Petroleum Fractions Research Articles

Genetic and metabolic engineering approaches for enhanced biodesulfurization of petroleum fractions.

Sulfur, an abundant component of crude oil, causes severe damage to the environment, poses risks to human health, and poisons the catalysts used in combustion engines. Hydrodesulfurization, the conventionally used method, is not sufficient to remove thiophenes like dibenzothiophene (DBT) and other aromatic heterocyclic compounds. The push for "ultra-clean" fuels, with sulfur content less than 15 ppm, drives the need for deep desulfurization. Thus, in conjunction with hydrodesulfurization, efficient and eco-friendly methods of deep desulfurization, like biodesulfurization, are desirable. In biodesulfurization, naturally desulfurizing microorganisms are used, with genetic engineering and biotechnology, to reduce the sulfur content of crude oil to below 15 ppm. In this review, we describe genetic and metabolic engineering approaches reported to date to develop more efficient methods to carry out biodesulfurization, making it a practically applicable reality.

Experimental evaluation of acid number effect on interfacial tension between nitrogen and mixtures of petroleum fractions including diesel fuel and gasoline at different pressures

Crude oil is made up of very complex compounds, which are found in polar organic substances especially organic acid compounds in the majority. Although organic acid content in crude oil is low, the presence of organic acids affects the interfacial tension (IFT) in oil reservoirs thereby altering the enhancement of oil recovery using nitrogen gas (N2) injection. Therefore, in this study, the effects of pressure (1 to 35 bar), the percentage of aromatic compounds (0.0 to 100 vol%) in the aliphatic hydrocarbon samples and the organic acid (benzoic acid) content (0.0 to 0.8 g.L− 1) on IFT between a mixture of gasoline/diesel fuel and N2 were investigated at a temperature of 298 K. IFT does not necessarily decrease as pressure increases for the sake of existence of aromatic compounds. IFT alteration for gasoline was more (about 8 dyne.cm− 1) than for diesel fuel (approximately 4 dyne.cm− 1) during pressure increased from 1 to 35 bar due to the replacement of heavy long chain aliphatic compounds instead of light aromatic matters. The effect of IFT alteration between N2 and diesel fuel during increasing the organic acid content was little (approximately 1.5 dyne.cm− 1), in contrast, this effect was more noticeable for N2/gasoline (about 8 dyne.cm− 1). In addition, a reduced cubic model for estimating IFT between N2 and petroleum fractions in terms of pressure, petroleum fraction composition and organic acid content was proposed with an average relative error of less than 2.6%.

Prospects and Challenges of Carbon Fiber Production from Heavy Petroleum Fractions

Prospects and Challenges of Carbon Fiber Production from Heavy Petroleum Fractions

Machine Learning in Complex Organic Mixtures: Applying Domain Knowledge Allows for Meaningful Performance with Small Data Sets.

The ability to quantify individual components of complex mixtures is a challenge found throughout the life and physical sciences. An improved capacity to generate large data sets along with the uptake of machine-learning (ML)-based analysis tools has allowed for various "omics" disciplines to realize exceptional advances. Other areas of chemistry that deal with complex mixtures often do not leverage these advances. Environmental samples, for example, can be more difficult to access, and the resulting small data sets are less appropriate for unconstrained ML approaches. Herein, we present an approach to address this latter issue. Using a very small environmental data set─35 high-resolution mass spectra gathered from various solvent extractions of Canadian petroleum fractions─we show that the application of specific domain knowledge can lead to ML models with notable performance.

Long-Term Coprocessing of Used Cooking Oils with Refinery Petroleum Fractions: A Comprehensive Study of Catalyst Activity and Biofuel Production Effects

Long-Term Coprocessing of Used Cooking Oils with Refinery Petroleum Fractions: A Comprehensive Study of Catalyst Activity and Biofuel Production Effects

Molecular Reconstruction of Heavy Petroleum Fractions: A Bayesian Approach

Molecular Reconstruction of Heavy Petroleum Fractions: A Bayesian Approach

Extraction of aromatic hydrocarbons from light petroleum fractions with lactam solvent

Extraction of aromatic hydrocarbons from light petroleum fractions with lactam solvent

Rapid On-Column Esterification and Separation of Carboxylic Acids in Petroleum Fractions

Rapid On-Column Esterification and Separation of Carboxylic Acids in Petroleum Fractions

