| 1.Research Institution | Kyushu University | |
| 2.Research Area | Physical and Engineering Sciences | |
| 3.Research Field | Next-generation Process Technologies | |
| 4.Term of Project | FY1996〜FY2000 | |
| 5.Project Number | 96P00401 | |
| 6.Title of Project | Fundamental Analysis and Design of Reaction and Separation Processes in Supercritical Fluids |
| Name | Institution,Department | Title of Position |
| Yasuhiko, Arai | Graduate School, Engineering | Professor |
8.Core Members
| Names | Institution,Department | Title of Position |
| Seiichiro, Koda | The University of Tokyo, Graduate School, Engineering | Professor |
9.Cooperating Researchers
| Names | Institution,Department | Title of Position |
| Hirokatsu, Masuoka | Hiroshima University, Graduate School, Engineering | Professor |
| Yoshio, Iwai | Kyushu University, Graduate School, Engineering | Associate Professor |
| Motonobu, Goto | Kumamoto University, Engineering | Professor |
10.Summary of Research Results
|
To develop a successful separation or purification process, we need several fundamental physical properties such as solubilities, phase equilibria, and diffusion coefficients as well as the solution structure and the interaction between a solute and supercritical fluid used as a solvent. Based on a precise density-measurement and spectroscopic analysis, the salvation structure and the interaction were elucidated for the supercritical carbon dioxide + solute systems. The information is very helpful to predict the solubilities and the entrainer effect using equations of state and solution models. Further, the anomalous behavior of diffusion coefficients near the critical point was observed and it was quantitatively explained by a thermodynamic model with an equation of state. Phase equilibria of water + hydrocarbon systems under high temperatures and pressures were also measured. Using supercritical carbon dioxide, citrus oil was effectively fractionated by a countercurrent extractor with temperature gradient. A new separation procedure was proposed by hybridizing adsorption or chromatography with supercritical fluid. The elemental processes and reactions involved in supercritical water oxidations (SCWO) and the mechanism of hydrolysis reactions in sub and supercritical water were studied. The modeling for the reactions and ideal reactor designs were also pursued. It was found that the SCWO reactions belong to the category of radical chain reactions with induction times and are characterized by the autocatalytic features, on which the practical reactor should be designed. During the study, a novel continuous stirred tank-type reaction apparatus was devised, being equipped with a Raman spectroscopic system for in situ measurements of the relevant species. Besides the study of homogeneous SCWO, the reaction engineering analysis was also successfully applied for the heterogeneous SCWO. In parallel with the study of supercritical water reactions, laser induced reactions in supercritical carbon dioxide were investigated. The mechanism of oxygen excitation to induce oxidative reactions was elucidated. All of the above experiments and results should be useful for the future development of supercritical fluid reaction technology. |
11.Key Words
(1)Supercritical carbon dioxide、(2)Supercritical water、(3)Phase equilibria
(4)Diffusion coefficient、(5)Countercurrent extraction column、(6)Pressure swing adsorption
(7)supercritical water oxidation、(8)Hydrolysis reaction、(9)Detailed chemical kinetics
12.References
| Author | Title of Article | |||
| Shigeki Takishima | Density of Supercritical Carbon Dioxide-Heavy Alkane Binary Systems | |||
| Journal | Volume | Year | Pages Concerned | |
| Proc. of 8th Int. Conf. on Prop. and Phase Equil. for Prod. and Proc. Des., Noordwijkerhout, Apr. 26-Mar.1 | 1998 | 128-137 | ||
| Author | Title of Article | |||
| Chommanad Thammanayakatip | Inhibition Effect in Supercritical Water Oxidation in Hydroquinone | |||
| Journal | Volume | Year | Pages Concerned | |
| Ind. Eng. Chem. Res. | 37 | 1998 | 2061-2063 | |
| Author | Title of Article | |||
