Effects of Pretreatment with Ionic Liquids on Cellulose Hydrolysis under Hydrothermal Conditions.

Hydrothermal hydrolysis in hot pressurized liquid water (HPLW) is attractive for biomass conversion into valuable products because it achieves high reaction rates without catalysts and additives. The hydrothermal hydrolysis of high crystalline cellulose requires higher reaction temperature than polysaccharides having low crystallinity. It can be expected to increase the reaction rate or decrease temperature by decreasing the crystallinity. In the present study ashless filter paper as a fibrous pure cellulose sample was pretreated with ionic liquids (ILs) such as imidazolium chloride ILs containing alkyl side chains ranging from two to six carbons, and with an aqueous solution of bis(ethylenediamine ammonium) copper (BEDC). Herein, the pretreatment with ILs was to regenerate filter paper: dissolving in ILs at 373 K for 120 min or in an aqueous BEDC solution at room temperature, precipitating by adding water, washing the solid, and then drying. Subsequently, the pretreated filter paper samples were hydrolyzed at 533 K and 5.0 MPa in HPLW in a small semi-batch reactor, and the effects of the pretreatment with ILs or BEDC on reaction rates and product yields were examined. While the crystallinity indexes with all ILs and BEDC after the pretreatments decreased to 44 to 47 from the original sample of 87, the reaction rates and product yields were significantly affected by the IL species. At 533 K and 5.0 MPa, the dissolution rate with [AMIM][Cl] was nine times as fast as that for untreated sample.

Density dependence of retention factors of trans-stilbene oxide for chiral separation by supercritical fluid chromatography.

Retention factors for two enantiomers of trans-stilbene oxide, k1 and k2, were measured with a chiral AD-H column using two syringe pumps to feed CO2 and methanol as a co-solvent at various temperatures, pressures and co-solvent mole fractions to determine the effects of these operating conditions on the retention factors. The retention factors k1 and k2 are for the (R,R)- and (S,S)-forms, respectively. When the isothermal compressibilities of a mixture of CO2 and MeOH were lower than 0.01, far from the critical locus of the CO2 and methanol mixture, both retention factors were well expressed with the solvent density and temperature with an average absolute relative deviation of 1-2%. In the vicinity of the critical locus, however, where the isothermal compressibilities were much larger than 0.01, the relationship between retention factor and density was complicated. Both retention factors were proportional to the isothermal compressibility, irrespective of methanol mole fraction at each temperature.

Role of water in complexation of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6) with Li+ and K+ in hydrophobic 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ionic liquid.

Complexation characteristics of 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6, 18C6) with Li+ and K+ in a hydrophobic ionic liquid of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide under dry and humid conditions at 298.2 K were studied by 1H and 13C NMR chemical shifts. The comparison of the 1H and 13C chemical shifts of 18C6 molecule between the dry and humid IL solutions without the alkali metal ions showed that uncomplexed 18C6 molecules are solvated by water molecules in the humid ionic liquid solution. The changes in the 1H and 13C chemical shifts of 18C6 ligand molecule with the increases in the Li+ and K+ concentrations revealed that in both dry and humid ionic liquid solutions 18C6 molecule forms 1:1 complexes with Li+ and K+. The 1H NMR data of water molecules in the humid ionic liquid solutions demonstrated that water molecules interact with Li+-18C6 complexes and free Li+, but do not with K+-18C6 complexes and free K+. The mechanisms of the formation of the Li+ and K+ complexes in the humid ionic liquid solution are different from each other due to the differences in the complex-water interactions.

Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.

The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide.

Effects of dissolved water on Li+ solvation in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ionic liquid studied by NMR.

(1)H and (7)Li NMR chemical shifts of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide-water solutions in the presence and absence of lithium bis(trifluoromethanesulfonyl)amide were determined at 293.2 K over a wide range of water concentrations from 0.0156 to 1.16 mol kg(-1). These results revealed the attractive interaction between water molecule and Li(+) as well as the hydrogen bonding among water molecules. Moreover, self-diffusion coefficients of water, 1-ethyl-3-methylimidazolium cation, Li(+), and bis(trifluoromethanesulfonyl)amide anion in the ionic liquid solutions at various water contents were determined by (1)H, (7)Li, and (19)F NMR techniques. It was found that Li(+) is averagely hydrated by eight water molecules in the ionic liquid solutions. Furthermore, (7)Li longitudinal relaxation times of Li(+) in the ionic liquid solutions at 293.2 K were measured with two different magnetic fields and various water contents. The mean one-jump distances of Li(+) in the ionic liquid solutions were estimated from the correlation times and the self-diffusion coefficients. A comparison between the hydrodynamic radius and the mean one-jump distance of Li(+) suggested the formation of water channels in the ionic liquid solutions.

