Catalytic performance of ternary Mg-Al-Ce oxides for ethanol conversion into 1-butanol in a flow reactor

1.
L.V. Pisarzhevsky Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, 31 Prosp. Nauky, 03028 Kyiv, Ukraine
2.
Institute of Physics of the National Academy of Sciences of Ukraine, 46 Prosp. Nauky, 03028 Kyiv, Ukraine
3.
Charles University, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, 18000 Prague, Czech Republic
4.
National Institute of Chemistry, Department of Inorganic Chemistry and Technology, Hajdrihova 19, SI-1001 Ljubljana, Slovenia

Funds: The project was supported by the Program of National Academy of Sciences of Ukraine KPKVK 6541230 “Support for the development of priority areas of scientific research” (0120U101212)

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Corresponding author: E-mail: olga.larina@ukr.net; pavlo_kyriienko@ukr.net

摘要

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Abstract: An investigation of hydrotalcite-derived ternary Mg-Al-Ce oxides as catalysts for vapour phase condensation of ethanol to 1-butanol in a flow reactor under atmospheric pressure was carried out. The Mg-Al-Ce oxide systems with Mg/(Al + Ce) ratio from 1 to 4 were synthesized and characterized by XRD, SEM, NMR, and XPS. The study of acid-base characteristics of the systems with different Mg/(Al+Ce) ratio by NH₃/CO₂ quasi-equilibrium thermal desorption techniques shows that the ratio of the catalyst oxide components (Mg, Al, Ce) can provide acid/base capacity ratio close to 3 for the effectivity of the target process. The highest selectivity 68% is reached over Mg-Al-Ce oxide catalyst with the ratio of Mg/(Al+Ce) = 2.
- ethanol /
- 1-butanol /
- Mg-Al-Ce hydrotalcite-derived oxides /
- acid-base properties

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Figure 1 XRD of the samples before (a) and after treatment at 873 K (b)

1: Mg-Al-Ce-4; 2: Mg-Al-Ce-2; 3: Mg-Al-Ce-1

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Figure 2 SEM images of the samples after a treatment at 873 K

(a): Mg-Al-Ce-4; (b): Mg-Al-Ce-2; (c): Mg-Al-Ce-1

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Figure 3 ²⁷Al MAS NMR spectra of the samples after a treatment at 873 K(a) and the corresponding fit calculating using DMFit software (b)

1: Mg-Al-Ce-4; 2: Mg-Al-Ce-2; 3: Mg-Al-Ce-1

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Figure 4 Ce 3d XPS spectra of the samples after a treatment at 873 K

1: Mg-Al-Ce-4; 2: Mg-Al-Ce-2; 3: Mg-Al-Ce-1; 4: CeO_x

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Figure 5 Catalytic behaviour of Mg-Al-Ce oxide catalysts in ethanol conversion in a flow reactor during 8 h time on stream (T = 548 and 573 K, atmospheric pressure, WHSV = 0.14 g/(g_cat∙h))

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Table 1 ²⁷Al NMR analysis of Mg-Al-Ce oxide compositions

Sample	Area/%
Sample	Al_{octa 1}, δ~11	Al_{octa 2}, δ = 14–18	Al_penta, δ = 33–35	Al_{tetra 1}, δ = 68–70	Al_{tetra 2}, δ = 80–84
Mg-Al-Ce-4	9.4	53.7	−	15.1+21.8^a	−
Mg-Al-Ce-2	−	50.6	1.4	−	48.0
Mg-Al-Ce-1	14.1	56.0	−	13.9	16.0
^a: Al_{tetra 2} signal for Mg-Al-Ce-4 is a sum of two components: δ₁~65 and δ₂ = 68–70

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Table 2 Acid-base characteristics of the Mg-Al-Ce oxide catalysts

Characteristics	Sites^a	Catalyst samples [S_sp]
Characteristics	Sites^a	Mg-Al-Ce-4 [78 m²·g⁻¹]	Mg-Al-Ce-2 [96 m²·g⁻¹]	Mg-Al-Ce-1 [122 m²·g⁻¹]	CeO_x [85 m²·g⁻¹]	Al₂O₃ [199 m²·g⁻¹]	MgO [71 m²·g⁻¹]
Acid capacity/(${\rm{mmo}}{{\rm{l}}_{{\rm{NH}}}}_{_{\rm{3}}} \cdot {{\rm{g}}^{{\rm{ - 1}}}}$)	sw	0.09	0.13	0.13	0.11	0.32	0.06
	w	0.20	0.29	0.30	0.11	0.39	0.09
	m	0.13	0.05	0.20	0.11	0.39	−
	s	0.14	0.16	0.20	0.08	0.23	−
	total	0.56	0.63	0.63	0.30	0.94	0.15
Acid density/(µ${\rm{mo}}{{\rm{l}}_{{\rm{NH}}}}_{_{\rm{3}}} \cdot {{\rm{m}}^{{\rm{ - 2}}}}$)	sw	1.15	1.35	1.07	1.29	1.61	0.85
	w	2.56	3.02	2.46	1.29	1.96	1.27
	m	1.67	0.52	1.64	1.29	1.96	−
	s	1.79	1.67	1.64	0.94	1.16	−
	total	7.18	6.56	5.16	3.52	4.72	2.12
Base capacity/(${\rm{mmo} }{ {\rm{l} }_{ {\rm{CO} } } }_{_{\rm{2} } } \cdot {\rm{g} }$⁻¹)	sw	0.03	0.06	0.05	0.08	0.07	0.01
	w	0.03	0.08	0.09	0.08	0.10	0.04
	m	0.05	0.07	0.06	0.05	0.04	0.08
	s	0.03	−	0.04	0.01	0.03	0.05
	total	0.14	0.21	0.24	0.14	0.24	0.18
Base density/(µ${\rm{mo} }{ {\rm{l} }_{ {\rm{CO} } } }_{_{\rm{2} } } \cdot {\rm{m} }$⁻²)	sw	0.38	0.63	0.41	0.94	0.35	0.14
	w	0.38	0.83	0.74	0.94	0.50	0.56
	m	0.64	0.73	0.49	0.59	0.20	1.13
	s	0.38	−	0.33	0.12	0.15	0.70
	total	1.79	2.19	1.97	1.65	1.21	2.53
Acid-base capacity ratio		4.0	3.0	2.6	2.1	3.9	0.8
^a: abbreviations: “sw”: super weak sites, “w”: weak sites, “m”: medium sites, “s”: strong sites

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Table 3 Specific rate values for Mg-Al-Ce oxide catalysts in the process of vapour phase of ethanol conversion in a flow reactor (T = 548 K, TOS = 4 h, atmospheric pressure, WHSV = 0.14 g∙g_cat⁻¹∙h⁻¹)

Sample	Rate/(mol·m⁻²·s⁻¹ × 10¹⁰)
	EtOH conversion	Formation
	EtOH conversion	BuOH	HeOH	AA	Et	DEE
Mg-Al-Ce-4	11.381	0.775	0.015	4.557	0.224	0.149
Mg-Al-Ce-2	7.573	1.264	0.043	1.504	0.162	0.104
Mg-Al-Ce-1	6.514	0.458	0.015	3.487	0.214	0.117

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