Ni含量对NiO/CeO<sub>2</sub>催化剂催化CO氧化性能的影响

金石山; 张大山; 冯旭浩; 张财顺; 庆绍军; 张磊; 高志贤

doi:10.19906/j.cnki.JFCT.2022019

Ni含量对NiO/CeO₂催化剂催化CO氧化性能的影响

doi: 10.19906/j.cnki.JFCT.2022019

1.
辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
2.
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
3.
中国科学院山西煤炭化学研究所, 山西太原 030001

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: 2021-12-25
- 修回日期: 2022-02-08
- 录用日期: 2022-03-15
- 网络出版日期: 2022-03-25
- 刊出日期: 2022-08-26

Effect of Ni content on catalytic oxidation of CO over NiO/CeO₂ catalyst

1.
School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China
2.
No.3 Refinery of Fushun Petrochemical Company, CNPC, Fushun 113001, China
3.
Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, 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CeO₂为载体，Ni为活性组分，采用球磨法制备了低温条件下性能较好的CO氧化NiO/CeO₂催化剂。通过XRD、BET、H₂-TPR、XRF和XPS等技术对催化剂进行了表征，考察了镍含量对催化剂结构和CO低温氧化性能的影响。结果表明，不同Ni/Ce比主要影响催化剂表面晶格氧空位的数量以及活性组分和载体之间的相互作用。其中，Ni/Ce物质的量比为1∶9时，催化剂表面氧空位数量较多，因此，表现出优良的催化性能。在反应温度为200 ℃、氧过量系数为5、气体总空速为60000 mL/(g_cat·h)的条件下，CO转化率为99.2%。此外，与传统液相制备催化剂技术相比，球磨法具有污染小、成本低、易操作等特点，有利于节约能源。
- 球磨法 /
- CO氧化 /
- CeO₂ /
- 低温
Abstract: The NiO/CeO₂ catalytic materials were prepared with ball milling method using CeO₂ as carrier and Ni as active component with good CO oxidation performance at low temperature. The catalysts were characterized by XRD, BET, H₂-TPR, XRF and XPS. The effects of nickel content on the structure and low temperature oxidation performance of CO were investigated. The results show that the Ni-Ce ratio mainly affects the number of lattice oxygen vacancies and the interaction between the active ingredient and the carrier. Among them, When the Ni/Ce mole ratios is 1∶9, there are more oxygen vacancies on the surface of the catalyst, so it shows excellent catalytic performance. When the reaction temperature is 200 ℃, oxygen excess coefficient is 5 and the total space velocity is 60000 mL/(g_cat·h), the CO conversion reaches 99.2%. In addition, compared with the traditional liquid phase catalyst preparation technology, ball milling has the advantages of low pollution, low cost and easy operation, which is beneficial to save energy.
- method of ball mill /
- CO oxidation /
- CeO₂ /
- low temperature

HTML全文

FIG. 1773. FIG. 1773.

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图 1 NiO/CeO₂催化剂和参比样的XRD谱图

Figure 1 XRD patterns of the NiO/CeO₂ catalysts and reference sample a: CeO₂; b: NC-0.5; c: NC-1; d: NC-2

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图 2 NiO/CeO₂催化剂N₂吸附-脱附等温线

Figure 2 N₂ adsorption desorption and desorption isotherms of NiO/CeO₂ catalysts a: CeO₂; b: NC-0.5; c: NC-1; d: NC-2

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图 3 NiO/CeO₂催化剂的H₂-TPR谱图

Figure 3 H₂-TPR spectra of NiO/CeO₂ catalysts a: CeO₂; b: NC-0.5; c: NC-1; d: NC-2

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图 4 NiO/CeO₂催化剂的Ce 3d XPS谱图

Figure 4 Ce 3d XPS spectra of the NiO/CeO₂ catalysts a: CeO₂; b: NC-0.5; c: NC-1; d: NC-2

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图 5 NiO/CeO₂催化剂的O 1s XPS谱图

Figure 5 O 1s XPS spectra of the NiO/CeO₂ catalysts a: 0.5-NiO/CeO₂; b: 1-NiO/CeO₂; c: 2-NiO/CeO₂

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图 6 NiO/CeO₂催化剂的Ni 2p XPS谱图

Figure 6 Ni 2p XPS spectra of the NiO/CeO₂ catalysts a: 0.5-NiO/CeO₂; b: 1-NiO/CeO₂; c: 2-NiO/CeO₂

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图 7 NiO/CeO₂催化剂的CO转化率

Figure 7 CO conversion diagram of NiO/CeO₂ catalyst

a: CeO₂; b: NC-0.5; c: NC-1; d: NC-2; e: complete conversion

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表 1 NiO/CeO₂催化剂的XRD分析

Table 1 XRD data of NiO/CeO₂ catalysts

Sample	Cell parameter/nm	Crystallite size of CeO₂/nm
CeO₂	0.5410	22.0
NC-0.5	0.5408	21.9
NC-1	0.5399	20.9
NC-2	0.5409	20.8

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表 2 NiO/CeO₂催化剂的BET分析

Table 2 BET analysis of NiO/CeO₂ catalyst

Sample	S_BET/(m²·g⁻¹)	Pore size/nm
CeO₂	24.3	9.49
CeO₂	34.6	9.46
NC-0.5	36.1	12.85
NC-1	34.5	11.90
NC-2	32.3	9.18

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表 3 NiO/CeO₂催化剂的Ni元素含量

Table 3 Ni element content of NiO/CeO₂ catalyst

Sample	Target content of Ni/%	Ni content/%^a
CeO₂	−	−
NC-0.5	2.20	2.08
NC-1	4.06	3.76
NC-2	9.80	9.85
^a: determined by XRF experiment

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表 4 NiO/CeO₂催化剂还原峰位置

Table 4 Location of reduction peak of NiO/CeO₂ catalyst

Sample	Location of reduction peak /℃
Sample	α	β	γ	ε/ε^，	k/k^，
CeO₂	−	−	−	500	833
NC-0.5	182	246	294	453	831
NC-1	180	223	294	455	824
NC-2	187	249	327	456	830

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表 5 NiO/CeO₂催化剂中晶格氧含量

Table 5 Lattice oxygen content in NiO/CeO₂ catalyst

Catalyst	O_lat/(O_lat+O_ads)/%
0.5-NiO/CeO₂	60
1-NiO/CeO₂	77
2-NiO/CeO₂	55

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表 6 NC-1催化剂与同类文献的转化率对比

Table 6 Comparison of conversion rate between NC-1 catalyst and similar literatures

Sample	t/℃	GHSV(/mL·g_cat⁻¹·h⁻¹)	λ	Conversion/%
NC-1	200	60000	5	99.2
Meso-Ni_0.1Ce^[16]	200	120000	21	80.0
Ni-CeO₂ NRs^[15]	200	28800	10	10.0
Ce-Ni^[14]	200	30000	28	100.0

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