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We report a mechanistic investigation of an aromatic dithioimide (2SS) displaying puzzling yet efficient photochemistry in ether solvents. Perplexingly, 2SS dissolved in ether solvents in a sealed and degassed vial was photochemically converted to the corresponding diimide (2OO), as determined by 1H NMR following product extraction. With no external sources of oxygen in the sample, could the oxygen in 2OO be from the ether itself? To study this unprecedented proposition, we attempt to uncover the ether's involvement in this reaction. As seen by laser‐flash photolysis, 2SS appears to first react with the solvent from its singlet excited state. Following the reaction by NMR under rigorously oxygen‐ and water‐free conditions led to the identification of a photoreductive pathway that quantitatively transformed one thione into a methylene to yield 2SH2. Subsequent oxidation of 2SH2 or irradiation of 2SS under air proved that molecular oxygen was indeed necessary to observe an oxidative pathway leading to 2OO, ruling out the initially proposed involvement of an ether oxygen. An explanation of 2SS desulfurization was further revealed through the study of solvent by‐products by GC‐MS analysis. Supported by DFT calculations, a mechanism is proposed to involve a chain reaction initiated by photochemically generated ether radical. [ABSTRACT FROM AUTHOR]

The desulfurization of carbons modified with SO2 was studied as a dispersion in boiling cyclohexane (81°C) using activated carbon (mAC) and graphene oxide (mGO), modified by SO2. The steady‐state species in the carbon matrix after the catalytic reduction of SO2 was considered a trisulfane. For mAC, there was a burst of a sulfur species identified as S2 by UV spectrum with a maximum at 217 nm (εM at 217 nm = 2.56 × 103) that showed a second‐order decay of absorbance with kS2 = 47.29 M‐1·sec‐1 (ΔG354‡= 18.1 kcal·mol‐1). The product was postulated to be S4. No other consecutive reaction was observed because of the possible adsorption of S4 in the carbon matrix. The desulfurization of mGO was shown by XPS and the kinetics were a second‐order decay up to 16 min (kS2= 18.41 M‐1·sec‐1; ΔG354‡= 18.8 kcal·mol‐1) followed by a second‐order increase of absorbance with kS4 = 3.84 M‐1·sec‐1 (ΔG354‡= 19.9), where the product showed a double maximum at 260‐285 nm typical of S8. These results are consistent with a mechanism of consecutive thermodynamically favorable dimerizations of S2 and S4 and with the desulfurization mechanism that has been previously postulated. [ABSTRACT FROM AUTHOR]

A study was carried out on the effect of the nature of the support, composition of the active phase, and heat treatment conditions on the activity of trimetallic Ni‑Co‑Mo catalysts in the hydrotreating of a mixed diesel fraction. Temperature‑programmed desorption was used to show the effect of the amount and strength of the acid sites of the support on the activity of catalysts with the same elemental composition. We established the nickel‑to‑cobalt as well as phosphorus‑to‑molybdenum ratios in these trimetallic hydrotreating catalysts corresponding to the greatest desulfurization and minimum formation of polycyclic aromatic hydrocarbons in the hydrogenate. [ABSTRACT FROM AUTHOR]

Desulfurization of petroleum derivatives is a topic of interest to researchers because compounds containing sulfur are harmful in the oil refining process and cause problems such as deactivation of catalysts and corrosion in pipelines and refining equipment. In order to improve the efficiency of desulfurization of dibenzothiophene, copper bismuth oxide/reduced graphene oxide (Bi7.38Cu0.62O11.69/rGO) nanocomposite was synthesized by a simple sonochemical method for the first time. The synthesized nanocomposite was identified by FESEM, FT-IR, XRD, DRS, and EDS analyses. Based on XRD analysis, pure copper bismuth oxide is formed using hydrazine, while using sodium hydroxide does not lead to the desired product. FESEM images showed that the size of Bi7.38Cu0.62O11.69 particles decreases in the presence of rGO. The desulfurization results showed that the presence of rGO causes a significant increase in efficiency due to increased light absorption and reduced recombination rate, so that Bi7.38Cu0.62O11.69/rGO nanocomposite has an efficiency of 87%, while pure Bi7.38Cu0.62O11.69 has an efficiency of 68%. Also, it was found that the purity of the copper bismuth oxide has a great effect on the photocatalytic efficiency, so that by calcining the product and removing the impurities, the efficiency increases from 55% to 68%. [ABSTRACT FROM AUTHOR]

Although Indonesia has set a target for increasing the use of renewable energy for electricity generation, the use of coal as a source of energy will still dominate at least until 2040. Sulfur dioxide (SO2) along with other gases and particulates released from the use of coal in coal-fired power plants (CFPPs) may cause air pollution. The use of seawater, an abundant source of absorbent in a maritime country such as Indonesia, in flue gas desulfurization (SWFGD) absorbers, is an economical option for treating SO2 in an absorption tower compared to other alkaline chemicals, e.g. limestone (CaCO3) or magnesium hydroxide (Mg(OH)2). A model, which correlates the equilibrium of the reaction with the salinity of the absorbent, was developed to predict the sulfur dioxide scrubbing process inside an SWFGD absorber. The simulation also took into account the mass and energy balance during the scrubbing process. The calibration using field SWFGD data showed a good correspondence between field data and modelling results. [ABSTRACT FROM AUTHOR]

Coal is still a great source of energy, but its high sulfur content causes environmental pollution and problems in its processing. This study used a method of combined oxidation and alkali leaching to desulfurize low-grade, high-sulfur Lakhra coal at different ranges of temperature, alkali concentration, leaching time, partial pressure of oxygen, and agitation speed. The optimum values for the leaching reaction were observed to be an alkali (NaOH) concentration of 0.8 mM, a leaching time of 1.5 h, an oxygen partial pressure of 150 psi, and an agitation speed of 800 rpm. The ash content of the coal initially increased at higher values of reaction time and temperature, and then became saturated at a certain peak. The raw coal was characterized for ultimate and proximate analysis, and the product was characterized for ash content and total sulfur content. [ABSTRACT FROM AUTHOR]

