氯苯与硫酸铜在亚临界水中溶解度及乙醇在超临界二氧化碳中溶解度研究
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摘要
超/亚临界流体由于其独特的理化性质,被广泛应用于化学合成、萃取分离、环境工程等诸多领域,具有很大的潜在优势。着眼于环保领域应用的超临界水氧化反应(SCWO)是目前研究最多的一类反应过程。运用SCWO处理有机废水是一种高效、环境友好的新兴技术。但在实际应用过程中遇到了盐沉积和管路腐蚀问题,严重阻碍其工业化应用。作为超临界水氧化反应器设计的基础,疏水性有机物和无机盐类在亚临界水中的溶解度研究引起了广泛关注。
二氧化碳作为一种无毒、临界温度低、价格低廉的绿色溶剂,在超临界流体萃取领域应用最为普遍。而醇类的加入可以改善超临界二氧化碳的溶剂化能力,极大拓宽其应用范围,将会成为热点课题。研究乙醇在超临界二氧化碳中的溶解度对于含醇物质中醇类的提取以及用醇作共溶剂体系的萃取都非常重要。
实验采用课题组新研发的一套显微原位在线石英毛细管溶解度测定装置,分别测定了氯苯和硫酸铜在亚临界水中的溶解度以及乙醇在超临界二氧化碳中的溶解度。实验结果表明,在温度范围173.3 ~ 266.9℃内,氯苯在水中的溶解度为43.5 ~ 71.4 mg·g~(-1) H_2O,并随着温度的升高而线性增加,通过线性拟合得到氯苯在水中的溶解度方程为S = 0.3069 T ~(-1)0.188。实验还研究了pH及投加物对硫酸铜盐水体系介稳态的影响,测定了硫酸铜在114.2 ~ 157.1℃水中的溶解度为10 ~ 180 mg·g~(-1) H_2O。选用拉乌尔定律结合水的饱和蒸汽压来估算毛细管中盐水体系在析晶点的压力为160333 ~ 571368 Pa。采用经典水合机理溶解模型对硫酸铜在亚临界水中的S-ρ-T数据进行了拟合。
此外实验测定乙醇在温度为77.6 ~ 183.8℃的超临界二氧化碳中的溶解度为0.085 ~ 0.485 mg·mg~(-1) CO2,并随着温度的升高而指数增加,通过指数拟合得到乙醇在超临界二氧化碳中的溶解度方程为S = 0.0231 e 0.016T。
实验采用课题组研发的一套显微原位在线石英毛细管溶解度测定装置,分别测定了氯苯和硫酸铜在亚临界水中的溶解度以及乙醇在超临界二氧化碳中的溶解度,补充和丰富了溶解度数据,开创了一种直观、安全、低耗、可逆向验证的测定方法,为该研究领域提供了一条新的思路,也为下一阶段的深入研究奠定基础。
Sup/sub-critical fluids which had been widely used in chemical synthesis, extraction, environmental engineering and many other areas were regarded as one of the most promising and potential solvents. Currently, the supercritical water oxidation (SCWO) that emphasizes on the application of environmental protection had been most studied. It is an environmentally friendly and efficient new technology for hazard-free treatments of toxic and high concentration organic wastewater. However, in the actual application process it was encountered salt-plugging and corrosion which impede its industrial application seriously. As the basis of supercritical water oxidation reactors, the research of the solubilities of hydrophobic organics and inorganic salts in subcritical water had aroused great attention.
Supercritical carbon dioxide (SC-CO_2) was regarded as one non-toxic, low critical temperature and low price solvent for chemical engineering application. The solubility of SC-CO_2 can be improved and the scope of its application will be widened by the addition of alcohol as a co-solvent. What’s more it will become a hot topic in the research. Determination of ethanol solubility in SC-CO_2 was also very important for the extraction of substances in solution containing alcohol or using alcohol as a co-solvent.
The solubilities of chlorobenzene and copper sulphate in SBCW and ethanol in SC-CO_2 were described in thesis, using a method which combined fused silica capillary with microscope by capturing the point of dissolution and precipitation. The results indicated that the solubility of chlorobenzene increased from 43.5 to 71.4 mg·g~(-1) in water when temperature rose from 173.3 to 266.9 oC, and the temperature effect could be represented by a linear equation—S =0.3069T ~(-1)0.188. The effects of pH and additives in copper sulfate solution on the metastability were also studied. And the solubility of copper sulphate increased from 10 to 180 mg·g~(-1) in water when temperature rose from 114.2 to 157.1 oC. The pressure calculated by the Raoul’s Law and saturated water vapor pressures is 160333 ~ 571368 Pa. The S-ρ-T curves of brine system derived from solubility data also fit the correlation with the Hydration Reaction Model.
In addition a set of devices was established, with ethanol and carbon dioxide loaded into a silica capillary, the solubility of ethanol in SC-CO_2 was determinated. The experimental results indicated that the solubility of ethanol increased from 0.085 to 0.485 mg·mg~(-1) in CO_2 when temperature rose from 77.6 to 183.8 oC, and the temperature effect could be represented by an exponential equation—S = 0.0231 e 0.016T.
