CuMgAlOx复合氧化物催化甲醇乙醇Guerbet反应:M2+/Al3+比的影响

程福龙; 郭荷芹; 崔静磊; 侯博; 李德宝

CuMgAlO_x复合氧化物催化甲醇乙醇Guerbet反应:M²⁺/Al³⁺比的影响

程福龙^{1, 2},
郭荷芹^2, ,,
崔静磊³,
侯博²,
李德宝^2, ,

1.
重庆三峡学院三峡库区水环境演变与污染防治重庆市级重点实验室, 重庆 404100
2.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
3.
山西大学资源与环境工程研究所, 山西太原 030006

基金项目:

国家自然科学基金 21736007

国家自然科学基金 21303241

详细信息

本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).
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出版历程
- 收稿日期: 2018-05-04
- 修回日期: 2018-08-14
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-12-10

Guerbet reaction of methanol and ethanol catalyzed by CuMgAlO_x mixed oxides: Effect of M²⁺/Al³⁺ ratio

CHENG Fu-long^{1, 2},
GUO He-qin^{2
, ,},
CUI Jing-lei³,
HOU Bo²,
LI De-bao^{2
, ,}

1.
Chongqing Three Gorges University, Key Laboratory of Water Environment Evolution and Pollution Control in Three Gorges Reservior, Chongqing 404100, China
2.
State Key Laborator of Coal Convercion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
Institute of Resources and Environment Engineering, Shanxi University, Taiyuan 030006, China

Funds:

the National Natural Science Foundation of China 21736007

the National Natural Science Foundation of China 21303241

More Information

Corresponding author: GUO He-qin, Tel: 0351-4040499, E-mail: heqinguo@sxicc.ac.cn; LI De-bao, dbli@sxicc.ac.cn

摘要

摘要: 以类水滑石为前驱体，通过调控M²⁺/Al³⁺比制备了系列具有不同表面性质的MgAlO_x（MA）和CuMgAlO_x（CMA）催化剂，并分别应用于甲醛乙醛缩合反应（甲醇乙醇Guerbet反应的第二步反应）和甲醇乙醇Guerbet反应。采用NH₃/CO₂-TPD、XPS、H₂-TPR和H₂-TPD技术对催化剂表面酸碱性以及铜物种的性质进行了表征。结果表明，甲醇乙醇Guerbet反应性能与催化剂表面Cu⁰比表面积和中强碱数目有关，提高Cu⁰比表面积有利于甲醇乙醇脱氢生成甲醛和乙醛，增强中强碱数目能促进甲醛乙醛缩合反应。
- CuMgAlO_x /
- M²⁺/Al³⁺比 /
- 甲醇和乙醇 /
- Guerbet反应
Abstract: A series of hydrotalcite-like derived MgAlO_x (MA) and CuMgAlO_x (CMA) catalysts with various M²⁺/Al³⁺ molar ratios were prepared and evaluated by the aldol condensation reaction of formaldehyde and acetaldehyde and Guerbet reaction of methanol and ethanol, respectively. The acidity and the alkalinity as well as the surface copper species of catalysts were characterized by NH₃/CO₂-TPD, XPS, H₂-TPR and H₂-TPD techniques. The results show that the catalytic performance of Guerbet reaction of methanol and ethanol is related to the surface Cu⁰ species and the number of moderate basic sites. Increasing the specific surface area of Cu⁰ is beneficial to the dehydrogenation of methanol and ethanol to formaldehyde and acetaldehyde. The increase of the amount of moderate basic sites can promote the condensation reaction of formaldehyde and acetaldehyde.
- CuMgAlO_x /
- M²⁺/Al³⁺ ratio /
- methanol and ethanol /
- Guerbet reaction
注释:

1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).

