This study aims efficient conversion of cotton stalks to cellulosic ethanol through ionic liquid pretreatment and enhanced enzymatic hydrolysis. Among several ionic liquids, EMIMAc exhibited the most striking impact on cotton stalks with respect to the changes in biomass structure and digestibility. Cotton stalks, which were subjected to EMIMAc pretreatment at 10% (w cotton stalks/w EMIMAc) of biomass loading and 150&deg / C for 30 minutes, were found to be 9 times more digestible than untreated cotton stalks. Besides, glucose and ethanol yields, which were based on the cellulose content of untreated cotton stalks, were found as 67% and 66%, respectively. These yields were insufficient regarding efficient conversion of the cellulosic portion of cotton stalks to glucose and ethanol which is linked to the superior solvation capability of EMIMAc towards biomass. In order to enhance aforementioned yields, EMIMAc pretreatment was conducted at 30% of biomass loading. Though lignin extracted was much lower, higher yields were obtained compared to the former case since 96% of cellulose was recovered upon EMIMAc pretreatment and reduced crystallinity was observed for pretreated biomass. Glucose yield was achieved as 84% even at a substrate loading of 15% (w/v). Additionally, 76% of ethanol yield and 3% (v/v) of ethanol titer were obtained upon fermentation. Accordingly, reduction in biomass crystallinity was satisfactory to improve enzymatic accessibility of the biomass. Besides, EMIMAc maintained its effectiveness as a pretreatment agent upon recycling since no change in terms of hydrolysis of pretreated samples was observed upon EMIMAc recycling for three times.

Silylated amines, also known as reversible ionic liquids (RevILs), have been designed and structurally modified by our group for potential use as solvents for CO₂ capture from flue gas. An ideal CO₂ capture ionic liquid should be able to selectively and reversibly capture CO₂ and have tolerance for other components in flue gas, including SO₂, NO₂, and O₂. In this project, we study the reactivity, selectivity, uptake capacity, and reversibility of RevILs in the presence of pure SO₂ and mixed gas streams tosimulate flue gas compositions. Tripropylsilylamine (TPSA), a candidate CO₂ capture RevIL, reacts with pure SO₂ to form an ionic liquid consisting of an ammonium group and a salfamate group, supported by IR and NMR results. The resulting IL with pure SO₂ partially reverses when heated to temperatures of upto 500 C in the TGA. TGA analysis of the ionic liquid formed from a 4 vol% SO₂ in CO₂ mixture indicates a possible reversal temperature in the 86-163 C range.

A novel ionic liquid crystal (ILC) system (C18IMCNBr) with a liquid crystal alignment used as an electrolyte for a dye-sensitized solar cell (DSSC) showed the higher short-circuit current density (Jsc) and the higher light-to-electricity conversion efficiency than the system using the non- alignment liquid crystalline ionic liquid (C18IMCNBr),due to the higher conductivity of liquid crystal alignment. The larger Jsc and efficiency value of liquid crystal alignment supported that the higher conductivity of liquid crystal alignment is attributed to the enhancement of the exchange reaction between iodide species. As a result of formation of the two-dimensional electron conductive pathways organized by the localized I3- and I- at liquid crystal alignment layers, the concentration of polyiodide species exemplified by Im- (m =5,7, ...) was higher in alignment C18IMCNBr. However, in the two-dimensional electron conductive pathways of C18IMCNBr, more collision frequencies between iodide species (I-,I3-, and Im-) could be achieved than that in the three-dimensional space of C18IMCNBr, which could lead to the promotion of the exchange reaction between iodide species, the contribution of a two-dimensional structure of the conductive pathway through the increase of collision frequency between iodide species was proposed.

This study used jatropha oil, waste cooing oil, and soybean oil as the raw materials for investigating effects of catalyst concentration, reaction time, reaction temperature, methanol-to-oil ratio, and catalyst types on biodiesel yield. The authors also heated up the oil to speed up the transesterification and to make the reaction more complete. Jatropha oil, waste cooing oil, and soybean oil were used as the raw materials, and three types of ionic liquid or zwitterionic liquid, [PyrMe][HSO4], [PyrMeBuS][HSO4], and [MorMeA][Br], were added as catalysts for co-catalysis while heating the oil raw materials to create the best operational condition for biodiesel production. For soybean oil used as the raw material, the best catalyzing effect (a 99.4% yield) was achieved by adding [MorMeA][Br] while the reaction time was 6min, reaction temperature was 70 ¢J, and the methanol-to-oil ratio was 9:1. Under the best reaction condition, catalyzing effect was compared between the addition of sulfate-containing ionic liquid and sulfate-containing zwitterionic liquid. The yield of the addition of sulfate-containing ionic liquid and sulfate-containing zwitterionic liquid were 97.2% and 98.7% respectively. It can be found from this study that for increasing biodiesel yield, the addition of zwitterionic liquid for co-catalysis is more effective than the addition of homogeneous ionic liquid. Comparing the best operational condition between jatropha oil and soybean oil, the best yield of jatropha oil and soybean oil was 98.5% and 99.4% respectively, while the concentration of sodium hydroxide was 0.75 wt%, [MorMeA][Br] of 1.00 wt% was added, the methanol-to-oil ratio was 9:1, the reaction time was 6 min, and the reaction temperature was 70¢J. As for disposed cooking oil, the best operational condition rendered a yield of 98.1% when the concentration of sodium hydroxide was 0.75 wt%, [MorMeA][Br] of 1.00 wt% was added, the methanol-to-oil ratio was 9:1, the reaction time was 7 min, and the reaction temperature was 70¢J. For waste cooking oil, because of the containing of impurities from frying, the yield was slightly lower and the reaction time was longer.

