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Petroleum Chemistry
Journal Prestige (SJR): 0.31  Citation Impact (citeScore): 1 Number of Followers: 1  Subscription journalISSN (Print) 0965-5441 - ISSN (Online) 1555-6239 Published by Springer-Verlag  [2468 journals]
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- Effect of Hydrothermal Treatment and Prolonged Extraction on the
Generation of Hydrocarbons from High-Carbon Low-Permeability Rocks from
Domanik Deposits-
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Abstract: The effect of hydrothermal treatment of high-carbon low-permeability Domanik rock on the efficiency of recovering hydrocarbons from this rock by prolonged four-step extraction for 20, 68, 116, and 220 h with a mixture of organic solvents (chloroform, toluene, and isopropyl alcohol) was studied. As compared to the extraction from the untreated rock, the hydrothermal treatment at 300°С in a СО2 medium allows recovery of a 6 times larger amount of the extract in the first step (in 20 h). In the second extraction step (68 h), the extract yield decreases by a factor of 8, but the relative content of saturated hydrocarbons in the extract increases by a factor of more than 3 compared to the first step, whereas the relative content of asphaltenes, resins, and aromatic compounds decreases. In the third extraction step (116 h), the extract yield is as low as 0.16%, the content of resins in it drastically decreases, whereas the content of asphaltenes increases to 52%. The extract of the fourth step (220 h) consists to 80.77% of asphaltenes. From the initial rock, the maximal yield of the extract enriched in saturated hydrocarbons with the minimal content of asphaltenes was observed after the second extraction step. In the course of prolonged extraction, the yield of petroleum fractions from the initial rock increases by a factor of almost 4, and in combination with the preliminary hydrothermal treatment, by a factor of 7. This fact demonstrates the possibility of generating an additional amount of hydrocarbons. Changes were revealed in the structural-group, hydrocarbon, elemental, and microelemental composition of petroleum fractions recovered from the low-permeability Domanik rock, depending on the extraction time and transformations of the organic matter of this rock in the course of hydrothermal treatment.
PubDate: 2024-07-25
DOI: 10.1134/S0965544124030149
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- New Composite Mesoporous Nano-Catalysts for Clean Fuel Produced by the
Oxidative Desulfurization Process-
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Abstract: Clean fuel production with strict limit on toxic contaminants is one of the most important aims for petroleum refinery industry regarding the improvement of environmental conditions. In this study, oxidative desulfurization (ODS) process has been used to achieve such goal. For this purpose, a new and efficient synthetic composite mesoporous nano-catalyst has been designed by enhancing morphological and mechanical properties of gamma alumina (γ-Al2O3) on a carbon nano fiber (CNF) as multiple supports. Four different catalysts based on different amount of CNF have been designed. X-Ray diffraction (XRD), X-Ray fluorescence (XRF), crash strength test, thermal gravimetric examination (TGA), and surface area (BET) have been used to characterize the catalysts. The catalyst with 10% loading of CNF (CAT-3) has been found to increase the tensile strength by more than 200% compared to the CNF-free sample (CAT-4). Then, a series of experiments has been conducted in a batch ODS reactor with air as an oxidant and light gas oil (LGO) as a real feedstock to evaluate the effectiveness of the designed catalysts and the performance of the reactor. The new catalyst has been clearly shown to be a significant factor in sulfur removal resulting in a clean fuel.
PubDate: 2024-07-25
DOI: 10.1134/S0965544124030150
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- Oil Deposits in Highly Paraffinic Crude Oils and in Model System
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Abstract: The effects of temperature gradient on the formation, composition, and strength of oil deposits were investigated. As the crude oil temperature and the wall surface temperature were lowered, the concentrations of the oil fraction and low-molecular-weight paraffins in the deposits increased; simultaneously, the amounts of resins and asphaltenes declined. In the asphalt–resin–paraffin deposits formed in an asphaltene-free oil sample, cooling led to a rise in the content of resins and a decline in the content of the oil fraction. Model experiments demonstrated that the highest inhibitory capacity with respect to paraffin wax deposition was achieved in the case of 0.5–1.0 wt % asphaltenes being added. This can be attributed to the steric effect of aromatic rings manifested in their ability to disrupt the nucleation of paraffin networks. Therefore, the model wax deposits formed after adding asphaltenes exhibited a lower strength than the samples obtained with the addition of benzene resins and alcohol–benzene resins.