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图 1 前驱体的XRD谱图

Figure 1 XRD patterns of HMA (a) and HCMA (b) samples

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图 2 催化剂的XRD谱图

Figure 2 XRD patterns of MA (a) and CMA (b) catalysts

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图 3 前驱体样品的热重曲线

Figure 3 TG-DTG curves of HMA (a) and HCMA (b) precursors

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图 4 催化剂的CO₂-TPD谱图

Figure 4 CO₂-TPD profiles of MA (a) and CMA catalysts (b)

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图 5 催化剂的NH₃-TPD谱图

Figure 5 NH₃-TPD profiles of MA catalysts (a) and CMA catalysts (b)

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图 6 CMA催化剂的Cu 2p XPS谱图

Figure 6 XPS Cu 2p spectra of CMA catalysts

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图 7 CMA催化剂的H₂-TPR谱图

Figure 7 H₂-TPR profiles of CMA catalysts

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图 8 CMA催化剂的H₂-TPD谱图

Figure 8 H₂-TPD profiles of CMA catalysts

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图 9 乙醛转化率以及正丙醛时空收率与中强碱数目的关系

Figure 9 Correlation between the conversion of acetaldehyde and the STY of propanal with the amount of moderate basic sites

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图 10 甲醇和乙醇转化率与Cu⁰比表面积之间的关系

Figure 10 Correlation between the conversion of methanol and ethanol with A_Cu⁰

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图 11 C3和C4产物时空收率与Cu⁰比表面积之间的关系

Figure 11 Correlation between STYs of C3 and C4 products with A_Cu⁰

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表 1 催化剂组成和织构性质

Table 1 Catalyst composition and structural and textural properties

Catalyst	Composition w_mol /%^a			M²⁺/Al³⁺ratio	a/nm	c/nm	Surface area A/(m²·g^-1)
Catalyst	Cu	Mg	Al	M²⁺/Al³⁺ratio	a/nm	c/nm	precusor	catalyst
MA-2/1	0	67.92	32.08	2.12	0.304	2.296	212.57	276.25
MA-3/1	0	71.26	28.74	2.48	0.306	2.324	209.53	249.24
MA-4/1	0	76.74	23.26	3.30	0.307	2.348	158.56	211.52
MA-5/1	0	80.59	19.41	4.15	0.307	2.357	166.37	212.52
CMA-2/1	0.99	63.69	35.32	1.83	0.304	2.291	131.06	217.83
CMA-3/1	1.02	73.10	25.88	2.86	0.305	2.323	231.31	355.26
CMA-4/1	1.08	76.43	22.49	3.45	0.307	2.354	112.02	202.30
CMA-5/1	1.06	80.70	18.24	4.48	0.307	2.368	114.63	167.41
^a：obtained from ICP

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表 2 催化剂的碱性和酸性分布

Table 2 The distribution of surface basic sites and acid sites of catalysts

Catalyst	Amount of basic sites /(μmol·g^-1)				Amount of acid sites /(μmol·g^-1)
Catalyst	total	weak	moderate	strong	total	weak	moderate	strong
MA-2/1	281.17	35.83	153.96	91.38	140.03	85.52	0	54.51
MA-3/1	283.59	27.16	167.00	89.43	116.63	61.98	0	54.65
MA-4/1	321.94	32.31	184.45	105.18	94.95	49.75	0	45.20
MA-5/1	353.46	36.05	191.48	125.93	94.44	35.43	0	59.01
CMA-2/1	161.25	11.05	103.31	46.89	204.22	38.37	111.91	53.94
CMA-3/1	180.10	23.48	106.96	49.66	171.80	33.34	101.78	36.68
CMA-4/1	203.28	21.05	124.98	57.25	138.76	24.27	69.06	45.43
CMA-5/1	236.87	59.18	127.76	49.93	131.69	23.96	67.89	39.84

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表 3 CMA催化剂表面组成和Cu⁰比表面积以及氢脱附量

Table 3 Surface composition, specific surface area of Cu⁰, and the amount of H₂ desorption of CMA catalysts

