【摘要】：有機物的溶解度數據是超臨界流體中物質分離與純化、配方篩選、工業(yè)應用與過程設計等的關鍵性參數,隨著超臨界流體得到日益關注和應用,物質在超臨界流體中的相平衡研究和溶解度數據也得到了人們的廣泛重視。然而,由于超臨界流體高溫高壓苛刻的實驗條件,獲取準確的溶解度數據十分困難。傳統(tǒng)用于測定溶解度數據的靜態(tài)法取樣過程中易破壞達到的相平衡,而動態(tài)法則難于保證體系已達到相平衡且溶質易于流失,基于以上原因超/亞臨界水中含氯有機物溶解度數據十分缺乏。利用課題組自主設計搭建的一套測定亞臨界水中疏水性有機物溶解度數據的裝置對亞臨界水中4-氯甲苯及2,4-二氯氟苯的溶解度進行了研究。實驗過程中對冷熱臺溫度進行了連續(xù)的校準和檢驗,并對亞臨界水中4-氯甲苯及2,4-二氯氟苯的穩(wěn)定性進行了研究。除采用拉曼光譜技術對石英毛細管反應器內溶液體系的擴散均勻度進行原位在線分析外,還對體系溫度升高溶質擴散過程中溶質,溶劑(水)及純水進行了原位拉曼光譜分析。實驗結果表明:亞臨界水中4-氯甲苯和2,4-二氯氟苯基本沒有發(fā)生氧化水解等反應;石英毛細管內溶質-水體系經過較長時間的恒溫后各處的溶質擴散均勻,不存在明顯的濃度梯度;實驗基于對亞臨界水中4-氯甲苯和2,4-二氯氟苯相態(tài)變化實時觀測的基礎上分別獲得了4-氯甲苯在262.3-293.8℃、2,4-二氯氟苯257.6-286.7℃溫度范圍內亞臨界水中的溶解度數據,對數據進行擬合后得到的溶解度方程分別為S=2.13109T-528.52、S=1.34338T-302.10。研究結果表明,隨溫度的升高亞臨界水中4-氯甲苯、2,4-二氯氟苯的溶解度數據呈線性增加。
[Abstract]:The solubility data of organic compounds are the key parameters for the separation and purification of substances in supercritical fluids, formula screening, industrial applications and process design, etc. With the increasing attention and application of supercritical fluids, The study of phase equilibrium and solubility data of substance in supercritical fluid has been paid more and more attention. However, due to the harsh experimental conditions of supercritical fluid at high temperature and high pressure, it is very difficult to obtain accurate solubility data. The traditional static sampling method used to measure solubility data is easy to destroy the phase equilibrium, while the dynamic rule is difficult to ensure that the system has reached phase equilibrium and solute is easy to lose. Based on the above reasons, the solubility data of chlorinated organic compounds in supercritical / subcritical water are very scarce. The solubility of 4-chlorotoluene and 2-trichloro-4-dichlorobenzene in subcritical water was studied by a set of apparatus designed by our research group to determine the solubility of hydrophobic organic compounds in subcritical water. During the experiment, the temperature of the cooling and hot table was continuously calibrated and tested, and the stability of 4-chlorotoluene and 2O4-dichlorofluorobenzene in subcritical water was studied. In addition to the in-situ on-line analysis of the dispersion uniformity of the solution system in a quartz capillary reactor by Raman spectroscopy, the solute, solvent (water) and pure water during solute diffusion at elevated temperature were also analyzed by in-situ Raman spectroscopy. The experimental results show that there is basically no oxidative hydrolysis reaction between 4-chlorotoluene and 2o _ 4-dichlorofluorobenzene in subcritical water, and solute diffusion in the solute water system in quartz capillary is uniform after a long time of constant temperature. There is no obvious concentration gradient. The solubility data of 4-chlorotoluene in subcritical water at 262.3-293.8 鈩，

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