水热合成时间对Cu/Ce-Zr催化水气变换反应性能的影响

康玉姝; 王丽宝; 李永志; 白金; 张财顺; 刘道胜; 张磊; 高志贤

doi:10.19906/j.cnki.JFCT.2022074

水热合成时间对Cu/Ce-Zr催化水气变换反应性能的影响

doi: 10.19906/j.cnki.JFCT.2022074

康玉姝^1,,
王丽宝^{1, 2},
李永志³,
白金¹,
张财顺¹,
刘道胜¹,
张磊^1, ,,
高志贤^1, ,

1.
辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
2.
中国石化石家庄炼化公司化工运行部, 河北石家庄 050099
3.
沈阳市生态环境事务服务经济开发区分中心, 辽宁沈阳 110000

基金项目: 国家自然科学基金(21673270)和辽宁省教育厅科学研究经费项目(L2019012)资助

详细信息

通讯作者:
E-mail: lnpuzhanglei@163.com

gaozx@lnpu.edu.cn

中图分类号: O643
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出版历程
- 收稿日期: 2022-06-10
- 修回日期: 2022-09-10
- 录用日期: 2022-09-20
- 网络出版日期: 2022-09-26
- 刊出日期: 2023-06-15

Effect of hydrothermal synthesis time on the performance of Cu/Ce-Zr catalysts for catalytic water-gas shift reaction

1.
School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China
2.
Chemical Operation Department, Sinopec Shijiazhuang Refining and Chemical Company, Shijiazhuang 050099, China
3.
Shenyang Ecological and Environmental Affairs Service Economic Development Zone sub-center, Shenyang 110000, China

Funds: The project was supported by the National Natural Science Foundation of China (21673270) and the Scientific Research Funds project of Education Department of Liaoning Province (L2019012)

摘要

摘要: 以硝酸盐为铈、锆原料，以柠檬酸代替碱类沉淀剂，固定n(Zr∶Ce)为2∶8，采用水热法合成Ce-Zr氧化物载体，再通过浸渍法制备Cu/Ce-Zr催化剂。通过XRD、BET、H₂-TPR、XPS等手段对载体和催化剂进行表征，研究水热时间对催化剂结构、性质和水气变换反应性能的影响。结果表明，催化活性主要与Cu比表面积、CuO的还原温度以及催化剂表面氧空位含量有关。其中，Cu/Ce-Zr-12催化剂的Cu比表面积较大、CuO的还原温度较低，催化剂表面的氧空位数量较多，表现出较好的催化活性。在320 ℃、水气比(W∶M)为2，体积空速GHSV=6600 h⁻¹的反应条件下，CO转化率为96.9%，与热力学平衡值97.1%接近。
- 水热法 /
- 水热时间 /
- 水气变换 /
- CeO₂-ZrO₂固溶体
Abstract: Ce-Zr oxide support was hydrothermally synthesized from metal nitrates of cerium and zirconium as the raw materials using citric acid instead of alkali precipitant, and then Cu/Ce-Zr catalyst was prepared by the impregnation method. The support and catalyst samples were characterized by XRD, BET, H₂-TPR, XPS techniques, and the effects of different hydrothermal time on the structure, properties and performance in water-gas shift reaction were investigated. The results show that the catalyst activity is mainly related to the Cu specific surface area, reduction temperature of CuO and the number of oxygen vacancies on the catalyst surface. Among them, the Cu/Ce-Zr catalyst with hydrothermal time of 12 h has a large Cu specific surface area, a lower reduction temperature of CuO, and a large number of oxygen vacancies, so it shows a good catalytic activity. When the reaction temperature is 320 ℃, the molar ratio of water to gas (W/M) is 2, and the gas space velocity GHSV=6600 h⁻¹, the CO conversion rate is 96.9%, which is close to the thermodynamic equilibrium value of 97.1%.
- hydrothermal method /
- hydrothermal time /
- water gas shift /
- CeO₂-ZrO₂ solid solution

HTML全文

FIG. 2382. FIG. 2382.