This study investigated a new method for controlling the emission of fine particles through heterogeneous condensation. Specifically, the research focuses on the application of single-tower double-cycle desulfurization technology in the wet flue gas desulfurization process. The establishment of a supersaturation environment necessary for heterogeneous condensation was achieved by reducing the temperature of desulfurization slurry in the oxidation zone. Numerical simulations were used to study the distribution of the supersaturation degree and fluid dynamics characteristics in the desulfurization tower after the cooling of desulfurization slurry. Furthermore, the impact of single-tower double-cycle technology on the removal efficiency of fine particles was examined. The results of the numerical simulations indicate that cooling the desulfurization slurry in the absorption zone could establish a supersaturated vapor environment, with the supersaturation degree and region increasing as the slurry temperature decreases. Under typical operating conditions, a temperature drop of approximately 8~10 °C was found to be most suitable for the desulfurization slurry. Moreover, lowering the temperature of the desulfurization slurry in the absorption zone increases the supersaturation degree from 0.93 to 1.85. Additionally, the use of single-tower double-cycle desulfurization technology is shown to significantly enhance the removal efficiency of fine particles, particularly those within the particle size range of 0.1~1 μm. Ultimately, this method could increase the removal efficiency of fine particles from 39.9% to 57.9%. [ABSTRACT FROM AUTHOR]

Marine bacteria contribute substantially to cycle macroalgae polysaccharides in marine environments. Carrageenans are the primary cell wall polysaccharides of red macroalgae. The carrageenan catabolism mechanism and pathways are still largely unclear. Pseudoalteromonas is a representative bacterial genus that can utilize carrageenan. We previously isolated the strain Pseudoalteromonas haloplanktis LL1 that could grow on ι-carrageenan but produce no ι-carrageenase. Here, through a combination of bioinformatic, biochemical, and genetic analyses, we determined that P. haloplanktis LL1 processed a desulfurization-depolymerization sequential pathway for ι-carrageenan utilization, which was initiated by key sulfatases PhSulf1 and PhSulf2. PhSulf2 acted as an endo/exo-G4S (4-O-sulfation-ß-D-galactopyranose) sulfatase, while PhSulf1 was identified as a novel endo-DA2S sulfatase that could function extracellularly. Because of the unique activity of PhSulf1 toward ι-carrageenan rather than oligosaccharides, P. haloplanktis LL1 was considered to have a distinct ι-carrageenan catabolic pathway compared to other known ι-carrageenan-degrading bacteria, which mainly employ multifunctional G4S sulfatases and exo-DA2S (2-O-sulfation-3,6-anhydro-a-D-galactopyranose) sulfatase for sulfate removal. Furthermore, we detected widespread occurrence of PhSulf1-encoding gene homologs in the global ocean, indicating the prevalence of such endo-acting DA2S sulfatases as well as the related ι-carrageenan catabolism pathway. This research provides valuable insights into the enzymatic processes involved in carrageenan catabolism within marine ecological systems. [ABSTRACT FROM AUTHOR]

This paper presents modern technologies to reduce pollutant emissions of sulfur oxides, which can be applied to energy groups operating on fossil fuels. The experimental measurements were carried out for the 330 MW energy groups at the Turceni thermal power plant. [ABSTRACT FROM AUTHOR]

Aiming at the problems of large lag and inertia in the PH control system of gypsum wet desulfurization in thermal power units, this paper proposes a cascade multi-step feed forward predictive control strategy based on proportional integral derivative (PID). Firstly, the paper establishes mechanism model through the transfer function of PH value influence factor to ensure a strong correlation between the control system parameters and the PH value; Secondly, based on the traditional PID control strategy, the paper introduces cascade and multi-step feed forward control mechanisms to solve the strong inertia of the control system; Then, the three-step predictive value of SO2 content in raw flue gas based on long short term memory network (LSTM) is introduced as the feed forward value, so as to better eliminate system lag characteristics and track the PH setting value; Finally, the simulation experiment is carried out using the desulfurization data of the plant. The simulation results show that, compared with the traditional PID and cascade PID control strategies, the control strategy proposed in this paper achieves more accurate and stable control of the PH value of desulfurization slurry in thermal power units, and improve the desulfurization efficiency. [ABSTRACT FROM AUTHOR]

Sulphur compounds and mercaptans in gas condensate cause corrosion problems, poison catalysts in catalytic processes, and have adverse environmental impact through SOx emission upon combustion. Therefore, it is essential to remove sulphur and mercaptan from gas condensate to standard levels. In this study, the oxidative desulphurization (ODS) process in the presence of a cobalt phthalocyanine sulfonamide‐based catalyst was investigated. The homogeneous catalyst containing 23 wt.% active material was used and optimum operating conditions of temperature, volume ratio of caustic to gas condensate, caustic concentration, and solvent amount were determined to decrease sulphur content to less than 500 ppm and mercaptan to less than 200 ppm. The catalyst consumption in all experiments was kept constant at a minimum level (0.01 g/400 mL gas condensate). Results showed that this catalyst improved the reaction rate in the lower temperature and lower caustic to feed ratio and lower caustic concentration. The maximum sulphur removal was obtained at 5°C and 4 vol.% of caustic to gas condensate ratio at 16.7 wt.% of caustic concentration. Moreover, this catalyst improved sulphur removal from the gas condensate to about 5% compared to caustic sweeting without catalyst. Sulphur compounds had higher solubility in acetone rather than methanol, and sulphur removal by acetone was 96% while it was 91% for methanol. Finally, the economical and acceptable solvent for sulfoxides removal was methanol with 5% volume fraction. [ABSTRACT FROM AUTHOR]

