Ce改性对CuLDH催化CO<sub>2</sub>加氢制甲醇性能的影响

刘昊然; 于志庆; 黄文斌; 魏强; 姜鹏; 周亚松

doi:10.1016/S1872-5813(23)60392-5

Ce改性对CuLDH催化CO₂加氢制甲醇性能的影响

doi: 10.1016/S1872-5813(23)60392-5

刘昊然^1,,
于志庆^1,,
黄文斌^1,,
魏强^1,,
姜鹏^2,,
周亚松^1, ,

1.
中国石油大学(北京)重质油全国重点实验室, 北京 102249
2.
中国石油集团昆仑资本有限公司, 海南海口 571127

基金项目: 国家自然科学基金(22078360)资助

详细信息

通讯作者:
E-mail: zhouyasong2011@163.com

中图分类号: O643
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出版历程
- 收稿日期: 2023-08-18
- 修回日期: 2023-09-21
- 录用日期: 2023-09-21
- 网络出版日期: 2023-11-10
- 刊出日期: 2024-02-02

Effect of Ce modification on the performance of CuLDH catalyst for CO₂ hydrogenation to methanol

LIU Haoran^1
,,
YU Zhiqing^1
,,
HUANG Wenbin^1
,,
WEI Qiang^1
,,
JIANG Peng^2
,,
ZHOU Yasong^{1
, ,}

1.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China
2.
CNPC Kunlun Capital Co., Ltd, Haikou 571127, China

Funds: The project was supported by National Natural Science Foundation of China (22078360).

摘要

摘要: 通过向CuMgAl水滑石（CuLDH）催化剂中添加不同量的Ce，合成了一系列Ce改性的CuLDH-Ce_x催化剂。采用X射线衍射（XRD）、N₂吸附-脱附（BET）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）等分析手段对催化剂的理化性质进行表征。结果表明，添加Ce会改变Cu-LDH催化剂的水滑石结构，适量的Ce会增大催化剂的比表面积，改善了Cu颗粒的分散度。同时，适量的Ce有利于增加催化剂表面强碱性位点的密度和氧空位的数量，促进了CO₂的吸附和转化。Ce有利于调变催化剂表面的Cu⁺/Cu⁰比例，较高的Cu⁺/Cu⁰比例有利于甲醇的生成。当Ce/Cu比例为0.3时，在空速为9000 mL/(g·h)，温度为240 ℃，压力为2.5 MPa的条件下，催化剂的CO₂的转化率为7.5%，甲醇选择性为78.4%，甲醇的时空收率最高可达362.8 g/(kg·h)。通过原位红外光谱（in-situ DRIFTS）证明CuLDH-Ce0.3催化剂在CO₂加氢合成甲醇过程中遵循HCOO*反应路径。
- Ce /
- 水滑石 /
- CO₂加氢 /
- 碱性位 /
- 氧空位 /
- 甲醇
Abstract: A series of Ce modified CuLDH-Cex catalysts were synthesized by adding different amounts of Ce to CuMgAl hydrotalcite (CuLDH) catalysts. The physicochemical properties of the catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption (BET), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), etc. The results showed that the addition of Ce changed the hydrotalcite structure of CuLDH catalyst, and an appropriate amount of Ce increased the surface area of the catalyst and improved the dispersion of Cu particles. At the same time, an appropriate amount of Ce was beneficial for increasing the density of strong alkaline sites and the number of oxygen vacancies on the catalyst surface, promoting the adsorption and conversion of CO₂. Ce was beneficial for adjusting the Cu⁺/Cu⁰ ratio on the catalyst surface, and a higher Cu⁺/Cu⁰ ratio was conducive to the formation of methanol. When the Ce/Cu ratio was 0.3, the catalyst exhibited higher activity with 7.5% CO₂ conversion, 78.4% methanol selectivity and 362.8 g/(kg·h) spatiotemporal yield at 240 ℃ under 2.5 MPa with a GHSV=9000 mL/(g·h). It was proved by in-situ DRIFTS that CuLDH-Ce0.3 catalyst followed HCOO* reaction path during CO₂ hydrogenation for methanol.
- Ce /
- hydrotalcite /
- CO₂ hydrogenation /
- alkaline sites /
- oxygen vacancies /
- methanol

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FIG. 2925. FIG. 2925.

