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Solubility enhancement in supercritical carbon dioxide by fluorination effect

通过氟化作用提高超临界二氧化碳的溶解度

基本信息

批准号：
17360376
负责人：
ARAI Yasuhiko
金额：
$ 8.06万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

In this study, solubilities of fluorinated compounds were measured to examine the fluorination effect on the solubility in supercritical carbon dioxide. Further, the mechanism of solubility enhancement was discussed by a molecular simulation and the following results were obtained.The solubilities of Rh complexes, which are used as catalysts for hydroformylation, in supercritical carbon dioxide were measured. As a ligand, triphenylphosphine (TTP) and tris (p-Trifluoromethylphenyl) phosphine (TTFMPP) were adopted. The solubilities were determined by IR absorbance. It is found that the solubilities of the ligand and the complex fluorinated, TTFMPP and Rh-TTFMPP, can be enhanced compared to non-fluorinated TPP and Rh-TPP.2-,3-trifluoromethyl benzoic acids, which are fluorinated compounds, were adopted as model substances and its sublimation pressures were measured. The sample was set in an equilibrium cell and the vapor phase concentration was determined by UV absorbance. The sublimation pressures were determined by using the equation of state for ideal gas. Reliable sublimation pressure data can be obtained based on the present experimental procedure. The sublimation pressures of 2-,3-trifuloromethyl benzoic acids show the cross point near 314K.MD simulation was performed for the supercritical carbon dioxide + fluorinated compounds mixtures. 2-,3-,4-,trifluoromethyl benzoic acids and 2-,3-,4-methyl benzoic acids were studied. It is found that carbon dioxide molecules are solvated around trifluoromethyl group and this fact is the reason for the solubility enhancement.As mentioned above, fluorination is effective to enhance the solubility in supercritical carbon dioxide and the mechanism is due to solvation.

本研究通过测定含氟化合物在超临界二氧化碳中的溶解度，考察超临界二氧化碳对含氟化合物溶解度的影响。进一步，通过分子模拟对增溶机理进行了探讨，得到了如下结果：测定了作为加氢裂化催化剂的Rh配合物在超临界CO2中的溶解度。作为配体，采用三苯基膦（TTP）和三（对三氟甲基苯基）膦（TTFMPP）。通过红外吸收测定溶解度。结果表明，与未氟化的TPP和Rh-TPP相比，含氟的TTFMPP和Rh-TTFMPP的溶解度均有所提高。以含氟化合物2，3-三氟甲基苯甲酸为模型物质，测定了其升华压力。将样品置于平衡池中，通过UV吸光度测定气相浓度。用理想气体状态方程确定了升华压力。根据本实验方法可以获得可靠的升华压力数据。2-，3-三氟甲基苯甲酸的升华压力在314 K附近有一个交叉点。研究了2-、3-、4-、三氟甲基苯甲酸和2-、3-、4-甲基苯甲酸。结果表明，CO2分子在三氟甲基周围发生了溶剂化作用，这是CO2分子在超临界CO2中溶解度增加的原因，而CO2分子在三氟甲基周围的溶剂化作用是CO2分子在超临界CO2中溶解度增加的主要原因。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Measurement of Solubilities for Rhodium Complexes in Supercritical Carbon Dioxide

铑配合物在超临界二氧化碳中溶解度的测量

DOI：
发表时间：
2006
期刊：
Proc.8th Int.Symp.Supercritical Fluids PA-1-02
影响因子：
0
作者：
Y.Machida;S.Morooka;Y.Yamasaki;M.Miyazaki;T.Honda;H.Maeda;Hisaaki MIYAMOTO et al.;Masanori SONODA et al.
通讯作者：
Masanori SONODA et al.

Measurement and Correlation of Sublimation Pressures for Trimethylbenzoic Acid Isomers

三甲基苯甲酸异构体升华压力的测量和关联

DOI：
发表时间：
2006
期刊：
Proc.8th Kyushu-Sogang Int. Conf. Thermodynam, and SCF Tech.
影响因子：
0
作者：
Y.Yamasaki;A.Kariyasaki;A.Ousaka;S.Morooka;Hisaaki MIYAMOTO et al.
通讯作者：
Hisaaki MIYAMOTO et al.

Measurement and Correlation of. Sublimation Pressures for Trimethylbenzoic Acid Isomers

的测量和相关性。

DOI：
发表时间：
2006
期刊：
Proc.8th Kyushu-Sogang Int.Conf.Thermodynam.and SCF Tech.
影响因子：
0
作者：
Y.Machida;S.Morooka;Y.Yamasaki;M.Miyazaki;T.Honda;H.Maeda;Hisaaki MIYAMOTO et al.
通讯作者：
Hisaaki MIYAMOTO et al.

Solubilities for Rhodium Complexes in Supercritical Carbon Dioxide

铑配合物在超临界二氧化碳中的溶解度

DOI：
发表时间：
2006
期刊：
Proc.19th Symp.Chem.Eng.Kyushu/Chungnam OD-03
影响因子：
0
作者：
幡手泰雄;ら;Masanori SONODA et al.
通讯作者：
Masanori SONODA et al.

Molecular Dynamics Simulation of Fluorination Effect for Solvation of Trifluoromethylbenzoic Acid Isomers in Supercritical Carbon Dioxide

超临界二氧化碳中三氟甲基苯甲酸异构体溶剂化氟化效应的分子动力学模拟

DOI：
发表时间：
2005
期刊：
Molecular Simulation Vol.31,No.10
影响因子：
0
作者：
Y.Machida;M.Miyazaki;T.Honda;H.Maeda;Y.Yamasaki;S.Morooka;Hidenori HIGASHI et al.
通讯作者：
Hidenori HIGASHI et al.