According to international standards, motor fuels require limits on the content of sulfur, benzene, aromatic and olefinic hydrocarbons. Achieving these standards requires the development of new, active, and selective catalysts alongside advancement in technologies for deep hydrotreating and hydroprocessing. Therefore, this study aimed to investigate tetradecane and diesel oil fraction hydroprocessing using modified zeolite-based Ni(Co)-Mo(W)/Al2O3-ZSM-5 catalysts under varying processing conditions. The novelty is attributed to the synthesis of new catalysts based on ZSM-5 type zeolite, modified with metals Ni(Co)-Mo(W) and active additives of rare earth metals and phosphorus. The results showed that after hydrotreating diesel oil fraction on KT-3 catalyst, the pour point and sulfur level decreased from -27 to -57°C and 0.141 to 0.059% respectively, while the yield of the liquid phase was 92.2%. The lowest residual sulfur content (0.005%) was observed on KT-4 catalyst at 400°C. Based on electron microscopic examinations, modified zeolite-based catalysts were distributed in a highly dispersed manner, and the metal components in the active phase were primarily in the oxidized state, generating associate clusters on the surface. The dispersion, structure, and state were influenced by the characteristics of catalyst components. In conclusion, modified zeolite-based catalysts had multifunctional properties, facilitating hydrocracking, hydroisomerization, hydrodesulfurization, and dehydrogenation reactions concurrently. [ABSTRACT FROM AUTHOR]

Reaching decisions on climate change, energy and resources is tied to expectations for adequate training of energy professionals. The article presents the results of a study of the formed professional competence of graduates from the „Heat Engineering“ bachelor‘s program of TU – Sofia. For this purpose, a toolkit was prepared for diagnosing the level of competence in the engineering ecology course, including four criterion tests for measuring achievements. The levels of formed competence are defined: nominal, functional, procedural and comprehensive competence. A novelty is the inclusion of authentic tasks from the exam for the qualification of the workers of the desulphurization installations in TPP “Maritsa Iztok 2” and “Toplofikatsia – Sliven Eng. Angel Angelov” in the test tasks of the students. The analysis of the results shows that in 28% of the students the professional competence is fully formed, and they are able to solve completely complex professional tasks. Basic technical knowledge and constructive engineering skills are possessed by 30% of students. In 37% of the graduates have developed procedural competence, and 5% of students have superficial factual knowledge that does not successfully manage professional. [ABSTRACT FROM AUTHOR]

Removal of sulfur compounds from transportation fuels is a requirement in the worldwide effort to reduce emissions from transportation fuels. Refineries use the hydrodesulfurisation (HDS) process to reduce sulfur compounds in fuels. However, the HDS process requires high hydrogen pressure and temperature, making it costly. An alternative to the HDS process is oxidative desulfurisation via solvent extraction, which requires low-temperature operating conditions. In this regard, deep eutectic solvents (DESs) are attractive for researchers to desulfurise transportation fuels via solvent extraction due to their low-cost. In our study, DESs were synthesised using phenylacetic acid (PAA) and salicylic acid (SAA) as hydrogen bond acceptors (HBAs) and tetraethylene glycol (TTEG) as hydrogen bond donor (HBD) in the mole ratio of 1:2. DESs were characterised by using Fourier transform infrared (FTIR) spectroscopy. Physicochemical properties of DESs, such as density, viscosity and refractive index, were also measured. The synthesised DESs were used to extract organosulfur compounds from model fuel and actual diesel. An oxidation study was carried out for model fuel and diesel, followed by solvent extraction using these synthesised DESs. The extraction efficiency for PAA/TTEG(1:2) and SAA/TTEG(1:2) was achieved as 50.16% and 38.89% for model fuel at a temperature of 30°C using a solvent to feed ratio of 1.0 while for diesel, it was 38% and 37%. However, it increased to 77%, 68% and 54%, 73%, respectively, for PAA/TTEG(1:2) and SAA/TTEG(1:2) when the feedstocks were oxidised. These results showed better extraction performance of DES PAA/TTEG(1:2) than that of SAA/TTEG(1:2) at low temperature 30°C using combined extractive catalytic oxidative desulfurisation. Hence, the DES synthesised using SAA and TTEG in the molar ratio of 1:2 works better as an extraction solvent for removing organic sulfur compounds from fuels at low temperatures. [ABSTRACT FROM AUTHOR]

The paper summarizes the results of numerous works performed by the employees of the Pobuzky Ferronickel Plant, the Department of Electrometallurgy of the USU of Science and Technology (Dnipro), RPC "Technosplavy" under the leadership of Mykhailo Hasyk, academician of NASU. A technology of low iron recovery has been implemented at the plant, which allows producing high-percentage black ferronickel, containing 30-50 % Ni, and almost hundredth fractions of carbon and silicon, directly in electric furnaces. The thermodynamic features of out-of-furnace ladle desulfurization of ferronickel with soda are considered. A complex technology has been developed and implemented, which involves mixing black ferronickel with a reduced silicon and carbon content (up to 0.01 %) and a high nickel content (over 50 %) produced in one furnace with an alloy from another furnace with a low nickel concentration (10-17 %) and a high concentration of silicon and carbon, which are so necessary for desulfurization with soda in a ladle. The developed and proposed technological schemes for the enrichment of electric furnace slags using the "wet" technology and refining slags using the "dry" technology make it possible to recycle about 1,200 tons of nickel per year, or to extract 31.6 % and 94.65 % of nickel from the slags, respectively. [ABSTRACT FROM AUTHOR]

