泡沫硅负载钴锰催化剂的制备及其合成气制低碳醇反应性能研究

杜鑫; 张明伟; 房克功

doi:10.1016/S1872-5813(24)60444-5

泡沫硅负载钴锰催化剂的制备及其合成气制低碳醇反应性能研究

doi: 10.1016/S1872-5813(24)60444-5

杜鑫^{1, 2,},
张明伟^1,,
房克功^1, ,

1.
中国科学院山西煤炭化学研究所煤炭高效低碳利用全国重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目: 国家自然科学基金 (22179137)资助

详细信息

通讯作者:
Tel:0351-4064505, Fax: 0351-4041153 , E-mail: kgfang@sxicc.ac.cn

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2024-01-23
- 修回日期: 2024-03-06
- 录用日期: 2024-03-07
- 网络出版日期: 2024-04-03

Preparation of silicon foam supported CoMn catalysts and their catalytic performances in higher alcohol synthesis via syngas

DU Xin^{1, 2
,},
ZHANG Mingwei^1
,,
FANG Kegong^{1
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by National Natural Science Foundation of China (22179137).

摘要

摘要: 本研究采用浸渍法、沉淀法和水热合成法制备了一系列泡沫硅负载CoMn基催化剂，并结合XRD、H₂-TPR、N₂物理吸附、TEM和XPS等表征技术考察了制备方法对催化剂在合成气制低碳醇反应中的性能影响。研究表明，催化剂表面存在Co²⁺(Co₂C)、Co⁰物种，水热合成法制备的催化剂表面Co₂C-Co⁰活性位点存在良好的协同作用有利于醇的生成，较高比例的Co₂C也促进了CO的非解离吸附和插入，从而呈现最高的醇选择性。在t=260 ℃，p=5.0 MPa，GHSV=4500 h⁻¹，H₂/CO(体积比)=2∶1的反应条件下，该泡沫催化剂可实现CO转化率11.1%，总醇选择性34.7%，C₂₊OH选择性34.5%的反应性能。
- 合成气 /
- 低碳醇 /
- 泡沫硅 /
- 钴锰催化剂
Abstract: A series of silicon foam supported CoMn catalysts were prepared using impregnation, precipitation, and hydrothermal methods. Combining the characterization techniques such as XRD, H₂-TPR, N₂ physical adsorption, TEM, and XPS, the effect of different catalyst preparation methods on the catalytic performance in the synthesis of higher alcohols from syngas was investigated. Research has shown that there are Co²⁺(Co₂C) and Co⁰ species on the surface of the catalyst. The active sites of Co₂C-Co⁰ on the surface of the catalyst prepared by hydrothermal synthesis have a good synergistic effect, which is conducive to the generation of alcohols. A higher proportion of Co₂C also promotes the associative adsorption and insertion of CO, resulting in the highest alcohol selectivity. Under the reaction conditions: t=260 ℃, p=5.0 MPa, GHSV=4500 h⁻¹, H₂/CO(volume ratio)=2∶1, the catalyst exhibited the best reaction performance to achieve CO conversion of 11.1%, total alcohol selectivity of 34.7%, and C₂₊OH selectivity of 34.5%.
- synthesis gas /
- higher alcohols /
- silicon foam /
- CoMn catalyst

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图 1 CoMn/MCF催化剂合成示意图

Figure 1 Schematic diagram of CoMn/MCF catalyst synthesis

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图 2 CoMn/MCF-IM（a）、（b）、（c）、CoMn/MCF-PM（d）、（e）、（f）和CoMn/MCF-HM（h）、（I）、（J）的TEM图像

Figure 2 TEM images of CoMn/MCF-IM (a), (b), (c), CoMn/MCF-PM (d), (e), (f), and CoMn/MCF-HM (h), (I), (J)

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图 3 载体及催化剂的N₂吸附-脱附曲线（a）和孔径分布（b）

Figure 3 N₂ adsorption and desorption curves (a) and pore size distribution (b) of carriers and catalysts

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图 4 载体的SAXRD谱图

Figure 4 SAXRD spectrum of the carrier

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图 5 焙烧后催化剂的XRD谱图

Figure 5 XRD spectrum of catalyst after calcination

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图 6 催化剂的H₂-TPR谱图

Figure 6 H₂-TPR diagram of catalyst

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图 7 催化剂（焙烧后）的Co 2p和Mn 2p XPS谱图

