助剂对Ni-Al合金和Raney-Ni催化剂结构及1,4-丁烯二醇加氢性能的影响  

Effect of Promoter on the Ni-Al Alloy&the Corresponding Raney-Ni Catalyst and Hydrogenation Performance of 1,4-Butylenediol

作　　者：郜宪龙 莫文龙[1] 马凤云[1] 樊星 GAO Xian-Long;MO Wen-Long;MA Feng-Yun;FAN Xing(Key Laboratory of Coal Clean Conversion&Chemical Engineering Process(Xinjiang Uyghur Autonomous Region),College of Chemistry and Chemical Engineering,Xinjiang Liniversity,Urumqi 830046,China)

机构地区：[1]煤炭洁净转化与化工过程新疆维吾尔自治区重点实验室,新疆大学化学化工学院,乌鲁木齐830046

出　　处：《无机化学学报》2020年第5期958-968,共11页Chinese Journal of Inorganic Chemistry

基　　金：新疆维吾尔自治区重点研发计划项目(No.2017B02012);新疆大学自然科学基金项目(No.BS160221)资助。

摘　　要：采用等体积浸渍法将助剂(MgO、CuO、Co2O3)引入商品Ni-Al合金粉,经10%(w/w)NaOH溶液浸取制备Raney-Ni催化剂。通过能量色散X射线(EDX)、X射线衍射(XRD)、N2吸附-脱附测试、透射电镜(TEM)、NH3程序升温脱附(NH3-TPD)、X射线光电子能谱(XPS)等方法表征和评价实验,考察了金属助剂对Ni-Al合金粉及Raney-Ni催化剂元素组成、晶相结构、孔结构特征、表面形貌、表面酸碱性的影响。表征分析显示,不同助剂催化剂的元素含量、比表面积及表面形貌均表现出明显的差异。其中,添加助剂Cu的催化剂表面检测到较多的活性组分Ni,接近90%(w/w),该催化剂平均孔径最小(3.87 nm)、活性组分Ni颗粒分散性好。评价结果表明,该催化剂具有较佳的加氢性能,其1,4-丁烯二醇(BED)转化率为100%,1,4-丁二醇(BDO)选择性和收率分别为59.62%和59.62%,这与该催化剂较大的活性组分Ni负载量、酸强度和适中的酸量及存在的Cu对Ni分散性的提高进一步防止了Ni的严重烧结(即"限域效应")等有较大关联。Three promoters(MgO,Cu O,Co2O3)were introduced individually into the commercial Ni-Al alloy powder by impregnation method,and the modified alloys were leached by 10%(w/w)NaOH solution to prepare Raney-Ni catalysts.Effect of promoter on the elemental composition,crystal structure,pore structure,surface morphology and surface acidity of the Ni-Al alloy and the corresponding Raney-Ni catalyst was investigated by energy dispersive X-ray(EDX),X-ray diffraction(XRD),N2 adsorption-desorption,transmission electron microscope(TEM),NH3 temperature programmed desorption(NH3-TPD)and X-ray photoelectron spectroscopy(XPS)methods.Results showed that the element content,specific surface area and surface morphology of the catalyst modified by different promoter proposed significant difference.Large amount of Ni-the active component on the Cu-modified catalyst was detected with the content of about 90%(w/w),showing excellent dispersion,and the catalyst presented small average pore size(3.87 nm).Evaluation results showed that the catalyst displayed well hydrogenation performance,with 1,4-butenediol(BED)conversion of 100%,both 1,4-butanediol(BDO)selectivity and yield of 59.62%,which was related to the high Ni content,the moderate amount of acid sites and the small Cu crystal for improving Ni dispersion without serious sintering by the"confinement effect".

关 键 词：Raney-Ni催化剂 1 4-丁烯二醇 1 4-丁二醇 助剂 加氢 

分 类 号：O643.32[理学—物理化学]