Ni-Co、Ni-Cu双金属合金催化剂用于CO甲烷化

李晶; 刘贵龙; 王嘉明; 刘源

Ni-Co、Ni-Cu双金属合金催化剂用于CO甲烷化

李晶¹,
刘贵龙²,
王嘉明¹,
刘源^1, ,

1.
天津大学化工学院, 天津 300350
2.
洛阳师范学院化学化工学院, 河南洛阳 471934

基金项目:

国家自然科学基金 51904152

国家自然科学基金 21872101

国家自然科学基金 21576192

国家自然科学基金 21962014

详细信息

通讯作者:
刘源Tel: 13702112319, E-mail：yuanliu@tju.edu.cn

中图分类号: O643.38
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- 文章访问数: 224
- HTML全文浏览量: 70
- PDF下载量: 21
- 被引次数: 0
出版历程
- 收稿日期: 2020-02-20
- 修回日期: 2020-04-20
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-05-10

Ni-Co and Ni-Cu bimetallic alloy catalysts for CO methanation

1.
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China
2.
School of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, China

Funds:

the National Natural Science Foundation of China 51904152

the National Natural Science Foundation of China 21872101

the National Natural Science Foundation of China 21576192

the National Natural Science Foundation of China 21962014

摘要

摘要: 以钙钛矿型复合氧化物LaNi_0.9Co_0.1O₃和LaNi_0.9Cu_0.1O₃为前驱体制备了Ni-Co/La₂O₃和Ni-Cu/La₂O₃双金属合金催化剂。结果表明，双金属合金催化剂中，各组分间相互稀释，具有较强的抗烧结性能；催化剂表面的积炭主要取决于CO在催化剂表面的吸附形态，Ni-Co双金属催化剂中，Co掺杂改变了CO在催化剂表面的吸附形式和吸附强度，使得Ni-Co双金属催化剂具有较强的抗积炭性能。Ni-Co双金属合金催化剂用于CO甲烷化反应时，显现出较好的活性、选择性和稳定性。
- 一氧化碳甲烷化 /
- 钙钛矿型氧化物 /
- 镍 /
- 双金属 /
- 合金催化剂
Abstract: Ni-Co/La₂O₃ and Ni-Cu/La₂O₃ bimetallic alloy catalysts were prepared by using LaNi_0.9Co_0.1O₃ and LaNi_0.9Cu_0.1O₃ perovskite-type oxides precursors. The results demonstrate that the components are diluted with each other in the bimetallic alloy catalyst and exhibit strong anti-sintering ability. The carbon deposited on the catalyst surface mainly depends on the adsorption state of CO, the modulated adsorption state and adsorption strength of CO contribute to the strong anti-carbon deposition ability of the Ni-Co bimetallic catalysts. The Ni-Co bimetallic alloy catalysts show remarkable activity, selectivity, and stability in the CO methanation reaction.
- CO methanation /
- perovskite oxide /
- nickel /
- bi-metal /
- alloy catalyst

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图 1 LaNiO₃、LaNi_0.9Co_0.1O₃和LaNi_0.9Cu_0.1O₃前驱体的H₂-TPR谱图

Figure 1 ₂-TPR profiles of the LaNiO₃, LaNi_0.9Co_0.1O₃ and LaNi_0.9Cu_0.1O₃ precursors

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图 2 LaNiO₃、LaNi_0.9Co_0.1O₃和LaNi_0.9Cu_0.1O₃前驱体(a)、还原后(b)和活性测试后(c)的XRD谱图; (c)图在2θ=43.5°-45.5°的局部放大图(d)

Figure 2 XRD patterns of the LaNiO₃, LaNi_0.9Co_0.1O₃ and LaNi_0.9Cu_0.1O₃ precursor (a), after reduction (b) and after reaction (c); the enlarged partial view of (c) with 2θ value between 43.5°-45.5° (d)

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图 3 N/L、NCo/L和NCu/L催化剂还原后的La 3d和Ni 2p的XPS谱图(a)；NCo/L催化剂还原后的Co 2p的XPS谱图(b)；NCu/L催化剂还原后的Cu 2p的XPS谱图(c)

Figure 3 XPS spectra for La 3d and Ni 2p of the N/L, NCo/L and NCu/L catalysts after reduction (a); XPS spectra for Co 2p of NCo/L after reduction (b); XPS spectra for Cu 2p of NCu/L catalysts after reduction (c)

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图 4 N/L、NCo/L和NCu/L催化剂的CO-TPD谱图

Figure 4 CO-TPD profiles of the N/L, NCo/L and NCu/L catalysts

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图 5 N/L、NCo/L和NCu/L催化剂的催化性能

Figure 5 Catalytic performance of the N/L, NCo/L and NCu/L catalysts reaction conditions: GHSV of 15000mL/(g_cat·h), H₂/CO/N₂=3:1:1, atmospheric pressure

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图 6 N/L、NCo/L和NCu/L催化剂的稳定性

Figure 6 Stability test of the N/L, NCo/L and NCu/L catalysts reaction conditions: 600℃, GHSV of 15000mL/(g_cat·h), H₂/CO/N₂=3:1:1, atmospheric pressure

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图 7 稳定性测试后N/L、NCo/L和NCu/L催化剂的催化性能

Figure 7 Catalytic performance of the N/L, NCo/L and NCu/L catalysts after the stability tests reaction conditions: GHSV of 15000mL/(g_cat·h), H₂/CO/N₂=3:1:1, atmospheric pressure

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图 8 N/L、NCo/L和NCu/L稳定性测试后样品的TG曲线

Figure 8 TG results of the N/L, NCo/L and NCu/L catalytst after the stability tests

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表 1 LaNiO₃、LaNi_0.9Co_0.1O₃和LaNi_0.9Cu_0.1O₃前驱体的耗氢量

Table 1 H₂ consumption of the LaNiO₃, LaNi_0.9Co_0.1O₃ and LaNi_0.9Cu_0.1O₃ precursors

Sample	Experiment values/(μmol·(0.05 g_cat)^-1)^a		Theoretical values/(μmol·(0.05 g_cat)^-1)
Sample	T_L	T_H	Ni³⁺-Ni²⁺	Co³⁺-Co²⁺	Cu²⁺-Cu⁺	Ni²⁺-Ni⁰	Co²⁺-Co⁰	Cu⁺-Cu⁰
NO	102.0	202.7	101.8	-	-	203.6	-
NCoO	101.6	203.6	91.6	10.2	-	183.2	20.4
NCuO	101.6	192.3	91.4	-	10.15	182.9	-	10.15
^a: calculated by using the TPR peak area of pure CuO as benchmark

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表 2 N/L、NCo/L和NCu/L催化剂及其稳定性测试后的晶粒粒径

Table 2 Average crystalline size of the N/L, NCo/L and NCu/L catalysts before and after the stability tests

Sample	D_metal^a /nm		Degree of sintering^b/%
Sample	after reduction	after stability test	Degree of sintering^b/%
N/L	12.1	18.6	52.7
NCo/L	15.8	20.9	32.3
NCu/L	14.9	20.8	39.6
^a: calculated from XRD results with Scherrer formula:$D = k\lambda /\left( {\beta \cos \theta } \right) $; ^b: calculated from XRD results by the design formula:${\rm{De}}{{\rm{g}}_{{\rm{sinter}}}} = \frac{{\left( {{D_{{\rm{spent}}}} - {D_{{\rm{reduction}}}}} \right)}}{{{D_{{\rm{reduction}}}}}} $

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