Measurement of physical properties of ionic liquid - CO2 systems for synthesis of hydrocarbons from cellulose

• Project/Area Number: 25289272
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Properties in chemical engineering process/Transfer operation/Unit operation
• Research Institution: Tohoku University
• Principal Investigator: Smith Richard Lee, Jr. 東北大学, 環境科学研究科, 教授 (60261583)
• Co-Investigator(Kenkyū-buntansha): Sato Yoshiyuki 東北大学, 大学院工学研究科, 准教授 (50243598)
• Co-Investigator(Renkei-kenkyūsha): Nakagawa Yoshinao 東北大学, 大学院工学研究科, 准教授 (10436545)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000); Fiscal Year 2015: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2014: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2013: ¥9,360,000 (Direct Cost: ¥7,200,000、Indirect Cost: ¥2,160,000)
• Keywords: イオン液体 / セルロース / 物性実験 / 物性理論 / 水素化分解

Outline of Final Research Achievements

For developing synthesis methods hydrocarbon by hydrogenolysis of cellulose in ionic liquid－supercritical CO2 biphasic systems, high pressure densities and CO2 solubilities were measured. Theoretical methods were developed for estimating both CO2 and H2 solubilities in ionic liquids. An apparatus for designed, built and tested for measuring H2 gas solubility in the presence of CO2 with ionic liquids. A theoretical metric, denoted as the enhancement ratio (ER) was proposed and used to assess the increase or decrease that H2 solubility that can be obtained with supercritical CO2. Ionic liquids that dissolve biomass were theoretically assessed with the metric and equations of state. The enhancement of H2 solubility by CO2 was observed from experimental measurements. The properties measured and the theoretical methods developed allow estimation of reaction conditions for the synthesis of many types of chemicals derived from cellulose.

