基于层状氢氧化物衍生复合氧载体的生物质化学链气化实验研究

Chemical looping gasification of biomass based on the oxygen carrier derived from the layered double hydroxide (LDH) precursor

  • 摘要: 通过低饱和共沉淀法合成了类水滑石结构的层状氢氧化物(Layered Double Hydroxide, LDH) 前驱体, 经煅烧获得衍生Cu/Al/Zn、Cu/Al/Ni、Cu/Al/Ni/Zn高分散复合氧载体.采用XRD、XRF、H2-TPR、SEM及BET等分析手段对氧载体的结构及反应性能进行了表征, 并通过固定床反应器开展了氧载体与生物质化学链气化实验.结果表明, 合成的三种前驱体都具有典型的水滑石特征衍射峰, 且层板稳定.Cu/Al/Zn前驱体层间厚度为0.2642nm, Ni2+引入后, 层间距减小.前驱体煅烧后形成的复合氧载体中元素含量与制备试剂基本一致.氧载体中Zn、Ni元素的引入可提升CuO的反应活性, 降低H2还原的反应温度, Zn元素与Cu具有更好的协同作用.Cu/Al/Ni/Zn氧载体在固定床化学链气化中具有较好的碳转化率和气体产率, 其碳转化率为82.03%.反应后氧载体比表面积为5.995m2/g, 具有较好的可再生性与抗烧结性, 是生物质化学链气化反应较为理想的氧载体.

     

    Abstract: Layered double hydroxide (LDH) precursors with different metal elements were prepared by co-precipitation method at constant pH value; highly dispersed Cu/Al/Zn, Cu/Al/Ni and Cu/Al/Ni/Zn mixed metal oxygen carriers were obtained by calculation of the corresponding precursors. These oxygen carriers were characterized by XRD, XRF, H2-TPR, SEM and nitrogen adsorption and their activity in the chemical looping gasification (CLG) of biomass was investigated in a fixed bed reactor. The results indicated that typical hydrotalcite structure appears in the three precursors with stable layer board. The interlayer spacing of Cu/Al/Zn precursor is 0.2642nm, larger than that of the Cu/Al/Ni precursor. The oxygen carriers derived from the corresponding precursors display similar elements contents as the preparation reagents. Due to the synergy among various metals, the Cu/Al/Ni/Zn oxygen carrier shows the highest reaction activity and anti-sintering ability. The addition of Ni and Zn has a positive effect on the activity of CuO and reduce its reduction temperature; Zn shows a better synergistic effect than Ni with Cu. The carbon conversion reaches 82.03% for the CLG of biomass with Cu/Al/Ni/Zn as oxygen carrier; the surface area of Cu/Al/Ni/Zn remanis 5.995m2/g after the CLG reaction, suggesting that it could be an ideal candidate for the CLG of biomass.

     

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