PubDate: 2024-07-19
DOI: 10.1134/S0965544124030137
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- Effect of Ultrasonic Treatment on the Properties and Composition of
High-Wax Crude Oil and Its Precipitates-
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Abstract: High-wax crude oil was treated with ultrasound (sample weight 50 g, frequency 22 kHz, field intensity 8 W/cm2) for 10 min. The ultrasonic treatment led to an increase in the crude oil viscosity, viscous flow activation energy, specific energy of the break of the disperse system, congealing point, pour point, and precipitate amount and to changes in the precipitate structure. The oil fraction of the crude oil, precipitates, and raffinates was analyzed by IR spectroscopy and chromatography–mass spectrometry. The content of high-molecular-mass n-alkanes in oils from the precipitate of the ultrasonically treated crude oil considerably decreases.
PubDate: 2024-07-19
DOI: 10.1134/S0965544124020026
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- Behavior of Nanocatalysts in Fischer–Tropsch Synthesis in Various Types
of Three-Phase Slurry Reactors-
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Abstract: The catalytic performance of iron-based nanodispersions in Fischer–Tropsch synthesis in two different slurry reactor types, specifically a continuous stirred-tank reactor (CSTR) and a slurry bubble column reactor (SBCR), was comparatively investigated. It was found that, at equal process temperatures, the CO conversion in the SBCR using a gas disperser with four equally spaced 1-mm holes was lower than that in the CSTR. However, this observation is inconsistent with other reports in the literature. Replacing this disperser with a plate with a single centered 2-mm hole enhanced the CO conversion up to values close to those obtained in the CSTR. The reaction rate constants were calculated for the different reactor types.
PubDate: 2024-07-08
DOI: 10.1134/S096554412403006X
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- Molecular Basis of Asphaltene Stability
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Abstract: The instability of asphaltenes in crude oils, manifested in their precipitation, is a major production issue that may arise both during the recovery and processing of petroleum feedstocks. The purpose of this study was to investigate the molecular structure of asphaltenes in order to shed light on the causes of their precipitation. To this end, the molecular structures of stable (remaining in the solution) and unstable (precipitated) asphaltenes were characterized by EPR, NMR, and IR spectroscopy. Using crude oil asphaltenes and air-blown asphalt as objects for the study, only weak increasing and decreasing trends were observed in the content of aromatics and oxygenates, respectively, in the unstable asphaltene fraction. The stable and unstable asphaltenes were found to differ in adsorption capacity. It was shown that the species adsorbed on asphaltenes are rich in moieties of aromatic acid esters, and that removing these species further eliminates the structural-group composition differences between stable and unstable asphaltenes. The study findings suggest that the stability of asphaltenes in crude oils can be controlled by introducing synthetic aromatic acid esters structurally similar to natural surfactants.
PubDate: 2024-07-08
DOI: 10.1134/S0965544124030010
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- CoMo Sulfide Catalysts Supported on Natural Halloysite Nanotubes:
Dealumination as an Effective Approach to Improve Catalytic Performance-
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Abstract: –CoMo sulfide catalysts supported on aluminosilicate halloysite nanotubes (CoMoS/HNT) and on dealuminated halloysite nanotubes (CoMoS/HNT(deAl)) were synthesized by incipient wetness impregnation using pseudoboehmite as a binder. Both the supports and related catalysts were characterized by low-temperature nitrogen adsorption, energy dispersive X-ray fluorescence analysis, temperature-programmed reduction by hydrogen, FTIR spectroscopy of adsorbed pyridine, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalyst samples were further tested in hydrotreating of diesel feedstocks. Dealumination of halloysite was found to increase the area of Si-enriched surface segments, thus weakening interaction between the sulfide phase and the support and, hence, increasing the content of highly active sulfide particles. In the case of a mixed feedstock, CoMoS/HNT(deAl) + Al2O3 achieved a reaction rate constant of 0.605 ppm S–0.4/g(L–0.4 h) compared to 0.429 ppm S–0.4/g(L–0.4 h) for an alumina-supported sample.