Binary Diffusion Coefficients of Platinum(II) Acetylacetonate in Supercritical Carbon Dioxide.

Binary diffusion coefficients (D12) and retention factors (k) of platinum(II) acetylacetonate at infinitesimal concentration in supercritical (sc) carbon dioxide (CO2) were measured by the chromatographic impulse response method with a poly(ethylene glycol) coated capillary column at temperatures from (308.15 to 343.15) K and pressures from (8.5 to 40.0) MPa, and D12 in liquid ethanol at temperatures from (298.15 to 333.15) K and atmospheric pressure by the Taylor dispersion method. As has been seen for our previously reported data on other metal complexes measured in sc CO2 and organic solvents, the D12 data in sc CO2 and liquid ethanol were represented by a function of temperature and solvent viscosity. The D12 values for metal complexes were not related to the solute molecular weights. The k values in sc CO2 were expressed by a function of temperature and CO2 density.

Reaction temperature variations on the crystallographic state of spinel cobalt aluminate.

In this study, we report a rapid and simple technique for obtaining cobalt aluminate having a spinel structure. The products were prepared from a hydroxide precursor synthesized by coprecipitation of cobalt (Co(2+)) and aluminum (Al(3+)) nitrates with an alkaline solution. The chosen precursor enabled low temperature fabrication of cobalt aluminate with a spinel structure by sintering it for 2 hours at low temperatures (>400 °C). Crystallographic and thermal analyses suggest that the low-temperature-sintered products contain Co(3+) ions stabilized by chemisorbed water and/or hydroxide groups, which was not observed for products sintered at temperatures higher than 1000 °C. The color of the products turned from clear blue (Thenard's blue) to dark green when sintering temperatures were below 1000 °C. Magnetic quantities, Curie constants, and Weiss temperatures show a strong dependence on the sintering temperature. These findings suggest that there are mixed valent states, i.e. Co(2+) and Co(3+), and unique cation distributions at the different crystallographic sites in the spinel structure, especially in the products sintered at lower temperatures.

Diffusion coefficients of phenylbutazone in supercritical CO2 and in ethanol.

The diffusion coefficients D(12) of phenylbutazone at infinite dilution in supercritical CO(2) were measured by the chromatographic impulse response (CIR) method. The measurements were carried out over the temperature range from 308.2 to 343.2 K at pressures up to 40.0 MPa. In addition, the D(12) data of phenylbutazone at infinite dilution in ethanol were also measured by the Taylor dispersion method at 298.2-333.2K and at atmospheric pressure. The D(12) value of phenylbutazone increased from 4.45×10(-10) m(2) s(-1) at 298.2 K and 0.1 MPa in ethanol to about 1.43×10(-8) m(2) s(-1) at 343.2 K and 14.0 MPa in supercritical CO(2). It was found that all diffusion data of phenylbutazone measured in this study in supercritical CO(2) and in ethanol can be satisfactorily represented by the hydrodynamic equation over a wide range of fluid viscosity from supercritical state to liquid state with average absolute relative deviation of 5.4% for 112 data points.

Applications of the chromatographic impulse response method in supercritical fluid chromatography.

The use of chromatographic impulse response (CIR) method with a coated open tubular capillary column has potential advantages in supercritical fluid chromatography. In this review, applications of the CIR method to measuring the thermodynamic properties such as diffusion coefficients, solubilities and partial molar volumes are presented. This survey gives the theoretical backgrounds for the CIR method with linear adsorption and nonlinear adsorption models. Furthermore, the brief theoretical backgrounds for using retention factors to determine solubilities and partial molar volumes are also provided. In addition, the data sources for the diffusion coefficients with an emphasis on the results published after 2004 and for the partial molar volumes in supercritical carbon dioxide are presented.

Simultaneous determination of binary diffusion coefficients from multiple response curves by chromatographic measurements.

The chromatographic impulse response technique with a polymer coated capillary column was applied to measurements of infinite dilution binary diffusion coefficients D and retention factors k in supercritical carbon dioxide by injecting a hexane solution dissolving a mixture of three unsaturated fatty acids such as alpha-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid. The coefficients were simultaneously estimated by the curve fitting analysis even from partially overlapping response curves with the resolution of 0.8. The D and k values for each solute were able to be so obtained as accurately as those determined by individually injecting a single component solution. Almost no effect of the interaction among the components in the mixture was found from various approaching ways for curve fitting and the consecutive injection of the mixture at a certain interval.

