Red Mud as Oxygen Carrier for Chemical Looping Combustion of Methane: Reactivity and Cyclic Performance†

doi:10.7503/cjcu20170341

Abstract

Abstract:

Chemical looping combustion(CLC) is a novel combustion technology with inherent CO₂ separation from the carbon-based fuels. The development of low-cost oxygen carrier(OC) with high reactivity and good recycl ability is the key factor for the application of CLC technology. Red mud, a byproduct from the alumina production, can be considered as an ideal candidate as a cheap OC due to the high content of iron oxide and high specific surface area. In this study, the red mud was proposed as an oxygen carrier for chemical looping combustion of methane, and the effects of calcination temperature and reaction temperature on the reactivity and cyclic performance of this OC was investigated. The physicochemical properties of the red mud were characterized by XRF, XRD, TG-DSC, BET and H₂-TPR technologies. It was found that high calcination tempe-rature result in the decrease of the OC reactivity but improve the thermal stability due to the formation of composite salts(e.g., Na₆Al₄Si₄O₁₇ and Ca₂Al₂SiO₇) via the reactions between alkali-metal oxide(Na₂O) or alkaline-earth-metal oxide(CaO) and the inert materials(Al₂O₃ and SiO₂). Among the different red mud OCs(e.g., 800-RM, 850-RM, 900-RM and 950-RM, which were obtained after calcination at 800, 850, 900 and 950 ℃, respectively), the 900-RM sample shows the highest CH₄ conversion(71%) and CO₂ selectivity(79%) during the performance testing, indicating high activity for methane oxidation. This phenomenon suggests that 900 ℃ is the most suitable calcination temperature. No obvious changes on the reactivity and phase structure of the red mud was observed after 30 redox cycles, which indicates that the calcined red mud OC owns excellentredox stability for CLC of methane.

Key words: Chemical looping combustion, Methane, Red mud, Oxygen carrier, Redox stability

CLC Number:

O643
O614

TrendMD:

DENG Guixian, LI Kongzhai, CHENG Xianming, GU Zhenhua, LU Chunqiang, ZHU Xing. Red Mud as Oxygen Carrier for Chemical Looping Combustion of Methane: Reactivity and Cyclic Performance^†[J]. Chem. J. Chinese Universities, 2018, 39(2): 327.

Figures/Tables 11

Scheme 1 Schematic diagram for chemical looping combustion

Scheme 2 Schematic diagram of activity test experimental set-up

Fig.1 TG-DSC curves of the raw red mud(A) and specific surface areas of red mud oxygen carrier samples calcinated at different temperatures(B)

Fig.2 XRD patterns of samples 800-RM(a), 850-RM(b), 900-RM(c) and 950-RM(d)◆ Na6Al4Si4O17, JCPDS No.76-2385;■ Ca2Al2SiO7, JCPDS No.35-0755;▼ Fe2O3, JCPDS No.33-0664;● Ca3TiFeSi3O12, JCPDS No.47-1877;★ Na6CaAl6Si6(CO3)O24·2H2O, JCPDS No.48-1862.

Fig.3 H2-TPR profiles(A) and XRD(B) patterns of samples 800-RM(a), 850-RM(b), 900-RM(c) and 950-RM(d) ▼ FeO, JCPDS No.06-0615; ▲ Na1.45Al1.45Si0.55O4, JCPDS No.49-0002; ◆ Fe, JCPDS No.06-0696; ■ Ca2Al2Si4O17, JCPDS No.35-0755.

Fig.4 Typical curves of the main products and reactants during the temperature programmed reactions with CH4 over the red mud oxygen carriers (A) 800-RM; (B) 850-RM; (C) 900-RM; (D) 950-RM. a. CO; b. CO2; c. H2; d. CH4.

Fig.5 Typical curves of the main products and reactant during the isothermal reactions with CH4 over the red mud oxygen carriers (A) 800-RM; (B) 850-Rm; (C) 900-RM; (D) 950-RM.

Fig.6 Typical curves of the main products and reactant during 5 cycles of redox reaction(A) 800-RM; (B) 850-RM; (C) 900-RM; (D) 950-RM. (A1)~(D1) The first; (A2)~(D2) the third;(A3)~(D3) the fifth. a. CO; b. CO2; c. H2; d. CH4.

Fig.7 Average CH4 conversion and CO2 selectivity for the 5 cycles of redox reaction (A) The first; (B) the third; (C) the fifth.

Fig.8 Typical curves of CO2 and CO during the successive redox testing at 900 ℃(A) and average CH4 conversion and CO2 selectivity for 30 cycles(B)

Fig.9 XRD patterns of the different 900-RM oxygen carriers a. Fresh; b. after 5 cycles; c. after 30 cycles.

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