Research Products

• [Journal Article] Measurement of infinite dilution partition coefficients of isomeric benzene derivatives in [bmim][Tf2N]-CO2 biphasic system and correlation with the ePC-SAFT equation of state (2016)
  • Author(s): Yuya Hiraga, Yoshiyuki Sato and Richard L. Smith, Jr
  • Journal Title: Fluid Phase Equilibria Volume: 印刷中 Pages: 36-43
  • DOI: 10.1016/j.fluid.2015.10.042
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Separation factors for [amim]Cl-CO2 biphasic systems from high pressure density and partition coefficient measurements (2015)
  • Author(s): Yuya Hiraga, Aya Kato, Yoshiyuki Sato, Taku M. Aida, Masaru Watanabe and Richard L. Smith, Jr.
  • Journal Title: Separation and Purification Technology Volume: 印刷中 Pages: 139-148
  • DOI: 10.1016/j.seppur.2015.03.008
  • Peer Reviewed
• [Journal Article] Densities at pressures up to 200 MPa and atmospheric pressure viscosities of ionic liquids, 1-ethyl-3-methylimidazolium methylphosphate, 1-ethyl-3-methylimidazolium diethylphosphate, 1-butyl-3-methylimidazolium acetate and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (2015)
  • Author(s): Yuya Hiraga, Aya Kato, Yoshiyuki Sato and Richard L. Smith, Jr.
  • Journal Title: Journal of Chemical & Engineering Data Volume: 60 Issue: 3 Pages: 876-885
  • DOI: 10.1021/je5009679
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Development of a simple method for predicting CO2 enhancement of H2 gas solubility in ionic liquids (2015)
  • Author(s): Yuya Hiraga Yoshiyuki Sato and Richard L. Smith, Jr.
  • Journal Title: Journal of Supercritical Fluids Volume: 96 Pages: 162-170
  • DOI: 10.1016/j.supflu.2014.09.010
  • Peer Reviewed / Open Access
• [Journal Article] Viscosity and density of poly(ethylene glycol) and its solution with carbon dioxide at 353.2 K and 373.2 K at pressures up to 15 MPa (2015)
  • Author(s): Masayuki Iguchi, Yuya Hiraga, Kazuhiro Kasuya, Taku M. Aida, Masaru Watanabe, Yoshiyuki Sato and Richard L. Smith, Jr.
  • Journal Title: Journal of Supercritical Fluids Volume: 97 Pages: 63-73
  • DOI: 10.1016/j.supflu.2014.10.013
  • Peer Reviewed
• [Journal Article] Removal of hydrophilic ionic liquids from aqueous solutions by adsorption onto high surface area oxygenated carbonaceous material (2014)
  • Author(s): Xinhua Qi, Luyang Li, Yu Wang, Nian Liu, Richard L. Smith Jr.
  • Journal Title: Chemical Engineering Journal Volume: 256 Pages: 407-414
  • DOI: 10.1016/j.cej.2014.07.020
  • Peer Reviewed
• [Journal Article] One-step preparation of carbonaceous solid acid catalysts by hydrothermal carbonization of glucose for cellulose hydrolysis (2014)
  • Author(s): Xinhua Qi, Youfen Lian, Lulu Yan, Richard L. Smith Jr.
  • Journal Title: Catalysis Communications Volume: 57 Pages: 50-54
  • DOI: 10.1016/j.catcom.2014.07.035
  • Peer Reviewed
• [Journal Article] Measurement of High-Pressure Densities and Atmospheric Viscosities of Ionic Liquids : 1-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)i mide and 1-Hexyl-3-methylimidazolium Chloride (2014)
  • Author(s): Iguchi, M., Hiraga, Y., Sato, Y., Aida, T. M., Watanabe M., Smith Jr., R. L.
  • Journal Title: Journal of Chemical and Engineering Data Volume: 59(3) Issue: 3 Pages: 709-717
  • DOI: 10.1021/je4007844
  • Peer Reviewed
• [Journal Article] Viscosity reduction of cellulose + 1-butyl-3-methylimidazolium acetate in the presence of CO2 (2013)
  • Author(s): Iguchi, M., Kasuya, K., Sato, Y., Aida, T.M., Watanabe M., Smith Jr., R.L.
  • Journal Title: Cellulose Volume: 20(3) Issue: 3 Pages: 1353-1367
  • DOI: 10.1007/s10570-013-9884-8
  • Peer Reviewed
• [Journal Article] Partition coefficients of furan derivative compounds in 1-n-butyl-3-methylimidazolium chloride ([bmim][Cl])–supercritical CO2 biphasic systems and their correlation and prediction with the LSER-delta model (2013)
  • Author(s): Hiraga, Y., Hayasaka, A., Sato, Y., Watanabe M., Smith Jr., R.L
  • Journal Title: Journal of Supercritical Fluids Volume: 79 Pages: 32-40
  • DOI: 10.1016/j.supflu.2012.11.010
  • Peer Reviewed
• [Presentation] Measurement and Correlation of Infinite Dilution Partition Coefficients for o, m, p-cresol and Related Benzene Derivatives in [bmim][Tf2N]-CO2 Biphasic System (2015)
  • Author(s): Yuya Hiraga, Yoshiyuki Sato, Masaru Watanabe, Taku M. Aida, Richard L. Smith, Jr.
  • Organizer: The 7th international symposium on “Molecular Thermodynamics and Molecular Simulation (MTMS’15)”
  • Place of Presentation: Fukuoka University (Fukuoka, Japan)
  • Year and Date: 2015-08-05
  • Int'l Joint Research
• [Presentation] Physical properties of ionic liquids that dissolve biomass (2015)