Experiments were carried out in Si-killed high carbon steels with an innovative and cost effective approach, coke dust as a slag de-oxidation agent to reduce reducible oxides quantity and also its activity in the slag to improve desulfurization efficiency. The flux addition practice was also modified by increasing lime addition compared to synthetic slag, in order to increase the activity of CaO throughout the LF refining process. Various parameters such as the amount of carryover slag, melting point, electrical conductivity, viscosity, activity of FeO, CaO of ladle slag were calculated and its effect on desulfurization efficiency was studied in detail. Finally, an optimized slag composition was suggested using an error function. Industrial trials demonstrated a reduction in reducible oxide content from 5 to 1.5% and the maintenance of an increased CaO activity throughout the refining process improved desulfurization efficiency from 38% to greater than 50%. [ABSTRACT FROM AUTHOR]

Granulated truck waste tire was first pyrolyzed in a fixed‐bed reactor under an inert atmosphere and at certain conditions. The highest oil yield of which was 47.0 wt %, was attained at 550 and 20°C/min. The oil was separated into a fraction of 150–300°C boiling points, so‐called diesel‐like fuel (DBY), with a calcium oxide (CaO) catalyst at an optimal ratio of 2 wt %. The fraction was subjected to desulfurization, bleaching, and deodorization, respectively, at specific conditions, and this process resulted in a decrease of 75.8 wt % compared to its initial sulfur content of 5000 ppm. The upgraded diesel‐like oil (DAF) fraction contained chemical compounds with carbon numbers C6–C26. In addition, its physicochemical characteristics showed a kinematic viscosity of 3.13 cSt (40°C), a density of 832 g/L (15°C), a lower heating value of 42.32 MJ/kg, and an H/C molar ratio of 1.73. Lastly, the DAF was tested with commercial diesel fuel for its motor and emission performance via a single‐cylinder diesel engine. All in all, it can be said that the DAF may be harnessed as a substitute for diesel fuels after its further upgrading via catalytic hydrodesulfurization etc. [ABSTRACT FROM AUTHOR]

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With the development of society, environmental protection is receiving increasing attention, and higher requirements have been put forward for the cleanliness of traditional energy sources. Fuels from distilled natural crude oils contain a variety of sulfur-containing compounds, which lead to serious environmental pollution. New technologies for deep desulfurization of fuels are urgently needed to meet the various stringent sulfur standards for liquid fuels (<15 ppm). In recent years, metal-organic frameworks (MOFs) have shown great potential in a variety of applications, especially in fuel desulfurization, such as hydrodesulfurization, oxidative desulfurization, and adsorptive desulfurization, due to their high porosity, high specific surface area and availability. In addition, the combination of MOFs with membranes or ionic liquids also has high desulfurization efficiency. In this review, the applications of MOFs and their composites in fuel desulfurization over the past decade are summarized. The factors affecting the desulfurization performance are pointed, and the desulfurization mechanism is tentatively clarified. Moreover, future recommendations have been discussed briefly. [ABSTRACT FROM AUTHOR]

[Display omitted] • Desulfurization in waste tire pyrolysis oil and gas was achieved by metal oxides. • Fe 2 O 3 shows the best removal efficiency of 87.7% for sulfur-containing gas. • The desulfurization mechanism was revealed by ReaxFF-MD and experiments analysis. • The removal of S involved Fe-S bonding, C-S breakage, dehydrogenation, O migration. • Fe 2 O 3 promotes cyclization and dehydrogenation to produce monoaromatics (57.4%). Pyrolysis can effectively convert waste tires into high-value products. However, the sulfur-containing compounds in pyrolysis oil and gas would significantly reduce the environmental and economic feasibility of this technology. Here, the desulfurization and upgrade of waste tire pyrolysis oil and gas were performed by adding different metal oxides (Fe 2 O 3 , CuO, and CaO). Results showed that Fe 2 O 3 exhibited the highest removal efficiency of 87.7 % for the sulfur-containing gas at 600 °C with an outstanding removal efficiency of 99.5 % for H 2 S. CuO and CaO were slightly inferior to Fe 2 O 3 , with desulfurization efficiencies of 75.9 % and 45.2 % in the gas when added at 5 %. Fe 2 O 3 also demonstrated a notable efficacy in eliminating benzothiophene, the most abundant sulfur compound in pyrolysis oil, with a removal efficiency of 78.1 %. Molecular dynamics simulations and experiments showed that the desulfurization mechanism of Fe 2 O 3 involved the bonding of Fe-S, the breakage of C-S, dehydrogenation and oxygen migration process, which promoted the conversion of Fe 2 O 3 to FeO, FeS and Fe 2 (SO 4) 3. Meanwhile, Fe 2 O 3 enhanced the cyclization and dehydrogenation reaction, facilitating the upgrade of oil and gas (monocyclic aromatics to 57.4 % and H 2 to 22.3 %). This study may be helpful for the clean and high-value conversion of waste tires. [ABSTRACT FROM AUTHOR]

Titanium silicon molecular zeolite (TS-1) plays an important role in catalytic reactions due to its unique nanostructure. The straight channel on TS-1 was parallel to the orientation of the short b-axis and directly exposed to the aperture of the 10-member ring with a diameter of 0.54 nm × 0.56 nm. This structure could effectively reduce the diffuse restriction of bulk organic compounds during the oxidative desulfurization process. As a kind of cationic polymer electrolyte, polydimethyldiallyl ammonium chloride (PDDA) contains continuous [C8H16N+Cl−] chain segments, in which the Cl− could function as an effective structure-directing agent in the synthesis of nanomaterials. The chain of PDDA could adequately interact with the [0 1 0] plane in the preparation process of zeolite, and then the TS-1 nanosheet with short b-axis thickness (6 nm) could be obtained. The pore structure of the TS-1 nanosheet is controlled by regulating the content of PDDA. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N2 physical adsorption analysis, infrared absorption spectrum and ultraviolet–visible spectrum were used to determine the TS-1. The thinner nanosheets exhibit excellent catalytic performance in oxidative desulfurization of dibenzothiophene (DBT), in which the removal rate could remain at 100% after three recycles. Here, the TS-1 nanosheet with short b-axis thickness has a promising future in catalytic reactions. [ABSTRACT FROM AUTHOR]

