铈基与钴基Co3O4-CeO2氧载体上甲烷化学链转化特性: 产物选择性控制

doi:10.7503/cjcu20160411

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (1): 115.doi: 10.7503/cjcu20160411

铈基与钴基Co₃O₄-CeO₂氧载体上甲烷化学链转化特性: 产物选择性控制

曾良鹏¹, 黄樊², 祝星¹, 郑敏¹, 李孔斋¹()

1. 昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室, 昆明 650093
2. 昆明理工大学化学工程学院, 昆明 650500

收稿日期:2016-06-07 出版日期:2017-01-10 发布日期:2016-12-15
作者简介:联系人简介: 李孔斋, 男, 博士, 教授, 主要从事能源催化方面的研究. E-mail: kongzhai.li@aliyun.com
基金资助:
国家自然科学基金(批准号: 51374004, 51204083)、云南省中青年学术技术带头人后备人才计划(批准号: 2014HB006)、云南省应用基础研究计划(批准号: 2014FB123)和昆明理工大学校人才培养项目(批准号: KKZ3201352038)资助.

Chemical Looping Conversion of Methane over CeO₂-based and Co₃O₄-based Co₃O₄-CeO₂ Oxygen Carriers:Controlling of Product Selectivity^†

ZENG Liangpeng¹, HUANG Fan², ZHU Xing¹, ZHENG Min¹, LI Kongzhai^1,^*()

1. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization,Kunming University of Science and Technology, Kunming 650093, China
2. Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China

Received:2016-06-07 Online:2017-01-10 Published:2016-12-15
Contact: LI Kongzhai E-mail:kongzhai.li@aliyun.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51374004, 51204083), the Candidate Talents Training Fund of Yunnan Province, China(No.2014HB006), the Applied Basic Research Program of Yunnan Province, China(No.2014FB123) and the Talents Training Program of Kunming University of Science and Technology, China(No.KKZ3201352038).

摘要/Abstract

摘要：

采用水热法制备了Co₃O₄/CeO₂(x)[x为钴铈原子摩尔比n(Co):n(Ce)=6:49:1]和Ce_1-_yCo_yO_2-_δ(y=0.10.4)2个系列复合氧化物, 并表征了材料的物理化学性质, 考察了这些氧化物作为氧载体参与甲烷化学链转化(化学链燃烧和化学链部分氧化)的反应性能. 结果表明, 2类复合氧化物的甲烷反应活性均明显优于单一氧化物CeO₂或Co₃O₄, 但2类氧载体上的甲烷反应产物的选择性具有明显差异. Ce_1-_yCo_yO_2-_δ氧载体形成了Ce-Co-O固溶体, 储氧能力明显增强, 体相晶格氧迁移速率与甲烷活化速率匹配较好, 甲烷反应产物以CO和H₂的合成气为主, 有利于甲烷的化学链部分氧化. Co₃O₄/CeO₂(x)氧载体中CeO₂与Co₃O₄之间的相互作用改善了材料的储氧能力和氧化活性, 其与甲烷反应时主要生成CO₂, 有利于甲烷化学链燃烧. 连续性化学链循环实验表明, 2类氧载体均具有较好的再生性能和循环稳定性.

关键词: 甲烷, Co₃O₄/CeO₂(x)氧载体, Ce_1-yCo_yO_2-δ氧载体, 化学链部分氧化, 化学链燃烧

Abstract:

