CIESC Journal

• 化工学报 • 上一篇    下一篇

反应条件对石蜡深度氧化制取二元酸的影响

奚祖威,杜文,宋树忠,袁启年   

  1. 中国科学院化学物理研究所 ,中国科学院化学物理研究所 ,中国科学院化学物理研究所 ,中国科学院化学物理研究所
  • 出版日期:1965-09-25 发布日期:1965-09-25

ON THE INFLUENCE OF REACTION CONDITIONS BY DEEP OXIDATION OF PARAFFIN WAX TO DIBASIC ACIDS

Institute of Chemical Physics, Academia Sinica Xi ZU-WBI, Du WEN, SONG SHU-ZHONG, YUAN QI-NIAN   

  • Online:1965-09-25 Published:1965-09-25

摘要: 研究了石蜡液相深度氧化过程中氧吸收量与氧化蜡组成变化的关系。结果说明,深度氧化蜡绝大部分是由多官能团酸组成,其官能团除羧基为主外,次为酯基,其量为羧基的一半,羰基较少,而羟基几无。C_4~C_(10)二元酸在氧化醋酸价为250毫克KOH/克左右时开始有明显的含量,并且随着氧化深度的增加而含量迅速增加。在适宜的催化剂和较好的气液接触情况下,石蜡能否快速定向深度氧化的关键在于恰当的选择温度和氧分压;使整个反应过程中氧化尽可能在化学动力学控制范围内进行,减少扩散因素的影响。试验结果表明,氧化蜡的酯价/酸价比值可作为反映氧扩散速度是否满足氧化动力学速度的需要,也可以估计氧化所能达到的最高酸价。氧化过程中物料收率变化的规律说明,在反应后期氧化蜡收率的显著降低,与此时CO_2和冷凝水相的生成速度迅速增加有关。氧化至酸价400以上后,C_4~C_(10)二元酸的收率最高可达40%(对原料石蜡)。从色谱分析结果得知,在C_4~C_(10)的单体二元酸分布中,一般皆以丁二酸为最多,次为戊二酸,并且C_4~C_5和C_6~C_(10)二元酸的收率相近。

Abstract: The relation between the oxygen absorption and the composition of oxidized wax in the course of liquid-phase deep oxidation of paraffin wax has been studied. The experimental results show that the oxidized wax is almost composed of acids with different functional groups, of which carboxyl group predominates, ester group is the next (about one half the quantity of carboxyl), then comes the carbonyl group, but the hydroxyl group is almost zero. When the acid value of oxidized wax amounts to about 250mg.KOH/g., an appreciable amount of C4-C10 dibasic acids commencos to be produced, and their yield will be rapidly increased as the oxidation proceeds more deeply. With a suitable catalyst and better contact between the gas and the liquid, the rate and selectivity of the deep oxidation reaction of paraffin wax are dependent on the reaction temperature and the partial pressure of oxygen used, so that the oxidation should be carried out as much as possible under chemical kinetic conditions to reduce the effect of diffusion. Furthermore, the experimental results show that the ratio between the ester value and acid value may be considered as an index to show whether the diffusion rate of oxygen meets the requirements of the kinetic velocity of oxidation or not. This ratio may also be used to estimate the maximum acid value that oxidation can produce. The variation of the product yields in the oxidation reaction indicates the rapid decrease of oxidized wax in the final reaction stage due to the very high velocity of formation of CO2 and condensed water phase. When acid value exceeds 400, the yield of C4-C10 dibasic acids up to 40% will result. By chromatographic analysis, it is found that the yield of succinic acid in general is the highest, glutaric acid the next and that of C4-C5 and C6-C10 dibasic acids in about equal quantities.