共沉淀法制备Cu-Mn-Al尖晶石催化剂用于甲醇水蒸气重整制氢  

Preparation of Cu-Mn-Al spinel catalysts by co-precipitation method for hydrogen preparation from methanol steam reforming

作　　者：吴浩飞 江志东[1] 马紫峰[1] WU Haofei;JIANG Zhidong;MA Zifeng(School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China)

机构地区：[1]上海交通大学化学化工院,上海200240

出　　处：《精细化工》2021年第10期2081-2088,共8页Fine Chemicals

摘　　要：以硝酸铜、硝酸铝和硝酸锰为原料,用共沉淀法制备了Cu-Mn-Al尖晶石固溶体催化剂,用于甲醇水蒸气重整制氢反应。采用BET、H_(2)-TPR、XRD、SEM、XPS等方法对催化剂进行了表征,考察了Mn的添加比例(CuMn_(x)Al_(4–x), x=0~0.5)对催化剂物理化学性质、形貌及催化性能的影响。结果表明,Mn添加比例不同,催化剂的比表面积、还原性能以及表面化学性质发生改变,随着Mn比例从0增大到0.5(以Cu的物质的量为基准,下同),CuAl尖晶石粒径增大、比表面积下降,并且更难被还原。催化剂的催化性能在x=0.25时最佳,在260℃、0.3MPa、n(H_(2)O)∶n(CH3OH)=1∶1、质量空速(WHSV)为3.0g-feed/(g-cat·h)的反应条件下,最高甲醇转化率为91.7%,连续运行150 h后甲醇转化率降至78.8%,均明显高于未含Mn的Cu Al尖晶石催化剂。Cu-Mn-Al spinel solid solution catalysts were prepared by coprecipitation method using copper nitrate, aluminum nitrate and manganese nitrate, and tested in methanol steam reforming reaction for the preparation of hydrogen. The catalysts were characterized by BET, H_(2)-TPR, XRD, SEM, XPS, etc. The effects of addition ratio of Mn(CuMn_(x)Al_(4–x), x = 0~0.5) on the catalyst physicochemical properties,morphology and catalytic performance were investigated. The results showed that the specific surface area,reduction properties and surface chemistry of catalyst samples were altered with the addition ratio of Mn.With the increase of Mn proportion from 0 to 0.5(based on the molar of Cu, the same below), the particle size of spinel particles increased, the specific surface area decreased, and it became more difficult to be reduced. The catalytic performance of catalyst CuMn_(0.25)Al_(3.75) was the best. Under the reaction conditions of 260 ℃, 0.3 MPa, n(H_(2)O)∶n(CH3OH) =1∶1, weight hourly space velocity(WHSV) 3.0 g-feed/(g-cat·h),the highest methanol conversion rate was 91.7% and dropped to 78.8% after 150 h running, which were obviously higher than that of CuAl spinel catalyst without Mn.

关 键 词：共沉淀法 甲醇水蒸气重整 Cu-Mn-Al尖晶石 制氢 催化技术 

分 类 号：TQ116.2[化学工程—无机化工] TQ426