Study of Oil/Water Interfacial Tension of Vacuum Residual Fractions from Iranian Light Crude Oil

The vacuum residual from Iranian Light crude oil are separated into a series of 16 narrow fractions according to the molecular weight by the supercritical fluid extraction and fractional (SFEF) technology. The chemical element and the UV spectrum of each fraction are analyzed. The effects of several factors on the interfacial tension are investigated, which are the fraction concentration in oil phase, the ratio of oil component, the salts dissolved in the water phase and the pH value. The interfacial tension decreases rapidly as the concentration of the residual fraction in the oil increases, showing a higher interfacial activity of the fraction. The interfacial tension changes, as the amount of absorption or the state of the fractions in the interface changes resulting from different ratios of oil, different kinds or concentrations of salts in water, and different pH values. It is concluded that the interfacial tension changes regularly, corresponding to the regular molecular parameters of the vacuum residual fractions.

Phytochemical Profile and <i>In Vitro</i>Antioxidant Properties of Essential Oils from Powder Fractions of <i>Eucalyptus camaldulensis</i>Leaves

Dried leaves of Eucalyptus camaldulensis were finely grinded and fractionated by sieving into four granulometric classes (<100 μm, 100 - 200 μm, 200 - 355 μm and >355 μm). The obtained powder fractions were used for essential oil (EO) extraction by hydrodistillation and their phytochemical profile and in vitro antioxidant activities were evaluated. The mother powder (unsieved powder) was used for comparison. Particle size exerted a significant influence (p < 0.05) on the phytochemical composition and in vitro antioxidant properties of the EOs. Comparatively, the mother powder had the highest contents of α-pinene (55.6%), camphene (3.4%) and limonene (3.7%), while 1,8-cineole (26.6% and 22.4%), exo-fenchol (5.6% and 3.5%), α-campholenol (4.2% and 3.4%), L-trans-pinocarveol (5.5% and 2.7%), L-borneol (12.6% and 6.8%) and α-terpineol (16.4% and 7.6%) are the main compounds of EOs from the <100 μm and 100 - 200 μm fractions, respectively. The antioxidant activities of the EOs revealed higher radical-scavenging activities DPPH (90.62% and 70.46%) and ABTS (89.59% and 73.31%) for finer fractions (<100 μm and 100 - 200 μm, respectively). The best reducing power (36.15% and 34.27%) were also found in these finer powder fractions which improved by more than 2 times the value of mother powder (reducing power of 17.01%). These results suggest that grinding followed by sieve fractionation concentrates the majority of antioxidant phytochemicals in the EOs of the finer powder fractions of E. camaldulensis leaves. Finer powders could be used as functional ingredients in food formulations for the management of chronic diseases.

Comparative pyrolysis kinetics of heavy oil and its SARA fractions using distributed activation energy model

The pyrolysis behaviors of Qingdao vacuum residue(QD-VR)and its SARA(saturates,aromatics,reins,and asphaltenes)fractions were evaluated by thermo-gravimetric with mass spectrometer(TG-MS).The pyrolysis kinetics were determined by Friedman,one-parallel and four-parallel distributed activation energy model(DAEM),respectively.The results indicated that the pyrolysis behavior of QD-VR was similar to that of aromatics.For saturates,the release of H_(2),CH_(4),CO,and CO_(2) occurred in 80-400℃,while the temperature range for QD-VR and other fractions is 200-800℃.The average activation energy(Ea)via Friedman method was 179.72 kJ/mol and increased with the conversion ratio.One-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of the single SARA fractions,while four-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of heavy oil.Furthermore,comparing the weighted E_(a) from one-parallel(227.64 kJ/mol)and four-parallel Gaussian DAEM(204.63 kJ/mol),the results suggested that during pyrolysis process of heavy oil,there was an interaction between the SARA fractions,which could reduce the E_(a) of heavy oil pyrolysis.Specifically,during heavy oil pyrolysis,resins and asphaltenes could increase the E_(a) of saturates and aromatics,while saturates and aromatics could decrease the E_(a) of resins and asphaltenes.

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.

THEORY AND APPLICATION OF FRACTIONAL STEP CHARACTERISTIC FINITE DIFFERENCE METHOD IN NUMERICAL SIMULATION OF SECOND ORDER ENHANCED OIL PRODUCTION

A kind of second-order implicit fractional step characteristic finite difference method is presented in this paper for the numerically simulation coupled system of enhanced （chemical） oil production in porous media. Some techniques, such as the calculus of variations, energy analysis method, commutativity of the products of difference operators, decomposition of high-order difference operators and the theory of a priori estimates are introduced and an optimal order error estimates in l^2 norm is derived. This method has been applied successfully to the numerical simulation of enhanced oil production in actual oilfields, and the simulation results ate quite interesting and satisfactory.

