It is important to understand the mechanism and implications of different modifiers on analytical and preparative processes under chromatography with supercritical fluids (SFs) and under extraction with SFs. Supercrit...It is important to understand the mechanism and implications of different modifiers on analytical and preparative processes under chromatography with supercritical fluids (SFs) and under extraction with SFs. Supercritical fluid chromatography (SFC) and supercritical fluid extraction are generally carried out with neat supercritical carbon dioxide (SCCO2) or with SCCO2 containing modifiers (or cosolvents), especially for strongly polar compounds. For example, methanol is added as a cosolvent/modifier to SCCO2 for the extraction/separation of polar compounds. This paper discusses the influence of the modifier on the colligative properties of the principal mobile phase, which may define the situation in the total mobile phase in a chromatography column or in parts of a column under SFC. No colligative behavior of solutions reflects individual properties of the solutes. Their cross-interactions with solvents are discussed.展开更多
A model for correlating the phase equilibria of solid-supercritical fluid systems has beendeveloped. The feature of the model is that it can be used to estimate the size of the solvent-soluteclusters and the local den...A model for correlating the phase equilibria of solid-supercritical fluid systems has beendeveloped. The feature of the model is that it can be used to estimate the size of the solvent-soluteclusters and the local density of the solvent in the solvent-solute clusters.展开更多
The solubilities of a number of solid solutes in supercritical CO2 have been correlated usingthe model proposed in previous paper. The numbers of CO2 in each CO2 -solute cluster and the localdensity of the CO2 in the...The solubilities of a number of solid solutes in supercritical CO2 have been correlated usingthe model proposed in previous paper. The numbers of CO2 in each CO2 -solute cluster and the localdensity of the CO2 in the clusters are predicted using the model. The results calculated agree fairly wellwith the experimental data.展开更多
The conversion of biomass into hydrogen-rich gas provides a competitive means for producing clean energy and chemicals from renewable resources.Based on the principle of Gibbs free energy minimization, a new method wa...The conversion of biomass into hydrogen-rich gas provides a competitive means for producing clean energy and chemicals from renewable resources.Based on the principle of Gibbs free energy minimization, a new method was presented with better effectiveness and simplicity to be used for the prediction of chemical equilibrium composition of hydrogen production by biomass gasification in supercritical water(SCW).Applying this method to analyzing the process of glucose gasification in SCW, it was found that the product gas consisted primarily of hydrogen and carbon dioxide as well as a small amount of methane and carbon monoxide.The gas yield was strongly affected by reaction temperature and feedstock concentration and less affected by reaction pressure in the following range:temperature 623—1073 K,pressure 22.5—35 MPa,and concentration 0.1—0.8 mol·L -1 .The hydrogen production in product gas increased with the increase of temperature and decreased with the increase of concentration.展开更多
The solubility of stearic acid in supercritical CO2 with acetonitrile (CH3CN) cosolvent was measured at 318.15 K in the pressure range from 9.5 to 16.5 MPa, and the cosolvent concentration ranges from 0. 0 to 5.5 mol%...The solubility of stearic acid in supercritical CO2 with acetonitrile (CH3CN) cosolvent was measured at 318.15 K in the pressure range from 9.5 to 16.5 MPa, and the cosolvent concentration ranges from 0. 0 to 5.5 mol% . The solubility increases with acetonitrile concentration and pressure, and it also increases with the apparent density of CO2 d1(moles of CO2 in per liter of fluid) at higher cosolvent concentrations. At lower d1, however, the solubility of the acid at lower acetonitrile concentrations is lower than that in pure CO2 provided that d1 is fixed, which is discussed qualitatively based on the clustering of the components in the system.展开更多
文摘It is important to understand the mechanism and implications of different modifiers on analytical and preparative processes under chromatography with supercritical fluids (SFs) and under extraction with SFs. Supercritical fluid chromatography (SFC) and supercritical fluid extraction are generally carried out with neat supercritical carbon dioxide (SCCO2) or with SCCO2 containing modifiers (or cosolvents), especially for strongly polar compounds. For example, methanol is added as a cosolvent/modifier to SCCO2 for the extraction/separation of polar compounds. This paper discusses the influence of the modifier on the colligative properties of the principal mobile phase, which may define the situation in the total mobile phase in a chromatography column or in parts of a column under SFC. No colligative behavior of solutions reflects individual properties of the solutes. Their cross-interactions with solvents are discussed.
文摘A model for correlating the phase equilibria of solid-supercritical fluid systems has beendeveloped. The feature of the model is that it can be used to estimate the size of the solvent-soluteclusters and the local density of the solvent in the solvent-solute clusters.
文摘The solubilities of a number of solid solutes in supercritical CO2 have been correlated usingthe model proposed in previous paper. The numbers of CO2 in each CO2 -solute cluster and the localdensity of the CO2 in the clusters are predicted using the model. The results calculated agree fairly wellwith the experimental data.
文摘The conversion of biomass into hydrogen-rich gas provides a competitive means for producing clean energy and chemicals from renewable resources.Based on the principle of Gibbs free energy minimization, a new method was presented with better effectiveness and simplicity to be used for the prediction of chemical equilibrium composition of hydrogen production by biomass gasification in supercritical water(SCW).Applying this method to analyzing the process of glucose gasification in SCW, it was found that the product gas consisted primarily of hydrogen and carbon dioxide as well as a small amount of methane and carbon monoxide.The gas yield was strongly affected by reaction temperature and feedstock concentration and less affected by reaction pressure in the following range:temperature 623—1073 K,pressure 22.5—35 MPa,and concentration 0.1—0.8 mol·L -1 .The hydrogen production in product gas increased with the increase of temperature and decreased with the increase of concentration.
基金Special article from the First International workshop on Green Chemistry, the University of ScienceTechnology of China, Hefei, China, May, 1998.Project (No. 29633020 and 629725308) supported by the National Natural Science Foundation of China.
文摘The solubility of stearic acid in supercritical CO2 with acetonitrile (CH3CN) cosolvent was measured at 318.15 K in the pressure range from 9.5 to 16.5 MPa, and the cosolvent concentration ranges from 0. 0 to 5.5 mol% . The solubility increases with acetonitrile concentration and pressure, and it also increases with the apparent density of CO2 d1(moles of CO2 in per liter of fluid) at higher cosolvent concentrations. At lower d1, however, the solubility of the acid at lower acetonitrile concentrations is lower than that in pure CO2 provided that d1 is fixed, which is discussed qualitatively based on the clustering of the components in the system.
