负载型金属催化剂催化1,6-己二醇选择性胺化反应的研究
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- 英文论文题名：Studies on Selective Amination of 1,6-Hexanediol over Supported Metal Catalysts
- 论文作者：李艳 ; 程海洋 ; 赵凤玉
- 英文论文作者：Yan Li ; Haiyang Cheng ; Fengyu Zhao ; State Key Laboratory of Electroanalytical Chemistry ; Changchun Institute of Applied Chemistry ; Chinese Academy of Sciences ; Laboratory of Green Chemistry and Process ; Changchun Institute of Applied Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院长春应用化学研究所电分析化学国家重点实验室;中国科学院长春应用化学研究所绿色化学与过程实验室;
- 论文关键词：1 ; 6-己二醇 ; 还原胺化 ; 多相催化
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十三分会：绿色化学
- 语种：中文
- 分类号：O621.251;O623.731
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十三分会 ; 绿色化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：206k
- 原文格式：D
- 会议级别：全国
摘要
1,6-己二胺是制造尼龙66盐的主要原料,在氨的存在下,使用负载型金属催化剂,以生物质基化学品1,6-己二醇选择性还原胺化制备1,6-己二胺的过程具有成本低、绿色环保等优点。采用气相色谱、气质联用及电喷雾质谱对1,6-己二醇选择性还原胺化的产物进行分析鉴定。考察反应温度、氨气及氢气压力、催化剂的活性组分(Ru、Pd、Pt)及载体酸碱性(Nb_2O_5、Al_2O_3、CaO)等因素对1,6-己二醇选择性还原胺化反应的影响。其中,系统压力及状态对反应影响非常显著,当压力达到15 MPa,体系变为超临界流体状态时,1,6-己二胺的选择性达到最大。以Ru/Al_2O_3为催化剂,讨论了反应基元步骤及动力学参数。结果证明,-OH的脱氢过程为反应的决速步骤,而且6-氨基-1-己醇及1,6-己二胺易发生环化及聚合反应,致使1,6-己二胺的选择性只有40%。
1,6-Hexanediamine(HDA) is one of the key intermediates in the preparation of nylon 6-6 by poly-condensation with adipic acid.Selective amination of bio-based product of 1,6-hexanediol with ammonia by supported metal catalysts is low-cost and environmentally attractive.The products of 1,6-hexanediol amination were analyzed by GC,GC-MS and ESI-MS.Reaction temperature,pressure of hydrogen and ammonia,the active component and acidic-basic properties of catalysts were investigated for the 1,6-hexanediol amination.The system pressure and state presented significant influence,at 15 MPa the system reached a supercritical state,and the largest selectivity of 1,6-diaminohexane was obtained.The reaction steps and the kinetic parameters of the 1,6-hexanediol amination were discussed with Ru/Al_2O_3 catalyst.The results showed that-OH dehydrogenation process is the rate-determining step,as the cyclization and polymerization of 6-amino-1-hexanol and 1,6-diaminohexane existed,resulting in a limited selectivity of 1,6-diaminohexane of 40%.
1,6-Hexanediamine(HDA) is one of the key intermediates in the preparation of nylon 6-6 by poly-condensation with adipic acid.Selective amination of bio-based product of 1,6-hexanediol with ammonia by supported metal catalysts is low-cost and environmentally attractive.The products of 1,6-hexanediol amination were analyzed by GC,GC-MS and ESI-MS.Reaction temperature,pressure of hydrogen and ammonia,the active component and acidic-basic properties of catalysts were investigated for the 1,6-hexanediol amination.The system pressure and state presented significant influence,at 15 MPa the system reached a supercritical state,and the largest selectivity of 1,6-diaminohexane was obtained.The reaction steps and the kinetic parameters of the 1,6-hexanediol amination were discussed with Ru/Al_2O_3 catalyst.The results showed that-OH dehydrogenation process is the rate-determining step,as the cyclization and polymerization of 6-amino-1-hexanol and 1,6-diaminohexane existed,resulting in a limited selectivity of 1,6-diaminohexane of 40%.
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