分子蒸馏过程稀薄气体的流动及天然产物提纯的研究
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摘要
分子蒸馏(又称短程蒸馏)是高真空下的非平衡连续蒸馏过程,是一种没有沸腾的特殊分离技术; 自二十世纪三十年代问世以来,以其诸多优点得到了前所未有的发展,特别是在热敏性物质分离中发挥了独特的作用。但由于分子蒸馏理论研究还不够深入,限制了分子蒸馏设备的进一步应用。因此,结合分子蒸馏液膜传质和传热过程,研究蒸发区间稀薄气体的运动规律对工艺优化和分子蒸馏器放大生产具有十分重要的意义。
本文中,稀薄气体在一维稳态流动基础上,从气体能量守恒和平板间多组分矩方程出发,将蒸发空间划分为蒸发动力层,稳态流动层和冷凝动力层; 研究了由蒸发和冷凝引起的稀薄气体的运动规律,建立了蒸气分子在蒸发空间的运动模型。通过四矩法方程得出了稀薄气体的宏观性质和微观性质分布,建立了蒸气传质和传热方程。该模型方程可以预测蒸发空间气体分子数密度、动力学温度和宏观速度的分布规律,还可以预测馏出产物的组成和收率,为分子蒸馏器的放大生产提供理论基础。
本文考察了操作参数蒸发温度、冷凝温度、液相组成和惰性气体分压,以及结构参数蒸发面与冷凝面间距等对传质效率和分离效率的影响。研究表明,当蒸发和冷凝温度恒定时,稳态流动层的平均温度随稀薄气体流速的增大而降低; 传质效率和分离效率均随蒸发温度的升高而降低; 分离效率随冷凝温度和原料组成的变化并不明显,而传质效率对冷凝温度比较敏感; 当残留惰性气体压力较低和不考虑其分压时,蒸发面和冷凝面间距对传质效率和分离效率的影响都不大。
本文采用分子蒸馏技术对海狗油乙酯中功效成分EPA-EE、DHA-EE和DPA-EE的提取浓缩进行工艺研究。分子蒸馏过程中,考察了蒸馏温度、系统压力、进料速率、刮膜转速、操作比和操作级数等工艺参数对功效成分总含量和收率的影响; 探讨了海狗油乙酯中各组分的分馏温度,并对该研究进行经济核算,为工业化放大生产奠定基础。
本文还对同分异构体间-对乙酰氨基苯乙酸乙酯的预分离给予了尝试,考察了上述工艺参数对两组分分离效率和相对含量的影响,通过验证性实验确定其最佳分离工艺条件,减轻同分异构体后序结晶工艺负荷,拓宽了分子蒸馏技术的应用领域。
Molecular distillation (MD), which also defined as short path distillation (SPD), is a special separation technology without boiling, non-equilibrium and continual distillation process at high vacuum condition. Since MD came out in 1930s, enormous developments of MD has been acquired with its lots of virtues, especially tremendous excess in separating thermal sensitive natural product. However, lack of deep studies on MD made the molecular distillatory in industry restrained. Therefore, combined with mass and heat transfer in liquid film, it is important for optimizing operation condition and enlarging equipment to study rarefied gas flowing in distillatory.
In this dissertation, the space in distillatory is divided into three sections, including evaporating kinetic layer, steady flowing layer and condensing kinetic layer. In fact, rarefied gas flowing is produced by temperature difference between evaporation surface and condensation surface. The flowing process, which can be simply regarded as one dimension flowing, is studied on basis of energy conservation law and multi-composition moment equation of two parallel planes. Many properties of rarefied gas can be established by four-moment equation, including macroscopic and microscopic properties, mass and heat transfer equations. What’s more, these equations are solved with Delphi program. The mathematical models can predict the profile of rarefied gas, such as numerical density, kinetic temperature and macroscopic velocity, and the profile of distillate, too. So the flowing model make it possible to apply experimental distillatory to industrial equipment.
The influence of operating and structure parameters on mass transfer efficiency and separation efficiency is studied, including composition in liquid film, partial pressure of inert gas, evaporation and condensation temperature, and distance between evaporating and condensing surfaces. It can be concluded from simulation that macroscopic temperature in steady flowing layer falls with velocity growing when evaporating and condensing temperature are constant, and that mass transfer efficiency and separation efficiency are decreasing with evaporating temperature increasing. However, the mass transfer efficiency is sensitive for condensing temperature. Besides, the effect of distance of two surfaces on mass transfer efficiency and separation efficiency is quite week whether taking inert partial pressure into consideration or not.
The technological conditions of concentrating effective compositions from seal oil
ethyl ester by molecular distillation are studied in this dissertation. In distillation process, the influence of operating parameters on total content and yield of effective compositions is investigated, such as distillation temperature, operating pressure, feed rate and operating stage. The fractionation temperatures of each composition in seal oil ethyl ester are discussed, and economic value on this item is evaluated. To meet the crystallization separation process for isomer, molecular distillation is applied to a preliminary separation of para-acetaminophenylacetate ethyl for the first time. The effect of above experimental parameters on relative content and separation efficiency of two components has been studied. In addition, several methods of improving product yield are presented in molecular distillation process. The optimal conditions could be included via repeated experiments, and reduces the crystallization load of isomer. The study of molecular distillation provides theoretical value for its new application yield.
