镍修饰的铁基载氧体甲烷化学链制氢实验  

Performance of Iron-Based Oxygen Carriers Modified by NiO in Chemical Looping Hydrogen Generation Process

作　　者：付甜甜 玉散·吐拉甫 王邑维 伍永明 张静[2] 王伟[1] Fu Tiantian;Yusan Turap;Wang Yiwei;Wu Yongming;Zhang Jing;Wang Wei(School of Environment,Tsinghua University,Beijing 100084,China;Meteorological Bureau of Gaoqing County of Shandong Province,Zibo 256300,China)

机构地区：[1]清华大学环境学院,北京100084 [2]山东省高青县气象局,淄博256300

出　　处：《燃烧科学与技术》2020年第2期125-132,共8页Journal of Combustion Science and Technology

基　　金：国家自然科学基金资助项目(21477061)。

摘　　要：化学链制氢工艺作为一种新型能源转化技术,能在实现CO_2内分离的同时,生产高纯氢气.为了提高铁基载氧体与甲烷的反应活性,本文添加第二活性组分NiO对铁基载氧体进行修饰,使用机械混合法制备载氧体材料.经NiO修饰后,载氧体的主要物相为Fe_2O_3、Al_2O_3与NiFeAlO_4.CH_4-TPSR实验表明,载氧体的还原反应分为两步:第一步为游离态的Fe_2O_3被还原为Fe_3O_4;第二步为Fe_3O_4与NiFeAlO_4被还原为单质态Fe与(Fe,Ni)合金.在TGA反应器中研究各载氧体的反应活性,结果表明,添加NiO修饰后,生成了高反应活性的NiFeAlO_4,显著提高了铁基载氧体与甲烷的反应活性.NiO修饰量分别为0、2.5%、5%、10%,在V_(CH_4)∶V_(CO_2)=2∶1条件下,各铁基载氧体的平均表观固相转化速率依次为2.6%/min、5.4%/min、7.2%/min、8.2%/min.固定床化学链制氢实验中,添加10%NiO的载氧体反应活性最高,且产氢性能良好.若进一步提高NiO修饰量,将降低铁基载氧体的产氢潜能,不利于化学链制氢工艺.As a new energy conversion technology,chemical looping hydrogen generation process can simultaneously produce sequestration-ready CO2 and high-purity hydrogen.To improve the reactivity between iron-based oxygen carriers and methane,the second additive NiO was added,and the oxygen carriers were prepared by a mechanical mixing method.After modification by NiO,the main phases of oxygen carriers were Fe2O3,Al2O3 and NiFeAlO4.In the CH4-TPSR process,the reduction reaction was divided into two steps:the free Fe2O3 was first reduced to Fe3O4,and then Fe3O4 and NiFeAlO4 were reduced to metallic Fe and(Fe,Ni)alloy.The reactivity of each oxygen carrier was investigated in a TGA reactor.The results showed that when modified by NiO,the highly reactive NiFeAlO4 was formed,which significantly improved the reactivity of iron-based oxygen carrier with methane.In this paper,the additions of NiO were 0,2.5%,5%,and 10% respectively.When reduced in VCH4 ∶VCO2 =2∶1 atmosphere,the average apparent solid conversion rates of each iron-based oxygen carrier were 2.6%/min,5.4%/min,7.2%/min,and 8.2%/min,respectively.In the fixed bed reactor,the oxygen carrier with 10% NiO addition had the highest reactivity and good hydrogen production performance.If the amount of NiO is further increased,the potential of hydrogen production will decrease,which is not favorable in chemical looping hydrogen generation process.

关 键 词：化学链制氢 甲烷 铁基载氧体 氧化镍 

分 类 号：TK16[动力工程及工程热物理—热能工程]