Abstract:

To overcome the shortcomings of the industrial production of 1,2-propanediamine by dihalopropane and ammonia, a series of supported Co-based catalysts were prepared to catalyze the synthesis of 1,2-propanediamine by 1,2-propanediol amination. The effects of support, second metal component and metal loading amount on their catalytic performance were investigated particularly on the basis of catalyst characterization by H₂-TPR, TEM and ICP-MS. The results show that the 15Co-1.05Pt/HAP prepared with hydroxyapatite (HAP) as a carrier with both acid and base active sites has the best catalytic effect, with a 1,2-propylene glycol conversion rate of 68.5%, a 1,2-propylene diamine selectivity of 27.0%, and a total selectivity of primary amines of 95.2%. There is an obvious interaction between metal Pt and Co in the catalyst, and further Co-Pt nanoparticles exist in the form of alloy. The introduction of Pt can promote the reduction of cobalt oxide and make the average metal particle size smaller, thereby effectively improving the catalytic performance of Co-based catalysts. Qualitative analysis for 1,2-propanediol amination reaction system was performed by gas chromatography-mass spectrometry (GC-MS). The reaction pathway of 1,2-propanediol amination catalyzed by Co-Pt/HAP was determined with the help of designed experiments.

Key words: 1,2-propanediamine, 1,2-propanediol, catalyst, catalytic amination, multiphase reaction, catalysis, reaction pathway

摘要：

为克服工业上氨与二卤丙烷反应合成1，2-丙二胺工艺的缺点，制备一系列负载型Co基催化剂，对其催化1，2-丙二醇氨化合成1，2-丙二胺反应性能进行研究。采用H₂-TPR、TEM、ICP-MS等方法对催化剂进行了表征，重点考察了载体、第二金属组分、金属负载量等的影响。结果表明，以兼具酸-碱活性位点的羟基磷灰石（HAP）为载体制备的15Co-1.05Pt/HAP催化效果最佳，1，2-丙二醇转化率为68.5%，1，2-丙二胺选择性为27.0%，伯胺总选择性达到95.2%。催化剂中Pt与Co之间存在明显相互作用，Co-Pt纳米颗粒以合金的形式存在；Pt的引入不仅可以促进氧化钴的还原，而且使金属平均粒径更小，从而有效提高了钴基催化剂的性能。利用气相色谱-质谱联用技术对1，2-丙二醇氨化反应体系进行了定性分析，结合设计实验确定了Co-Pt/HAP催化1，2-丙二醇氨化的主要反应路径。

关键词: 1, 2-丙二胺, 1, 2-丙二醇, 催化剂, 催化氨化, 多相反应, 催化作用, 反应路径