Summary of Research Project Results Under the JSPS FY2000
"Research for the future Program"



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

7.Projetct Leader
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

[Reference Articles]
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


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