山梨醇催化氨化合成腈类化合物  

Synthesis of nitriles from catalytic amination of sorbitol

作　　者：孙福曾 牛保强 曹艳璐 周鹏程 于淼 张月成[1] Sun Fuzeng, Niu Baoqiang, Cao Yanlu, Zhou Pengcheng, Yu Miao , Zhang Yuecheng(School of Chemical Engineering, HebeiUniversity of Technology, Tianjin 300130, China)

机构地区：[1]河北工业大学化工学院,天津300130

出　　处：《石油化工》2018年第8期813-819,共7页Petrochemical Technology

基　　金：国家自然科学基金项目(21476057);河北省杰出青年科学基金项目(B2016202393);河北省自然科学基金项目(B2015202284)

摘　　要：采用负载法制备了一系列γ-Al_2O_3负载过渡金属Fe催化剂,并在固定床反应器上考察了其对山梨醇催化氨化合成腈类化合物的催化性能。以Fe_(15)/γ-Al_2O_3为催化剂,对反应温度、原料配比、气态空速(GHSV)等反应条件进行考察。采用XRD、N_2吸附-脱附、TEM、XPS及Py-FTIR对催化剂进行表征。实验结果表明,以Fe_(15)/γ-Al_2O_3为催化剂时最佳反应条件为:常压、510℃、n(氨气)∶n(山梨醇)=14∶1和GHSV=982 h^(-1)。在此反应条件下,山梨醇的转化率接近100%,乙腈和丙腈的总选择性可达40.1%,同时副产物吡啶的选择性为7.1%。表征结果显示,在γ-Al_2O_3上负载适量的Fe后,可形成一定量的B酸性位点,从而加快乙醛和氨气缩合生成亚胺,进而促进山梨醇向腈类化合物的转变;催化剂中Fe以Fe_2O_3纳米粒子形式存在,并且是山梨醇催化氨化反应中主要的脱氢-加氢活性催化物种。A series of catalysts were prepared by doping iron int oγ-Al2O3.The catalysts were evaluated in the transformation of sorbitol with ammonia to nitrile compounds in a fixed-bed reactor.Reaction temperature,ratio of raw material,gas hourly space velocity（GHSV）,and other reaction conditions were investigated with Fe（15）/γ-Al2O3 as catalyst.The catalysts were characteriz ed by XRD,N（2 ）adsorption measurement,TEM,XPS and Py-FTIR.The experimental results showed that the optimum reaction conditions with Fe（15）/γ-Al2O3 as catalyst were：temperature of 510℃,atmospheric pressure with a molar ratio of ammonia to sorbitol of 14∶1 and GHSV of 982 h^（-1）.Under the reaction conditions,the conversion of sorbitol was about 100%,the total carbon yield of acetonitrile and propionitrile reached 40.1%,and the selectivity of the by-products of pyridine was 7.1%.Characterization results revealed that the doping of a suitable amount of iron could create B acid centers in the catalyst,which could accelerate the condensation of aldehydes with ammonia to generate imines and were beneficial to the selective conversion of sorbitol to nitriles.The doped iron existed in the form of Fe2O3 nanoparticles.The Fe2O3 nanoparticles acted as dehydrogenation-hydrogenation active species in the catalytic conversion of sorbitol with ammonia.

关 键 词：山梨醇 氨化 乙腈 丙腈 Fe/γ-Al2O3 

分 类 号：TQ032.4[化学工程]