Effect of petroleum chemical fraction and residual oil content in saline lacustrine organic-rich shale: A case study from the Paleogene Dongpu Depression of North China

Halite and gypsum minerals in saline shale make the retention mechanism and chemical fractionation of residual oil unique. The Dongpu Depression in North China is a typically saline lacustrine basin with developing halite and gypsum. The effect of gypsum minerals on residual oil content and chemical fractionation remains unclear. In this study, shale samples with different gypsum contents were used in organic geochemical experiments, showing that the high total organic matter (TOC) content and type II kerogen leads to a high residual oil content, as shown by high values of volatile hydrocarbon (S1) and extractable organic matter (EOM). XRD and FE-SEM result indicate that the existence of gypsum in saline shale contributes to an enhanced pore space and a higher residual oil content in comparison to non-gypsum shale. Additionally, the increase in the gypsum mineral content leads to an increase in the saturated hydrocarbon percentage and a decrease in polar components percentage (resins and asphaltene). Furthermore, thermal simulation experiments on low-mature saline shale show that the percentage of saturated hydrocarbons in the residual oil is high and remains stable and that the storage space is mainly mesoporous (> 20 nm) in the oil expulsion stage. However, the saturated hydrocarbons percentage decreases rapidly, and oil exists in mesopores (> 20 nm and < 5 nm) in the gas expulsion stage. In general, gypsum is conducive to the development of pore space, the adsorption of hydrocarbons and the occurrence of saturated hydrocarbon, leading to large quantities of residual oil. The data in this paper should prove to be reliable for shale oil exploration in saline lacustrine basins.

Flow Characteristics of Crude Oil with High Water Fraction during Non-heating Gathering and Transportation

In order to ensure the safety of the non-heating gathering and transportation processes for high water fraction crude oil,the effect of temperature,water fraction,and flow rate on the flow characteristics of crude oil with high water fraction was studied in a flow experimental system of the X Oilfield.Four distinct flow patterns were identified by the photographic and local sampling techniques.Especially,three new flow patterns were found to occur below the pour point of crude oil,including EW/O&W stratified flow with gel deposition,EW/O&W intermittent flow with gel deposition,and water single-phase flow with gel deposition.Moreover,two characteristic temperatures,at which the change rate of pressure drop had changed obviously,were found during the change of pressure drop.The characteristic temperature of the first congestion of gel deposition in the pipeline was determined to be the safe temperature for the non-heating gathering and transportation of high water cut crude oil,while the pressure drop reached the peak at this temperature.An empirical formula for the safe temperature was established for oil-water flow with high water fraction/low fluid production rate.The results can serve as a guide for the safe operation of the non-heating gathering and transportation of crude oil in high water fraction oilfields.

NMR chemical shifts of carbon atoms and characteristic shift ranges in the oil sample

Application of high resolution^(13)C nuclear magnetic resonance(NMR)spectroscopy to characterize crude oil was demonstrated.The chemical shifts of^(13)C NMR functional groups that determine the composition of the oil sample were determined.Molar fractions of primary,secondary,quaternary,tertiary,aromatic groups,aromatic factor and average hydrocarbon chain length of aliphatic hydrocarbons of the oil sample according to^(13)C NMR spectra were determined.Detailed description of the^(13)C NMR spectra of the oil sample using a single consideration of three NMR spectra:^(13)C,^(13)C Attached Proton Test(APT),^(13)C with Gated Decoupling(GD)was performed.The different contribution of the studied oil sample in the aliphatic(10e75 ppm)and aromatic(115e165 ppm)areas of the^(13)C NMR spectra was determined.The presence of all major hydrocarbon components in the studied oil sample was established on the quantitative level,the aromaticity factor and the mean length of the hydrocarbon chain were evaluated.Quantitative fractions of aromatic molecules and functional groups constituting oil hydrocarbons were determined.In this work we demonstrate that the attached proton test and gated decoupling^(13)C NMR spectroscopy can afford all information to complete the chemical shift assignment of an oil sample,especially for determination of long range 1He^(13)C coupling constants and^(13)C multiplicity.

Diffusion Kinetics of Components of Asphalt Into Waste Rubber

The use of waste crumb rubber powder as a modifier for modified asphalt can recycle waste rubber to ease pressure on the environment and improve the performance of asphalt. Diffusion of components of asphalt into waste rubber is of vital importance to improve the performance of rubber modified asphalt,while the related researches are scarce. Diffusion of components of asphalt into waste rubber at different temperatures has been investigated in this work. Rectangle rubber was immersed in asphalt at certain temperature for a period of time. And the mass increment of rubber was measured to determine the diffusion rate of components of asphalt into rubber. The experimental results indicated that the diffusion rate of components of asphalt into waste rubber increases along the temperature,but the diffusion rate of components of fractions oil which is distillated from catalytic cracking slurry is much higher than that of components of asphalt. Compared with asphalt,fractions oil enjoys lower viscosity and better permeability with higher content of saturates and aromatics. All the characteristics are contributed to the efficient diffusion of components of fractions into waste rubber.