Figure 7 XPS spectra of Co 2p and Mn 2p catalysts (after calcination)

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图 8 催化剂CoMn/MCF-IM（a）、CoMn/MCF-PM（b）、CoMn/MCF-HM（c）的产物分布

Figure 8 Product distribution diagram of catalysts CoMn/MCF-IM (a), CoMn/MCF-PM (b), and CoMn/MCF-HM (c)

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图 9 反应后催化剂的XRD谱图

Figure 9 XRD spectrum of the catalyst after reaction

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图 10 催化剂（反应后）的 Co 2p和Mn 2p XPS谱图

Figure 10 XPS spectra of Co 2p and Mn 2p catalysts (after reaction)

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图 11 催化剂的醇选择性与Co²⁺/Co⁰比值

Figure 11 Relationship diagram between alcohol selectivity of catalyst and Co²⁺/Co⁰ ratio 260 ℃, 5.0 MPa, GHSV=4500 h⁻¹。

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图 12 CoMn/MCF催化剂合成气制低碳醇机理示意图

Figure 12 The schematic mechanism of CoMn/MCF catalyst for higher alcohols synthesis from syngas

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表 1 实验用化学试剂

Table 1 Experimental chemical reagents

Chemical reagent	Reagent grade	Manufacturer
Co(NO₃)₂·6H₂O	AR	Sinopharm Chemical Reagent Co Ltd
50% Mn(NO₃)₂ solution	AR	Sinopharm Chemical Reagent Co Ltd
PEG-PPG-PEG, Pluronic^®P-123, Average Mn ~5800	AR	Sinopharm Chemical Reagent Co Ltd
C₈H₂₀O₄Si	AR	Sinopharm Chemical Reagent Co Ltd
C₆H₆	AR	Sinopharm Chemical Reagent Co Ltd
HCl	AR	Sinopharm Chemical Reagent Co Ltd
K₂CO₃	AR	Sinopharm Chemical Reagent Co Ltd
CH₄N₂O	AR	Sinopharm Chemical Reagent Co Ltd
NH₄F	AR	Aladdin
Experimental water	deionized water	Laboratory homemade

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表 2 样品的织构性质

Table 2 Texture properties of the samples

Sample	S_BET/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Average pore size^a/nm
MCF	668	1.3	6.0
CoMn/MCF-IM	383	0.5	4.5
CoMn/MCF-PM	159	0.5	10.9
CoMn/MCF-HM	229	0.6	8.4
^a: Average pore size = 4(pore volume/S_BET)

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表 3 催化剂的元素含量

Table 3 The element contents of the catalysts

Sample	Co/%	Mn/%	Si/%
CoMn/MCF-IM	12.91	4.65	29.90
CoMn/MCF-PM	13.36	4.70	30.89
CoMn/MCF-HM	13.48	4.02	30.82

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表 4 催化剂的催化性能

Table 4 The catalytic performance of catalysts^a

Sample	x_CO/%	Selectivity/%			Alcohol distribution		STY_ROH/(g·g·h⁻¹)
Sample	x_CO/%	ROH	CHn	CO₂	MeOH	C₂₊OH	STY_ROH/(g·g·h⁻¹)
CoMn/MCF-IM	36.7	6.9	89.6	3.6	29.1	71.0	0.06
CoMn/MCF-PM	6.3	26.8	73.3	0.0	54.6	45.4	0.02
CoMn/MCF-HM	11.1	34.7	65.4	0.0	65.5	34.5	0.04
^a: Reaction conditions: t=260 ℃, p=5.0 MPa, GHSV=4500 h⁻¹, H₂/CO=2.0。

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表 5 反应后催化剂表面钴元素相对含量

Table 5 Relative contents of cobalt element on the surface of the catalyst after reaction^a

Catalyst	Co²⁺(area%)	Co⁰(area%)	Co²⁺/Co⁰
CoMn/MCF-IM	0.68	0.32	2.13
CoMn/MCF-PM	0.81	0.19	4.26
CoMn/MCF-HM	0.89	0.11	8.09
^a: Integrated area based on Co 2p_3/2 main peak。

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