PubDate: 2024-07-08
DOI: 10.1134/S0965544124030071
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- Complex-Oxide Catalysts in Cracking of Propane
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Abstract: The study investigates propane conversion in the presence of rare-earth metal zirconates Ln2Zr2O7 (Ln = La, Gd, and Lu) prepared by high-temperature solid-phase synthesis at 500, 1000, and 1500°C. In the La2Zr2O7 → Gd2Zr2O7 → Lu2Zr2O7 series, the phase transitions were found to follow the pyrochlore → defective fluorite → δ-phase route. This changed the parameters of the crystalline and local structures and, in particular, led to the appearance of oxygen vacancies in pyrochlore-based compounds. As a result of the structural changes, propane dehydrogenation prevailed over propane degradation. Therefore, the Lu2Zr2O7 catalyst exhibited a higher propylene selectivity (up to 65%) than La2Zr2O7, with 100% propane conversion being achieved.
PubDate: 2024-06-21
DOI: 10.1134/S0965544124030083
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- Plasma-Assisted Carbon Dioxide Methane Reforming: Relationships of the
Formation of Oxygenates on Adding a Catalyst (a Review)-
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Abstract: Published data on plasma-assisted carbon dioxide methane reforming using heterogeneous catalysts are analyzed. The pathways of the CH4 and CO2 transformation under the conditions of thermal catalysis, plasma action, and plasma-assisted catalysis are considered. Various types of plasma installations are described. The mechanisms of the formation of oxygenates under the conditions of plasma-assisted catalysis are presented. The process selectivity with respect to final products depends on the ratio of the gases and on the structure, dielectric properties, and composition of the catalysts. The important parameters influencing the oxygenate ratio are the metal oxidation state in the catalyst, kind of metal, and support acidity. The catalyst introduction into the plasma can also lead to negative phenomena, namely, to recombination of radicals into the starting compounds.
PubDate: 2024-06-21
DOI: 10.1134/S0965544124030034
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- Hydrogenation of Furfural over Ruthenium Catalysts Supported on Porous
Aromatic Frameworks-
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Abstract: The paper describes an investigation into hydrogenation of furfural over ruthenium catalysts supported on porous aromatic frameworks. The supports were designated as PAF-30-SO3H, PAF-30-NH2, and PAF-30. The synthesized catalysts were tested in furfural hydrogenation carried out in water and in tetrahydrofuran (with a concentration of 10 wt %) at 90–250°C and a hydrogen pressure of 3 MPa. Although the highest furfural conversion (96%) was achieved in the case of its hydrogenation in water at 250°C over Ru-PAF-30, these conditions did not favor product selectivity. The reaction products mainly consisted of furfuryl alcohol, tetrahydrofurfuryl alcohol, and cyclopentanone. The highest yield of cyclopentanone, 71% (with 80% conversion and 89% selectivity) was observed in furfural hydrogenation over Ru-PAF-30 at 200°C, whereas the conditions optimal for selective hydrogenation of furfural into furfuryl alcohol were found to include either tetrahydrofuran as a solvent or water as a solvent and low temperatures (90–150°C).
PubDate: 2024-06-14
DOI: 10.1134/S0965544124020191
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- Molybdenum Catalysts Supported on Porous Aromatic Frameworks in
Epoxidation of Olefins-
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Abstract: A novel catalyst was synthesized by immobilizing a MoO2(acac)2 complex on the surface of a porous aromatic framework functionalized with pyridine-2-carboxaldehyde (PAF-30-NPy). The immobilization was confirmed by IR spectroscopy, X-ray photoelectron spectroscopy, and elemental analysis. The synthesized catalyst was tested in the epoxidation of cyclohexene, cycloheptene, 1-hexene, 1-octene, styrene, and trans-stilbene. The effects of the solvent type and the oxidant content on the olefin conversion were described. The catalyst reusability was further tested, and its activity was evaluated.
