【摘要】：有機(jī)物的溶解度數(shù)據(jù)是超臨界流體中物質(zhì)分離與純化、配方篩選、工業(yè)應(yīng)用與過(guò)程設(shè)計(jì)等的關(guān)鍵性參數(shù),隨著超臨界流體得到日益關(guān)注和應(yīng)用,物質(zhì)在超臨界流體中的相平衡研究和溶解度數(shù)據(jù)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(shí)驗(yàn)條件,獲取準(zhǔn)確的溶解度數(shù)據(jù)十分困難。傳統(tǒng)用于測(cè)定溶解度數(shù)據(jù)的靜態(tài)法取樣過(guò)程中易破壞達(dá)到的相平衡,而動(dòng)態(tài)法則難于保證體系已達(dá)到相平衡且溶質(zhì)易于流失,基于以上原因超/亞臨界水中含氯有機(jī)物溶解度數(shù)據(jù)十分缺乏。利用課題組自主設(shè)計(jì)搭建的一套測(cè)定亞臨界水中疏水性有機(jī)物溶解度數(shù)據(jù)的裝置對(duì)亞臨界水中4-氯甲苯及2,4-二氯氟苯的溶解度進(jìn)行了研究。實(shí)驗(yàn)過(guò)程中對(duì)冷熱臺(tái)溫度進(jìn)行了連續(xù)的校準(zhǔn)和檢驗(yàn),并對(duì)亞臨界水中4-氯甲苯及2,4-二氯氟苯的穩(wěn)定性進(jìn)行了研究。除采用拉曼光譜技術(shù)對(duì)石英毛細(xì)管反應(yīng)器內(nèi)溶液體系的擴(kuò)散均勻度進(jìn)行原位在線分析外,還對(duì)體系溫度升高溶質(zhì)擴(kuò)散過(guò)程中溶質(zhì),溶劑(水)及純水進(jìn)行了原位拉曼光譜分析。實(shí)驗(yàn)結(jié)果表明:亞臨界水中4-氯甲苯和2,4-二氯氟苯基本沒(méi)有發(fā)生氧化水解等反應(yīng);石英毛細(xì)管內(nèi)溶質(zhì)-水體系經(jīng)過(guò)較長(zhǎng)時(shí)間的恒溫后各處的溶質(zhì)擴(kuò)散均勻,不存在明顯的濃度梯度;實(shí)驗(yàn)基于對(duì)亞臨界水中4-氯甲苯和2,4-二氯氟苯相態(tài)變化實(shí)時(shí)觀測(cè)的基礎(chǔ)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(nèi)亞臨界水中的溶解度數(shù)據(jù),對(duì)數(shù)據(jù)進(jìn)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(jié)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(shù)據(jù)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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