Application of Ce1-xNixOy oxygen carriers in chemical-looping reforming of methane coupled with CO2 reduction

doi:10.11949/0438-1157.20201787

Abstract

Abstract:

Chemical-looping reforming of methane coupled with CO₂ reduction technology can not only produce syngas, but also reduce CO₂ to generate CO. In this paper, a series of Ce_1-_xNi_xO_y_{(x = 0, 0.2, 0.4, 0.6, 0.8, 1) oxygen carriers with different Ce/Ni molar ratios were prepared by co-precipitation method. The physical and chemical properties of oxygen carriers were characterized by means of XRD, BET, XPS and CH₄-TPR. The performance of Ce_1-_xNi_xO_y oxygen carriers in chemical-looping reforming of methane coupled with CO₂ reduction reaction was systematically investigated. Compared with single metal oxide NiO and CeO₂, Ce_1-_xNi_xO_y composite oxygen carriers have higher activity and thermal stability in this reaction. During the partial oxidation of methane, Ce_0.2Ni_0.8O_y and Ce_0.4Ni_0.6O_y oxygen carriers have higher CH₄ conversion. After 20 redox cycle experiments, the CO₂ conversion rate of the Ce_0.2Ni_0.8O_y oxygen carrier remained almost unchanged, indicating that the Ce_0.2Ni_0.8O_y oxygen carrier has high thermal stability.}

Key words: chemical-looping, reforming of methane, CO₂ reduction, syngas, Ce_1-_xNi_xO_y oxygen carriers

摘要：

化学链甲烷重整耦合CO₂还原技术既能生产合成气还可以还原CO₂生成CO。采用共沉淀法制备不同Ce/Ni摩尔比的系列Ce_1-_xNi_xO_y_{（x = 0,0.2,0.4,0.6,0.8,1）氧载体。通过XRD、BET、XPS及CH₄-TPR等表征对氧载体的理化性质进行了研究。系统考察了Ce_1-_xNi_xO_y氧载体在化学链甲烷重整耦合CO₂还原反应中的反应性能。与单一金属氧化物NiO和CeO₂相比，Ce_1-_xNi_xO_y复合氧载体在该反应中具有更高的活性和热稳定性。在甲烷部分氧化阶段，Ce_0.2Ni_0.8O_y和Ce_0.4Ni_0.6O_y氧载体具有较高的CH₄转化率。经历了20次redox循环实验，Ce_0.2Ni_0.8O_y氧载体的CO₂转化率几乎保持不变，表明Ce_0.2Ni_0.8O_y氧载体具有较高的热稳定性。}

关键词: 化学链, 甲烷重整, CO₂还原, 合成气, Ce_1-_xNi_xO_y氧载体

CLC Number:

TE 665

Linzhou ZHAO, Yan'e ZHENG, Kongzhai Li, Yaming WANG, Lihong JIANG, Haoxi FAN, Yajing WANG, Xing ZHU, Yonggang WEI. Application of Ce_1-_xNi_xO_y oxygen carriers in chemical-looping reforming of methane coupled with CO₂ reduction[J]. CIESC Journal, 2021, 72(8): 4371-4380.

赵林洲, 郑燕娥, 李孔斋, 王亚明, 蒋丽红, 范浩熙, 王雅静, 祝星, 魏永刚. Ce_1-_xNi_xO_y氧载体在化学链甲烷重整耦合CO₂还原中的应用[J]. 化工学报, 2021, 72(8): 4371-4380.

