Ni/ZrO_(2)-Al_(2)O_(3)催化剂催化沼气蒸汽重整制氢性能研究  

Study on catalytic performance of Ni/ZrO_(2)-Al_(2)O_(3) catalyst in biogas steam reforming for hydrogen production

作　　者：张中亮 刘吉[2] 马宗虎 胡锶菡 冯冰 胡斌[2] 李凯[2] 陆强[2] ZHANG Zhongliang;LIU Ji;MA Zonghu;HU Sihan;FENG Bing;HU Bin;LI Kai;LU Qiang(CHINA HUADIAN ENGINEERING Co.,Ltd.,Beijing 100711,China;National Engineering Research Center of New Energy Power Generation,North China Electric Power University,Beijing 102206,China)

机构地区：[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

出　　处：《低碳化学与化工》2024年第9期19-25,32,共8页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(52276189,52376182);中国华电科工集团有限公司研发项目(CHEC.BE-ZQZQ-JS-2023-09)。

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ZrO_(2)-Al_(2)O_(3)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N_(2)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°C、空速12000 h^(-1)条件下,焙烧温度为550°C制得的Ni/ZrO_(2)-Al_(2)O_(3)表现出突出的催化性能,CH_(4)转化率和H_(2)产率分别稳定在89.94%和81.49%。ZrO_(2)-Al_(2)O_(3)复合载体相比于Al_(2)O_(3)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°C制得的Ni/ZrO_(2)-Al_(2)O_(3)的比表面积和孔体积比焙烧温度为700°C制得的Ni/ZrO_(2)-Al_(2)O_(3)大。Fe与ZrO_(2)的耦合改性提升了催化剂的还原性能,生成了更多高活性Ni^(0),有利于甲烷干重整制氢反应的发生,调控了气体产物中的n_(H_(2))/n_(CO)。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 ZrO_(2)-Al_(2)O_(3) 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 N_(2) 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/ZrO_(2)-Al_(2)O_(3) exhibits outstanding catalytic performance for hydrogen production at 700 ℃ and gas volume space velocity of 12000 h^(-1),with CH_(4) conversion rate of 89.94% and H_(2) yield of 81.49%.Compared with Al_(2)O_(3) support,ZrO_(2)-Al_(2)O_(3) 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/ZrO_(2)-Al_(2)O_(3) calcined at 550 ℃ are larger than those of Ni/ZrO_(2)-Al_(2)O_(3) calcined at 700 ℃.The coupled modification of Fe and ZrO_(2) improves the reduction performance of catalysts,and more highly active Ni~0 is formed,which is conducive to the occurrence of methane dry reforming for hydrogen production,and the n_(H_(2))/n_(CO) in the gas product is also modified.

关 键 词：沼气 重整制氢 ZrO_(2)-Al_(2)O_(3)复合载体 NI基催化剂 

分 类 号：TQ203.2[化学工程—有机化工]