Cr掺杂对Cu-Ce复合催化剂催化甲醇水蒸气重整制氢的影响

王东哲; 王丽宝; 张磊; 庆绍军; 韩蛟; 张财顺; 高志贤; 冯旭浩

Cr掺杂对Cu-Ce复合催化剂催化甲醇水蒸气重整制氢的影响

1.
辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001
2.
中国科学院山西煤炭化学研究所, 山西太原 030001
3.
中国石油天然气股份有限公司抚顺石化分公司石油三厂, 辽宁抚顺 113001

基金项目:

国家自然科学基金 21376237

辽宁省教育厅科学研究经费项目 L2019038

辽宁省自然科学基金面上项目 2019-MS-221

辽宁省自然科学基金指导计划项目 2019-ZD-0371

详细信息

通讯作者:
张磊Email:lpuhangcie163.com

中图分类号: O643
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- 文章访问数: 317
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- 被引次数: 0
出版历程
- 收稿日期: 2020-03-30
- 修回日期: 2020-05-05
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-05-10

Effect of Cr doping on hydrogen production via methanol steam reforming over Cu-Ce composite catalysts

1.
College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, China
2.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
No.3 Refinery of Fushun Petrochemical Company of CNPC, Fushun 113001, China

Funds:

the National Natural Science Foundation of China 21376237

Scientific Research Fund Project of Liaoning Provincial Department of Education L2019038

General Program of Liaoning Natural Science Foundation 2019-MS-221

Guidance Project of Liaoning Natural Science 2019-ZD-0371

摘要

摘要: 采用浸渍法制备了不同Cr含量的Cr/Cu-Ce催化剂，通过N₂O滴定、H₂-TPR和XPS等表征，对其结构、性质和催化性能进行了探究。结果表明，Cr助剂会改变Cu-Ce催化剂的铜比表面积、CuO还原温度以及氧空穴含量。其中，添加3%Cr的催化剂的Cu比表面积较大，CuO还原温度较低，氧空穴较多，进而表现出优良的催化性能。当反应温度为533 K，n（水）：n（甲醇）=1.2：1，甲醇和水的进料量为0.072 mL/min时，其催化效率达100%，重整气体组分中的CO体积分数为0.15%。与未掺杂Cr助剂的催化剂相比，其催化效率提高了10%，重整气体组分中的CO体积分数降低了0.34%。
- Cr掺杂 /
- 氧空穴 /
- Cu-Ce催化剂 /
- 还原温度
Abstract: Cr/Cu-Ce catalyts with different Cr contents were prepared by impregnation method, and their structures, properties and catalytic performance were investigated using N₂O titration, H₂-TPR and XPS techniques. It is found that the Cr doping changs the specific surface area of copper, the reduction temperature of CuO and oxygen vacancies of the Cu-Ce catalysts. In addition, the catalyst with 3% Cr addition has larger Cu specific surface area, lower CuO reduction temperature and more oxygen vacancies, thus exhibits excellent catalytic performance. The catalytic efficiency reaches 100% and CO volume fraction in outlet gas is 0.15% when the reaction temperature is 533 K, n(water):n(methanol) is 1.2:1 and the feeding rate of methanol and water is 0.072 mL/min. Compared with the un-doped Cr catalyst, the catalytic efficiency increases by 10% and the volume fraction of CO in the outlet gas decreases by 0.34%.
- Cr content /
- oxygen vacancy /
- Cu-Ce catalyst /
- reduction temperature

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图 1 载体CeO₂的SEM照片

Figure 1 SEM image of the CeO₂ support

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图 2 未添加Cr和添加不同含量Cr的催化剂的XRD谱图

a: Cu-Ce; b: 1%Cr/Cu-Ce; c: 3%Cr/Cu-Ce; d: 5%Cr/Cu-Ce; e: 7%Cr/Cu-Ce

Figure 2 XRD spectra of the catalysts with no Cr addition and with different content of Cr

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图 3 未添加Cr和添加不同含量Cr的催化剂的H₂-TPR谱图

a: Cu-Ce; b: 1%Cr/Cu-Ce; c: 3%Cr/Cu-Ce; d: 5%Cr/Cu-Ce; e: 7%Cr/Cu-Ce

Figure 3 H₂-TPR profiles of the catalysts with no Cr addition and with different content of Cr

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图 7 催化效率随反应温度的变化

a: Cu-Ce; b: 1%Cr/Cu-Ce; c: 3%Cr/Cu-Ce; d: 5%Cr/Cu-Ce; e: 7%Cr/Cu-Ce; f: equilibrium