Figures/Tables 15

Fig.1 XRD patterns of Ce1-xNixOyoxygen carriers

Fig.2 Nitrogen adsorption-desorption isotherms (a) and pore-size distributions (b) of Ce1-xNixOy oxygen carriers

Table 1 The pore volumes， average pore diameter and BET surface areas of oxygen carriers

样品	孔体积/(cm³/g)	平均孔径/nm	比表面积/(m²/g)
NiO	0.031	10.725	11.45
Ce_0.2Ni_0.8O_y	0.120	16.092	29.59
Ce_0.4Ni_0.6O_y	0.079	13.857	22.74
Ce_0.6Ni_0.4O_y	0.070	13.726	20.25
Ce_0.8Ni_0.2O_y	0.054	9.989	21.53
CeO₂	0.056	16.015	13.97

Fig.3 XPS spectra of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers

Table 2 The relevant XPS parameters of Ce0.2Ni0.8Oyand Ce0.4Ni0.6Oy oxygen carriers

Ce³⁺/

Ce⁴⁺

Ni²⁺/Ni³⁺

Ce³⁺

Ce⁴⁺

Ni²⁺

Ni³⁺

Fig.4 CH4-TPR profiles of Ce1-xNixOyoxygen carriers

Fig.5 The gas content change of Ce1-xNixOy oxygen carriers in the CH4 isothermal reaction at 800℃

Fig.6 The gas content change of Ce1-xNixOy oxygen carriers in the CO2 reduction reaction at 800℃

Fig.7 H2 and CO contents change of Ce0.2Ni0.8Oy(a) and Ce0.4Ni0.6Oy(b) oxygen carriers in CH4 oxidation stage in 20 redox cycles

Fig.8 CO contents change of Ce0.2Ni0.8Oy(a) and Ce0.4Ni0.6Oy(b) oxygen carriers in CO2 reduction stage in 20 redox cycles

Fig.9 XRD patterns of oxygen carriers after 20 redox cycles

Fig.10 Nitrogen adsorption-desorption isotherms (a) and pore-size distributions (b) of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

Table 3 The pore volumes， average pore diameter and BET surface areas of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

样品	孔体积/(cm³/g)	平均孔径/nm	比表面积/(m²/g)
Ce_0.2Ni_0.8O_y	0.038	11.525	10.09
Ce_0.4Ni_0.6O_y	0.028	11.531	7.24

Fig.11 XPS spectra of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

Table 4 The relevant XPS parameters of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

氧载体	氧百分比			O_surf/O_latt	Ce百分比		Ce³⁺/Ce⁴⁺	Ni百分比		Ni²⁺/Ni³⁺
氧载体	OⅠ	OⅡ	OⅢ	O_surf/O_latt	Ce³⁺	Ce⁴⁺	Ce³⁺/Ce⁴⁺	Ni²⁺	Ni³⁺	Ni²⁺/Ni³⁺
Ce_0.2Ni_0.8O_y	23.45	39.03	37.53	1.66	10.65	89.35	0.12	39.28	60.72	0.65
Ce_0.4Ni_0.6O_y	14.35	27.01	58.64	0.70	7.89	92.11	0.08	34.28	65.72	0.52

