碱/碱土金属修饰Ni基催化剂的CO2吸附与甲烷化性能

doi:10.16085/j.issn.1000-6613.2020-2553

摘要/Abstract

摘要：

采用分步浸渍法制备了碱/碱土金属修饰Ni基催化剂Ni-M/Al₂O₃ (M=K₂CO₃, Na₂CO₃, MgO, CaO)。探究了碱/碱土金属的添加对改性Ni基催化剂CO₂吸附和甲烷化性能的影响。研究发现，碱/碱土金属的添加提高了Ni/Al₂O₃催化剂表面的碱性活性位点密度，强化了其CO₂吸附性能。碱/碱土金属类型影响Ni-M/Al₂O₃催化剂碱性活性位点的分布、NiO物相的转化及Ni的分散度，进而影响其甲烷化性能。MgO添加使NiO物相转化为与载体呈强相互作用的β型和γ型NiO，降低了催化剂表面的强碱性活性位点比例，有利于CO₂吸附活化。Ni-MgO/Al₂O₃的CO₂吸附容量最高为0.68mmolCO₂/g，其CO₂转化率和CH₄选择性分别高达58.4%和95.4%，其在烟气CO₂捕集与原位甲烷化中极具应用前景。

关键词: 碱/碱土金属, 催化剂, CO₂捕集, 加氢, 甲烷化, 选择性

Abstract:

A series of nickel-based catalysts modified with alkali/alkaline-earth metals (Ni-M/Al₂O₃, M= K₂CO₃, Na₂CO₃, MgO, CaO) were prepared by step impregnation method. Effects of the doped alkali/alkaline-earth metals on CO₂ adsorption and methanation performance of the modified Ni-M/Al₂O₃ catalysts were investigated. Doping alkali/alkaline-earth metals increased the surface density of basic active sites of Ni/Al₂O₃ catalyst and therefore enhanced the CO₂ adsorption capacity. The doped alkali/alkaline-earth metals could also affect the distribution of the surface basic active sites, the transformation of NiO phase and the dispersion of Ni on the support, and therefore the Ni-M/Al₂O₃ catalysts exhibited different methanation performance. MgO doping would promote the transformation of NiO to β- and γ-type NiO phases, which exhibited strong interaction with the support. Besides, MgO doping reduced the proportion of strong basic active sites, which could be favorable for CO₂ adsorption and activation. Amongst the Ni-M/Al₂O₃ catalysts, Ni-MgO/Al₂O₃ exhibited the highest CO₂ adsorption capacity of 0.68 mmol CO₂/g, the maximum CO₂ conversion of 58.4% and the greatest CH₄ selectivity of 95.4%. The Ni-MgO/Al₂O₃catalyst showed potential application in CO₂ capture from flue gas and in-situ methanation.

Key words: alkali/alkaline-earth metals, catalysts, CO₂ capture, hydrogenation, CO₂ methanation, selectivity

中图分类号:

TK09

王国栋, 郭亚飞, 李佳媛, 姚睿璇, 孙健, 赵传文. 碱/碱土金属修饰Ni基催化剂的CO₂吸附与甲烷化性能[J]. 化工进展, 2021, 40(12): 6925-6933.

WANG Guodong, GUO Yafei, LI Jiayuan, YAO Ruixuan, SUN Jian, ZHAO Chuanwen. CO₂ adsorption and methanation performance of nickel-based catalysts modified with alkali/alkaline-earth metals[J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6925-6933.

图/表 12

参考文献 39

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催化剂	比表面积/m²?g^-1	孔体积/cm³?g^-1	平均孔径/nm
Ni-K₂CO₃/Al₂O₃	88.1	0.19	7.6
Ni-Na₂CO₃/Al₂O₃	91.7	0.19	7.9
Ni-MgO/Al₂O₃	52.0	0.14	9.4
CaO-Ni/Al₂O₃	85.2	0.18	8.1
Ni/Al₂O₃	121.8	0.26	7.4

催化剂	比表面积/m²?g^-1	孔体积/cm³?g^-1	平均孔径/nm
Ni-K₂CO₃/Al₂O₃	88.1	0.19	7.6
Ni-Na₂CO₃/Al₂O₃	91.7	0.19	7.9
Ni-MgO/Al₂O₃	52.0	0.14	9.4
CaO-Ni/Al₂O₃	85.2	0.18	8.1
Ni/Al₂O₃	121.8	0.26	7.4

催化剂	温度/℃			耗氢量/%
催化剂	α	β	γ	α	β	γ
NiO/Al₂O₃	493	630	—	81.1	18.9	—
Ni-CaO/Al₂O₃	501	—	746	81.7	—	18.3
Ni-MgO/Al₂O₃	—	683	763	—	59.0	41.0
Ni-Na₂CO₃/Al₂O₃	457	549/709	—	59.2	40.8	—
Ni-K₂CO₃/Al₂O₃	433	709	—	81.1	18.9	—

催化剂	温度/℃			耗氢量/%
催化剂	α	β	γ	α	β	γ
NiO/Al₂O₃	493	630	—	81.1	18.9	—
Ni-CaO/Al₂O₃	501	—	746	81.7	—	18.3
Ni-MgO/Al₂O₃	—	683	763	—	59.0	41.0
Ni-Na₂CO₃/Al₂O₃	457	549/709	—	59.2	40.8	—
Ni-K₂CO₃/Al₂O₃	433	709	—	81.1	18.9	—

催化剂	H₂吸附量 /mL?g^-1	Ni分散度 /%	Ni活性比表面积 /m²?g^-1
Ni-K₂CO₃/Al₂O₃	0.59	3.1	20.7
Ni-Na₂CO₃/Al₂O₃	0.64	3.3	22.2
Ni-MgO/Al₂O₃	0.71	3.7	24.9
Ni-CaO/Al₂O₃	0.68	3.5	23.8
Ni/Al₂O₃	0.93	4.9	32.6

碱/碱土金属修饰Ni基催化剂的CO₂吸附与甲烷化性能

CO₂ adsorption and methanation performance of nickel-based catalysts modified with alkali/alkaline-earth metals

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催化剂	弱碱性位点（<200℃）/%	中碱性位点（200~420℃）/%	强碱性位点（>450℃）/%	碱性位点密度/μmol?m^-2
Ni-K₂CO₃/Al₂O₃	39.8	26.7	33.5	3.7
Ni-Na₂CO₃/Al₂O₃	15.5	54.5	30.0	3.7
Ni-MgO/Al₂O₃	23.7	64.6	11.7	3.6
Ni-CaO/Al₂O₃	12.5	63.4	24.1	3.3
Ni/Al₂O₃	34.7	23.9	41.4	2.1

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