The Non-thermal plasma has a wide range of applications in different areas. In this study, the oxidation of a model fuel containing organo-sulfur compounds (benzothiophene and dibenzothiophene) was investigated using plasma. The process involved ozone generation through dielectric barrier discharge, followed by extraction using acetonitrile. The results demonstrated the efficient oxidation and removal of dibenzothiophene and benzothiophene by non-thermal plasma. The desulfurization efficiency reached 93.78% under the optimum conditions, including a voltage of 11Kv, temperature of 50ºC, duration of 4 hours, and a flow rate of 75 ml/min. [ABSTRACT FROM AUTHOR]

A series of heterogeneous catalysts for peroxide oxidative desulfurization and denitrogenation based on imidazolium phosphomolybdates with different cation structures and acidic properties was prepared. Thiophene, dibenzothiophene, methyl phenyl sulfide, and pyridine were used as model substrates. The composition and structure of the initial ionic derivatives and heterogeneous compositions based on them were determined using a number of physicochemical methods. It was found that the structure of the imidazole cation affected the stability of the heteropolyanion, the distribution of an active phase on the surface of silica gel, and, as a consequence, the efficiency in catalysis. The catalysts were tested in solutions containing either a substrate or a mixture of nitrogen- and sulfur-containing compounds. [ABSTRACT FROM AUTHOR]

Titanium modified UiO-66(Zr)-type metal–organic framework (MOF) nanophotocatalysts have been prepared via a modified one-step solvothermal methodology and evaluated in photocatalytic oxidative desulfurization. Extensive characterization by X-ray diffraction (XRD), Fourier transforms infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), photoluminescence spectroscopy (PL), nitrogen adsorption–desorption, and thermogravimetric analysis (TGA), have revealed the role of Ti loading, on Ti speciation and the structure of the synthesized materials. The performance of nanophotocatalysts have been evaluated for photocatalytic oxidative desulfurization (PODS). PODS reaction parameters, including temperature, photocatalyst dosage, oxidant to sulfur ratio, and solvent to fuel ratio, were optimized, with dibenzothiophene (DBT) conversion reaching 100% under optimal conditions (T = 50 °C, photocatalyst dosage = 2 g/L, oxidant to sulfur molar ratio (O/S = 8), and solvent/fuel = 1). Recyclability studies performed for the optimal catalyst showed good stability over six recycles, with total conversion dropping by only 18%. Kinetic studies showed that DBT PODS follows pseudo-first-order kinetics, with an activation energy value of 55.1 kJ mol−1. [ABSTRACT FROM AUTHOR]

SBA-15 and Zn/SBA-15 mesoporous materials were synthesized by coprecipitation and incipient impregnation methods, respectively. Both materials were tested as adsorbents of quinoline (Q) adsorption in the presence of dibenzothiophene (DBT), changing temperature and nitrogen concentration. The textural and structural adsorbents results revealed that the Zn incorporation reduced the pore volume and the surface area by 23% and 27%, respectively, compared to the SBA-15 adsorbent. However, both adsorbents presented a hexagonal structure in the form of cylindrical channels of ordered porosity with a domain of (100), (110) and (200) crystalline planes. SEM micrographs of the SBA-15 adsorbent showed rod-shaped particles with 1.20 × 0.65 μm dimensions. Zn incorporation did not significantly change the final SBA-15 morphology. In general, the Q removal percentage in the presence of DBT for the SBA-15 adsorbent at different nitrogen concentrations was between 10 and 20% higher than for the Zn/SBA-15 adsorbent at 308, 315, 323, and 336 K, associated with the basic nature of Q. However, the highest sulfur removal was observed at 308 K, where the Zn/SBA-15 adsorbent showed 2.5 times more sulfur removal compared to the SBA-15 adsorbent. For both adsorbents, the pseudo second-order kinetic model better fitted the Q adsorption data in the presence of DBT compared to the first-order model. Langmuir and Freundlich models were studied to describe the adsorption parameters of Q at different concentrations and temperatures, the experimental data were adjusted to a Langmuir-type isotherm at temperatures from 308–328 K using mesoporous adsorbents. Additionally, thermodynamic parameters of Q adsorption in the presence of DBT were determined and the parameters like a Gibbs free energy (ΔG0), adsorption enthalpy (ΔH0) and adsorption entropy (ΔS0) were estimated. The results of thermodynamics study and adsorption parameters indicated that the removal of Q in both adsorbents was a spontaneous and exothermic process, and the SBA-15 adsorbent at various nitrogen concentrations and low temperatures obtained high capacities and rates of Q adsorption in DBT presence. Particle size distribution and separation factor for SBA-15 and Zn/SBA-15 adsorbents in Quinoline (Q) adsorption as a function of operating temperature. [ABSTRACT FROM AUTHOR]

Cutting off refractory organosulfur compounds is an immense need in the modern age of petroleum refineries. The oxidation of these hard organosulfur compounds is dynamic in the course of deep oxidative desulfurization. Atmospheric molecular oxygen is an organic, innocuous, abundant, and economical oxidant. Microorganisms synthesize dendritic fibrous nanoparticles (DFNPs) in exposure to metal ions. In this research, microorganisms were used to produce Zn2MnO4 DFNPs in a biological process instead of a chemical method as a nanocatalyst. This biogenic nanoparticle has been used for the first time as a recyclable catalyst with external magnet and efficient in desulfurization process under environmentally friendly conditions with support of oxygen green oxidant, at atmospheric pressure, at low temperature, green water extraction agent, Distilled with the help of ultrasound as a source of green energy in a shorter time. This strategy has marvelous profits, including high economic yield and tolerance of functional groups. The present study underscores how metabolic processes in anaerobic bacteria could be mixed with green chemical technologies to generate extremely efficient catalytic reactions for ultrasound-assisted oxidative desulfurization of simulated fuel, natural gasoline, and sulfur mustard analogs. [ABSTRACT FROM AUTHOR]