Fractional pyrolysis of Cyanobacteria from water blooms over HZSM-5 for high quality bio-oil production

Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.

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.

Migration Fractionation of Neutral Nitrogen Compounds of Crude Oils from Tabei Oilfield in the Tarim Basin, China

The absolute amounts and relative distributions of neutral nitrogen compounds in the Tabei oilfield (e.g. blocks Ln1-Ln11) showed remarkable migration fractionation in the vertical direction. From Ordovician reservoirs (O) to oil legs T-Ⅲ and T-Ⅰ of Triassic reservoirs in blocks LN1-LN11, the concentrations of + decreased from {1.59}μg/g, {0.49}μg/g to {0.17}μg/g (oil). The ratios of various alkylcarbazole isomers, such as 1,8-dimethylcarbazole/nitrogen-partially shielded isomers and 1,8-dimethylcarbazole/nitrogen-exposed isomers, were adopted as the indicators of petroleum migration. The ratios increased from {0.13}, {0.20} to {0.67} and from {0.42}, {0.87} to {3.30}, corresponding to those of Ordovician oil leg and oil legs T-Ⅲ and T-Ⅰ. In going from the south to the north of the Tabei oilfield, the absolute concentrations of neutral nitrogen compounds decreased drastically, and the nitrogen-shielded isomers were enriched relative to nitrogen-exposed isomers and nitrogen-partially shielded isomers. Crude oils in the Tabei oilfield migrated laterally from the Jilake structure to the Sangtamu fault uplift and Lunnan fault uplift, and crude oils in the same fault uplift migrated and remigrated vertically from Ordovician reservoirs, to oil legs T-Ⅲ to T-Ⅰ of Triassic reservoirs.

Fractional Yield, Extract Composition and Variability from Jordanian Oil Shales

Surface and subsurface oil shale (OS) rocks in Jordan have potential economic value for the country and still unutilized. This research paper focuses on central and southern OS deposits in Jordan. Brief characterization of four OS deposits is presented. Size distribution test and elemental analysis were performed. Shale oil was extracted via three solvation methods: Soxhlet extraction, extraction via mixing and stirring, and lastly super-critical fluid extraction. Major shale oil fractions were obtained from extract fractionation on chromatographic column. The nuclear magnetic resonance spectroscopy technique was used to study qualitatively the fractional composition of OS extract. Results show that all studied OS deposits have quite similar trend in their particle size distribution and their elemental composition. These OS deposits are found to be varying in their solvation behavior, fractional yield, and shale oil composition. Highest yield is obtained from polar solvents. The OS extraction via solvation processes is promising under certain extraction conditions such as super-critical conditions. The solvation variability of Jordanian OS indicates that different extraction techniques suit different OS deposits. Such variability should be considered in any future extraction options.

Production of Cocoa Butter Replacer by Dry Fractionation, Partial Hydrogenation, Chemical and Enzymatic Interesterification of Tea Seed Oil

Production of cocoa butter replacer (CBR) from tea seed oil through common modification methods of oils (dry fractionation, partial hydrogenation, chemical and enzymatic interesterification) was evaluated. Some physico-chemical properties (iodine, saponification, acid and peroxide values) and fatty acid composition (FAC) of modified samples were analyzed and compared with a reference cocoa butter (CB). Solid and liquid fractions for large amounts of unsaturated fatty acids (approx. 80%) and thereby lower iodine values (81 - 85 gI2/100g) than that of CB (37% and 34 gI2/100 g, respectively), are not suitable as CBR. Among all ratios of chemically and enzaymatically interesterified oil blends (20%, 25% and 30% of hydrogenated tea seed oil with 80%, 75% and 70% of tea seed oil/liquid fraction/solid fraction), the samples with ratio of 30:70 from both chemical and enzymatic interesterification had FAC and iodine value closer to that of CB. A comparision between chemically and enzymatically interesterified samples (CISs and EISs, respectively), in terms of solid fat content (SFC) indicated that although the SFC values in EIS were much lower than that of CB, but the thermal behavior of this sample is comprable to CB at 20℃- 30℃ (sharp melting point of CB).

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.

