甘氨酸高温热解含氮产物生成机理及实验研究  

Theoretic and experiment study on nitrogen-containing products of glycine during high temperature pyrolysis

作　　者：龚千代 刘亮[1] 田红[1] 刘成[1] 艾锦瑾 GONG Qiandai LIU Liang TIAN Hong LIU Cheng AI Jinjin(School of Energy ＆ Power Engineering, Changsha University of Science ＆ Technology, Changsha 410114, China)

机构地区：[1]长沙理工大学能源与动力工程学院,湖南长沙410114

出　　处：《西北大学学报（自然科学版）》2016年第5期695-701,共7页Journal of Northwest University（Natural Science Edition）

基　　金：国家自然科学基金资助项目(51276023);湖南省自然科学基金资助项目(2015JJ4005)

摘　　要：以甘氨酸分子为研究对象,用密度泛函理论B3LYP/6-31G基组对甘氨酸热解过程中的各反应物、过渡态、中间体及产物进行了结构优化和频率计算,并采用热重红外联用仪对甘氨酸进行了实验。研究结果表明,初反应以R1-1,R1-2以及R2-1为主。其中R2-1为氨基的脱离,所以热解的最终含氮产物中NH3所占比例最大。随后的实验也证明了这一点。R1-1和R1-2为两分子脱水形成DKP的反应。该路径的次反应包括R1-8和R1-14,最终产物分别是HCN和HNCO,在实验的最终产物中也被检出。在初反应中占劣势的路径R3-1有两条次反应路径R3-3和R3-11,其中前者的焓变相对较小,是该路径上的主要反应。最后将实验结果与理论计算结果进行对比,发现吻合度较好。Glycine are investigated as a research object by using DFT B3LYP/6-31G. All the reactants, transition states, intermediates and products during the pyrolysis are optimized and their frequencies are calculated. The experiment is conducted using a thermogravimetric analyzer coupled with a Fourier transform infrared spectrometer （TG-FTIR）. The results show that at the beginning of the reaction, the main pathways are R1.1, R1-2 and R2-1. R2.1 is the separation of the amino group, hence NH3 accounts for the largest percentage in the final nitrogen-containing products, the experiment also proved it. R1-1 and R1-2 are dehydration between two molecules. The secondary reaction of this pathway includes RI.s and R1-14, their final nitrogen-containing product is HCN and HCNO, which was detected in the experiment. R3-1 , which is at a disadvantage during the first stage, includes two second pathways, R3-3 and R3-11. R3-11 is the main pathway for the less enthalpy changes. Then the result of experiment is compared with the result of calculation, and the matching degree is relatively high.

关 键 词：甘氨酸 高温热解 密度泛函理论 含氮产物 热重红外联用 

分 类 号：TK16[动力工程及工程热物理—热能工程] TK6