Thiobacillus ferrooxidans, abbreviated as T. ferrooxidans is one of the important microorganisms in the field of biological desulfurization. Effects of ferrous iron and sulfur-containing substrates on biological desulfurization of T. ferrooxidans were studied. Results show that in the absence of Fe2+, T. ferrooxidans can utilize three kinds of sulfur-containing substrates of Na2S2O3, elemental S and Na2SO3 for growth and metabolism. For utilization complexity, Na2S2O3 was easiest to use, next was elemental S, and Na2SO3 was the worst for use. During the utilization of ferrous iron and sulfur-containing substrates by T. ferrooxidans, the iron oxidation system was first started. With the decrease of the Fe2+ concentration, the sulfur oxidation system was started, and then the two systems synergistically acted. The presence of three sulfur-containing substrates had different effects on Fe2+ oxidation, and elemental S did not inhibit the oxidation of Fe2+, while Na2S2O3 and Na2SO3 had some inhibition on the oxidation of Fe2+, especially the inhibition of Na2SO3 was significant, and complete oxidation of ferrous iron needed more time. The isolated T. ferrooxidans is applied to the removal of H2S gas, aiming to provide a new technological approach for biological removal of H2S. [ABSTRACT FROM AUTHOR]

In the relentless pursuit of sustainable energy solutions, the petroleum industry faces the imperative challenge of mitigating sulfur emissions. This comprehensive review scrutinizes Titanium Dioxide (TiO2) as an extraordinary catalyst, pushing the boundaries of desulfurization performance in petroleum refining. The abstract begins by underscoring the urgent need for advanced desulfurization technologies, driven by stringent environmental mandates and escalating global energy demands. The spotlight then shifts to the unparalleled physicochemical attributes of TiO2, showcasing its inherent advantages such as exceptional surface area, stability, and photocatalytic process. A profound exploration of TiO2's catalytic mechanisms follows, unraveling its capacity to disintegrate stubborn sulfur–carbon bonds, thereby elevating desulfurization efficiency to unprecedented levels. This review meticulously dissects diverse forms of TiO2, ranging from nanoparticles to mesoporous structures, and provides a critical analysis of their respective strengths and limitations in catalyzing sulfur removal. Delving into operational nuances, this review examines the impact of temperature, pressure, and catalyst loading on TiO2 performance, offering crucial insights for optimizing desulfurization processes. The narrative then unfolds to explore cutting-edge developments in TiO2-based catalysts, encompassing ingenious modifications, composites, and hybrid materials designed to augment catalytic activity and selectivity. Anticipating the road ahead, this review contemplates the challenges and prospects of deploying TiO2 on an industrial scale, pointing toward avenues for future research and development. This abstract encapsulates a wealth of knowledge, serving as an indispensable resource for researchers, engineers, and policymakers navigating the dynamic landscape of sustainable petroleum refining. TiO2 emerges as a transformative force, propelling the industry toward cleaner, greener, and more efficient energy production. [ABSTRACT FROM AUTHOR]

In the world, the largest reserves of low-grade coal or lignite coal are available. Low-ranking coal with high mineral content, sulfur, moisture, and low calorific value (CV) greatly contributes to environmental pollution via the emission of greenhouse gases, Sox, and NOx. To resolve this, the coal must be extracted or reduced of its minerals and sulfur through the processes called demineralization and desulfurization. In this regard, previous studies used different leaching agents to treat low-grade coal; however, their removal efficiencies were lower. Herein, demineralization and desulfurization of coal were carried out using alkali and alkali-acid hybrid treatments. In the first method, the samples were treated solely with alkali while in the second, they were treated with acid followed by alkali. The coal samples were analyzed via SEM, TGA, XRD, and FTIR; their chemical compositions were determined through ONH and SC analyzers. As per the results, the alkali-acid hybrid treatment was more efficient than just the alkali treatment. The hybrid treatment of 100 g/L NaOH followed by 10% HCl exhibited higher porosity, thermal stability, demineralization of 90.9%, desulfurization of 63.46%, and CV of 26585.924 KJ/Kg in the respective coal samples. On the other hand, alkali treatment with 100 g/L NaOH resulted in comparatively lower porosity, thermal stability, demineralization of 63.86%, desulfurization of 49.42%, and CV of 23770.905 KJ/Kg, respectively. When compared with six relevant studies, the coal sample with the least sulfur and mineral content in the present work indicated the lowest impurities. [ABSTRACT FROM AUTHOR]

Sulfur in fossil fuels is a major environmental and public health concern worldwide due to emissions of sulfur oxides formed during combustion. This may require new developments or upgrades of existing refining technologies. Hence, further desulfurization of gasoline and diesel to combat hazardous emissions could be a significant step toward environmental protection. In this study, adsorptive desulfurization of gasoline and diesel was achieved using a low‐cost fly ash‐derived faujasite (FAU) zeolite as complementary to the conventional hydrodesulfurization method. Sulfur levels of fuel samples, brought to the laboratory from typical fuel stations, were detected by a turbidimetric method before and after desulfurization. FAU zeolite sorbent, prepared from coal fly ash, was contacted with the fuel samples at stopped flow, and the residual fuels were analyzed to determine the sorbent's desulfurization performance. The process was optimized to enhance the sorbent's performance by varying the reaction conditions such as temperature, fuel volume, and the sorbent chemical composition. The results indicated that, at ambient temperature and pressure, the zeolitic desulfurization could reduce the sulfur content approximately by 40 % of its initial concentration, from 61 to 37 ppm and 155 to 97 ppm, in gasoline and diesel, respectively. Therefore, fly ash zeolites offer a possible opportunity for further desulfurization of refining petroleum fuels which may lead to economic and environmental gains. [ABSTRACT FROM AUTHOR]