Analysis of Silver Nanoparticles in Engine Oil: Atangana–Baleanu Fractional Model

The present article aims to examine the heat and mass distribution in a free convection flow of electrically conducted,generalized Jeffrey nanofluid in a heated rotatory system.The flow analysis is considered in the presence of thermal radiation and the transverse magnetic field of strength B0.The medium is porous accepting generalized Darcy’s law.The motion of the fluid is due to the cosine oscillations of the plate.Nanofluid has been formed by the uniform dispersing of the Silver nanoparticles in regular engine oil.The problem has been modeled in the form of classical partial differential equations and then generalized by replacing time derivative with Atangana–Baleanu(AB)time-fractional derivative.Upon taking the Laplace transform technique(LTT)and using physical boundary conditions,exact expressions have been obtained for momentum,energy,and concentration distributions.The impact of a number of parameters on fluid flow is shown graphically.The numerical tables have been computed for variation in the rate of heat and mass transfer with respect to rooted parameters.Finally,the classical solution is recovered by taking the fractional parameter approaching unity.It is worth noting that by adding silver nanoparticles in regular engine oil,its heat transfer rate increased by 14.59%,which will improve the life and workability of the engine.

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 ℃.

Investigation of Biochemical Properties and Fractional Composition of Amaranth Oil

The aim of the study is to conduct comprehensive experiments and developments of innovative technologies to produce the oil extract of amaranth for their application as food additives in the food industry. To achieve the aim, the following tasks were identified： （I） study the physicochemical, biochemical properties and the composition of amaranth seeds; （2） improving the methods for producing the oil extract of amaranth. This article is devoted to complex research of processes of manufacture of vegetable oils. Authors have developed scientific bases of improvement and an intensification of technological processes for production of oil from amaranth seeds. The authors have developed a new technology for extracting of oil from amaranth seeds using hexane as a solvent. The proposed method provides to obtain oil without great technical effort and keeps it all the nutrients that promote the highest taste of the product and with little labor and time costs.

Control Scheme Discussion for Bottom Oil Slurry System of FCCU Fractionator

流化催化裂化装置（FCCU）分馏塔底油浆系统的控制效果对整个装置的平稳安全运行具有重要意义。近年来国内新建了许多大型FCCU，既包含国内各设计院自己的技术，也有部分引进国外的工艺包，其分馏塔底油浆系统的控制方案也有多种形式。总结了近年来国内新建FCCU常用的三种较为典型的油浆系统控制方案，阐述了各方案的特点，对其进行了简要的对比和分析。在此基础上尝试性地提出了这三种方案的适用场合，方便设计人员根据每个项目的特点设计合理的控制方案，达到最佳控制效果。

GEANT4 simulation of water volume fraction measurement in dehydrated crude oil

Online measurement of water volume fraction (WVF) in dehydrated crude oil is a difficult task due to very little water in dehydrated crude oil and high precision requirements. We presents a method to measure water volume fraction in dehydrated crude oil with γ-ray densitometry. The Monte Carlo computer simulation packet GEANT4 was used to analyze the WVF measuring sensitivity of the γ-ray densitometry at different γ-ray energies, and effects of temperature, pressure, salinity and oil components on WVF measurement. The results show that the γ-ray densitometry has high sensitivity in γ-ray energy ranges of 16~25keV, and it can distinguish WVF changes of 0.0005. The calculated WVF decreases about 0.0002 with 1℃ of temperature increase and they have approximately linear relation with temperature when water volume fraction remains the same. Effects of pressure, salinity and oil components on water volume fraction can be neglected. Experiments were done to analyze sensitivity of the γ-ray densitometry. The results , as compared with simulations, demonstrate that simulation method is reliable and it is feasible to gauge low water volume fraction using low energy γ-rays.

The evolution characteristics and fractionation mechanism of carbon isotopes in the process of “multi-stage hydrocarbon generation”

The Jiyang Sag and the Liaohe Basin are the two important areas where immature oil resources are distributed in China. From these two areas immature-low mature to mature oil samples were collected for carbon isotopic analysis. The extracts of source rocks are dominant in the Jiyang Sag while crude oils are dominant in the Liaohe Basin. The maturity index, R-o, for source rocks varies from {0.25%} (immature) to {0.65%} (mature). Studies have shown that within this range of R-o values the extracts of source rocks and crude oils, as well as their fraction components, have experienced observable carbon isotope fractionation. The carbon isotopic values tend to increase with burial depth, the oils become from immature-low mature to mature, and the rules of evolution of oils show a three-stage evolution pattern, i.e., light→heavy→light→heavy oils. Such variation trend seems to be related to the occurrence of two hydrocarbon-generating processes and the main hydrocarbon-forming materials being correspondingly non-hydrocarbons and possessing MAB characteristics, lower thermodynamic effects and other factors. In the process towards the mature stage, with increasing thermodynamic effects, the thermal degradation of kerogens into oil has become the leading factor, and correspondingly the bond-breaking ratio of {}+{12}C-{}+{13}C also increases, making the relatively {}+{12}C-rich materials at the low mature stage evolve again towards {}+{13}C enrichment.