Kinetic modeling of dual-stage oxidative extractive denitrogenation of model fuel

The petroleum fraction of crude oil is laden with notorious nitrogen compounds, whose removal facilitates fuel oil transport and enhances the longevity of hydrodesulfurization catalysts. Petroleum refining operation thus demands the adoption of unconventional techniques, such as coupled oxidative–extractive denitrogenation. Kinetic models can provide insights into the reaction mechanism and the design and performance of reactors. In this work, nine different kinetic models were developed by applying the Langmuir–Hinshelwood and Eley–Rideal approaches to various reaction pathways. The screening of the kinetic models was done based on the values of the rate law parameters and corresponding R 2 and adjusted R 2 values calculated through a multi-parametric, non-linear regression based on the Levenberg–Marquardt algorithm. Out of all the models, the Eley–Rideal model corresponding to the rate expression rs9 was found to be the best fit, reflecting that hydrogen peroxide remained in bulk while pyridine alone was adsorbed on the catalyst. The selection of suitable extractants for the extractive removal of oxidation products was made based on their extraction efficiency and partition coefficients. The ternary liquid–liquid equilibrium (LLE) data for the (acidulated water-pyridine-isooctane) and (acidulated water-pyridine N-oxide-isooctane) systems were plotted, and Othmer–Tobias, Hand, and Bachman correlations explained the consistency of the experimental LLE data.

Prospect of Controlled Autoxidation to Produce High-Value Products from the Low-Value Petroleum Fractions.

Substantial amounts of low-value light petroleum fractions and low-value heavy petroleum fractions, such as light naphtha, HVGO, and vacuum residue, are generated during the upgrading and refining of conventional and unconventional petroleum resources. The oil industry emphasizes economic diversification, aiming to produce high-value products from these low petroleum fractions through cost-effective and sustainable methods. Controlled autoxidation (oxidation with air) has the potential to produce industrially important oxygenates, including alcohols, and ketones, from the low-value light petroleum fractions. The produced alcohols can also be converted to olefin through catalytic dehydration. Following controlled autoxidation, the low-value heavy petroleum fractions can be utilized to produce value-added products, including carbon fiber precursors. It would reduce the production cost of a highly demandable product, carbon fiber. This review highlights the prospect of developing an alternative, sustainable, and economic method to produce value-added products from the low-value petroleum fractions following a controlled autoxidation approach.

Application of Intercriteria and Regression Analyses and Artificial Neural Network to Investigate the Relation of Crude Oil Assay Data to Oil Compatibility

The compatibility of constituents making up a petroleum fluid has been recognized as an important factor for trouble-free operations in the petroleum industry. The fouling of equipment and desalting efficiency deteriorations are the results of dealing with incompatible oils. A great number of studies dedicated to oil compatibility have appeared over the years to address this important issue. The full analysis of examined petroleum fluids has not been juxtaposed yet with the compatibility characteristics in published research that could provide an insight into the reasons for the different values of colloidal stability indices. That was the reason for us investigating 48 crude oil samples pertaining to extra light, light, medium, heavy, and extra heavy petroleum crudes, which were examined for their colloidal stability by measuring solvent power and critical solvent power utilizing the n-heptane dilution test performed by using centrifuge. The solubility power of the investigated crude oils varied between 12.5 and 74.7, while the critical solubility power fluctuated between 3.3 and 37.3. True boiling point (TBP) analysis, high-temperature simulation distillation, SARA analysis, viscosity, density and sulfur distribution of narrow petroleum fractions, and vacuum residue characterization (SARA, density, Conradson carbon, asphaltene density) of the investigated oils were performed. All the experimentally determined data in this research were evaluated by intercriteria and regression analyses. Regression and artificial neural network models were developed predicting the critical solubility power with correlation coefficients R of 0.80 and 0.799, respectively.