Measurements of binary diffusion coefficients, retention factors and partial molar volumes for myristoleic acid and its methyl ester in supercritical carbon dioxide.

The binary diffusion coefficients, D(12), and retention factors for myristoleic acid and its methyl ester at infinite dilution were measured by the chromatographic impulse response technique in supercritical carbon dioxide at temperatures of 313.2, 333.2 and 343.2 K and pressures from 9.2 to 30 MPa for the acid, and from 8.0 to 14 MPa for the ester. Although the D(12) values were represented by the two correlations, the D(12)/T vs. CO(2) viscosity and the Schmidt-number correlations, which are valid for more than 40 compounds that we have measured so far, significant temperature dependences were observed for the ester. Moreover, the D(12) values for the ester at 313.2 K downward deviated from the background values around 400 kg m(-3), where the partial molar volumes, obtained from the correlation between the retention factors measured and CO(2) densities, showed large negative values.

Noncatalytic hydrolysis of guar gum under hydrothermal conditions.

Guar gum, a naturally occurring heteropolysaccharide made of mannose and galactose, was hydrolytically degraded without a catalyst in a batch reactor to produce water-soluble (WS) saccharides including mono- and oligosaccharides. The degradation was carried out under hydrothermal conditions over ranges of temperature from 180 to 240 degrees C and of reaction time from 3 to 60min. Guar gum was readily dissolved and hydrolyzed, and the major products identified in the WS components were oligosaccharides with degrees of polymerization up to about 20, monosaccharides containing mannose and galactose, and 5-hydroxymethyl-2-furaldehyde (5-HMF). At 200 degrees C, the oligosaccharide yield, obtained from the difference between the yields of the total WS saccharides and monosaccharides, showed the highest value of 94.4% at 7min among all conditions studied, on the basis of the saccharide content in the initial sample. The oligosaccharide yield decreased with reaction time, and the yield of monosaccharides correspondingly increased, and reached the highest value of 34.5% (mannose 22.8%, galactose 11.7%) at 60min. The monosaccharides produced were further decomposed to secondary products such as 5-HMF. The maximum yield of 5-HMF obtained was 26.3% at 220 degrees C and 30min. The production and the decomposition of galactose somewhat preceded those of mannose.

Polysaccharide hydrolysis accelerated by adding carbon dioxide under hydrothermal conditions.

Polysaccharides such as agar, guar gum, starch, and xylan were hydrolyzed to produce mono- and oligosaccharides under hydrothermal conditions with and without carbon dioxide in a small batch reactor. The molecular weight distributions of the polysaccharide hydrolyzates shifted to lower molecular weights by increasing the carbon dioxide load, corresponding to higher pressures of carbon dioxide. For example, the yield of glucose produced from the hydrolysis of starch at 200 degrees C was increased significantly from 3.7% to 53.0% (on a carbon weight basis) of the initial polysaccharide by increasing carbon dioxide load in a reaction time of 15 min. Carbonic acid generated from water and carbon dioxide appeared to lower the pH of high-temperature and high-pressure water. Polysaccharide hydrolysis under hydrothermal conditions in the presence of carbon dioxide is an environmentally benign method to produce mono- and oligosaccharides because the process does not require the use of conventional acids and bases followed by neutralization and separation.

Impulse response techniques to measure binary diffusion coefficients under supercritical conditions.

This review describes impulse response techniques with a curve-fitting method to measure thermodynamic properties, such as binary diffusion coefficient, retention factor, and partial molar volume, under supercritical conditions. Theoretical background, parameter sensitivity, sources of experimental error, noise elimination technique, and the correction of apparent binary diffusion coefficients due to column coiling are discussed based on recent studies, together with data sources and predictive correlations for binary diffusion coefficients.

Chromatographic impulse response technique with curve fitting to measure binary diffusion coefficients and retention factors using polymer-coated capillary columns.

The theoretical basis of a Gaussian-like approximate solution was applied to a chromatographic impulse response technique with curve fitting for measuring binary diffusion coefficients and retention factors using a polymer-coated capillary column. The formulae were derived for evaluating both the accuracy of the approximate solution and the sensitivity of the parameters. The validity of the solution also was confirmed experimentally for pulse injection of phenol in acetone into supercritical carbon dioxide flowing at 313.15 K and 11.6-28.6 MPa. Potential sources for experimental errors of the method are discussed.