PubDate: 2024-06-14
DOI: 10.1134/S0965544124020208
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- Interfacial Shear Rheology of the Waxy Oil-Water Interfacial Layer
Construction by Span80/60/65: Influence of Hydrophobic Chain Structure-
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Abstract: The waxy oil-water interface has become a topic issue in the field of a two-phase oil-water pipe flow. Although some progress has been achieved in the understanding of interfacial rheological properties of the water-in-oil emulsion (W/O), the effect of surfactants (the main constituents of petroleum crude oil) still remains unclear. To test whether the structure of hydrophobic chains of surfactants influences the waxy oil-water interface, we monitored interfacial rheological parameters under different nonionic surfactants (Span80/60/65) using a DWR interfacial shear rheometer. Among these surfactants, the oil-water interface of Span65 characterized by multi-hydrophobic chains had the largest interfacial viscosity and critical storage modulus. A weak strain overshoot interface of Span65 suggested that sorbitan tristearate molecules provided a dominant contribution to the interfacial rheological properties of the waxy oil-water interface with much fewer effects of the interaction between wax molecules and surfactants. However, Span60/80 with a single hydrophobic chain was coupled to wax molecules and reshaped the waxy oil-water interface structure, which replaced the original wax crystal position (the interfacial viscosity and critical storage modulus decrease) and yielded an interfacial structure (the critical strain increase). The wax-surfactant interactions of Span60/80 with different hydrophobic chain saturation were discussed. These interfacial properties are of practical importance for the technological operations in oil production.
PubDate: 2024-06-06
DOI: 10.1134/S0965544124020087
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- Ethylene/Propylene Copolymerization and Their Terpolymerization with
5-Ethylidene-2-norbornene over Catalytic Systems Based on Half-Sandwich
Titanium Complexes with Organoaluminum and Organoboron Activators-
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Abstract: Half-sandwich titanium complexes, specifically Cp*TiCl3 and Cp*Ti[O(2,6-iPr2-Ph)]Cl2, were investigated as catalytic precursors for the synthesis of ethylene/propylene copolymers and ethylene/propylene/5-ethylidene-2-norbornene terpolymers. For this purpose, a variety of activators were tested: modified polymethylaluminoxane; boron-containing compounds such as B(C6F5)3 and Ph3CB(C6F5)4 in combination with triisobutylaluminum (TIBA); isobutylaluminoxane (IBAO), and isobutylaluminum aryloxide (2,6-tBu2,4-Me-PhO-)AliBu2 (AlBHT). In the copolymerization of ethylene and propylene, the catalysts exhibited high activity when activated by MMAO-12 and TIBA+Ph3CB(C6F5)4 but low activity with TIBA+B(C6F5)3 and AlBHT. With IBAO as an activator, these catalysts were found to be totally ineffective. The catalysts exhibited low activity in terpolymerization. It was further revealed that more than one type of active sites was generated in the catalytic systems: these sites were responsible for simultaneous formation of low-molecular-weight and ultrahigh-molecular-weight polymers. The composition of the copolymers as well as their thermophysical and physicomechanical properties were shown to depend on the type and composition of the catalytic system.
PubDate: 2024-05-18
DOI: 10.1134/S0965544124010158
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- Geochemistry of Biomarkers and Asphaltenes of Precambrian Organic Matter
in the Aldan–Maya Depression (Siberian Platform)-
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Abstract: The study compares the elemental composition of asphaltenes with the parameters of hydrocarbon biomarkers and Precambrian insoluble organic matter (OM) of the Aldan–Maya depression. The elemental composition of the asphaltenes was found to depend on the pyrolytic characteristics of the OM. Using asphaltene compositions in combination with biomarker parameters, the genetic and catagenetic features of difficult-to-study objects such as Precambrian bitumens can be characterized more accurately and reliably. The elemental composition of the asphaltenes was shown to correlate with the aromatic parameters that reflect the OM maturity. In contrast, the parameters of the asphaltenes show essentially no correlation with biomarker data for the saturated components.