Investigation of controlled autoxidation of HVGO to produce carbon fibres precursors: Role of oxygen availability and mixing

Carbon fibre is an ultra-light, strong, and durable material that has growing demand in different industries. About 95 % of currently produced carbon fibre is PAN-based which is expensive. Considering the expense and accessibility, heavy vacuum gas oil (HVGO) shows significant promise. However, it necessitates appropriate pre-treatment to generate carbon fibre precursors. The present study examined the influence of oxygen availability and mixing on controlled autoxidation (oxidation with air) in order to establish a cost-effective and efficient pre-treatment technique for assessing the feasibility of generating carbon fibre precursors from the low-value heavy petroleum fraction HVGO. Experiments were performed while maintaining temperature (130–260 ℃), time (4–24 hours), and oxygen partial pressure (N2/air) maintaining bubbling with mixing, and also blowing without mixing. Blowing without mixing at 200 ℃ for 24 h showed the highest viscosity of 7959 cP (measured at 25 ℃), and HVGO heated at 240 ℃ in 8 h in the presence N2 resulted in a maximum 26 % increase in aromaticity. It was also noticed that there was an improvement in softening point (maximum 5.4 times), volatility, and heavy products, which are crucial properties of a carbon fibre precursor. Understanding from the current research can also be applied in the area of asphalt hardening, weathering, fouling, fuel transportation and storage stability, and sludge formation.

Exploring ionic liquids for the extraction separation of aromatic hydrocarbons from diesel via multiple interaction analyses coupled with experimental evaluation

The separation of aromatic hydrocarbons from petroleum fractions is of great significance for both the quality upgrading of products and value-added utilization of aromatic compounds. However, the separation of polycyclic aromatic hydrocarbons (PAHs) and their derivatives from diesel remains challenging because of their lower solubility and selectivity as compared to the monocyclic aromatic compounds. In this work, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][TF2N]) was screened from 320 ionic liquid (IL) candidates through solvent capacity predication using COSMO-RS method. Liquid-liquid equilibrium experiments were carried out using a series of tetralin/n-decane mixtures with different tetralin concentrations to evaluate the extraction performance of several solvents. The results indicate that [EMIM][TF2N] has high selectivity up to 95.73 for tetralin over n-decane, which is 4.5 and 3.9 times higher than that of dimethyl sulfoxide and sulfolane. During five regeneration cycles, the [EMIM][TF2N] exhibits consistent extraction performance and nearly complete recovery. Molecular polarity index (MPI) analysis indicates that tetralin has larger dissolving affinity to solvents as compared to n-decane. Combined analyses of interaction energy, energy decomposition, and visualization of weak interaction reveal that the crucial role of weak hydrogen bond in dominating the complex solvent–solute interactions. Compared to n-decane, tetralin shows a stronger interaction with the solvents due to the existence of C-H···π and hydrogen bond interactions. The great difference in interaction energy between {[EMIM]+ + tetralin} and {[EMIM]+ + n-decane}, therefore, endows [EMIM][TF2N] with high selectivity for tetralin. Given the dominant role of cation, a IL, [CN1 = C2SCCS2(CC = C)C1][TF2N] having both high selectivity and high solvent capacity was subsequently explored using the cation generation method based on the SeqVAE model. Furthermore, present study proposes a strategy for the design of ILs for separation and other specific application circumstances.

Multi-objective optimization of simultaneous oxidative desulfurization and denitrogenation of model fuel

Petroleum fractions are accompanied with sulfur and nitrogen compounds, and nitrogen compounds tend to compete for the catalyst active sites, reducing desulfurization efficiency. They can be removed by oxidative desulfurization and denitrogenation, wherein the sulfur and nitrogen compounds are converted into corresponding oxides with higher polarity than their parent forms, thus favoring their extractive or adsorptive removal from the oil phase. The introduction of ultrasound into the oxidation system can significantly improve the process efficiency and oxidation kinetics through strong cavitation phenomena involving physical and chemical effects. In this work, ultrasound-assisted simultaneous oxidation of pyridine and dibenzothiophene (DBT) contained in a model fuel was performed. Response surface methodology (RSM) was employed to study the effect of six parameters, viz., catalyst dose (5–12.5 g/L), reaction time (5–60 min), ultrasonic amplitude (10–60 %), volume of hydrogen peroxide (0.5–2 mL), volume of acetic acid (0.5–2 mL) and reaction temperature (40–60 °C) on the conversion of DBT and pyridine. A face-centered central composite design was employed as the RSM tool, and the effect of the parameters and their interactions on the two responses was investigated. The two responses were simultaneously optimized via desirability functions and overlaying individual contour plots. The results revealed that sonication significantly enhanced the conversion of both compounds. All six factors significantly influenced the oxidation of pyridine, while DBT conversion was mainly affected by four factors. The desirability for the process under consideration ranged from 0.85 to 0.89, and at the optimum conditions, 100 % conversion of pyridine and 46.06 % conversion of DBT were obtained. Two-staged oxidation of the fuel at optimum conditions resulted in 100 and 93.7 % conversion of pyridine and DBT, respectively.

