摘要
为了研究1,4-丁二醇脱水反应机理和催化调控机制,基于密度泛函理论和变分过渡态理论,使用Gaussian软件计算了该反应网络中各物质的热力学参数,通过对各反应过渡态及反应路径的搜索,确定反应基元步骤,明确了反应催化剂设计与反应过程强化的基本策略。结果表明,在研究的温度范围内,各反应平衡常数较大,整个过程为动力学控制。生成四氢呋喃的平行副反应和生成1,3-丁二烯的串联副反应势垒最低,对主产物3-丁烯-1-醇选择性的影响最大。可通过酸碱双功能催化剂的设计对1,4-丁二醇端羟基及β-H同时实施活化,使1,4-丁二醇更易脱水生成3-丁烯-1-醇,同时缩短3-丁烯-1-醇停留时间来抑制串联副反应的发生。
The dehydration reaction mechanism of 1,4-butanediol and the regulation mechanism of catalyst were studied using Gaussian 09 based on the DFT theory and transition state theory,and the thermodynamic parameters of the 1,4-butanediol reaction network were calculated.The elementary steps were determined by searching the transition state and pathway of each reaction.The strategies of both catalyst design and reaction process intensification were also clarified.Results show that the reaction network was under kinetic control within the studied temperature range due to large equilibrium constants.Kinetic studies indicated that the parallel side reaction of tetrahydrofuran formation and the tandem side reaction of 1,3-butadiene formation greatly influenced the selectivity of 3-buten-1-ol due to their low potential energy barriers.The terminal hydroxyl group andβ-H can be simultaneously activated by designing an acid-base bifunctional catalyst to make 1,4-butanediol dehydrating to 3-buten-1-ol more easily.Meanwhile,the method of reducing the residence time of 3-buten-1-ol could be used to suppress the occurrence of tandem side reactions.
作者
米容立
吴志强
杨伯伦
MI Rong-li;WU Zhi-qiang;YANG Bo-lun(School of Chemical Engineering and Technology,Xi’an Jiaotong University,Xi’an 710049,China;State Key Laboratory of Multiphase Flow in Power Engineering,Xi’an Jiaotong University,Xi’an 710049,China)
出处
《高校化学工程学报》
EI
CAS
CSCD
北大核心
2021年第2期287-297,共11页
Journal of Chemical Engineering of Chinese Universities
基金
陕西煤业化工集团有限责任公司(20160109)。
关键词
热力学
反应机理
量子化学
动力学
thermodynamics
reaction mechanisms
quantum chemistry
kinetics