In summary, a new method using a silica capillary, in combination with a microscope and a video recorder system, has been applied to determine the solubility of chlorobenzene and copper sulphate in SBCW and ethanol in SC-CO_2. Moreover, it was demonstrated that the silica capillary method used here was low in energy and materials consumptions, safe, repeatable, and efficient. It has a great potential to be applied for the solubility determination of other organics and also inorganic salt crystals in sup/sub-critical fluids.
二氧化碳作为一种无毒、临界温度低、价格低廉的绿色溶剂,在超临界流体萃取领域应用最为普遍。而醇类的加入可以改善超临界二氧化碳的溶剂化能力,极大拓宽其应用范围,将会成为热点课题。研究乙醇在超临界二氧化碳中的溶解度对于含醇物质中醇类的提取以及用醇作共溶剂体系的萃取都非常重要。
实验采用课题组新研发的一套显微原位在线石英毛细管溶解度测定装置,分别测定了氯苯和硫酸铜在亚临界水中的溶解度以及乙醇在超临界二氧化碳中的溶解度。实验结果表明,在温度范围173.3 ~ 266.9℃内,氯苯在水中的溶解度为43.5 ~ 71.4 mg·g~(-1) H_2O,并随着温度的升高而线性增加,通过线性拟合得到氯苯在水中的溶解度方程为S = 0.3069 T ~(-1)0.188。实验还研究了pH及投加物对硫酸铜盐水体系介稳态的影响,测定了硫酸铜在114.2 ~ 157.1℃水中的溶解度为10 ~ 180 mg·g~(-1) H_2O。选用拉乌尔定律结合水的饱和蒸汽压来估算毛细管中盐水体系在析晶点的压力为160333 ~ 571368 Pa。采用经典水合机理溶解模型对硫酸铜在亚临界水中的S-ρ-T数据进行了拟合。
此外实验测定乙醇在温度为77.6 ~ 183.8℃的超临界二氧化碳中的溶解度为0.085 ~ 0.485 mg·mg~(-1) CO2,并随着温度的升高而指数增加,通过指数拟合得到乙醇在超临界二氧化碳中的溶解度方程为S = 0.0231 e 0.016T。
实验采用课题组研发的一套显微原位在线石英毛细管溶解度测定装置,分别测定了氯苯和硫酸铜在亚临界水中的溶解度以及乙醇在超临界二氧化碳中的溶解度,补充和丰富了溶解度数据,开创了一种直观、安全、低耗、可逆向验证的测定方法,为该研究领域提供了一条新的思路,也为下一阶段的深入研究奠定基础。
Sup/sub-critical fluids which had been widely used in chemical synthesis, extraction, environmental engineering and many other areas were regarded as one of the most promising and potential solvents. Currently, the supercritical water oxidation (SCWO) that emphasizes on the application of environmental protection had been most studied. It is an environmentally friendly and efficient new technology for hazard-free treatments of toxic and high concentration organic wastewater. However, in the actual application process it was encountered salt-plugging and corrosion which impede its industrial application seriously. As the basis of supercritical water oxidation reactors, the research of the solubilities of hydrophobic organics and inorganic salts in subcritical water had aroused great attention.
Supercritical carbon dioxide (SC-CO_2) was regarded as one non-toxic, low critical temperature and low price solvent for chemical engineering application. The solubility of SC-CO_2 can be improved and the scope of its application will be widened by the addition of alcohol as a co-solvent. What’s more it will become a hot topic in the research. Determination of ethanol solubility in SC-CO_2 was also very important for the extraction of substances in solution containing alcohol or using alcohol as a co-solvent.
The solubilities of chlorobenzene and copper sulphate in SBCW and ethanol in SC-CO_2 were described in thesis, using a method which combined fused silica capillary with microscope by capturing the point of dissolution and precipitation. The results indicated that the solubility of chlorobenzene increased from 43.5 to 71.4 mg·g~(-1) in water when temperature rose from 173.3 to 266.9 oC, and the temperature effect could be represented by a linear equation—S =0.3069T ~(-1)0.188. The effects of pH and additives in copper sulfate solution on the metastability were also studied. And the solubility of copper sulphate increased from 10 to 180 mg·g~(-1) in water when temperature rose from 114.2 to 157.1 oC. The pressure calculated by the Raoul’s Law and saturated water vapor pressures is 160333 ~ 571368 Pa. The S-ρ-T curves of brine system derived from solubility data also fit the correlation with the Hydration Reaction Model.
In addition a set of devices was established, with ethanol and carbon dioxide loaded into a silica capillary, the solubility of ethanol in SC-CO_2 was determinated. The experimental results indicated that the solubility of ethanol increased from 0.085 to 0.485 mg·mg~(-1) in CO_2 when temperature rose from 77.6 to 183.8 oC, and the temperature effect could be represented by an exponential equation—S = 0.0231 e 0.016T.
In summary, a new method using a silica capillary, in combination with a microscope and a video recorder system, has been applied to determine the solubility of chlorobenzene and copper sulphate in SBCW and ethanol in SC-CO_2. Moreover, it was demonstrated that the silica capillary method used here was low in energy and materials consumptions, safe, repeatable, and efficient. It has a great potential to be applied for the solubility determination of other organics and also inorganic salt crystals in sup/sub-critical fluids.
引文
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