采用载氧体催化剂化学链直接分解水一步制纯氢，并将其与生物质热转化耦合，开发具有应用前景和经济性的制氢同时制合成气的新方法具有重要意义。探究金属螯合溶胶-凝胶方法制备掺杂Ce-Ni的铁基载氧体，以化学链水分解耦合乙酸热分解方式制取纯氢和富氢合成气，首先在氧化态载氧体作用下，乙酸催化热分解制取富氢合成气，载氧体被还原，实现了载氧体晶格氧的迁移，通过原位CO2吸附实现热分解过程强化；其次是利用还原态载氧体与水发生铁-蒸汽过程制氢。研究发现，在乙酸催化热分解过程进行原位CO2吸附强化，提高了合成气H2纯度并减少积碳。与无掺杂纯氧化铁与空白石英砂对照，掺杂适量的Ce与Ni的Fe基载氧体具有显著制氢作用，随Ce、Ni量增加，乙酸分解阶段CO2和CO生成量减少，水分解阶段H2先增后降，最佳载氧体Fe、Ce和Ni组分物质的量比为100∶10∶3，加入相对于载氧体不同质量比的CO2吸附剂均可有效降低合成气中CO2与CO气体量，最佳质量比为1∶2，在该条件下合成气中H2体积分数提高了11.96%～26.17%，CO2体积分数减少了22.85%～49.28%，CO体积分数减少了29.18%～34.05%，15次循环后载氧体仍保持较好的稳定性。

It is of great significance to develop a new method for hydrogen production and syngas production that utilizes oxygen carrier catalysts to directly decompose water to produce pure hydrogen in one stepand  couple it with biomass thermal conversion. Iron-based oxygen carriers doped with Ce-Ni were prepared by metal chelating sol-gel method. Pure hydrogen and hydrogen-rich synthesis gas were prepared by chemical looping water decomposition coupled with acetic acid thermal decomposition. Firstly, under the action of oxidized oxygen carriers, acetic acid catalyzed thermal decomposition to produce hydrogen-rich syngas. And the oxygen carrier was reduced to realize the migration of lattice oxygen in the oxygen carrier, and the thermal decomposition process was strengthened by in-situ CO2 adsorption. Secondly,hydrogen production was achieved through the iron steam process using the reduced oxygen carrier with water. It is found that the in-situ CO2 adsorption is enhanced during the catalytic thermal decomposition of acetic acid, which can improve the purity of H2 in syngas and reduce carbon deposition. Compared with undoped pure iron oxide and blank quartz samples, the Fe-based oxygen carrier doped with appropriate amount of Ce and Ni has obvious hydrogen production effect. With the increase of Ce and Ni, the amount of CO2 and CO produced in the acetic acid decomposition stage decrease, while H2 increases firstly and then decreases during water decomposition. The optimum molar ratio of oxygen carrier Fe, Ce and Ni is 100∶10∶3.The addition of CO2 adsorbent with different mass ratio of oxygen carrier can effectively reduce the amount of CO2 and CO in syngas, and the best mass ratio is 1∶2.Under this condition, the syngas composition of H2 is increased by 11.96%-26.17%, CO2 is reduced by 22.85%-49.28%, CO is reduced by 29.18%-34.05%, and the oxygen carriers remain good stability after 15 cycles.

0 引言

1 试验

   1.1 试验原料

   1.2 Ni-Ce掺杂的Fe基催化剂制备

   1.3 试验过程

   1.4 数据分析

   1.5 材料表征

2 试验结果与讨论

   2.1 化学链水分解耦合乙酸热分解

   2.2 化学链水分解耦合吸附强化乙酸热分解

   2.3 Ni-Ce修饰Fe基催化剂的表征

3 结论