PubDate: 2024-05-14
DOI: 10.1134/S0965544124010031
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- Feature Extraction and Clustering of Feed Oil from a S Zorb Unit Based on
AE and PCA Algorithms-
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Abstract: Based on the 5-year data on the feed oil characteristics obtained from the S Zorb unit, the outliers in the data were detected using the boxplot and LOF methods, and 536 modeling samples were obtained. Combining MIC with the Pearson correlation coefficient, six characteristics of feed oil including RON, sulfur content, olefin content, aromatic content, density, and vapor pressure were chosen as input variables for the clustering model. Two features were extracted from the six variables by the autoencoder (AE) characterized by the 6-32-2-32-6 neural network structure and PCA algorithm for clustering. Three clustering models were built using AE+K-means, PCA+K-means, and K-means. The results of evaluation showed that the optimal clustering number in these models was three, and the AE+K-means model provided the best clustering effect. According to the clustering centers and the property distribution, the dividing boundaries between three types of feed oils are obvious indicating that the AE+K-means model is available to classify feed oils from the S Zorb unit. On this basis, prediction models for the RON of refined gasoline were built for different types of feed oils to get the optimal operation conditions for the reduction of RON losses of refined gasoline in the S Zorb unit.
PubDate: 2024-04-18
DOI: 10.1134/S0965544124010109
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- Experimental Investigation of the Nanoparticle Effect on the Pipeline Flow
Behavior of Emulsions-
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Abstract: Considering the lifespan of wells and the increment of water production over time, which is associated with the increase in emulsion volumes, the need for technology able to overcome these challenges becomes paramount. In this study, the flow characteristics of a nanoparticle-stabilized water-oil emulsion were investigated for different nanoparticle concentrations and water fraction. The influence of different concentrations of silica dioxide nanoparticles on the pipeline flow behavior of emulsions was studied in a 13-m horizontal pipe with the inlet diameter of 0.0145 m. The effect of nano-silica (1, 3, and 5 wt %) on the emulsion stability, rheological type, viscosity, and pressure drop as well as on the energy consumption (for the water volume ratios of 35 and 50% v/v) was also investigated. The study showed that as the water cut increased, the viscosity of the produced oil increased proportionally to the water/oil volume ratio. Use of nanoadditives provided the viscosity reduction for two water cuts (35 and 50%). In the case of a 50% water cut, addition of 3% of nano-silica provided the most significant trend in reducing viscosity. In the case of addition of 1% nano-silica to a 35% water cut, the viscosity level decreased, and the shear-thinning behavior was observed for all the prepared emulsions. Nevertheless, the most significant amount of stable emulsion was produced at a water ratio of 35%, when a 3% nano-silica was added. The results also show that the addition of nanoparticles caused a decrease in the pressure drop, and the addition of 3% of nano-silica resulted in a highly stable emulsion and increased power consumption by a pump.
PubDate: 2024-04-18
DOI: 10.1134/S0965544124010122
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- Distribution Patterns of the Main Structural-Group Parameters of Crude
Oils from the Timan–Pechora Oil-and-Gas Basin, According to 1Н NMR Data
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Abstract: A representative set of crude oils from the Timan–Pechora oil-and-gas basin (OGB) (75 samples of crude oils and natural-gas condensates from 51 fields) was studied, and data on the structural-group composition of the crude oils from this field were obtained. The distributions of all the parameters are far from the normal distribution. Therefore, only methods of nonparametric statistics can be used for the data processing. Among Timan–Pechora crudes, there are samples with abnormally high content of unsaturated compounds of radiogenic nature. Their highest concentration corresponds to the irradiation dose of no less than 11 MGy. On the whole, Timan–Pechora crudes differ from those studied previously (from the West Siberian, East Siberian, Volga–Urals, and North Caucasus OGBs) primarily in the content of monoaromatic components. The Timan–Pechora crudes occupy an intermediate position between those from West Siberia and Volga–Urals, on the one hand, and from East Siberia and North Caucasus, on the other hand. As compared to crude oils of the second group, Timan–Pechora crudes have considerably higher content of aromatic compounds. In the content of bi- and polycyclic aromatic components, Timan–Pechora crudes are close to those from West Siberia and Volga–Urals. All the large tectonic structures are combined in four groups with respect to crude oil composition: (1) Varandei–Adzva zone + Khoreivei and Kos’yu-Rogovskaya depressions; (2) Izhma–Pechora syneclise + Upper Pechora depression; (3) Pechora–Kozhva aulacogene; and (4) East Timan megalithic bank.