本文中,稀薄气体在一维稳态流动基础上,从气体能量守恒和平板间多组分矩方程出发,将蒸发空间划分为蒸发动力层,稳态流动层和冷凝动力层; 研究了由蒸发和冷凝引起的稀薄气体的运动规律,建立了蒸气分子在蒸发空间的运动模型。通过四矩法方程得出了稀薄气体的宏观性质和微观性质分布,建立了蒸气传质和传热方程。该模型方程可以预测蒸发空间气体分子数密度、动力学温度和宏观速度的分布规律,还可以预测馏出产物的组成和收率,为分子蒸馏器的放大生产提供理论基础。
本文考察了操作参数蒸发温度、冷凝温度、液相组成和惰性气体分压,以及结构参数蒸发面与冷凝面间距等对传质效率和分离效率的影响。研究表明,当蒸发和冷凝温度恒定时,稳态流动层的平均温度随稀薄气体流速的增大而降低; 传质效率和分离效率均随蒸发温度的升高而降低; 分离效率随冷凝温度和原料组成的变化并不明显,而传质效率对冷凝温度比较敏感; 当残留惰性气体压力较低和不考虑其分压时,蒸发面和冷凝面间距对传质效率和分离效率的影响都不大。
本文采用分子蒸馏技术对海狗油乙酯中功效成分EPA-EE、DHA-EE和DPA-EE的提取浓缩进行工艺研究。分子蒸馏过程中,考察了蒸馏温度、系统压力、进料速率、刮膜转速、操作比和操作级数等工艺参数对功效成分总含量和收率的影响; 探讨了海狗油乙酯中各组分的分馏温度,并对该研究进行经济核算,为工业化放大生产奠定基础。
本文还对同分异构体间-对乙酰氨基苯乙酸乙酯的预分离给予了尝试,考察了上述工艺参数对两组分分离效率和相对含量的影响,通过验证性实验确定其最佳分离工艺条件,减轻同分异构体后序结晶工艺负荷,拓宽了分子蒸馏技术的应用领域。
Molecular distillation (MD), which also defined as short path distillation (SPD), is a special separation technology without boiling, non-equilibrium and continual distillation process at high vacuum condition. Since MD came out in 1930s, enormous developments of MD has been acquired with its lots of virtues, especially tremendous excess in separating thermal sensitive natural product. However, lack of deep studies on MD made the molecular distillatory in industry restrained. Therefore, combined with mass and heat transfer in liquid film, it is important for optimizing operation condition and enlarging equipment to study rarefied gas flowing in distillatory.
In this dissertation, the space in distillatory is divided into three sections, including evaporating kinetic layer, steady flowing layer and condensing kinetic layer. In fact, rarefied gas flowing is produced by temperature difference between evaporation surface and condensation surface. The flowing process, which can be simply regarded as one dimension flowing, is studied on basis of energy conservation law and multi-composition moment equation of two parallel planes. Many properties of rarefied gas can be established by four-moment equation, including macroscopic and microscopic properties, mass and heat transfer equations. What’s more, these equations are solved with Delphi program. The mathematical models can predict the profile of rarefied gas, such as numerical density, kinetic temperature and macroscopic velocity, and the profile of distillate, too. So the flowing model make it possible to apply experimental distillatory to industrial equipment.
The influence of operating and structure parameters on mass transfer efficiency and separation efficiency is studied, including composition in liquid film, partial pressure of inert gas, evaporation and condensation temperature, and distance between evaporating and condensing surfaces. It can be concluded from simulation that macroscopic temperature in steady flowing layer falls with velocity growing when evaporating and condensing temperature are constant, and that mass transfer efficiency and separation efficiency are decreasing with evaporating temperature increasing. However, the mass transfer efficiency is sensitive for condensing temperature. Besides, the effect of distance of two surfaces on mass transfer efficiency and separation efficiency is quite week whether taking inert partial pressure into consideration or not.
The technological conditions of concentrating effective compositions from seal oil
ethyl ester by molecular distillation are studied in this dissertation. In distillation process, the influence of operating parameters on total content and yield of effective compositions is investigated, such as distillation temperature, operating pressure, feed rate and operating stage. The fractionation temperatures of each composition in seal oil ethyl ester are discussed, and economic value on this item is evaluated. To meet the crystallization separation process for isomer, molecular distillation is applied to a preliminary separation of para-acetaminophenylacetate ethyl for the first time. The effect of above experimental parameters on relative content and separation efficiency of two components has been studied. In addition, several methods of improving product yield are presented in molecular distillation process. The optimal conditions could be included via repeated experiments, and reduces the crystallization load of isomer. The study of molecular distillation provides theoretical value for its new application yield.
引文
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