The Characteristic of Teak Growing in Three Areas (Mine, Non-Mining, and Ex-Mining) Forest Management Unit Parengan Bojonegoro, Indonesia

Bojonegoro Regency has an oil mining location where it is estimated that Indonesia’s crude oil reserves are 25 % of national needs. The location is in Forest Management Unit (Kesatuan Pengelolaan Hutan - KPH) Parengan which has a teak forest (Tectona grandis L.) with a very close oil mining radius. The aim of the research is to determine the differences in the characteristics of teak growing places and to determine the types of petroleum fractions in active oil mines, former oil mines and those without oil mines. The research method uses a circle plot (17.8 m) with a Sampling Intensity (IS) of 20 % with data analysis results using a one sample test and a Least Significant Difference (LSD) alpha test of 5 %. The characteristics of the teak growing area at each location have different values for height, P content, C content, number of oil fractions and temperature. The types of petroleum fractions in active oil mines are naphtha, kerosene, fuel oil and wax. Ex-oil mines contain gasoline (premium), kerosene, aviation fuel, light gas, fuel oil, lubricating oil, wax and asphalt. In locations without oil mines there is kerosene, aviation fuel, gasoline (premium) and light gas.

Approximation method for the potential composition of petroleum fractions

The paper gives a brief review of mathematical models of potential composition of oil fractions. The stages of obtaining approximating dependence of the fractional composition of oil are defined. A multicomponent mixture is represented as a discrete series of narrow hydrocarbon fractions. Each of them is characterized by its average boiling point. The results of approximation obtained for oil of different fields are given. The criterion for choosing dependence is the sum of squared deviations of factored values from experimental (reference) values. The following approximating dependencies of the curve of true boiling points for oil of different deposits are obtained. They are cubic parabola, power function, arctangence, exponentiation function, cubic parabola-arctangence. It is shown that the best results are obtained for combined ‘cubic parabolaarctangent’ model. In case of data deviation on oil fractional composition coming from chemical analytical laboratory coefficients are corrected in TBP approximation. Oil fractional composition awareness is important when choosing the direction of oil refining, in process and simulation modeling, when determining the top performance of processing units.

Antibacterial activity of crude methanol extract of Anacardium occidentale leaf and its fractions on isolates of diarrhoea-causing pathogenic Escherichia Coli and Salmonella enterica

This study investigated the antibacterial activity of Anacardium occidentale leaf crude extract and it’s derived; petroleum, chloroform and methanol fractions on isolates of diarrhoea-causing pathogenic Escherichia. coli, and Salmonella enterica. The protocol described by Kupchan and Tsou as modified by Houghton and Raman was used to partition the crude extract. Field strains of Salmonellae enterica and E. coli enterobacteria, were obtained using standard procedures adopted by Mufandaedza.. Holes were bored in the agar, using a sterile borer which enabled the application of crude extract and the fractions, and thereafter, incubated for 24 hours. Results of the study showed that the crude extract elicited better (p<0.05) growth inhibitory (56.11 and 58.14%) effect on the E. coli and S. enterica isolates respectively, better than any of the derived fractions that recorded less than 30% activity, suggesting an additive, complementary or synergistic effect of individual composite fraction, rather than the role of a single biomolecular fraction in the leaf extract of A. occidentale, hence partitioning, adversely reduced or disintegrated the additive effect of the crude extract on enterogenic bacteria investigated. In conclusion, the crude extract of Anacardium occidentale, have shown good anti-bacterial activity, principally by inhibiting the growth of diarrhoea causing enterogenic E. coli and Salmonella organisms’ growth in vitro, hence supporting its folkloric use in the management of enterogenic diarrhoea by traditional healers.