Desulfurization is a necessary process to reduce the corrosiveness of natural gas. In this regard, H2S adsorption on porous materials has gained attention in the development of new eco-friendly technologies. Although there are many experimental and theoretical studies about gas adsorption on MOFs, so far, there has been no theoretical work about desulfurization of natural gas or biogas through H2S adsorption on MOF BTC. Therefore, the objective of this study was to preselect by ab initio calculations which metal center M2+, such as Co2+, Ni2+, Cu2+, or Zn2+, has the highest potential for selective desulfurization of natural gas. DFT calculations were performed at B3LYP-D3/6-311++G(2d,p)+LanL2DZ level for H2O, H2S, COS, CO2, and CH4 adsorption on M-BTC MOF clusters in order to obtain adsorption complex equilibrium geometries, adsorption energies and thermodynamic properties. It was found that Zn-BTC MOF cluster has the highest potential for selective H2S removal from dry natural gas streams, since its adsorption energy is −79.4 kJ mol−1, which is 2.4 times higher than CH4. Furthermore, H2S adsorption on Zn-BTC MOF is an exothermic process and thermodynamically favorable. Through NBO and EDA analyses, it was found that d electrons transfer from adsorbate to metal center unoccupied orbitals contributes mainly to a possible H2S chemisorption on Zn-BTC and Co-BTC, while for CO2 and CH4 adsorption, non-bonded interactions predominate. Most of the gases coordinate to coordinatively unsaturated site of BTC MOF cluster at axial position, indicating a stronger interaction with metal center compared to linkers. [ABSTRACT FROM AUTHOR]

Oxidative desulfurization (ODS) has emerged as a prominent technique for the removal of sulfur compounds from fuels, aiming to comply with stringent environmental regulations and minimize sulfur dioxide emissions. Herein, Fenton-like deep eutectic solvents (DESs) were synthesized as a catalyst and reaction medium and their application for the ODS process was investigated. The study encompassed the optimization of DES composition, reaction conditions, and the influence of different parameters on the desulfurization efficiency. The experimental findings demonstrated that the Fenton-like DES exhibited outstanding catalytic activity in the oxidative desulfurization of fuel. The optimized conditions involved conducting the reaction at room temperature for 2.5 h, using 200 mg of the prepared DES (HNFM-FeCl4) as both the extraction solvent and catalyst. An oxidant-to-sulfur (O/S) ratio of approximately 3:1 was maintained, with a 30 wt% H2O2 solution utilized as the oxidant. The analysis of the reaction products using GC–MS revealed a remarkable yield of 98% for dibenzothiophene sulfone. The DES provided a suitable medium for the reaction, enhancing the solubility and availability of sulfur compounds. The iron catalyst, in the presence of hydrogen peroxide, facilitated the oxidation of sulfur-containing compounds to their corresponding sulfones, which can be easily separated from the fuel phase. The DES catalysts exhibited stability and recyclability, making them suitable for practical applications in fuel desulfurization processes. [ABSTRACT FROM AUTHOR]

The sulfur in petroleum coke is harmful to carbon products, underscoring the importance of desulfurization for high-sulfur petroleum coke. This paper proposes a method combining alkaline catalytic roasting with ultrasonic oxidation for the deep desulfurization of high-sulfur petroleum coke. The results show that the desulfurization rate reaches 88.99% and the sulfur content is reduced to 0.83 wt.% under a coke particle size of 96–75 μm, sodium-hydroxide-to-petroleum-coke ratio of 50%, roasting temperature of 700 °C, and holding time of 2 h. The alkali-calcined petroleum coke is ultrasonically oxidized and desulfurized in peracetic acid. The results show that, under a hydrogen peroxide content of 10%, hydrogen-peroxide-(liquid)-to-petroleum-coke (solid) ratio of 20 mL/g, acetic acid content of 5 mL, ultrasonic power of 300 W, reaction temperature of 60 °C, and reaction duration of 4 h, the sulfur content is reduced to 0.15 wt.% and the total desulfurization reaches 98.01%. Through a series of characterizations, the proposed desulfurization mechanism is verified. Alkali roasting effectively removes a significant portion of sulfur in petroleum coke. However, the elimination of certain sulfur compounds, such as the more complex thiophene, presents challenges. The thiophene content is subsequently removed via ultrasonic oxidation. [ABSTRACT FROM AUTHOR]

