Ni/ZrO2-Al2O3催化剂催化沼气蒸汽重整制氢性能研究
Study on catalytic performance of Ni/ZrO2-Al2O3 catalyst in biogas steam reforming for hydrogen production
张中亮 1刘吉 2马宗虎 1胡锶菡 2冯冰 1胡斌 2李凯 2陆强2
作者信息
- 1. 中国华电科工集团有限公司,北京 100711
- 2. 华北电力大学新能源发电国家工程研究中心,北京 102206
- 折叠
摘要
沼气蒸汽重整是重要的制氢方式,开发高效稳定的催化剂是其规模化应用的重要环节.基于此,采用连续浸渍法制备了一系列基于ZrO2-Al2O3复合载体的Ni基催化剂,对其进行了沼气蒸汽重整制氢催化性能测试.利用N2吸/脱附、XRD等表征方法,分析了催化剂的织构性质、晶相组成等.探究了催化剂的物理结构和化学性质对沼气蒸汽重整制氢的影响机制,并探讨了焙烧温度与金属助剂Fe对催化剂催化性能的影响.结果表明,在700 ℃、空速12000 h1条件下,焙烧温度为550 ℃制得的Ni/ZrO2-Al2O3表现出突出的催化性能,CH4转化率和H2产率分别稳定在89.94％和81.49％.ZrO2-Al2O3复合载体相比于Al2O3载体增大了催化剂的比表面积,促进了平均粒径较小的Ni在载体表面的高度分散,进而提高了催化剂的催化沼气蒸汽重整制氢性能.焙烧温度可以调控催化剂的比表面积和孔体积,焙烧温度为550 ℃制得的Ni/ZrO2-Al2O3的比表面积和孔体积比焙烧温度为700 ℃制得的Ni/ZrO2-Al2O3大.Fe与ZrO2的耦合改性提升了催化剂的还原性能,生成了更多高活性Ni0,有利于甲烷干重整制氢反应的发生,调控了气体产物中的nH2/nCO.
Abstract
Biogas steam reforming is one important way for hydrogen production,and the development of efficient and stable catalysts is the key for its large-scale application.Based on this,a series of Ni-based catalysts based on ZrO2-Al2O3 composite support were prepared by continuous impregnation method,and the catalytic performances for hydrogen production by biogas steam reforming were tested.The texture properties and crystal phase compositions of catalysts were analyzed by characterization methods such as N2 adsorption/desorption and XRD.The influence mechanisms of the physical structure and chemical properties of catalysts on their catalytic performances of biogas steam reforming for hydrogen production were studied.The effects of calcination temperatures and metal promotor Fe on the catalytic performances of catalysts were also discussed.The results show that Ni/ZrO2-Al2O3 exhibits outstanding catalytic performance for hydrogen production at 700 ℃ and gas volume space velocity of 12000 h1,with CH4 conversion rate of 89.94％and H2 yield of 81.49％.Compared with Al2O3 support,ZrO2-Al2O3 composite support increases the specific surface area of catalysts,promotes the high dispersion of small particle size Ni on the surface of the support,and thus improves the catalytic performances of catalysts in biogas steam reforming for hydrogen production.The calcination temperature can regulate the specific surface area and pore volume of catalysts.The specific surface area and pore volume of Ni/ZrO2-Al2O3 calcined at 550 ℃ are larger than those of Ni/ZrO2-Al2O3 calcined at 700 ℃.The coupled modification of Fe and ZrO2 improves the reduction performance of catalysts,and more highly active Ni0 is formed,which is conducive to the occurrence of methane dry reforming for hydrogen production,and the nH2/nCO in the gas product is also modified.
关键词
沼气/重整制氢/ZrO2-Al2O3复合载体/Ni基催化剂Key words
biogas/reforming for hydrogen production/ZrO2-Al2O3 composite support/Ni-based catalyst引用本文复制引用
基金项目
国家自然科学基金(52276189)
国家自然科学基金(52376182)
中国华电科工集团有限公司研发项目(CHEC.BE-ZQZQ-JS-2023-09)
出版年
2024
国家科技期刊平台
NSTL
万方数据