Catalyst	Surface composition^a w_mol/%			A_Cu⁰^b/(m²·g^-1)	H₂ desorption^c/(μmol·g^-1)
Catalyst	Cu	Mg	Al	A_Cu⁰^b/(m²·g^-1)	H₂ desorption^c/(μmol·g^-1)
CMA-2/1	0.94	57.09	41.97	4.93	57.84
CMA-3/1	1.28	65.15	33.57	6.10	71.25
CMA-4/1	1.12	68.87	30.01	9.16	104.86
CMA-5/1	1.01	79.41	19.58	4.35	52.39
^a: obtained from XPS; ^b: calculated by N₂O chemisorptions; ^c: obtained from H₂-TPD

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表 4 MA催化剂甲醛和乙醛反应的催化性能

Table 4 Formaldehyde and acetaldehyde reaction performance of MA catalysts

Catalyst	x/%	s/%							STY /(g·kg^-1·h^-1)
Catalyst	x/%	PA	MO	CO₂	IBA	PO	MF	EO	PA	MO	CO₂
MA-2/1	24.77	67.07	13.34	13.33	2.71	1.16	0.68	1.71	62.77	20.66	28.35
MA-3/1	28.28	61.19	17.11	16.11	2.73	0.99	0.87	1.00	70.56	32.65	42.25
MA-4/1	31.89	56.29	19.01	19.78	2.28	0.75	0.58	1.31	85.68	47.89	68.44
MA-5/1	33.96	53.52	20.45	20.92	2.42	0.90	0.56	1.23	90.90	57.47	80.74
reaction conditions: t=260 ℃, p=0.1 MPa, GHSV=750 mL·g_cat^-1·h^-1, LHSV=2 mL·g_cat^-1·h^-1, formaldehyde/acetaldehyde (molar ratio)=4; x: acetaldehyde conversion; s: selectivity; STY: space time yield; PA: propanal; MO: methanol; IBA: isobutanal; PO: propanol; MF: methyl formate; EO: ethanol

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表 5 CMA催化剂甲醇和乙醇Guerbet反应的催化性能

Table 5 Methanol and ethanol coupling reaction performance of CMA catalysts

	CMA-2/1	CMA-3/1	CMA-4/1	CMA-5/1
Conversion x/%
Methanol	6.76	8.13	10.56	5.89
Ethanol	24.79	27.46	43.92	18.00
Products selectivity s/%
C3+C4 aldehydes
Propanal	30.79	25.77	30.45	32.26
Isobutanal	15.28	26.91	17.87	4.81
1-butanal	6.91	5.76	7.20	0.93
C3+C4 alcohols
Propanol	29.16	22.46	23.15	48.69
Isobutanol	6.73	4.99	3.81	1.37
1-butanol	3.14	5.98	6.75	1.85
Esters
MF	0.72	1.25	0.80	0.70
MA	1.76	1.43	3.76	1.93
Others
DME	1.34	1.22	0.52	3.82
CO₂	4.17	4.23	5.69	3.64
Products STY /(g·kg^-1·h^-1)
C3+C4 alcohols	7.93	11.89	27.39	7.43
C3+C4 aldehydes	12.11	22.79	47.98	5.35
reaction conditions：t=260 ℃, p=0.1 MPa, GHSV=750 mL·g_cat^-1·h^-1, LHSV=2 mL·g_cat^-1·h^-1, methanol/ethanol (molar ratio)=4/1; STY: space time yield; MF: methyl formate; MA: methyl acetate; DME: dimethyl ether; C3+C4 alcohols: propanol, isobutanol, and n-butanol; C3+C4 aldehydes: propanal, isobutanal, and n-butanal; Esters: methyl formate and methyl acetate

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CuMgAlO_x复合氧化物催化甲醇乙醇Guerbet反应:M²⁺/Al³⁺比的影响

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Guerbet reaction of methanol and ethanol catalyzed by CuMgAlO_x mixed oxides: Effect of M²⁺/Al³⁺ ratio

Corresponding author: GUO He-qin, Tel: 0351-4040499, E-mail: heqinguo@sxicc.ac.cn; LI De-bao, dbli@sxicc.ac.cn

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