The electrochemical behavior of a poly(2,2,6,6-tetramethylpiperidin- 1-oxyl-4-yl methacrylate) (PTMA) cathode in organic radical batteries with lithium bis(trifluoromethylsulfonyl)imide in N-butyl-N-methyl- pyrrolidinium bis(trifluoromethylsulfonyl)imide (LiTFSI/BMPTFSI) ionic liquid electrolytes is investigated. The ionic liquid electrolytes containing a high concentration of the LiTFSI salt have a high polarity, preventing the dissolution of the polyvinylidene fluoride (PVdF) binder and PTMA in the electrolytes. The results of cyclic voltammetry and AC impedance indicate that an increase in the LiTFSI concentration results in a decrease in the impedance of the lithium electrode, which affects the C-rate performance of batteries. The discharge capacity of the PTMA composite electrode in a 0.6 m LiTFSI/BMPTFSI electrolyte is 92.9 mAh g−1 at 1 C; its C-rate performance exhibits a capacity retention, 100 C/1 C, of 88.3%. Moreover, the battery with the 0.6-m LiTFSI/BMPTFSI electrolyte has very good cycle-life performance.

New catalytic synthetic methods in organic chemistry that satisfy increasingly stringent environmental constraints are in great demand by the pharmaceutical and chemical industries. Studies over last 15 years have revealed that activity of enzymes can be increased in organic solvents rather than their natural aqueous environment. Because of their ease of use, high selectivity and environment friendliness, enzymes are enjoying increasing popularity in today's synthesis world. Chapter 1 describes chemo-enzymatic synthesis of various glycolipid analogs. A highly regioselective macrolactonization was achieved using lipase from Candida antarctica as a catalyst. It also describes evaluation of lipases from different source and their efficiency in catalyzing the macrolactonization reaction. These analogs were synthesized using commercially available agriculture based disaccharides (maltose, lactose, cellobiose, melibiose). These glycolipid analogues have potential applications in the cosmetic industry, formulation, food production, and pharmaceutical industry.In Chapter 2, ring opening polymerization of epsilon-caprolactone in ionic liquid, [bmim][PF6] was investigated. A comparative study of ROP in different solvents (toluene, Ionic liquid, and bulk condition) was conducted. Effect of time and enzyme concentration on molecular weight and % yield was investigated. It was concluded that enzymatic ring opening polymerization of epsilon-caprolactone in ionic liquid, [bmim][PF6 ] is a very competitive and environmental friendly way of synthesizing high molecular weight polyesters.

The objectives of the research are to establish the process of obtaining regenerated fibers and films from wood pulp and bagasse pulp with the ionic liquid 1-Butyl-3-methylimidazolium Chloride (BMIMCl) as a solvent; to study the impacts on tensile strength of different spinning parameters; to find the optimal spinning condition, and to obtain regenerated cellulose products with flame retardant properties. Solutions were obtained by dissolving cellulose (wood/bagasse) pulp into the BMIMCl. The solutions were extruded in a dry-jet and wet-spinning method using water as a coagulation bath. The obtained fibers were tested to evaluate the properties such as tensile strength, thermal property, thermal mechanical property, crystal order, and ionic liquid residue in obtained fiber. The orthogonal experiments were designed to find out the strongest affective variable and the optimal condition of the spinning process. The regenerated cellulose films with melamine resin or zinc oxide were obtained. Their flame retardant properties were tested. Cellulose fiber with melamine resin was also obtained. Thermo-gravimetric analyzer (TGA) was used to measure the thermal properties of obtained products, and to calculate their activation energies. Dynamic mechanical analysis (DMA) was used to determine the thermal mechanical properties of obtained fibers. Wide angle X-ray diffraction (WAXD) was used to measure the degree of crystallinity and degree of crystal orientation. The tensile strength was tested by a tensile machine. To evaluate the quantity of ionic liquid residue in the regenerated fibers, the instrumental methods of FT-IR and Mass Spectrometry were applied. Research results indicated increases in the degree of crystallinity and storage modulus under a higher fiber drawing speed. Both regenerated bagasse fibers and regenerated wood fibers had similar thermal properties. However, the regenerated bagasse fibers showed a higher degree of crystallinity and a higher tenacity than the regenerated wood fibers obtained under the same condition. The study also revealed water treatment would be helpful for eliminating the ionic residue in regenerated fibers. It was also found the concentration of cellulose in the BMIMCl solution affected the tensile strength of regenerated fiber mostly. Certain amount of melamine or zinc oxide nanoparticles contained in the cellulose matrix could improve the flame retardant property effectively. / text

