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

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

Abstract

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

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

CLC Number:

TK09

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.

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.

Figures/Tables 12

References 39

1	LEE S C, CHO M S, JUNG S Y, et al. Effects of alumina phases on CO₂ sorption and regeneration properties of potassium-based alumina sorbents[J]. Adsorption, 2014, 20(2/3): 331-339.
2	MEUL S, DAMERIS M, LANGEMATZ U, et al. Impact of rising greenhouse gas concentrations on future tropical ozone and UV exposure[J]. Geophysical Research Letters, 2016, 43(6): 2919-2927.
3	DOWELL N MAC, FENNELL P S, SHAH N, et al. The role of CO₂ capture and utilization in mitigating climate change[J]. Nature Climate Change, 2017, 7(4): 243-249.
4	GÖTZ M, LEFEBVRE J, MÖRS F, et al. Renewable power-to-gas: a technological and economic review[J]. Renewable Energy, 2016, 85: 1371-1390.
5	CIMINO S, BOCCIA F, LISI L. Effect of alkali promoters (Li, Na, K) on the performance of Ru/Al₂O₃ catalysts for CO₂ capture and hydrogenation to methane[J]. Journal of CO₂ Utilization, 2020, 37: 195-203.
6	AZIZ M A A, JALIL A A, TRIWAHYONO S, et al. CO₂ methanation over heterogeneous catalysts: recent progress and future prospects[J]. Green Chemistry, 2015, 17(5): 2647-2663.
7	GHAIB K, NITZ K, BEN-FARES F Z. Chemical methanation of CO₂: a review[J]. ChemBioEng Reviews, 2016, 3(6): 266-275.
8	GAO J J, WANG Y L, PING Y, et al. A thermodynamic analysis of methanation reactions of carbon oxides for the production of synthetic natural gas[J]. RSC Advances, 2012, 2(6): 2358.
9	孟凡会, 常慧蓉, 李忠. Ni-Mn/Al₂O₃催化剂在浆态床中CO甲烷化催化性能[J]. 化工学报, 2014, 65(8): 2997-3003.
	MENG F H, CHANG H R, LI Z. Catalytic performance of Ni-Mn/Al₂O₃ catalyst for CO methanation in slurry-bed reactor[J]. CIESC Journal, 2014, 65(8): 2997-3003.
10	GAO J J, LIU Q, GU F N, et al. Recent advances in methanation catalysts for the production of synthetic natural gas[J]. RSC Advances, 2015, 5(29): 22759-22776.
11	FRONTERA P, MACARIO A, FERRARO M, et al. Supported catalysts for CO₂ methanation: a review[J]. Catalysts, 2017, 7(12): 59.
12	REN J, QIN X, YANG J Z, et al. Methanation of carbon dioxide over Ni-M/ZrO₂ (M = Fe, Co, Cu) catalysts: effect of addition of a second metal[J]. Fuel Processing Technology, 2015, 137: 204-211.
13	ALDANA P A U, OCAMPO F, KOBL K, et al. Catalytic CO₂ valorization into CH₄ on Ni-based ceria-zirconia. Reaction mechanism by operando IR spectroscopy[J]. Catalysis Today, 2013, 215: 201-207.
14	WANG S D, PAN Q S, PENG J X, et al. In situ FTIR spectroscopic study of the CO₂ methanation mechanism on Ni/Ce_0.5Zr_0.5O₂[J]. Catalysis Science and Technology, 2014, 4(2): 502-509.
15	WANG W, GONG J L. Methanation of carbon dioxide: an overview[J]. Frontiers of Chemical Science and Engineering, 2011, 5(1): 2-10.
16	王东旭, 肖显斌, 高静, 等. 助剂钾对镍基催化剂性能影响研究进展[J]. 化工进展, 2014, 33(3): 668-672.
	WANG D X，XIAO X B，GAO J，et al. A review of potassium promoter effect on nickel-based catalyst performance[J]. Chemical Industry and Engineering Progress, 2014, 33(3): 668-672.
17	OSAKI T, MORI T. Role of potassium in carbon-free CO₂ reforming of methane on K-promoted Ni/Al₂O₃ catalysts[J]. Journal of Catalysis, 2001, 204(1): 89-97.
18	ANG M L, OEMAR U, SAW E T, et al. Highly active Ni/xNa/CeO₂ catalyst for the water-gas shift reaction: effect of sodium on methane suppression[J]. ACS Catalysis, 2014, 4(9): 3237-3248.
19	XU L L, WANG F G, CHEN M D, et al. Alkaline-promoted Ni based ordered mesoporous catalysts with enhanced low-temperature catalytic activity toward CO₂ methanation[J]. RSC Advances, 2017, 7(30): 18199-18210.
20	TAN J J, WANG J M, ZHANG Z Y, et al. Highly dispersed and stable Ni nanoparticles confined by MgO on ZrO₂ for CO₂ methanation[J]. Applied Surface Science, 2019, 481: 1538-1548.
