CuCo双金属催化剂催化糠醛加氢制备1,5-戊二醇的研究  

Hydrogenation of furfural to 1,5-pentanediol over CuCo bimetallic catalysts

作　　者：海雪清 谭静静 何静 杨新玲 那逸飞 王永钊[1] 赵永祥[1] HAI Xue-qing;TAN Jing-jing;HE Jing;YANG Xin-ling;NA Yi-fei;WANG Yong-zhao;ZHAO Yong-xiang(Engineering Research Center of Ministry of Education for Fine Chemicals,School of Chemistry and Chemical Engineering,Shanxi University,Taiyuan 030006,China)

机构地区：[1]山西大学化学化工学院精细化学品教育部工程研究中心,山西太原030006

出　　处：《燃料化学学报（中英文）》2023年第7期959-969,共11页Journal of Fuel Chemistry and Technology

基　　金：国家自然科学基金(22005182,U1710221);山西省高等学校科技创新项目(2020L0012)资助。

摘　　要：通过尿素均匀沉淀法合成了一系列具有不同Cu/Co物质的量比的Cu_(x)Co_(3-x)Al类水滑石催化剂,并将其用于糠醛(FAL)直接加氢-氢解制备1,5-戊二醇(1,5-PeD)。研究结果表明,Cu/Co物质的量比对催化剂的织构性质及其催化性能具有显著的影响。当Cu/Co物质的量比为1∶29(Cu_(0.1)Co_(2.9)Al)时,催化剂表现出优异的催化性能,在140℃,4 MPa H_(2)条件下反应6 h,糠醛的转化率为100%,戊二醇的收率为51.1%,其中,1,5-戊二醇的收率为41.1%。采用程序升温还原(H_(2)-TPR)、程序升温脱附(H_(2)-TPD)、X射线光电子能谱(XPS)和拉曼光谱(Raman)等表征技术证实,Cu_(0.1)Co_(2.9)Al催化剂具有高活性的原因在于其表面具有最高含量的Cu^(0)和CoO_(x),且两者具有协同催化效应。Cu^(0)用于吸附和活化H_(2),CoO_(x)具有一定氧空位,可以促进糠醛分子中C=O基的吸附与活化,使其快速加氢生成糠醇,同时氧空位可以锚定中间体糠醇中–OH使其在催化剂表面产生C2端斜式吸附,促使C2=C3加氢,弱化C2–O1键使其断裂,进而提高1,5-戊二醇的选择性。A series of Cu_(x)Co_(3-x)Al hydrotalcite-like catalysts with different Cu/Co molar ratios were synthesized by the urea homogeneous precipitation method and used for the direct hydrogenation–hydrogenolysis of furfural to 1,5-pentanediol.The results showed that the Cu/Co molar ratio of the catalyst had a significant effect on its textural properties and catalytic performance.The catalyst exhibited excellent catalytic performance when the molar ratio of Cu/Co was 1∶29(Cu_(0.1)Co_(2.9)Al),and the conversion of furfural was 100%together with 51.1%yield of pentanediol among which the yield of 1,5-pentanediol was 41.1%,under the reaction condition of 140oC,4 MPa H_(2) for 6 h.Extensive characterization techniques,including temperature-programmed reduction(H_(2)-TPR),temperature-programmed desorption(H_(2)-TPD),X-Ray photoelectron spectroscopy(XPS)and Raman confirmed that the excellent catalytic activity of Cu_(0.1)Co_(2.9)Al catalyst was attributed to the highest content of Cu^(0) and CoO_(x) on its surface,and a synergistic catalytic effect was present between them.Typically,Cu^(0) was used to adsorb and activate H_(2),and CoO_(x) with much oxygen vacancies promoted the adsorption and activation of C=O groups in furfural molecules,leading to the quick conversion of furfural to furfuryl alcohol.In addition,the oxygen vacancies anchored the–OH in the intermediate furfuryl alcohol to produce a C2-terminal oblique adsorption on the catalyst surface.Then it promoted the hydrogenation of C2=C3 with the weakening and cleavage of C2–O1 bond,and enhanced the selectivity of 1,5-pentanediol.

关 键 词：糠醛 1 5-戊二醇 加氢 CuCo双金属 协同催化 活性 

分 类 号：O643.36[理学—物理化学]