Efficient heat management in energy intensive applications such as server and data centers has become a national concern due to the magnitude of the energy consumed. In that matter, the absorption refrigeration system is an attractive solution because the abundant waste heat available in the data centers can be recycled to run the heat pump, which will bring about significant cooling cost savings. The use of absorption refrigeration has been limited due to the drawbacks related to the working fluids in commercially available equipment. Recently, ionic liquids (ILs) have been suggested as the absorbent in absorption heat pumps due to their tunable properties, negligible volatility and high thermal stability. The non-random-two-liquid-model was initially used to analyze the feasibility of the new IL based working fluid. Hydrofluorocarbons (HFCs) were paired with IL absorbents due to their good properties as refrigerants. The cooling-to-total-energy (CE) efficiency had a local maximum with respect to desorber temperature due to the solubility limit at lower temperatures and large heating requirements at higher temperatures. The waste heat recycling coefficient of performance (COP) continually increased with respect to desorber temperature and among the HFCs studied in this work, R134 gave the highest COP value, which is up to 40 times higher than that of typical vapor compression systems and 60 times higher than NH3/H2O and H2O/LiBr absorption refrigeration systems. A Redlich-Kwong equation of state (RK-EOS) was employed for accurate computation of mixture properties over a wide range of operating conditions. Analysis using the RK-EOS model showed that the CE trend in refrigerants followed the trend of solubility in the [bmim][PF6] IL. However, the trend in COP was different from that of CE as the operating pressure ranges became an important factor. Required pumping work of the working fluids has also been analyzed using a two phase pressure drop equation and the results show that the impact of viscous IL flow is insignificant compared to the total pumping work. The HFCs studied in this work have very similar structures. However, the extent of solubility and system efficiency in the same IL, [bmim][PF6], made a large difference. Most surprisingly, even when the refrigerant had the same chemical formula, the change in fluorine position in tetrafluoroethane showed significantly different system performance. The symmetrical tetrafluoroethane had superior CE and COP over the asymmetrical tetrafluoroethane most likely due to the higher probability to form hydrogen bonding with the absorbent. The computational results for various HFC/IL pairs show that in selecting the working fluid pairs, the refrigerant should have high overall solubility in the IL and a large gradient of solubility with respect to temperature. Also, refrigerants with small pressure ranges are preferred. In addition to the simulation study, a bench-top absorption refrigeration system was built and operated using IL based working fluids for the first time. The effect of cooling was observed by operating the test system. The experimental results were congruent with the predictions from the modeling work. In conclusion, an absorption refrigeration system based on the IL chemical compressor has been shown to be a promising solution in applications which need efficient cooling and generate abundant waste heat.

Green chemistry principles served as a guide for three industrially-relevant projects. In the first project, silylamines were applied as reversible ionic liquids for carbon dioxide capture from post-combustion flue gas streams. The effect of silylamine structure was thoroughly researched to develop a comprehensive library of silylamines and an accompanying set of structure-property relationships. The proposed solvent systems have the potential to present significant energy savings, as design has focused on their use in a non-aqueous, solvent-free environment. The second project also dealt extensively with carbon dioxide capture, as a reversible, in-situ protecting group for amines. Three strategies for the reversible protection of amines using carbon dioxide were developed and evaluated. Further, a chemoselective reaction was performed using carbon dioxide to protect a reactive amine and consequentially direct reactivity elsewhere within the same molecule. The carbon dioxide-protection technology developed has significant impact in multi-step industrial syntheses, as reversible, in-situ protection with carbon dioxide could eliminate the need for separate protection and deprotection unit operations. Lastly, a study was performed on the thermal degradation and stabilization of PVC in the presence of both plasticizers and thermal stabilizers. The study combined both model compound experiments as well as work with bulk PVC blends to gain a holistic understanding of the processes that take place during the degradation and stabilization of PVC. A bio-based plasticizer was investigated as a replacement for petroleum-based phthalate plasticizers. Additionally, two novel thermal stabilizers for PVC were presented and evaluated.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24003号 / エネ博第439号 / 新制||エネ||83(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 佐川 尚, 教授 野平 俊之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM