【作者】 季艳；

【导师】 周兴贵；

【作者基本信息】 华东理工大学 ， 化学工程， 2012， 硕士

【摘要】 有机过氧化物是化学工业,特别是高分子领域中一种重要助剂,被广泛用作引发剂、固化剂、交联剂、氧化剂等。烷烃均相氧化反应是有效且直接利用烷烃的一种方式,具有广阔的工业应用前景和高度的学术研究价值。丙烷作为同时具有α-H和β-H,结构最简单的烷烃,可以作为低碳烷烃均相氧化的典型代表。本文旨在研究丙烷非催化氧化制备过氧化物的过程。采用连续反应方式,首先建立主要反应产物的定性和定量方法,特别是液相产品中有机过氧化物,即异丙基过氧化氢。然后再此基础上考察操作条件变化对反应过程的影响,从而确定了制备过氧化物最适合的反应条件,即C3H8:02=1:3,反应物流量30 ml/min,递减的温度分布330-300-250℃,结果实现了较为理想的反应状态,即没有气相产品并且液相产品中过氧化物含量较高。丙烷均相氧化是自由基反应过程,其中,非均相反应发挥着不可忽视的作用。在了解丙烷均相氧化机理的基础之上,还考察了反应器壁面效应对反应过程的影响。发现壁面对反应有着促进和抑制双重效果,一方面促进了反应链引发,另一方面,壁面附着物质累积到一定程度后反而会改变反应途径,严重破坏过氧化物的结构。更多还原

【Abstract】 Peroxide is an important addition agent in chemical industry, especially in polymer field, and widely used as reaction intermediates such as initiators, curing agents, crosslinkers, oxidants and so on. Homogeneous oxidation of alkanes is an effective and direct method to make full use of alkanes which is interested and pursued in industry and academy. Propane is chosen as the smallest molecule with bothα-H andβ-H, which can be taken as a representative of alkanes. The aim of the issue is to research the process of homogeneous oxidation of propane to produce peroxides, in which flow reactor is used. Firstly, qualitative and quantitative methods of the reaction productions are established, especially for the organic peroxide isopropylhydroperoxide in the liquid products. Based on the analysis, the influence of operation conditions is investigated, defining the available region, that is C3Hg:O2=1:3, total flow 30 ml/min, decreasing temperature distribution 330-300-250℃, besides the perfect condition, that is having high active oxygen content with nearly no gas phase products. Homogeneous oxidation of propane is a kind of radical reaction, in which heterogeneous reaction plays an important role. Based on the homogeneous oxidation mechanism of propane, the wall effect is also included. It shows that wall has both objective and inhibitive effects on the process. On one hand, the wall effect improves the chain initiation, on the other hand, the accumulations on the wall change the reaction path to decompose the peroxides as it is accumulated to some extent.更多还原