Two series of Co₃O₄/CeO₂(x)[x is the molar ratio of cobalt and cerium atoms, n(Co)/n(Ce)=5:5―9:1] and Ce_1-_yCo_yO_2-_δ(y=0.1—0.4) composite oxides were prepared by the hydrothermal method. The physicochemical properties of these oxides were characterized by means of X-ray powder diffraction(XRD), BET(Brunauer-Emmett-Teller) surface area, temperature-programmed reduction(TPR) and Raman spectrum technologies. The prepared materials were used as an oxygen carrier for chemical looping conversion of methane in a fixed-bed reactor. The results showed that both the Co₃O₄/CeO₂(x) and Ce_1-_yCo_yO_2-_δ oxygen carriers exhibited higher reactivity for methane conversion than single cerium oxide and cobalt oxide. However, the selectivity of CO₂ and CO in the CH₄ reaction over the two types of samples are significantly different. Owing to a larger surface area and the formation of Ce-Co-O solid solution, the oxygen storage capacity of Ce_1-_yCo_yO_2-_δ oxygen carrier was improved significantly. Moreover, the reaction of Ce_1-_yCo_yO_2-_δ with methane mainly generated CO and H₂ due to good matching between the lattice oxygen mobility and the methane activation rate. On the other hand, the strong interaction between CeO₂ and Co₃O₄ also strongly enhanced the oxygen storage capacity and activity of Co₃O₄/CeO₂(x) oxygen carriers. But they mainly concerted the methane to CO₂ and H₂O owning to the relatively high concentration of active oxygen. In conclusion, the Co₃O₄/CeO₂(x) composite oxides can be used as oxygen carriers for chemical looping combustion of methane, while the Ce_1-_yCo_yO_2-_δ oxidesare more suitable for the chemical looping partial oxidation of methane to produce syngas. The sequential cyclic reaction experiments indicated that both the two types of oxygen carriers showed high stability during the successive redox testing.

Key words: Methane, Co₃O₄/CeO₂(x) oxygen carriers, Ce_1-yCo_yO_2-δ oxygen carriers, Chemical looping partial oxidation, Chemical looping combustion

中图分类号:

O643.3
O614

TrendMD:

曾良鹏, 黄樊, 祝星, 郑敏, 李孔斋. 铈基与钴基Co₃O₄-CeO₂氧载体上甲烷化学链转化特性: 产物选择性控制. 高等学校化学学报, 2017, 38(1): 115.

ZENG Liangpeng, HUANG Fan, ZHU Xing, ZHENG Min, LI Kongzhai. Chemical Looping Conversion of Methane over CeO₂-based and Co₃O₄-based Co₃O₄-CeO₂ Oxygen Carriers:Controlling of Product Selectivity^†. Chem. J. Chinese Universities, 2017, 38(1): 115.

图/表 11

Fig.1 Schematic diagram for chemical looping combustion or chemical looping partial oxidation MeO/Me denotes the recyclable oxygen carrier.

Fig.2 Schematic diagram of the performance evaluation device for the oxygen carrier

Fig.3 XRD patterns of different Co3O4/CeO2(x)(A) and Ce1-yCoyO2-δ(B) oxygen carriers(A) a. Co3O4; b. Co3O4/CeO2(9:1); c. Co3O4/CeO2(8:2); d. Co3O4/CeO2(7:3); e. Co3O4/CeO2(6:4).(B) a. Ce0.6Co0.4O2-δ; b. Ce0.7Co0.3O2-δ; c. Ce0.8Co0.2O2-δ; d. Ce0.9Co0.1O2-δ; e. CeO2.

Table 1 Specific surface areas and lattice constants of Co3O4 and CeO2 phases detected in the CeO2-Co3O4 oxygen carriers

Oxygen carrier	S_BET/(m²·g^-1)	Lattice constant/nm
Oxygen carrier	S_BET/(m²·g^-1)	Co₃O₄	CeO₂
Co₃O₄	39.30	0.5681
Co₃O₄/CeO₂(9:1)	35.57	0.5662	0.5410
Co₃O₄/CeO₂(8:2)	31.22	0.5679	0.5410
Co₃O₄/CeO₂(7:3)	24.30	0.5679	0.5417
Co₃O₄/CeO₂(6:4)	34.45	0.5681	0.5416
Ce_0.6Co_0.4O_2-_δ	40.94	0.5686	0.5410
Ce_0.7Co_0.3O_2-_δ	42.84	0.4224	0.5406
Ce_0.8Co_0.2O_2-_δ	43.60	0.4219	0.5404
Ce_0.9Co_0.1O_2-_δ	58.29	0.4670	0.5404
CeO₂	131.06		0.5419

Fig.4 H2-TPR profiles of Co3O4/CeO2(x)(A) and Ce1-yCoyO2-δ(B) oxygen carriers with different Co/Ce molar ratios(A) a. Co3O4; b. Co3O4/CeO2(9:1); c. Co3O4/CeO2(8:2); d. Co3O4/CeO2(7:3); e. Co3O4/CeO2(6:4). (B) a. Ce0.6Co0.4O2-δ; b. Ce0.7Co0.3O2-δ; c. Ce0.8Co0.2O2-δ; d. Ce0.9Co0.1O2-δ; e. CeO2.