Utilizing polycyclic aromatic sulphur heterocycles to develop hypercrosslinked microporous polymeric adsorbents for deep desulphurization of fuels

Adsorptive desulphurization is a well-known method for removing polycyclic aromatic sulphur heterocycles (PASHs) from petroleum fractions. Nevertheless, due to the non-destructive adsorption mechanism, managing the adsorbed carcinogenic PASHs remains a major challenge. In the present research, a prototype is presented to manage three PASHs (thiophene, benzothiophene and dibenzothiophene) by using them to develop hypercrosslinked microporous polymeric adsorbents (yield > 90%) within 60 min via microwave assisted synthesis. Textural properties including specific surface area (401–628 m2 g−1), controlled pore size (1.1–1.7 nm) and pore volume (0.24–0.29 cm3 g−1) have been estimated. The developed adsorbents are used for desulphurizing diesel fuels. Batch adsorption studies result in the sulphur adsorption capacities of 6.7 and 6.4 mgS g−1, for 100 ppm and 10 ppm-dosed simulated fuels respectively. Thermodynamic, kinetics and adsorption isotherm studies are performed using the batch adsorption studies. Column adsorption studies exhibit sulphur breakthrough capacities of 7.2 and 0.62 mgS g−1 for 100 ppm and 10 ppm-dosed simulated fuels respectively. The combine effect of textural properties and π electron density on the adsorption capacity is discussed. The present work not only demonstrates a sustainable management cycle of PASHs but also utilized them for deep desulphurization of fuels.

Synthesis and characterization of new nanocomposite Cu6W18O70⊂CuFe2O4 as an efficient nanocatalyst for oxidative desulfurization of real and model gasoline

AbstractThe primary objective of this investigation was to develop a new nanocatalyst that could produce materials with a lower sulfur content, thereby reducing its environmental harm. To achieve this, the researchers used the sol‐gel method to synthesize a heterogeneous nanocatalyst by attaching sandwich‐type polyoxotungstate [(CuW9O34)2Cu4(H2O)2−10] (denoted as Cu6W18O70) clusters on the surface of copper ferrite nanoparticles (CuFe2O4 NPs). To characterize the nanocatalyst, several analysis techniques were employed, including Fourier transform infrared spectroscopy, ultraviolet‐visible, powder X‐ray diffraction, and scanning electron microscope. The oxidative desulfurization of hazardous sulfur‐containing real and model fuel oils was effectively catalyzed by the Cu6W18O70⊂CuFe2O4 nanocatalyst. According to the experimental findings, the best efficiencies in oxidation reaction were achieved in 1 h contracting time at 35°C, which was as high as 95%. The Cu6W18O70⊂CuFe2O4 nanocatalyst exhibited impressive removal rates (%) on dibenzothiophene (C12H8S), benzothiophene (C8H6S), and thiophene (C4H4S) of model fuels, with figures reaching 97%, 96% and, 96% respectively. Furthermore, multiple recycling of the uniform nanocatalyst can be achieved effortlessly through filtration, without experiencing any notable decline in activity. Therefore, the authors suggest that this study will pave the way for the widely used mentioned nanocatalyst in the practical and workable organization of petroleum fractions.

Impact of petroleum expulsion and evaporation losses on shale oil assessment using pyrolysis techniques

Shale reservoirs contain petroleum that undergoes losses through oil expulsion and evaporation, with uncertain implications on shale oil reserves and mobility evaluation. This study focuses on understanding the influence of these losses on open‐system pyrolysis, the primary method for assessing shale oil content and mobility. Comprehensive analyses were performed on 26 lacustrine shale samples from the Chang7 Member, encompassing total organic carbon (TOC), programmed pyrolysis, solvent extraction, and gas chromatography–mass spectrometry (GC–MS). The research examines the impact of petroleum losses on petroleum fractions, the oil saturation index (OSI), and multi‐step pyrolysis outcomes. The findings indicate that Chang7 shale with TOC content above 7% experiences more substantial petroleum losses than those with TOC below 7%. Petroleum losses result in significant fractional distillation of crude oil in the shale, leading to the deterioration of shale oil properties and a notable reduction in free oil content in S1, ultimately causing a decline in OSI values. As a result, Chang7 shale with TOC below 7% demonstrates a higher potential for shale oil recovery, whereas Chang7 shale with TOC exceeding 7% should be considered more significant as a hydrocarbon source rock. Moreover, multi‐step pyrolysis is not suitable for assessing petroleum mobility in shale with low free oil content (OSI values below 100 mg/g). This limitation arises from the loss of free low‐boiling components in Chang7 shale, and the currently detected low‐boiling pyrolysis products may predominantly exist in an adsorbed state.