相转移催化剂对模拟原油脱氯反应的影响

Study on impact of phase-transfer catalyst on simulated crude oil dechlorination

原油中的有机氯很难在原料油加工之前脱除,造成加工设备腐蚀、催化剂中毒。有机氯脱除的工艺设计是实现低成本炼油的关键所在。自行设计模拟原油脱有机氯的工艺过程,用3种季铵盐类相转移催化剂和2种亲核试剂,考察模拟油中有机氯脱除的工艺条件。实验结果表明,以亚硝酸钠(D)为亲核试剂,四正丁基溴化铵(A1),四甲基硝酸铵(A2),四丁基硫酸氢铵(A3)分别在不同温度下反应60 min时,脱氯效果最佳,脱氯率分别为A1:109℃,19.65%;A2:104℃,17.25%;A3:106℃,14.76%。催化剂的用量增加对脱氯率影响显著,其中A1催化剂在最佳温度条件下用量为0.15 g、催化脱氯反应1 h,脱氯率达到27.68%。以乙醇钠(E)为亲核试剂,A1为催化剂时,最佳脱氯条件为:106℃、反应1 h,A1用量为0.15 g,脱氯率提高到45.77%。

It is difficult to remove organic chlorines from crude oil before processing. The presence of organic chlorines causes corrosion of process equipment and catalyst poisoning. The good process design for the removal of organic chlorines is very critical for the low-operating-cost refinery. The simulation of organic chlorine removal process for crude oil is self designed. The process conditions for the removal of organochlorines in simulation oil are studied with three kinds of quaternary ammonium phase transfer catalysts and two kinds of nucleophiles. The experimental results show that,when sodium nitrite（ D） is used as the nucleophile and tetra-n-butylammonium bromide（ A1）,tetramethylammonium nitrate（ A2） and Tetrabutyl ammonium bisulfate（ A3） are applied as catalysts for the 60 minutes＇ reaction at different temperatures,the best dechlorination condition and dechlorination rate are： 109 ℃ and 19. 65% for A1,104 ℃ and 17. 25% for A2 and 106 ℃and 14. 76% for A3. The increased amount of catalyst has a significant impact on the dechlorination rate.When A1 is used for the 1 hour＇s dechlorination reaction at conditions of 0. 15 g dosage and preferred reaction temperature,the dechlorination rate reaches 27. 68%. When sodium ethoxide（ E） is applied as nucleophile and A1 as the catalyst,the optimal dechlorination conditions are 106 ℃ reaction temperature,1h reaction time and 0. 15 g catalyst dosage,and the dechlorination rate is increased to 45. 77%.