21	GUO M, LU G X. The difference of roles of alkaline-earth metal oxides on silica-supported nickel catalysts for CO₂ methanation[J]. RSC Advances, 2014, 4(102): 58171-58177.
22	YANG W, FENG Y Y, CHU W. Promotion effect of CaO modification on mesoporous Al₂O₃-supported Ni catalysts for CO₂ methanation[J]. International Journal of Chemical Engineering, 2016, 2016: 1-7.
23	CHENG C B, SHEN D K, XIAO R, et al. Methanation of syngas (H₂/CO) over the different Ni-based catalysts[J]. Fuel, 2017, 189: 419-427.
24	ZHANG L J, BIAN L, ZHU Z T, et al. La-promoted Ni/Mg-Al catalysts with highly enhanced low-temperature CO₂ methanation performance[J]. International Journal of Hydrogen Energy, 2018, 43(4): 2197-2206.
25	BERMEJO-LÓPEZ A, PEREDA-AYO B, GONZÁLEZ-MARCOS J A, et al. Ni loading effects on dual function materials for capture and in situ conversion of CO₂ to CH₄ using CaO or Na₂CO₃[J]. Journal of CO₂ Utilization, 2019, 34: 576-587.
26	BERMEJO-LÓPEZ A, PEREDA-AYO B, GONZÁLEZ-MARCOS J A, et al. Mechanism of the CO₂ storage and in situ hydrogenation to CH₄. Temperature and adsorbent loading effects over Ru-CaO/Al₂O₃ and Ru-Na₂CO₃/Al₂O₃ catalysts[J]. Applied Catalysis B: Environmental, 2019, 256: 117845.
27	JIMÉNEZ-GONZÁLEZ C, BOUKHA Z, DE RIVAS B, et al. Behavior of coprecipitated NiAl₂O₄/Al₂O₃ catalysts for low-temperature methane steam reforming[J]. Energy & Fuels, 2014, 28(11): 7109-7121.
28	ZHOU L, LI L D, WEI N N, et al. Corrigendum: effect of NiAl₂O₄ formation on Ni/Al₂O₃ stability during dry reforming of methane[J]. ChemCatChem, 2015, 7(16): 2406.
29	ZHAO A M, YING W Y, ZHANG H T, et al. Ni-Al₂O₃ catalysts prepared by solution combustion method for syngas methanation[J]. Catalysis Communications, 2012, 17: 34-38.
30	HU D C, GAO J J, PING Y, et al. Enhanced investigation of CO methanation over Ni/Al₂O₃ catalysts for synthetic natural gas production[J]. Industrial & Engineering Chemistry Research, 2012, 51(13): 4875-4886.
31	CUI D M, LIU J, YU J, et al. Necessity of moderate metal-support interaction in Ni/Al₂O₃ for syngas methanation at high temperatures[J]. RSC Advances, 2015, 5(14): 10187-10196.
32	SONG K H, YAN X, KOH D J, et al. La effect on the long-term durability of Ni-Mg-Al₂O₃ catalysts for syngas methanation[J]. Applied Catalysis A: General, 2017, 530: 184-192.
33	XU L L, YANG H M, CHEN M D, et al. CO₂ methanation over Ca doped ordered mesoporous Ni-Al composite oxide catalysts: the promoting effect of basic modifier[J]. Journal of CO₂ Utilization, 2017, 21: 200-210.
34	SONG G, DING Y D, ZHU X, et al. Carbon dioxide adsorption characteristics of synthesized MgO with various porous structures achieved by varying calcination temperature[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2015, 470: 39-45.
35	ASHOK J, KATHIRASER Y, ANG M L, et al. Bi-functional hydrotalcite-derived NiO-CaO-Al₂O₃ catalysts for steam reforming of biomass and/or tar model compound at low steam-to-carbon conditions[J]. Applied Catalysis B: Environmental, 2015, 172/173: 116-128.
36	TAN C, GUO Y F, SUN J, et al. Structurally improved MgO adsorbents derived from magnesium oxalate precursor for enhanced CO₂ capture[J]. Fuel, 2020, 278: 118379.
37	PAN Q S, PENG J X, SUN T J, et al. CO₂ methanation on Ni/Ce_0.5Zr_0.5O₂ catalysts for the production of synthetic natural gas[J]. Fuel Processing Technology, 2014, 123: 166-171.
38	SHOKROLLAHI Y M, RADFARNIA H R, ILIUTA M C. High temperature CO₂ sorbents and their application for hydrogen production by sorption enhanced steam reforming process[J]. Chemical Engineering Journal, 2016, 283: 420-444.
39	ZHOU Z J, SUN N N, WANG B D, et al. 2D-layered Ni-MgO-Al₂O₃ nanosheets for integrated capture and methanation of CO₂[J]. ChemSusChem, 2020, 13(2): 360-368.

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

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

碱/碱土金属修饰Ni基催化剂的CO₂吸附与甲烷化性能

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Figures/Tables 12

References 39

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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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