| Morio Yamamoto | Fourier Transform Infrared Study on Hydrogen Bonding Species of Carboxylic Acids in Supercritical Carbon Dioxide with Ethanol | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Phys. Chem. A | 103 | 1999 | 3525-3529 | |
| Author | Title of Article | |||
| Hidenori Higashi | Correlation of Diffusion Coefficients for Naphthalene and Dimethylnaphthalene Isomers in Supercritical Carbon Dioxide | |||
| Journal | Volume | Year | Pages Concerned | |
| Fluid Phase Equil. | 166 | 1999 | 101-110 | |
| Author | Title of Article | |||
| Tatsuo Morotomi | High-Pressure Vapor-Liquid Equilibria for Carbon Dioxide + Limonene + Linalool | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Chem. Eng. Data | 44 | 1999 | 1370-1372 | |
| Author | Title of Article | |||
| Siichiro Koda | Raman Spectroscopic Study of Methanol-Water Interaction and Methanol Oxidation in High Pressure and High Temperature Water | |||
| Journal | Volume | Year | Pages Concerned | |
| Proc. of 13th Int. Conf. on Prop. of Water and Steam, Toronto, Sept. 12-16 | 1999 | 402-408 | ||
| Author | Title of Article | |||
| Yoshito Oshima | Kinetics of the Catalytic Oxidation of Phenol over Manganese Oxide in Supercritical Water | |||
| Journal | Volume | Year | Pages Concerned | |
| Ind. Eng. Chem. Res. | 38 | 1999 | 4183-4188 | |
| Author | Title of Article | |||
| Tokuro Ebukuro | Raman Spectroscopic Studies on Hydrogen Bonding in Methanol and Methanol/Water Mixtures under High Temperature and High Pressure | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Supercritical Fluids | 15 | 1999 | 73-78 | |
| Author | Title of Article | |||
| Junichiro Otomo | UV Absorption Shifts of Benzenes in Supercritical Carbon Dioxide | |||
| Journal | Volume | Year | Pages Concerned | |
| Chem. Phys. | 242 | 1999 | 241-252 | |
| Author | Title of Article | |||
| Hisashi Kitagawa | PVTx Relations of Supercritical Carbon Dioxide + Solute Systems | |||
| Journal | Volume | Year | Pages Concerned | |
| Proc. of 65th Annual Meeting of Chem. Engrs. Japan, Tokyo, Mar. 29-31 | 2000 | R106 | ||
| Author | Title of Article | |||
| Masashi Haruki | Measurement and Correlation of Phase Equilibria for Water + Hydrocarbon Systems near the Critical Temperature and Pressure of Water | |||
| Journal | Volume | Year | Pages Concerned | |
| Ind. Eng. Chem. Res. | 39 | 2000 | 4516-4520 | |
| Author | Title of Article | |||
| Gopalan Began | Response Surfaces of Total Oil Yield of Turmeric (Curcuma Longa) in Supercritical Carbon Dioxide | |||
| Journal | Volume | Year | Pages Concerned | |
| Food Res. Int. | 33 | 2000 | 341-345 | |
| Author | Title of Article | |||
| Gopalan Began | Supercritical Carbon Dioxide Extraction of Turmeric (Cucuma Longa) | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Agr. & Food Chem | 48 | 2000 | 2189-2192 | |
| Author | Title of Article | |||
| Mitsuru Kondo | Fractional Extraction by Supercritical Carbon Dioxide for the Deterpenation of Bergamot Oil | |||
| Journal | Volume | Year | Pages Concerned | |
| Ind. Eng. Chem. Res. | 39 | 2000 | 4745-4748 | |
| Author | Title of Article | |||
| Gou Fukui | Fractionation Process of Bergamot Peel Oil by Supercritical Pressure Swing Adsorption Cycle | |||
| Journal | Volume | Year | Pages Concerned | |
| Proc. of 13th Symp. on Chem. Eng. Kyushu-Taejon/Chungnam, Fukuoka, Oct. 14 | 2000 | 175-176 | ||
| Author | Title of Article | |||
| Yoshito Oshima | PFR and CSTR Analyses of Supercritical Water Oxidation of Methanol | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Chem. Eng. Japan | 33 | 2000 | 507-513 | |
| Author | Title of Article | |||
| Junichiro Otomo | KrF Excimer Laser-Induced Ozone Formation in Supercritical Carbon Dioxide | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Phys. Chem. A | 104 | 2000 | 3332-3340 | |
| Author | Title of Article | |||
| Yoshito Oshima | Kinetics of Methylene Chloride Hydrolysis and the Salt Effect under Hydrothermal Conditions | |||
| Journal | Volume | Year | Pages Concerned | |
| Ind. Eng. Chem. Res. | 2000 | in press | ||
| Author | Title of Article | |||
| 北川 久 | 超臨界二酸化炭素+溶質系のPVTx関係 | |||
| Journal | Volume | Year | Pages Concerned | |
| 化学工学会第65年会、東京 | 2000 | Ｒ106 | ||