高铝耐火砖负载CuO氧载体的化学链氧解耦特性实验

doi:10.16085/j.issn.1000-6613.2019-0425

摘要/Abstract

摘要：

耐火砖常用作高温炉膛材料，具有较高的破碎强度和较强的抗烧结性能。以耐火砖颗粒为惰性载体，采用连续浸渍法制备CuO质量分数为10%～30%的Cu10RefBri、Cu25RefBri和Cu30RefBri氧载体样品，并在热重分析仪（TGA）和批次进料流化床反应器中900～950℃下进行了化学链氧解耦燃烧过程氧载体的释氧-吸氧循环实验测试。结果显示，在上述氧载体样品中Cu25RefBri的释氧速率最高，可达9×10^-5kgO₂/(s?kgOC)，流化床中稳定的O₂体积分数可达1.1%。然而，随着循环次数增加，Cu25RefBri的释氧速率逐渐降低至2.0×10^-5kgO₂/(s?kgOC)，同时流化床尾气中O₂体积分数降低至0.7%，该值远低于对应温度下的平衡O₂浓度值。氧浓度和释氧速率降低的主要原因在于：循环过程氧载体中形成的低释氧活性的CuAl₂O₄尖晶石含量逐渐增加，导致氧载体总体活性下降。此外，在950℃流化床实验过程，还检测到氧载体颗粒的烧结现象。

关键词: 化学链氧解耦, 铜基氧载体, 团聚, 流化床, 失活

Abstract:

Refractory brick which is usually used as high-temperature furnace material has high crushing strength and high agglomeration resistance. In this work, a type of high-alumina refractory brick particles were used as support material for Cu-based oxygen carrier preparation. Three samples containing 10%—30% of CuO, denoted as Cu10RefBri, Cu25RefBri and Cu30RefBri, were prepared with successive impregnation method and then subjected to the tests in TGA and fluidized bed reactor under 900—950℃ to explore their characteristics on oxygen release and uptake. The Cu25RefBri sample showed the highest rate of oxygen release in TGA tests (as high as 9×10^-5kgO₂/(s?kgOC)), thus presented a stable O₂ volume fraction of 1.1%. However, as the number of cycles increased , the rate of oxygen release decreased to as low as 2.0×10^-5kgO₂/(s?kgOC), meanwhile the O₂ volume fraction reduced to 0.7%, which is much lower than that for equilibrium case. The main reason for the decrease of oxygen release activity could be the formation of low-reactive crystalline CuAl₂O₄, the concentration of which increased as a function of cycles. Moreover, agglomeration of Cu25RefBri was noticed at a temperature of 950℃ in the fluidized bed reactor.

Key words: chemical looping with oxygen uncoupling, Cu-base oxygen carrier, agglomeration, fluidized bed, deactivated

中图分类号:

TQ534

刘沛聪,梅道锋,晏水平. 高铝耐火砖负载CuO氧载体的化学链氧解耦特性实验[J]. 化工进展, 2019, 38(12): 5351-5359.

Peicong LIU,Daofeng MEI,Shuiping YAN. Characteristics tests of a high-alumina refractory supported CuO oxygen carrier during chemical looping with oxygen uncoupling[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5351-5359.

图/表 12

表1 氧载体样品的主要特性

样品

载氧率R_OC

堆积密度ρ_s

/g·cm^-3

破碎强度

CuO，α-Al₂O₃

CuAl₂O₄

Al₂SiO₅

图1 化学链氧解耦（CLOU）燃烧示意图

图2 不同温度时CuO/Cu2O体系的O2平衡浓度

图3 批次进料流化床反应器示意

图4 TPD测试过程Cu25RefBri的质量变化ω和温度T随反应时间的变化

图5 900和950℃时TGA中吸氧-释氧20次循环过程ω与ΔT随反应时间的变化情况

图6 不同反应温度下氧载体Cu10RefBri、Cu25RefBri和Cu30RefBri的释氧速率随循环次数演变

图7 Cu25RefBri分解和氧化反应过程

图8 900℃下流化床中Cu25RefBri的分解过程的氧气浓度

图9 新鲜煅烧后、循环12次、循环25次的氧载体的XRD分析结果

图10 流化床反应器内Cu25RefBri的颗粒磨损率随实验时间的变化

图11 新鲜煅烧后、12次循环后和25次循环后Cu25RefBri氧载体颗粒的SEM形貌

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