Fig.5 H2 consumption of H2-TPR test(A) and oxygen storage capacity(B) over different Co3O4/CeO2(x) and Ce1-yCoyO2-δoxygen carriersa. Co3O4; b. Co3O4/CeO2(9:1); c. Co3O4/CeO2(8:2); d. Co3O4/CeO2(7:3); e. Co3O4/CeO2(6:4); f. Ce0.6Co0.4O2-δ; g. Ce0.7Co0.3O2-δ; h. Ce0.8Co0.2O2-δ; i. Ce0.9Co0.1O2-δ; j. CeO2.

Fig.6 CH4-TPR profiles of Co3O4/CeO2(x) and Ce1-yCoyO2-δ oxygen carriers with different Co/Ce molar ratios(A) and the corresponding CO and CO2 average content bar charts of CH4-TPR test(B)(A) a. Co3O4; b. Co3O4/CeO2(8:2); c. Ce0.8Co0.2O2-δ; d. CeO2.(B) a. Co3O4; b. Co3O4/CeO2(9:1); c. Co3O4/CeO2(8:2); d. Co3O4/CeO2(7:3); e. Co3O4/CeO2(6:4); f. Ce0.6Co0.4O2-δ; g. Ce0.7Co0.3O2-δ; h. Ce0.8Co0.2O2-δ; i. Ce0.9Co0.1O2-δ; j. CeO2.

Fig.7 Evolution profiles of CO and CO2 for CH4 oxidation at 650 ℃ over Co3O4/CeO2(x) and Ce1-yCoyO2-δ oxygen carriers with different Co/Ce molar ratios(A) Co3O4; (B) Co3O4/CeO2(8:2); (C) Co3O4/CeO2(6:4); (D)Ce0.8Co0.2O2-δ; (E) Ce0.9Co0.1O2-δ; (F) CeO2.

Fig.8 Corresponding CO and CO2 production on Co3O4/CeO2(x) in previous 6 min(A) and on Ce1-yCoyO2-δ in the whole reaction process(B) at 650 ℃(A) a. Co3O4; b. Co3O4/CeO2(9:1); c. Co3O4/CeO2(8:2); d. Co3O4/CeO2(7:3); e. Co3O4/CeO2(6:4); (B) a. Ce0.6Co0.4O2-δ; b. Ce0.7Co0.3O2-δ; c. Ce0.8Co0.2O2-δ; d. Ce0.9Co0.1O2-δ; e. CeO2.

Fig.9 Raman spectra of Co3O4/CeO2(8:2)(A) and Ce0.8Co0.2O2-δ(B) after various reaction time with CH4 at 650 ℃Reaction time/min: a. 3; b. 5; c. 7. (A) d. Co3O4; (B) d. CeO2.

Fig.10 Transient responses of the cyclic reaction between CH4-Ar flow(10 min) and O2-Ar flow(20 min) over(A) Co3O4/CeO2(8:2) and(B) Ce0.8Co0.2O2-δ oxygen carrier at 650 ℃, and CH4 conversion or the selectivity of product gas over Co3O4/CeO2(8:2)(C), Ce0.8Co0.2O2-δ(D) as a function of redox cycle number

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铈基与钴基Co₃O₄-CeO₂氧载体上甲烷化学链转化特性: 产物选择性控制

Chemical Looping Conversion of Methane over CeO₂-based and Co₃O₄-based Co₃O₄-CeO₂ Oxygen Carriers:Controlling of Product Selectivity^†

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