Figure 7 Relationship between the reaction temperature and catalytic efficiency

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图 4 未添加Cr和添加不同含量Cr的催化剂的Ce 3d谱图

a: Cu-Ce; b: 1%Cr/Cu-Ce; c: 3%Cr/Cu-Ce; d: 5%Cr/Cu-Ce; e: 7%Cr/Cu-Ce

Figure 4 Ce 3d spectra of the catalysts with and without Cr doping

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图 5 未添加Cr和添加不同含量Cr的催化剂的Cu 2p谱图

a: Cu-Ce; b: 1%Cr/Cu-Ce; c: 3%Cr/Cu-Ce; d: 5%Cr/Cu-Ce; e: 7%Cr/Cu-Ce

Figure 5 Cu 2p spectra of the catalysts with and without Cr doping

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图 6 添加不同Cr含量的催化材料的Cr 2p XPS谱图

a: 1%Cr/Cu-Ce; b: 3%Cr/Cu-Ce; c: 5%Cr/Cu-Ce; d: 7%Cr/Cu-Ce

Figure 6 Cr 2p XPS spectra of the catalysts with and without Cr doping

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图 8 反应温度对重整气中CO体积分数的影响

a: Cu-Ce; b: 1%Cr/Cu-Ce; c: 3%Cr/Cu-Ce; d: 5%Cr/Cu-Ce; e: 7%Cr/Cu-Ce; f: equilibrium

Figure 8 Effect of reaction temperature on volume fraction of CO in outlet gas

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图 9 3%Cr/Cu-Ce催化剂的稳定性

Figure 9 Stability test of the 3%Cr/CuO/CeO₂ catalyst

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表 1 不同Cr含量的催化剂中元素含量

Table 1 Elemental content of the catalysts with different Cr contents

Catalyst	Elemental content w/%
Catalyst	Cu	Ce	O	Cr^a	Cr^b
Cu-Ce	7.9	73.4	18.7	-	-
1%Cr/Cu-Ce	7.8	72.5	18.9	0.8	1.0
3%Cr/Cu-Ce	7.3	70.7	19.3	2.7	2.9
5%Cr/Cu-Ce	7.0	69.2	19.5	4.3	4.8
7%Cr/Cu-Ce	6.9	67.5	19.8	5.8	6.5
^a: test value; ^b: designed value

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表 2 催化剂的H₂产率和物化性质

Table 2 H₂ production rate and physicochemical properties of the catalysts

Catalyst	Surface areaA/(m²·g^-1)	Pore volumev/(cm³·g^-1)	d_CuO /nm	Cu dispersion /%	Cu surface area^aA/(m²·g^-1)	H₂ production rate^b /(cm³·g^-1·min^-1)
CeO₂	37.4	0.10	-	-	-	-
Cu-Ce	21.9	0.09	29.9	15.3	8.8	20.4
1%Cr/Cu-Ce	20.3	0.06	28.1	15.4	8.9	24.6
3%Cr/Cu-Ce	18.6	0.08	20.2	16.8	9.7	35.5
5%Cr/Cu-Ce	18.2	0.06	21.6	16.6	9.6	32.7
7%Cr/Cu-Ce	14.3	0.05	24.8	15.8	9.1	30.4
^a: measured by N₂O titration; ^b: reaction conducted at 533 K

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表 3 CuO还原温度

Table 3 CuO reduction temperature

Catalyst	Peak positionT/K
Catalyst	α	β	γ
Cu-Ce	451	495	522
1%Cr/Cu-Ce	445	492	523
3%Cr/Cu-Ce	423	478	508
5%Cr/Cu-Ce	436	490	524
7%Cr/Cu-Ce	441	479	503

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表 4 催化剂的Ce 3d拟合

Table 4 Ce 3d fitting results of the catalysts

Catalyst	Ce(III)/(Ce(III)+Ce(IV))/%
Cu-Ce	18.5
1%Cr/Cu-Ce	20.5
3%Cr/Cu-Ce	34.4
5%Cr/Cu-Ce	33.9
7%Cr/Cu-Ce	27.4

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表 5 催化剂的CO、CO₂以及H₂选择性

Table 5 Selectivity of CO, CO₂ and H₂

Catalyst	Selectivity^as/%
Catalyst	CO	CO₂	H₂
Cu-Ce	0.59	25.04	74.37
1%Cr/Cu-Ce	0.14	25.43	74.43
3%Cr/Cu-Ce	0.15	25.46	74.39
5%Cr/Cu-Ce	0.23	25.48	74.29
7%Cr/Cu-Ce	0.33	25.23	74.44
^a: reaction conducted at 533 K

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