References 37

1	Liu L P, Ryu B, Sun Z L, et al. Monitoring and research on environmental impacts related to marine natural gas hydrates: review and future perspective[J]. Journal of Natural Gas Science and Engineering, 2019, 65: 82-107.
2	Wei C, Wang M H. Spatial distribution of greenhouse gases (CO₂ and CH₄) on expressways in the megacity Shanghai, China[J]. Environmental Science and Pollution Research, 2020, 27(25): 31143-31152.
3	Niu J T, Ran J Y, Chen D. Understanding the mechanism of CO₂ reforming of methane to syngas on Ni@Pt surface compared with Ni (1 1 1) and Pt (1 1 1)[J]. Applied Surface Science, 2020, 513: 145840-145873.
4	Liu C C, Chen Y, Zhao Y X, et al. Nano-ZSM-5-supported cobalt for the production of liquid fuel in Fischer-Tropsch synthesis: effect of preparation method and reaction temperature[J]. Fuel, 2020, 263: 116619.
5	Angeli S D, Monteleone G, Giaconia A, et al. State-of-the-art catalysts for CH₄ steam reforming at low temperature[J]. International Journal of Hydrogen Energy, 2014, 39(5): 1979-1997.
6	Abdullah B, Abd Ghani N A, Vo D V N. Recent advances in dry reforming of methane over Ni-based catalysts[J]. Journal of Cleaner Production, 2017, 162: 170-185.
7	Christian Enger B, Lødeng R, Holmen A. A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts[J]. Applied Catalysis A: General, 2008, 346(1/2): 1-27.
8	Sheu E J, Mokheimer E M A, Ghoniem A F. A review of solar methane reforming systems[J]. International Journal of Hydrogen Energy, 2015, 40(38): 12929-12955.
9	Mikheyev P A, Demyanov A V, Kochetov I V, et al. Ozone and oxygen atoms production in a dielectric barrier discharge in pure oxygen and O₂/CH₄ mixtures. Modeling and experiment[J]. Plasma Sources Science and Technology, 2020, 29(1): 015012.
10	Carrillo A J, Kim K J, Hood Z D, et al. La_0.6Sr_0.4Cr_0.8Co_0.2O₃ perovskite decorated with exsolved Co nanoparticles for stable CO₂ splitting and syngas production[J]. ACS Applied Energy Materials, 2020, 3(5): 4569-4579.
11	Yang Z Y, Zheng Y E, Li K Z, et al. Chemical-looping reforming of methane over La-Mn-Fe-O oxygen carriers: effect of calcination temperature[J]. Chemical Engineering Science, 2021, 229: 116085.
12	Wang Y J, Zheng Y E, Wang Y H, et al. Syngas production modified by oxygen vacancies over CeO₂-ZrO₂-CuO oxygen carrier via chemical looping reforming of methane[J]. Applied Surface Science, 2019, 481: 151-160.
13	Pérez-Vega R, Abad A, Izquierdo M T, et al. Evaluation of Mn-Fe mixed oxide doped with TiO₂ for the combustion with CO₂ capture by chemical looping assisted by oxygen uncoupling[J]. Applied Energy, 2019, 237: 822-835.
14	Wu Y J, Luo C H, Su Q Q. Study of NH₃ removal based on chemical-looping combustion[J]. Industrial & Engineering Chemistry Research, 2019, 58(12): 5054-5063.
15	Liu R, Pei C L, Zhang X H, et al. Chemical looping partial oxidation over FeWO_x/SiO₂ catalysts[J]. Chinese Journal of Catalysis, 2020, 41(7): 1140-1151.
16	Forero C R, Gayán P, García-Labiano F, et al. High temperature behaviour of a CuO/γ-Al₂O₃ oxygen carrier for chemical-looping combustion[J]. International Journal of Greenhouse Gas Control, 2011, 5(4): 659-667.
17	Zhu M, Song Y H, Chen S Y, et al. Chemical looping dry reforming of methane with hydrogen generation on Fe₂O₃/Al₂O₃ oxygen carrier[J]. Chemical Engineering Journal, 2019, 368: 812-823.
18	Cao Y, He B S, Tong W X, et al. On the kinetics of Mn₂O₃/ZrO₂ oxygen carrier for chemical looping air separation[J]. Chemical Engineering and Processing - Process Intensification, 2019, 136: 82-91.
19	Zheng Y E, Wei Y G, Li K Z, et al. Chemical-looping steam methane reforming over macroporous CeO₂-ZrO₂ solid solution: effect of calcination temperature[J]. International Journal of Hydrogen Energy, 2014, 39(25): 13361-13368.
20	Liu Y K, Long Y H, Tang Y Q, et al. Effect of preparation method on the structural characteristics of NiO-ZrO₂ oxygen carriers for chemical-looping combustion[J]. Chemical Research in Chinese Universities, 2019, 35(6): 1024-1031.
