废塑料裂解油加氢脱有机氯化物复杂反应体系的热力学分析

THERMODYNAMIC ANALYSIS OF THE COMPLEX REACTION SYSTEM FOR HYDRODECHLORINATION IN WASTE PIASTICS PYROLYSIS OIL

采用Aspen Plus软件,对从废塑料裂解油中鉴定出的13种有机氯化物在指定加氢反应条件下的加氢脱氯复杂反应体系的热力学进行了分析。首先,基于吉布斯自由能最小化原理的热力学分析方法,使用Aspen Plus软件中的Gibbs反应器进行模拟分析,确定在指定初始组成及反应条件下各种有机氯化物的平衡组成;然后,采用灵敏度分析工具,考察了氢油比、反应温度及压力等因素对该复杂反应体系平衡组成的影响,并探究了氢气与各种有机氯化物反应的先后顺序。分析结果表明:在指定的反应条件下,该复杂反应体系中13种有机氯化物的加氢脱氯反应均可自发进行,且基本上均可反应完全;对于给定有机氯化物初始组成的废塑料裂解油,其加氢脱氯的适宜反应条件为反应温度300-320℃、压力3-5 MPa、氢油体积比3.7;与氯代芳烃相比,氯代烯烃和氯代烷烃优先与氢气进行加氢脱氯反应;在氢气过量的条件下,氯代烷烃的反应完全程度低于氯代烯烃和氯代芳烃。

The thermodynamics of the complex hydrodechlorination reaction system of 13 kinds of organochlorides identified from the waste plastics pyrolysis oil was analyzed by using Aspen Plus software.First,simulations were performed using a Gibbs reactor in Aspen Plus software using thermodynamic analysis based on the principle of Gibbs free energy minimization,determining the equilibrium composition of the various organic chlorides under the specified initial composition and reaction conditions;then using the sensitivity analysis tool,the effects of the hydrogen-oil volumetric ratio,reaction temperature and pressure on the equilibrium composition of the complex reaction system were investigated.The results showed that the hydrodechlorination reaction of 13 kinds of organochlorides in the complex reaction system could be carried out spontaneously and completely under the given reaction conditions.For a given initial composition of organochlorides,hydrodechlorination effect was the best when the hydrogen-oil volumetric ratio was 3.7,the reaction temperature was 300-320℃,and the reaction pressure was 3-5 MPa.Under the condition of excess hydrogen,the reaction degree of chloroalkanes was lower than that of chloroalkenes and aryl chlorides.