Ethanol upgrading to higher alcohols over ordered mesoporous alumina supported Cu-based catalysts

doi:10.11949/0438-1157.20221517

Abstract

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

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

CLC Number:

O 643.3

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.

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.

Figures/Tables 12

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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

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

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

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

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