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图 1 Ce-Zr-t载体的XRD谱图

Figure 1 XRD patterns of Ce-Zr-t

a:CeO₂; b: Ce-Zr-6; c: Ce-Zr-9; d: Ce-Zr-12; e: Ce-Zr-15

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图 2 Cu/Ce-Zr-t催化剂的XRD谱图

Figure 2 XRD patterns of Cu/Ce-Zr-t

a: Cu/Ce; b: Cu/Ce-Zr-6; c:Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

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图 3 Cu/Ce-Zr-t催化剂的H₂-TPR谱图

Figure 3 H₂-TPR spectra of Cu/Ce-Zr-t catalysts

a: CeO₂; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

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图 4 Cu/Ce-Zr-t催化剂的Ce 3d XPS谱图

Figure 4 Ce 3d XPS spectra of Cu/Ce-Zr-t catalysts

a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

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图 5 Cu/Ce-Zr-t催化剂的O 1s XPS谱图

Figure 5 O 1s XPS spectra of Cu/Ce-Zr-t catalysts

a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

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图 6 Cu/Ce-Zr-t催化剂的Cu 2p XPS谱图

Figure 6 Cu 2p XPS spectra of Cu/Ce-Zr-t catalysts

a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

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图 7 Cu/Ce-Zr-t催化剂的Cu LMM XPS谱图

Figure 7 Cu LMM XPS spectra of Cu/Ce-Zr-t catalysts

a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15

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图 8 Cu/Ce-Zr-t催化剂的Zr 3d XPS谱图

Figure 8 Zr 3d XPS spectra of Cu/Ce-Zr-t catalysts

a: Cu/Ce-Zr-6; b: Cu/Ce-Zr-9; c: Cu/Ce-Zr-12; d: Cu/Ce-Zr-15

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图 9 反应温度对催化活性的影响

Figure 9 Effect of reaction temperature on catalytic activity (reaction conditions: GHSV=6600 h⁻¹, n(H₂O)/n(CO)=2∶1, no carrier gas)

a: Cu/Ce; b: Cu/Ce-Zr-6; c: Cu/Ce-Zr-9; d: Cu/Ce-Zr-12; e: Cu/Ce-Zr-15; f: thermodynamic equilibrium

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表 1 Ce-Zr-t和Cu/Ce-Zr-t的物化性质

Table 1 Physical and chemical properties of Ce-Zr-t and Cu/Ce-Zr-t

Catalyst	Cell parameters /nm	S_BET /(m²·g⁻¹)	Pore volume /(mL·g⁻¹)	Cu surface area^a /(m²·g⁻¹)
CeO₂	0.54075	23.9	0.08	−
Ce-Zr-6	0.53881	71.5	0.13	−
Ce-Zr-9	0.54017	76.8	0.14	−
Ce-Zr-12	0.53875	69.2	0.15	−
Ce-Zr-15	0.54026	61.8	0.10	−
Cu/Ce	0.54073	21.2	0.07	1.5
Cu/Ce-Zr-6	0.53871	56.9	0.11	3.7
Cu/Ce-Zr-9	0.53944	60.6	0.12	4.9
Cu/Ce-Zr-12	0.53732	58.8	0.14	5.5
Cu/Ce-Zr-15	0.53926	50.2	0.09	3.5
^a: determined by N₂O experiments

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表 2 CuO还原峰位置

Table 2 Reduction peak positions of CuO

Catalyst	Peak position t/℃
Catalyst	peak α	peak β
Cu/Ce-Zr-6	156	182
Cu/Ce-Zr-9	155	181
Cu/Ce-Zr-12	144	171
Cu/Ce-Zr-15	157	189

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表 3 催化剂Ce 3d和O 1s的XPS曲线拟合

Table 3 XPS curve fitting results of catalysts Ce 3d and O 1s

Catalyst	Ce³⁺/(Ce³⁺ + Ce⁴⁺)/%	O_ads/(O_lat + O_ads)/%
Cu/Ce	24.2	28.2
Cu/Ce-Zr-6	21.9	26.7
Cu/Ce-Zr-9	24.4	28.7
Cu/Ce-Zr-12	28.6	31.1
Cu/Ce-Zr-15	18.3	24.5

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