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.

Biomarker responses in the bivalve Chlamys farreri to the water-soluble fraction of crude oil

To investigate the effect of the water soluble fraction of crude oil(WSF) on marine bivalves, the scallop C hlamys farreri was exposed to three WSF concentrations(0.18 mg/L, 0.32 mg/L, and 0.51 mg/L, respectively) in seawater. Petroleum hydrocarbon contents in scallops and a suite of enzymes [7-Ethoxyresorufin-O-deethylase(EROD), aryl hydrocarbon hydroxylase(AHH), glutathione S-transferase(GST), and glutathione peroxidase(GPx)] in gills and digestive glands were monitored over 10 days. The results revealed that WSF affected the activity of the four enzymes in the gills and digestive glands. EROD activity in the gills was significantly induced in most individuals of the three test groups, while in the digestive gland it was significantly induced in the low-concentration group within 4 days but was inhibited in the middle- and high-concentration groups on days 1, 4, and 10. AHH activity in the gills of all treatment groups was significantly induced on day 1. In the digestive gland, AHH activity was induced in most individuals from the treatment groups. In all treatment groups, GST activity was significantly inhibited from days 2 to 10 in the gills and was induced after day 4 in the digestive gland. GPx activity in the gills was significantly inhibited throughout the exposure period in all treatment groups. There was no overall significant difference in GPx activity in the digestive gland between the control and treatment groups. Our results also revealed that petroleum hydrocarbon concentrations in the tissues increased linearly with exposure time. EROD activity in the digestive gland and GST and GPx activity in the gill tissue were negatively correlated with petroleum hydrocarbon body burden. These enzymes play important roles in detoxification and can act as potential biomarkers for monitoring petroleum hydrocarbon contaminants in the marine environment.

Research on Synthesizing Disperser with Fraction of Anthracene Oil for Coal Water Slurry

Experiment of synthesizing a disperser for coal water slurry (CWS) by using fractions of anthracene oil from high-temperature coal tar was performed. The orthogonal test was used to investigate the influence of temperature, time, quantity of sulfonation agent and condensation agent and the interaction of these factors on properties of the disperser. The result shows that the influence of temperature, time, quantity of sulfonation agent and condensation agent, and the interaction of sulfonation time and sulfonation agent has a significant influence on the properties of disperser. The optimal condition of synthesis is that in 150g of the fractions of anthracene oil, 40 mL of sulfonation agent is added and sulfonated for 3 h at 130℃, then, 10 mL of condensing agent is added and condensated for 1.5 h at 115 ℃.

Molten waste plastic pyrolysis in a vertical falling film reactor and the influence of temperature on the pyrolysis products

Molten plastics are characterised with high viscosity and low thermal conductivity. Applying falling film pyrolysis reactor to deal with waste plastics can not only improve heat transfer efficiency, but also solve the flow problem. In this work, the pyrolysis process of molten polypropylene （PP） in a vertical falling film reactor is experimentally studied, and the influence of heating temperature on pyrolysis products is discussed. It has been found that with the temperature increases from 550 ℃ to 625 ℃, the yield of pyrolysis oil decreases from 74.4 wt% （ 4- 2.2 wt/%） to 53.5 wt% （± 1.3 wt%）. The major compositions of the pyrolysis oil are C9, C12 and C18, and β-scission reactions are predominant. The content of the light fraction C6-C12 of pyrolysis oil is 69.7 wt%. Compared with other pyrolysis reactors, the yield ofoil from vertical falling film pyrolysis reactor is slightly higher than that from tubular reactor, equal to that from rotary kiln reactor, and slightly lower than that in medium fluidised-bed reactor.

Formation mechanism of condensates, waxy and heavy oils in the southern margin of Junggar Basin, NW China

It is a challenge to determine the source and genetic relationship of condensate, waxy and heavy oils in one given complicated petroliferous area, where developed multiple sets of source rocks with different maturity and various chemical features.The central part of southern margin of Junggar Basin, NW China is such an example where there are condensates, light oils, normal density oils, heavy crude oils and natural gases. The formation mechanism of condensates has been seriously debated for long time;however, no study has integrated it with genetic types of waxy and heavy oils. Taking the central part of southern margin of Junggar Basin as a case, this study employs geological and geochemical methods to determine the formation mechanism of condensates,waxy and heavy oils in a complicated petroliferous area, and reveals the causes and geochemical processes of the co-occurrence of different types of crude oils in this region. Based on detailed geochemical analyses of more than 40 normal crude oils, light oils,condensates and heavy oils, it is found that the condensates are dominated by low carbon number n-alkanes and enriched in light naphthenics and aromatic hydrocarbons. Heptane values of these condensates range from 19% to 21%, isoheptane values from1.9 to 2.1, and toluene/n-heptane ratios from 1.5 to 2.0. The distribution of n-alkanes in the condensates presents a mirror image with high density waxy crude oils and heavy oils. Combined with the oil and gas-source correlations of the crude oils, condensates and natural gas, it is found that the condensates are product of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils which were derived from mature Cretaceous lacustrine source rocks in the relatively early stage. The waxy oils are the intermediate products of evaporative fractionation and/or phase-controlled fractionation of reservoir crude oils, while the heavy oils are in-situ residuals. Therefore, evaporative fractionation and/or phase-controlled fractionation would account for the formation of the condensate, light oil, waxy oil and heavy oil in the central part of southern margin of Junggar Basin, resulting in a great change of the content in terms of light alkanes, naphthenics and aromatics in condensates, followed by great uncertainties of toluene/n-heptane ratios due to migration and re-accumulation. The results suggest that the origin of the condensate cannot be simply concluded by its ratios of toluene/n-heptane and n-heptane/methylcyclohexane on the Thompson's cross-plot, it should be comprehensively determined by the aspects of geological background, thermal history of source rocks and petroleum generation,physical and chemical features of various crude oils and natural gas, vertical and lateral distribution of various crude oils in the study area.

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.