废油脂生物柴油副产甘油制备环氧氯丙烷的研究

Preparation of epichlorohydrin from by-product glycerine of waste oil biodiesel

为了延长生物柴油产业链,以废油脂生物柴油副产物粗甘油为原料,高值化利用生产衍生物环氧氯丙烷(ECH)。粗甘油原料被提纯成工业级甘油,经氯化反应和环化反应制备了环氧氯丙烷。以200 m L/min的氯化氢气体为氯化剂、己二酸为催化剂,在反应温度为105℃、己二酸质量分数为7.5%的条件下,通过降温真空除水3次,制得二氯丙醇(DCP),氯化收率达93.2%,甘油转化率达96.7%。在氢氧化钠催化下二氯丙醇环化制得环氧氯丙烷。通过单因素实验得到环化反应的最佳工艺条件为:反应时间为30 min、氢氧化钠与二氯丙醇摩尔比为1.2∶1、反应温度为90℃,在此条件下的环化收率为89.5%。

In order to extend the industrial chain of biodiesel,epichlorohydrin(ECH)is produced from crude glycerol,a by-product of biodiesel from waste oils.Crude glycerol is firstly purified into industrial grade glycerol and then ECH is prepared from industrial grade glycerol through chlorination and cyclization.Using a flow of 200 m L/min HCL gas as chlorinating agent and adipic acid as catalyst,dichloropropanol(DCP)is synthesized by three times of vacuum dehydration under the optimum conditions that the reaction temperature maintains at 105℃and the mass content of adipic acid is 7.5%.The chlorination yield reaches 93.2%and the conversion of glycerol is 96.7%.ECH is obtained through cyclization of DCP over sodium hydroxide.Through single factor experiments,the optimum conditions of cyclization reaction are obtained as follows:the reaction lasts for 30 min,the molar ratio of sodium hydroxide to DCP is1.2∶1,and reaction temperature maintains at 90℃.Under these conditions,the yield of cyclization can achieve 89.5%.