PubDate: 2024-04-03
DOI: 10.1134/S0965544124010055
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- A Simple Method to Determine Low Metal Concentrations in Naphtha by
Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)-
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Abstract: Inductively coupled plasma optical emission spectrometry (ICP-OES) was used in this study as an alternative analytical approach for measuring Al, Ca, Cu, Na, Ni, Si, Fe, P, V, and Zn in high-volatile petroleum products (naphtha) at the part per billion (ppb) sensitivity level. The distillation stage was intended for pre-concentrating metals by the matrix removal. Such multiplication of metal concentrations provided the possibility to measure them within the sensitivity range of the ICP-OES instrument. The reliability of such measurements was demonstrated for a wide concentration range of each metal, and the validation of the method was performed. Based on the standard deviations of nine successive measurements performed for 10 metals, the precision (repeatability) of the method for samples with concentrated metals was calculated. The values of this index (in ppb) were the following: 20.8 (Al), 20.4 (Ca), 13.7 (Na), 19.09 (Ni), 13.4 (Fe), 1.4 (P), 26.9 (V), and 45.15 (Zn). The reproducibility of the method was determined for nine measurements performed within several days. The results of recovery studies were excellent for the most part of the tested metals including Al (100.33%), Na (102%), and V (96.55%). The linearity test performed for calcium and silicon showed R = 0.999 for both elements. Depending on the standard deviation obtained in the linearity test, the limit of detection (LOD) range for all studied metals was determined to be between 2 and 10 ppb.
PubDate: 2024-03-23
DOI: 10.1134/S0965544123110063
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- Insight into Relationship between the Products Distribution and Molecular
Properties in Carboxylation between Benzene Polycarboxylic Acids and CO2-
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Abstract: CO2 is an important carbon resource, which could be chemically utilized by carboxylation. In this paper, the carboxylation between benzene polycarboxylic acids (BPCAs) and CO2 was conducted using Cs2CO3 as a catalyst. The relationship between the product distribution and Mulliken charge at the reaction site of BPCAs was explored by combining experiments and quantum chemical calculations of molecular properties in the reaction of carboxylation between BPCAs and CO2. The negative Mulliken charge was found to facilitate carboxylation at the reaction site of BPCAs. Hydrogen abstraction was the rate-determining step for carboxylation, and its energy barrier was calculated for different C–H in the BPCA molecule. The results showed that the C–H bond with the more negative Mulliken charge was more easily deprotonated, which further verified the above conclusion. The study provides a convenient approach to predict a product distribution for carboxylation between BPCAs and CO2 according to the Mulliken charge of BPCAs.
PubDate: 2024-03-23
DOI: 10.1134/S0965544124010018
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- Functionalized Ionic Liquids as Asphaltene Dispersants: A Comparison
between Aliphatic and Aromatic Cations-
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Abstract: In this study, two groups of functionalized aliphatic and aromatic ILs with the same anions were synthesized and used as asphaltene dispersants. The quartz crystal microbalance and ultraviolet spectroscopy were used in this study, and the results obtained from these two techniques were in relatively good agreement with each other. The results showed that aromatic ILs generally possess better inhibitory performance than aliphatic ones. The molecular structure of IL anions also greatly influenced the dispersion of asphaltenes in a toluene solution. It seems that π-π interactions between asphaltene molecules and aromatic cations represent the main cause of the better performance of aromatic ILs. This hypothesis was also confirmed by observing the high dispersion ability of a maleate anion, which has a carbon-carbon double bond, compared to other studied anions.
PubDate: 2024-03-09
DOI: 10.1134/S0965544123110075
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