21	Zheng Y E, Li K Z, Wang H, et al. Structure dependence and reaction mechanism of CO oxidation: a model study on macroporous CeO₂ and CeO₂-ZrO₂ catalysts[J]. Journal of Catalysis, 2016, 344: 365-377.
22	Zheng Y E, Li K Z, Wang H, et al. Enhanced activity of CeO₂-ZrO₂ solid solutions for chemical-looping reforming of methane via tuning the macroporous structure[J]. Energy & Fuels, 2016, 30(1): 638-647.
23	Atzori L, Cutrufello M G, Meloni D, et al. Highly active NiO-CeO₂ catalysts for synthetic natural gas production by CO₂ methanation[J]. Catalysis Today, 2018, 299: 183-192.
24	Zhou G L, Liu H R, Cui K K, et al. Role of surface Ni and Ce species of Ni/CeO₂ catalyst in CO₂ methanation[J]. Applied Surface Science, 2016, 383: 248-252.
25	Hosseini S Y, Khosravi-Nikou M R, Shariati A. Kinetic study of the reduction step for chemical looping steam methane reforming by CeO₂-Fe₂O₃ oxygen carriers[J]. Chemical Engineering & Technology, 2020, 43(3): 540-552.
26	Nurbaisyatul E S, Azhan H, Kasim A, et al. Effect of CeO₂ nanoparticle on the structural and electrical properties of BSCCO-2223 high temperature superconductor[J]. Solid State Phenomena, 2020, 307: 104-109.
27	Lu C Q, Deng R R, Xu R D, et al. Design of hybrid oxygen carriers with CeO₂ particles on MnCo₂O₄ microspheres for chemical looping combustion[J]. Chemical Engineering Journal, 2021, 404: 126554.
28	Ma S W, Chen S Y, Ge H J, et al. Synergistic effects of Zr and Sm co-doped Fe₂O₃/CeO₂ oxygen carrier for chemical looping hydrogen generation[J]. Energy & Fuels, 2020, 34(8): 10256-10267.
29	Zheng Z M, Luo L X, Chen S B, et al. Activating Fe₂O₃ using K₂CO₃-containing ethanol solution for corn stalk chemical looping gasification to produce hydrogen[J]. International Journal of Hydrogen Energy, 2020, 45(41): 21004-21013.
30	Lim H S, Kang D, Lee J W. Phase transition of Fe₂O₃-NiO to NiFe₂O₄ in perovskite catalytic particles for enhanced methane chemical looping reforming-decomposition with CO₂ conversion[J]. Applied Catalysis B: Environmental, 2017, 202: 175-183.
31	Isarapakdeetham S, Kim-Lohsoontorn P, Wongsakulphasatch S, et al. Hydrogen production via chemical looping steam reforming of ethanol by Ni-based oxygen carriers supported on CeO₂ and La₂O₃ promoted Al₂O₃[J]. International Journal of Hydrogen Energy, 2020, 45(3): 1477-1491.
32	Medrano J A, Hamers H P, Williams G, et al. NiO/CaAl₂O₄ as active oxygen carrier for low temperature chemical looping applications[J]. Applied Energy, 2015, 158: 86-96.
33	Li T Y, Jayathilake R S, Taylor D D, et al. Structural studies of the perovskite series La_1-_xSr_xCoO_3-_δ during chemical looping with methane[J]. Chemical Communications, 2019, 55(34): 4929-4932.
34	Löfberg A, Guerrero-Caballero J, Kane T, et al. Ni/CeO₂ based catalysts as oxygen vectors for the chemical looping dry reforming of methane for syngas production[J]. Applied Catalysis B: Environmental, 2017, 212: 159-174.
35	Shan W J, Fleys M, Lapicque F, et al. Syngas production from partial oxidation of methane over Ce_1-_XNi_XO_Y catalysts prepared by complexation-combustion method[J]. Applied Catalysis A: General, 2006, 311: 24-33.
36	Nematollahi B, Rezaei M, Lay E N. Preparation of highly active and stable NiO-CeO₂ nanocatalysts for CO selective methanation[J]. International Journal of Hydrogen Energy, 2015, 40(27): 8539-8547.
37	Che W, Wei M R, Sang Z S, et al. Perovskite LaNiO_3-_δ oxide as an anion-intercalated pseudocapacitor electrode[J]. Journal of Alloys and Compounds, 2018, 731: 381-388.

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Application of Ce_1-_xNi_xO_y oxygen carriers in chemical-looping reforming of methane coupled with CO₂ reduction

Ce_1-_xNi_xO_y氧载体在化学链甲烷重整耦合CO₂还原中的应用

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