The Effects of Ultrasonic Treatment on the Molecular Structure of Residual Oil

To upgrade residual oil, the residual oil was subjected to ultrasonic treatment with an output of 800 W, at a temperature of 70 ℃ and at intervals ranging from 0 to 11 minutes. The experiment illustrated that 7 minutes of ultrasonic treatment reduced viscosity and carbon residue by 14.1% and 7.4%, respectively. This also produced an increase in saturates content and a decrease in the content of aromatics, resins and asphaltenes. Furthermore, the parameters of the average molecular structure were characterized by FT-IR, and ~1 H-NMR, while an increasingly greater change in the parameters were produced by an ultrasonic treatment interval of up to 7 minutes. The mechanical stirring and cavitation from ultrasonic treatment caused a series of changes in the molecules of residual oil. Microscopic changes affected the parameters of the average molecular structure, as usually shown in SARA fractions. The changes in the thermal reaction properties of residual oil after ultrasonic treatment were analyzed by thermogravimetry. As the ultrasonic treatment time increased, the apparent activation energy needed for pyrolysis decreased gradually, as did the temperature.

Reservoir geochemistry of the Tazhong Oilfield in the Tarim Basin, China, Part II. Migration, accumulation and mixing of crude oils

Measurements of the absolute and relative concentrations of nitrogen-containing compounds in crude oils from different reservoir strata (Ordovician, Silurian and Carboniferous) in the Tazhong region of the Tarim Basin, Xinjiang, China, showed that even though there are quite a number of factors affecting the distributional and compositional characteristics of neutral nitrogen-containing compounds in crude oils, the distributional and compositional characteristics of crude oils whose source conditions are approximate to one another are influenced mainly by the migration and fractionation effects in the process of formation of oil reservoirs. In addition, crude oils in the Tazhong region show obvious migration-fractionation effects in the vertical direction. Carboniferous crude oils are characterized by high migration parameters and low compound concentrations, just in contrast to Ordovician crude oils. This indicates that crude oils from shallow-level oil reservoirs were derived from those of deep-level oil reservoirs via faults, unconformable contact or carrier beds. Crude oils from the Tazhong region show some migration-fractionation effects in the lateral direction, but mixing of crude oils derived from different hydrocarbon source rocks in the process of formation of oil reservoirs made it more complicated the migration and accumulation of crude oils, as well as the formation of oil reservoirs.

CONVERGENCE ANALYSIS OF MIXED VOLUME ELEMENT-CHARACTERISTIC MIXED VOLUME ELEMENT FOR THREE-DIMENSIONAL CHEMICAL OIL-RECOVERY SEEPAGE COUPLED PROBLEM

The physical model is described by a seepage coupled system for simulating numerically three-dimensional chemical oil recovery, whose mathematical description includes three equations to interpret main concepts. The pressure equation is a nonlinear parabolic equation, the concentration is defined by a convection-diffusion equation and the saturations of different components are stated by nonlinear convection-diffusion equations. The transport pressure appears in the concentration equation and saturation equations in the form of Darcy velocity, and controls their processes. The flow equation is solved by the conservative mixed volume element and the accuracy is improved one order for approximating Darcy velocity. The method of characteristic mixed volume element is applied to solve the concentration, where the diffusion is discretized by a mixed volume element method and the convection is treated by the method of characteristics. The characteristics can confirm strong computational stability at sharp fronts and it can avoid numerical dispersion and nonphysical oscillation. The scheme can adopt a large step while its numerical results have small time-truncation error and high order of accuracy. The mixed volume element method has the law of conservation on every element for the diffusion and it can obtain numerical solutions of the concentration and adjoint vectors. It is most important in numerical simulation to ensure the physical conservative nature. The saturation different components are obtained by the method of characteristic fractional step difference. The computational work is shortened greatly by decomposing a three-dimensional problem into three successive one-dimensional problems and it is completed easily by using the algorithm of speedup. Using the theory and technique of a priori estimates of differential equations, we derive an optimal second order estimates in 12 norm. Numerical examples are given to show the effectiveness and practicability and the method is testified as a powerful tool to solve the important problems.