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

doi:10.7503/cjcu20160411

Abstract

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

CLC Number:

O643.3
O614

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2017, 38(1): 115.

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

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