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图 1 CuLDH-Ce_x催化剂前驱体的XRD谱图

Figure 1 XRD patterns of CuLDH-Ce_x catalysts precursors

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图 2 CuLDH-Ce_x催化剂煅烧后的XRD谱图

Figure 2 XRD patterns of CuLDH-Ce_x catalysts after calcination

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图 3 CuLDH-Ce_x 催化剂煅烧后的SEM图片

Figure 3 SEM images of CuLDH-Ce_x catalysts after calcination

(a): CuLDO-Ce0; (b): CuLDO-Ce0.1; (c): CuLDO-Ce0.3; (d): CuLDO-Ce0.5; (e): CuLDO-Ce0.7.

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图 4 CuLDH-Ce_x催化剂的（a）N₂吸附-脱附等温线和(b)孔径分布

Figure 4 (a) N₂ adsorption-desorption isotherm and (b) pore size distribution of CuLDH-Ce_x catalysts

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图 5 CuLDH-Ce_x 催化剂还原后的TEM图和CuLDO-Ce0.3 的EDX元素图

Figure 5 TEM images of CuLDH-Ce_x catalysts after reduction and EDX elemental mapping of CuLDO-Ce0.3 (a): CuLDO-Ce0; (b): CuLDO-Ce0.1; (c): CuLDO-Ce0.3; (d): CuLDO-Ce0.5; (e): CuLDO-Ce0.7.

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图 6 CuLDH-Ce_x催化剂还原后的XPS谱图

Figure 6 XPS spectra of CuLDH-Ce_x catalysts after reduction

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图 7 CuLDH-Ce_x催化剂的H₂-TPR谱图

Figure 7 H₂-TPR profiles of CuLDH-Ce_x catalysts

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图 8 CuLDH-Ce_x催化剂的CO₂-TPD谱图

Figure 8 CO₂-TPD profiles of CuLDH-Ce_x catalysts

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图 9 CuLDH-Ce_x催化剂的催化活性

Figure 9 Catalytic performance of CuLDH-Ce_x catalysts Reaction condition: 240 ℃, 2.5 MPa, 9000 mL/(g·h).

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图 10 CuLDH-Ce0.3催化剂的催化性能随时间的变化(a), 反应前后的XRD谱图 (b)和反应后的TEM图（c）

Figure 10 Catalytic performance of CuLDH-Ce0.3 catalyst over time (a), XRD patterns before and after reaction (b), and TEM images after reaction (c) Reaction condition: 240 ℃, 2.5 MPa, 9000 mL/(g·h).

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图 11 CuLDH-Ce0.3催化剂在CO₂加氢过程中中间物种浓度的原位红外光谱谱图

Figure 11 In-situ infrared spectra of intermediate species concentration during CO₂ hydrogenation on CuLDH-Ce0.3 catalyst

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表 1 CuLDH-Ce_x催化剂的物理化学性质

Table 1 Physical and chemical properties of CuLDH-Ce_x catalysts

Catalyst	Molar ratio Cu/Mg/Al/Ce^a	S_BET^b/ (m²·g⁻¹)	v_p^b/ (cm³·g⁻¹)	d_p^b/ nm	d_Cu ^c/ nm	d_Cu^d / %	S_Cu^d/ (m²·g⁻¹)
CuLDH-Ce0	9.9/29.7/10.4/0	199.5	0.41	6.2	4.9	23.5	32.1
CuLDH-Ce0.1	10.2./29.9/9.8/1.1	208.4	0.47	7.3	3.7	26.3	35.4
CuLDH-Ce0.3	10.1/30.3/9.7/2.9	205.6	0.43	6.5	4.5	24.2	33.2
CuLDH-Ce0.5	9.8/29.8/10.2/5.2	194.9	0.35	5.3	5.2	20.4	29.6
CuLDO-Ce0.7	10.3/29.7/9.9/7.1	182.3	0.31	4.4	7.2	18.1	25.3
^a: Measured by ICP; ^b: Calculated by BET and BJH equations; ^c: Measured by TEM; ^d: Measured by N₂O titration.

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表 2 CuLDH-Ce_x催化剂碱性位点密度

Table 2 The basic sites density of CuLDH-Ce_x catalysts

Catalyst	Total basic sites/ (μmol·g⁻¹)	Weakly basic sites/ (μmol·g⁻¹)	Moderately basic sites/ (μmol·g⁻¹)	Density of moderately basic site/ (μmol·m²)
CuLDH-Ce0	232.8	55.7	177.1	0.89
CuLDH-Ce0.1	256.5	23.2	233.3	1.12
CuLDH-Ce0.3	297.2	34.5	262.7	1.28
CuLDH-Ce0.5	210.3	48.8	161.5	0.83
CuLDO-Ce0.7	198.6	64.3	134.3	0.74

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