生物质甘油催化氨化制备有机胺的反应过程分析  

Reaction process analysis on catalytic amination of biomass-based glycerol to organic amine

作　　者：左志帅 郑广宗 安华良[1] 王桂荣[1] 赵新强[1] 王延吉[1] ZUO Zhishuai;ZHENG Guangzong;AN Hualiang;WANG Guirong;ZHAO Xinqiang;WANG Yanji(Hebei Provincial Key Lab of Green Chemical Technology and Efficient Energy Saving,Hebei University of Technology,Tianjin 300130,China)

机构地区：[1]河北工业大学绿色化工与高效节能河北省重点实验室,天津300130

出　　处：《高校化学工程学报》2023年第5期776-786,共11页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(21978066,U21A20306);河北省自然科学基金重点项目(B2020202048)。

摘　　要：针对生物柴油产业中副产甘油过剩的问题,提出基于甘油直接制备高附加值有机胺的方法。采用γ-Al_(2)O_(3)为载体,以Co为主金属组分制备负载型双金属催化剂,对甘油催化氨化反应进行了探索性研究。结果表明,甘油氨化反应体系复杂,其中Co-Ni/γ-Al_(2)O_(3)更有利于催化甘油氨化生成伯胺,伯胺的选择性之和为54.2%。采用气相色谱-质谱联用技术对甘油氨化反应体系进行定性分析,建立了反应网络,明晰了直链胺类以及哌嗪类衍生物的合成路径,得出生成乙二胺和1,2-丙二胺反应分别有2条可能路径。利用Aspen Plus对甘油催化氨化合成二元胺—乙二胺和1,2-丙二胺的反应路径进行了热力学分析,根据结果确定甘油氨化合成乙二胺很可能按照以3-氨基-1,2-丙二醇为中间产物的路径进行;对于甘油氨化合成1,2-丙二胺反应,在较低温度下,2-氨基丙醇路径和1-氨基-2-丙醇路径2种反应路径并存,而随着反应温度的升高变为以1-氨基-2-丙醇路径为主。In order to solve the problem of excessive glycerol in biodiesel production,a method of directly preparing high value-added organic amines based on glycerol was proposed.A series of supported bimetallic catalysts were prepared usingγ-Al_(2)O_(3) as the support and Co as the main metal component.Their catalytic performance for the amination of glycerol was investigated.The results show that the amination of glycerol is a complex reaction system and Co-Ni/γ-Al_(2)O_(3) is more conducive for catalyzing glycerol to primary amines with a primary amine selectivity of 54.2%.The reaction system was qualitatively analyzed by gas chromatography-mass spectrometry(GC-MS),and a reaction network was established with the synthesis pathways to straight-chain amines and piperazines clarified.Based on the GC-MS results,two possible reaction pathways to ethylenediamine and 1,2-propanediamine were proposed,respectively.To determine the most possible pathway,a thermodynamic analysis for the amination of glycerol to diamine—ethylenediamine and 1,2-propanediamine was performed using Aspen Plus.The synthesis of ethylenediamine from glycerol used 3-amino-1,2-propanediol as the intermediate.For the 1,2-propanediamine synthesis from glycerol,the pathways of 2-aminopropanol and 1-amino-2-propanol as intermediates happened simultaneously at a lower temperature.With the increase of reaction temperature,the latter becomes the main pathway.

关 键 词：甘油 催化氨化 有机胺 反应路径 热力学分析 

分 类 号：TQ032.4[化学工程]