Integration of a fused silica capillary and in-situ Raman spectroscopy for investigating CO_(2) solubility in n-dodecane at near-critical and supercritical conditions of CO_(2)

To determine the solubility of CO_(2)in n-dodecane at T=303.15-353.15 K,P≤11.00 MPa,an integrated fused silica capillary and in-situ Raman spectroscopy system was built.The Raman peak intensity ratio(I_(CO_(2))/IC-H)between the upper band of CO_(2)Fermi diad(I_(CO_(2)))and the C-H stretching band of n-dodecane(IC-H)was employed to determine the solubility of CO_(2)in n-dodecane based on the calibrated correlation equation between the known CO_(2)molality in n-dodecane and the I_(CO_(2))/IC-Hratio with R^(2)=0.9998.The results indicated that the solubility of CO_(2)decreased with increasing temperature and increased with increasing pressure.The maximum CO_(2)molality(30.7314 mol/kg)was obtained at 303.15 K and7.00 MPa.Finally,a solubility prediction model(lnS=(P-A)/B)based on the relationship with temperature(T in K)and pressure(P in MPa)was developed,where S is CO_(2)molality,A=-8×10^(-6)T^(2)+0.0354T-8.1605,and B=0.0405T-10.756.The results indicated that the solubilities of CO_(2)derived from this model were in good agreement with the experimental data.

CHROMATOGRAPHIC SEPARATION OF THE ENANTIOMERS OF 3-PHENYL-1,2-EPOXYETHANE AND 1-PHENYL-1-PROPANOL ON A FUSED SILICA CAPILLARY COLUMN COATED WITH PERBENZYL-β-CYCLODEXTRIN

A β-cyclodextrin derivative, perbenzyl-β-cyclodextrin, was prepared and used as a chiral stationary phase for capillary gas chromatography. Using FID detector and the column temperature between 70 and 80℃, the chiral separations of racemic 3-phenyl-1, 2-epoxyethane and 1-phenyl-1-propanol on a 14m×0.23mm I. D. fused silica column with the β-cyclodextrin derivative were carried out and the optical purities of optically active 1-phenyl-1-propanol samples prepared by asymmetric synthesis were determined.

Interactions between hydrocarbon-bearing fluids and calcite in fused silica capillary capsules and geological implications for deeply-buried hydrocarbon reservoirs

During the burial processes of deep/ultra-deep hydrocarbon reservoirs,the interactions between hydrocarbon-bearing fluids and reservoirs significantly affect the quality evolution of hydrocarbons and reservoirs;thus,this topic requires further investigation.In this study,the continuous evolution and the coupling mechanisms in various anhydrous and hydrous nC_(16)H_(34)-(water)-(calcite)systems in fused silica capillary capsules(FSCCs)were investigated using laser Raman spectroscopy,fluorescence color analysis,and fluorescence spectroscopy,and the mineral alterations were analyzed using scanning electron microscopy(SEM).The experimental results show that extensive organic-inorganic interactions occur in the systems if water is present,and different inorganic components have different effects on hydrocarbon degradation.Distilled water promotes freeradical thermal cracking and steps oxidation,forming more low-molecular-weight hydrocarbons,CO_(2),and organic acids(e.g.,acetic acids)but suppresses the free-radical cross-linking,generating less high-molecular-weight hydrocarbons.However,in the presence of CaCl_(2) water,the yields of hydrocarbon gases are lower than in the distilled water system because high concentrations of Ca ions inhibit the generation of free radicals.Calcites,which exhibit different surface reactivities in different fluid conditions,affect hydrocarbon degradation in different ways.In the anhydrous nC16H34-calcite system,calcites promote the generation of both hydrocarbon gases and high-molecular-weight hydrocarbons.In contrast,in the hydrous nC16H34-distilled(CaCl_(2))watercalcite system,calcites promote the generation of hydrocarbon gases and suppress the generation of high-molecular-weight hydrocarbons.Calcite also reacts with organic acids via surface reactions to form secondary pores.Therefore,except for the formation temperature and pressure,organic-inorganic interactions are controlled by multiple factors,such as the water saturation,water type,water salinity,and the mineral content,resulting in different evolutions of the hydrocarbon degradation and reservoir properties.

CO_2 Density-Raman Shift Relation Derived from Synthetic Inclusions in Fused Silica Capillaries and Its Application

The densities of CO2 inclusions in minerals are commonly used to determine the crystallizing conditions of the host minerals. However, conventional microthermometry is difficult to apply for inclusions of small size （〈 5-10 μm） or low density. Raman analysis is an alternative method for determining CO2 density, provided that the CO2 density-Raman shift relation is known. This study aims to establish this CO2 density-Raman shift relation by using CO2 inclusions synthesized in fused silica capillaries. By using this newly-developed synthetic technique, we formed pure CO2 inclusions, and their densities were determined by microthermometry. The Raman analysis showed that the relation between CO2 density （D in g/cm^3） and the separations （△ in cm^-1） between the two main bands （i.e. Fermi diad bands） in CO2 Raman spectra can be represented by a cubic equation： D （g/cm^3）=0.74203（-0.019^3＋5.90332△^2-610.79472△＋21050.30165）-3.54278 （r^2=0.99920）. Our calculated D value for a given A is between those obtained from two previously-reported equations, which were derived from different experimental methods. An example was given in this study to demonstrate that the densities of natural CO2 inclusions that could not be derived from microthermometry could be determined by using our method.