去氢枞酸固液溶解度及其反应-结晶耦合单离方法  

Solid-liquid Solubility of Dehydroabietic Acid and Its Reaction Crystallization Coupled Single Separation Method

作　　者：任宝光 杨和见 陈小鹏 侯文彪 张众尧 李前 黄卫 REN Baoguang;YANG Hejian;CHEN Xiaopeng;HOU Wenbiao;ZHANG Zhongyao;LI Qian;HUANG Wei(Wuzhou Huangpu Chemical Pharmaceutical Co.,Ltd.,Wuzhou 543000,China;School of Chemistry and Chemical Engineering,Guangxi University,Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology,Nanning 530004,China;Wuzhou Sun Shine Forestry&Chemicals Co.,Ltd.,Wuzhou 543100,China)

机构地区：[1]梧州黄埔化工药业有限公司,广西梧州543000 [2]广西大学化学化工学院,广西石化资源加工及过程强化技术重点实验室,广西南宁530004 [3]广西梧州日成林产化工股份有限公司,广西梧州543100

出　　处：《生物质化学工程》2024年第3期39-47,共9页Biomass Chemical Engineering

基　　金：国家自然科学基金资助项目(32160349,31960294);广西石化资源加工及过程强化技术重点实验室课题基金资助项目(2019Z002)。

摘　　要：采用激光监视技术判断平衡终点,由动态法测定了282~325 K去氢枞酸在甲醇、无水乙醇、正丙醇、正丁醇中的固液溶解度;应用λh模型、Wilson模型、简化模型分别对溶解度数据进行关联;采用超/亚临界CO_(2)强化胺化反应-结晶耦合方法单离去氢枞酸,以GC分析、熔点和旋光率检测去氢枞酸纯度。结果表明:去氢枞酸在4种醇类溶剂中的溶解度均随温度的升高而增大,其溶解度大小在不同溶剂中顺序为:正丁醇>正丙醇>无水乙醇>甲醇;去氢枞酸在4种醇类溶剂中的溶解度数据用λh模型、Wilson模型和简化模型关联的平均相对误差最大值分别为1.23%、2.15%和0.87%;通过正交试验得到超/亚临界CO_(2)强化胺化反应-结晶耦合单离去氢枞酸的最优反应条件为:反应时间50 min,反应温度308 K,CO_(2)压强7.5 MPa,溶剂乙醇体积分数50%,搅拌转速400 r/min,所得去氢枞酸的收率为81.85%,纯度为99.62%;去氢枞酸熔点为446.0~446.5 K,旋光率[α]^(20) _(D)为+62.2°。The laser monitoring technique was used to determine the equilibrium end point.The solid-liquid solubility of dehydroabietic acid at 282-325 K in methanol,absolute ethanol,n-propanol and n-butanol was determined by dynamic method.Theλh model,Wilson model and simplified model were used to correlate the solubility data.Dehydroabietic acid was isolated by supercritical/subcritical CO_(2)-enhanced amination reaction-crystallization coupling method.The purity of dehydroabietic acid was detected by gas chromatography(GC)analysis,melting point and optical rotation rate.The results showed that the solubility of dehydroabietic acid in four alcohol solvents increased with the increase of temperature,and the order of the solubility in different solvents was as follows:n-butanol>n-propanol>absolute ethanol>methanol.The maximum average relative error values of the solubility data of dehydroabietic acid in four alcohol solvents correlated byλh model,Wilson model and simplified model were 1.23%,2.15%and 0.87%,respectively.Through orthogonal experiment,the optimal reaction conditions of supercritical/subcritical CO_(2)amination reaction-crystallization coupling single-separation dehydroabietic acid were obtained as follows:reaction time of 50 min,reaction temperature of 308 K,CO_(2)pressure of 7.5 MPa,solvent ethanol volume fraction of 50%,stirring speed of 400 r/min.The yield of dehydroabietic acid was 81.85%and the purity was 99.62%.The melting point of dehydroabietic acid was 446.0-446.5 K,and the optical rotation[α]^(20) _(D) was+62.2°.

关 键 词：去氢枞酸 溶解度 超/亚临界CO_(2) 胺化反应-结晶 单离 

分 类 号：TQ35[化学工程] O629.61[理学—有机化学]