  • Author(s): Richard L. Smith, Jr.
  • Organizer: 4th Green Solvent Mini Symposium (GSMS)
  • Place of Presentation: Nihon University (Koriyama, Japan)
  • Year and Date: 2015-08-03
  • Int'l Joint Research / Invited
• [Presentation] バイオマス可溶性イオン液体の粘度に対する超臨界CO2および水の添加効果 (2015)
  • Author(s): 馬場史織，平賀佑也, 佐藤善之, 相田卓, 渡邉賢, R. L. Smith, Jr.
  • Organizer: 化学工学会第80年会
  • Place of Presentation: 芝浦工業大学（東京）
  • Year and Date: 2015-03-19 – 2015-03-21
• [Presentation] イミダゾリウム系およびピロリジニウム系イオン液体の高圧密度測定と状態式による相関 (2015)
  • Author(s): 平賀佑也, 佐藤善之, 渡邉賢, 相田卓, R. L. Smith, Jr.
  • Organizer: 化学工学会第80年会
  • Place of Presentation: 芝浦工業大学（東京）
  • Year and Date: 2015-03-19 – 2015-03-21
• [Presentation] イオン液体に対するH2 溶解度のCO2添加効果 (2014)
  • Author(s): 平賀佑也, 佐藤善之, 渡邉賢, 相田卓, R. L. Smith, Jr.
  • Organizer: 化学工学会新潟大会2014
  • Place of Presentation: 新潟大学（新潟）
  • Year and Date: 2014-11-22 – 2014-11-23
• [Presentation] Viscosity Reduction of Ionic Liquid [bmim]Cl with Carbon Dioxide (2014)
  • Author(s): W. Endo, S. Baba, Y. Hiraga, Y. Sato, M. Watanabe, T. M. Aida, R. L. Smith Jr.
  • Organizer: International Symposium on Chemical-Environmental-Biomedical Technology 2014 (isCEBT 2014)
  • Place of Presentation: Taipei（Taiwan）
  • Year and Date: 2014-09-10 – 2014-09-14
• [Presentation] Green engineering for extracting and processing of bioactive compounds for nutraceuticals (2014)
  • Author(s): Smith Jr., R.L.
  • Organizer: International Conference on Industrial Pharmacy (ICIP)
  • Place of Presentation: Kuantan,（Malaysia）
  • Year and Date: 2014-08-16 – 2014-08-17
  • Invited
• [Presentation] Infinite Dilution Partition Coefficients of Solutes in Biomass Soluble Ionic Liquid - Supercritical Carbon Dioxide Systems (2014)
  • Author(s): Yuya Hiraga, Aya Kato, Yoshiyuki Sato, Taku M. Aida, Masaru Watanabe, Richard L. Smith, Jr.
  • Organizer: ILSEPT - 2nd International Conference on Ionic Liquids in Separation and Purification Technology
  • Place of Presentation: Toronto (Canada)
  • Year and Date: 2014-07-02
• [Presentation] イオン液体－CO2相平衡ならびに2 相間の無限希釈分配係数推算法構築に向けた検討 (2014)
  • Author(s): 平賀佑也, 加藤彩, 佐藤善之, R. L. Smith, Jr.
  • Organizer: 分離技術会 年会2014
  • Place of Presentation: 名古屋大学（愛知）
  • Year and Date: 2014-05-30 – 2014-05-31
• [Presentation] Supercritical fluids in energy and biofuel applications (2013)
  • Author(s): Smith Jr., R.L.
  • Organizer: Workshop on Supercritical Fluids and Energy (SFE-2013)
  • Place of Presentation: Sao Paulo, Brazil
  • Invited
• [Presentation] Review of fundamental properties of using fluids in their subcritical technologies for green process and green product design (2013)
  • Author(s): Smith Jr., R.L.
  • Organizer: The 8th International Conference on Supercritical Fluids (Super Green-2013)
  • Place of Presentation: Taipei, Taiwan
  • Invited
• [Presentation] Estimation of H2 solubility in ionic liquids - CO2 mixtures with equations of state (2013)
  • Author(s): Hiraga, Y., Kato, A., Sato, Y., Watanabe M., Smith Jr., R.L.
  • Organizer: International Conference on Ionic Liquids 2013 (ICIL 13)
  • Place of Presentation: Langkawi Island, Malaysia
• [Presentation] Application of PC-SAFT Model to Infinite Dilution Partition Coefficient of Aromatic Compounds in Ionic Liquid and Supercritical CO2 (2013)
  • Author(s): Hiraga, Y., Kato, A., Sato, Y., Watanabe M., Smith Jr., R.L.
  • Organizer: The International Symposium for the 70th Anniversary of the Tohoku Branch of the Chemical Society of Japan
  • Place of Presentation: Sendai, Japan
• [Presentation] Measurement of solubility of supercritical CO2 in allyl-based ionic liquid with a magnetic suspension balance apparatus (2013)
  • Author(s): Kato, A., Hiraga, Y., Sato, Y., Watanabe M., Smith Jr., R.L.
  • Organizer: The International Symposium for the 70th Anniversary of the Tohoku Branch of the Chemical Society of Japan
  • Place of Presentation: Sendai, Japan
• [Presentation] イオン液体‐超臨界CO2間におけるCresolの無限希釈分配係数測定と相関モデルの検討 (2013)
  • Author(s): 平賀佑也, 加藤彩, 佐藤善之, 渡邉 賢, Richard Lee Smith, Jr.
  • Organizer: 第4回イオン液体討論会
  • Place of Presentation: 日本、慶應義塾大学日吉キャンパス（横浜）
• [Presentation] 磁気浮遊天秤を用いたアリル系イオン液体中へのCO2溶解度測定および相関モデルの検討 (2013)
  • Author(s): 加藤彩, 平賀佑也, 佐藤善之, 渡邉 賢, Richard Lee Smith, Jr.
  • Organizer: 第4回イオン液体討論会
  • Place of Presentation: 日本、慶應義塾大学日吉キャンパス（横浜）
• [Book] Introduction to Supercritical Fluids, A spreadsheet-based Approach (Volume 4) (2013)
  • Author(s): Richard Smith, Hiroshi Inomata, Cor Peters
  • Publisher: Elsevier Science
• [Book] Production of Biofuels and Chemicals with Ionic Liquids, Biofuels and Biorefineries (2013)
  • Author(s): Zhen Fang, Richard L. Smith, Jr., Xinhua Qi
  • Total Pages: 337
  • Publisher: Springer