous alumina for the hydrogenolysis of glycerol to 1,2-propanediol[J]. Catalysis Science & Technology, 2014, 4(9): 3191-3202.
21	Liu Q, Gao J, Gu F, et al. One-pot synthesis of ordered mesoporous Ni-V-Al catalysts for CO methanation[J]. Journal of Catalysis, 2015, 326: 127-138.
22	Yuan Q, Yin A X, Luo C, et al. Facile synthesis for ordered mesoporous gamma-aluminas with high thermal stability[J]. Journal of the American Chemical Society, 2008, 130(11): 3465-3472.
23	Morris S M, Fulvio P F, Jaroniec M. Ordered mesoporous alumina-supported metal oxides[J]. Journal of the American Chemical Society, 2008, 130(45): 15210-15216.
24	Chein R, Yang Z W. Experimental study on dry reforming of biogas for syngas production over Ni-based catalysts[J]. ACS Omega, 2019, 4(25): 20911-20922.
25	Yan B, Gao Y, Wang B L, et al. Enhanced carbon dioxide oxidative dehydrogenation of 1-butene by iron-doped ordered mesoporous alumina[J]. ChemCatChem, 2017, 9(24): 4480-4483.
26	Aslam S, Subhan F, Yan Z F, et al. Dispersion of nickel nanoparticles in the cages of metal-organic framework: an efficient sorbent for adsorptive removal of thiophene[J]. Chemical Engineering Journal, 2017, 315: 469-480.
27	Zang Y H, Dong X F, Wang C X. One-pot synthesis of mesoporous Cu-SiO₂-Al₂O₃ bifunctional catalysts for hydrogen production by dimethyl ether steam reforming[J]. Chemical Engineering Journal, 2017, 313: 1583-1592.
28	Gallo J M R, Bisio C, Gatti G, et al. Physicochemical characterization and surface acid properties of mesoporous [Al]-SBA-15 obtained by direct synthesis[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2010, 26(8): 5791-5800.
29	Pérez L L, Perdriau S, ten Brink G, et al. Stabilization of self-assembled alumina mesophases[J]. Chemistry of Materials, 2013, 25(6): 848-855.
30	He Y X, Zhang L M, An X, et al. Enhanced fluoride removal from water by rare earth (La and Ce) modified alumina: adsorption isotherms, kinetics, thermodynamics and mechanism[J]. Science of the Total Environment, 2019, 688: 184-198.
31	Morterra C, Magnacca G. A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species[J]. Catalysis Today, 1996, 27(3/4): 497-532.
32	Alphonse P, Faure B. Thermal stabilization of alumina modified by lanthanum[J]. Microporous and Mesoporous Materials, 2014, 196: 191-198.
33	Kumar P, With P, Srivastava V C, et al. Dimethyl carbonate synthesis from carbon dioxide using ceria-zirconia catalysts prepared using a templating method: characterization, parametric optimization and chemical equilibrium modeling[J]. RSC Advances, 2016, 6(111): 110235-110246.
34	Di Cosimo J I, Diez V K, Xu M, et al. Structure and surface and catalytic properties of Mg-Al basic oxides[J]. Journal of Catalysis, 1998, 178(2): 499-510.

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