赤泥作为氧载体用于甲烷化学链燃烧:反应与循环性能

doi:10.7503/cjcu20170341

摘要/Abstract

摘要：

将拜耳法赤泥作为氧载体用于甲烷化学链燃烧, 研究了不同预处理条件对赤泥氧载体的反应与循环性能的影响. 对赤泥氧载体的物理化学性质的表征结果表明, 高温焙烧导致氧载体反应活性下降, 但有利于赤泥中各组分之间发生反应生成稳定的复合物(如Na₆Al₄Si₄O₁₇和Ca₂Al₂SiO₇), 从而提高了赤泥氧载体的热稳定性. 通过测试不同温度(800, 850, 900和950 ℃)下制备的赤泥氧载体(800-RM, 850-RM, 900-RM和950-RM)与CH₄的反应性能发现, 900-RM的反应活性和循环性能均优于其它样品, CH₄转化率和CO₂选择性分别达到了71%和79%, 说明900 ℃为最佳焙烧温度. 在900 ℃下经30次redox循环后, 赤泥氧载体的反应性能和物相结构未发生明显变化, 表明其具有优良的循环稳定性.

关键词: 化学链燃烧, 甲烷, 赤泥, 氧载体, 氧化还原循环

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

中图分类号:

O643
O614

TrendMD:

邓贵先, 李孔斋, 程显名, 顾振华, 卢春强, 祝星. 赤泥作为氧载体用于甲烷化学链燃烧:反应与循环性能. 高等学校化学学报, 2018, 39(2): 327.

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^†. Chem. J. Chinese Universities, 2018, 39(2): 327.

图/表 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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