The pathways of the phthalic anhydride selectivity and yield increase at C4-C5-hydrocarbons oxidation

O. Kiziun, V. Zazhigalov
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Abstract

The investigation of n-butane and n-pentane oxidation in system with two consecutive reactors confirmed the mechanism of phthalic anhydride formation by Diels-Alder reaction between maleic anhydride and C4 unsaturated hydrocarbons. The process is limited by low stationary concentration of C4 unsaturated hydrocarbons in reaction mixture which is connected with high rate of their oxidation to maleic anhydride. It was shown that n-butane oxidation leads to formation of maleic anhydride only but the introduction of unsaturated C4-hydrocarbons on inlet of the second catalytic reactor accompanied by phthalic anhydride appearance on outlet of these two consecutive reactors system. It was established that in case of 1,3-butene introduction in the second reactor the quantity of phthalic anhydride formed is more than in case of 2-butene addition. It was predicted that a decrease of the temperature in the second reactor can leads to an increase the phthalic anhydride selectivity and its yield as result of Diels-Alder reaction effectiveness. This assumption was confirmed by experimental results. In results the method of phthalic anhydride production by the use of two consecutive reactors was proposed. The summary yield of this product on this new process can reach up to 35 mol. %. In the case of n-pentane oxidation the formation of maleic and phthalic anhydrides was observed with excess of first product but the introduction of unsaturated C4-hydrocarbons in the inlet of second reactor leads to an increase of the phthalic anhydride concentration and its selectivity and yield. In result the yield of phthalic anhydride equal to 35 mol. % can be obtained. So, the proposed by us mechanism of phthalic anhydride was confirmed by new experimental results and other pathways for the selectivity and yield of this product can be predicted.
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研究了邻苯二酸酐在c4 - c5 -烃类氧化过程中选择性和产率提高的途径
对正丁烷和正戊烷在两个连续反应器中的氧化反应进行了研究,证实了马来酸酐与C4不饱和烃Diels-Alder反应生成邻苯二甲酸酐的机理。反应混合物中C4不饱和烃的固定浓度低,氧化成马来酸酐的速率高,限制了该工艺的发展。结果表明,正丁烷氧化反应只生成马来酸酐,但在第二催化反应器入口处引入不饱和c4 -烃,并在两个连续的催化反应器系统的出口处出现邻苯二酸酐。结果表明,在第二反应器中引入1,3-丁烯时,邻苯二酸酐的生成量大于加入2-丁烯时。结果表明,降低第二反应器温度可以提高邻苯二酸酐的选择性和产率,这是由于Diels-Alder反应的有效性。实验结果证实了这一假设。结果提出了用两个连续反应器生产邻苯二酸酐的方法。新工艺的总收率可达35 mol. %。在正戊烷氧化反应中,第一反应产物过量生成马来酸酐和邻苯二甲酸酐,但第二反应入口引入不饱和c4 -烃后,邻苯二甲酸酐的浓度、选择性和产率均有所提高。结果可得到邻苯二甲酸酐的产率为35 mol. %。由此,我们提出的邻苯二甲酸酐反应机理得到了新的实验结果的证实,同时也可以通过其他途径预测该产物的选择性和产率。
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