The Val-d'Or vein field (VVF), located in the southern Abitibi subprovince (Québec, Canada), is host to ~ 47 Moz gold and is therefore an example of a greenstone-hosted orogenic gold district. Gold is contained in quartz-tourmaline-carbonate veins that cut As-poor intermediate to mafic volcanic and intrusive rocks, including dioritic, granodioritic and gabbroic sills, dikes, stocks, and plutons. Five investigated orebodies (Goldex, Triangle, Plug #4, Pascalis Gold Trend, Beaufor) host gold in vein- and wallrock-hosted pyrite-rich sulfide aggregates (> 95 vol%) that show a porous core domain (Py1), with abundant inclusions of carbonate, silicate, and Fe-oxides up to several tens of µm in size. A homogeneous pyrite rim domain (Py2) surrounds Py1 and contains most of the gold as native gold and polymetallic (Au-Ag-Te-Bi) inclusions, primarily calaverite and petzite. The two pyrites show different Au and As contents (Py1 = Au ≤ 30 ppm; As ≤ 67 ppm; Py2 = Au ≤ 1250 ppm; As ≤ 550 ppm). Pyrite shows a ubiquitous shift in δ34S values of up to + 3.0‰ from Py1 (δ34S = − 0.4‰ to 5.8‰, n = 32) to Py2 (δ34S = 0.0‰ to 6.3‰, n = 59) and records a small, slightly negative Δ33S signature between – 0.20‰ and 0.01‰. The δ34S shift suggests that removal of reduced sulfur species from auriferous hydrothermal fluids causes the formation of inclusion-hosted gold in Py2 by a decrease in the fluid sulfur fugacity (fS2) through wallrock sulfidation of Fe-oxides. The shift also correlates with locally enriched Co and Ni concentrations in Py1 (< 1 wt%), compared to lower, oscillatory zoned concentrations (< 0.1 wt%) in Py2, respectively, indicating an overall decrease in fluid oxygen fugacity (fO2). Contemporaneously, a decrease in fluid tellurium fugacity (fTe2) drives polymetallic inclusion-hosted gold formation in Py2, initially as calaverite followed by increasingly Ag-bearing petzite and hessite. The multiple sulfur isotopes and trace element compositions recorded in pyrite in the VVF indicate that a homogeneous fluid reservoir introduced gold-sulfide complexes. Even if considered a localized process at the ore-shoot scale, fluid-wallrock sulfidation reactions can lead to a coupled decrease in fS2, fO2, and fTe2 of auriferous hydrothermal fluids in a greenstone-hosted As-poor gold district. [ABSTRACT FROM AUTHOR]

Catalytic defunctionalization of complex molecules has attracted significant attention in organic synthesis. This reaction enables common functional groups to serve as "traceless handles" for the new bond construction. In this mini-review, we have summarized the latest advances, methodologies and mechanistic insights into the selective cleavage of C-C and C-X bonds catalysed by cobalt complexes, shedding light on their increasing importance in modern chemical synthesis. The content of this review is categorized according to the type of functional group being removed from molecules. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Petroleum Research & Studies is the property of Republic of Iraq Ministry of Higher Education & Scientific Research (MOHESR) and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

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The 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. [ABSTRACT FROM AUTHOR]

The dispersion of crumb rubber in road bitumen is essential for enhancing the elasticity of asphalt coatings. However, elastomer cross-linking through vulcanization can reduce the colloidal stability of bitumen. This study aims to enhance compatibility by partially devulcanizing crumb rubber using a pulverulent catalyst, specifically phosphomolybdic acid, in a batch reactor at 270°C. The use of a molybdenum-based catalyst is preferred due to its effectiveness in catalyzing the devulcanization process. Additionally, further conditioning of the catalyst through grinding optimizes contact with crumb rubber, enhancing catalyst activity and improving overall compatibility with road bitumen. [ABSTRACT FROM AUTHOR]

Owing to its high energy density and wide availability, jet fuel is a promising fuel for solid oxide fuel cell (SOFC) power systems. However, fuel‐reforming catalysts and SOFC anodes are easily poisoned by sulfur compounds present in the jet fuel. Therefore, effective removal of sulfur from the jet fuel is essential before its feeding to the SOFC system. Herein, a novel adsorptive desulfurization reactor for onboard desulfurization of jet fuel in mobile SOFC systems is developed. A laser‐based 3D printing method is used to fabricate the one‐piece stainless steel reactor that significantly simplifies the assembly and reduces the overall weight. The desulfurization performance of the reactor is evaluated using a regenerable nickel‐based sorbent under varying operating conditions. A strong influence of temperature and fuel flow rate on the desulfurization performance is observed. The results confirm that the developed desulfurization system is capable of reducing the sulfur content in jet fuel to a few ppm to sub‐ppm level. The proposed desulfurization system offers unique advantages in terms of geometric design flexibility, space optimization, scalability, and modularity for any onboard and/or on‐demand deep desulfurization needs in addition to fuel cell power systems for transport and portable applications. [ABSTRACT FROM AUTHOR]

Copyright of Iraqi Journal of Chemical & Petroleum Engineering is the property of Republic of Iraq Ministry of Higher Education & Scientific Research (MOHESR) and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Hydrogen sulfide is characterized with strong toxicity and corrosivity, so it is important to efficiently minimize its pollution. In this laboratory experiment a series of HPAs@UiO-66 were prepared by one-step hydrothermal method with molybdenum-based heteropoly acid (HPAs) as active centers and UiO-66 as a carrier, and a multi-acid-based solid phase desulfurization system with various active centers was set up. The effects of Keggin and Dawson structures, the central atoms (P and Si), and the substitutional atoms (V and W) of HPAs on desulfurization performance were studied, and their physico-chemical properties were analyzed by BET, FT-IR, XRD, SEM, and TEM. As a result, it was showed that PMo12@UiO-66 had excellent desulfurization activity, its H2S removal ability was maximized at 100 °C with a absorbing capacity being able to reach 17.18 mg/g, and it was found the presence of water in the mixed gas can promote PMo12@UiO-66 to remove H2S. In comparison with PMo12 and UiO-66, PMo12@UiO-66 was far better in desulfurization, its H2S absorbing capacity was 7.5 and 14.2 times PMo12 and UiO-66, respectively, demonstrating the synergistic desulfurization effect of PMo12 and UiO-66. Analysis by use of XPS (X-ray photo-electron spectroscopy) showed that the redox reaction took place between PMo12 and H2S, during which H2S was converted into elemental sulfur due to the oxidizing action of PMo12. In conclusion, this study proved that the introduction of PM012 had exhibited the most remarkable effect on enforcing the desulfurization performance of UiO-66, which could provide a reference for exploiting more novel HPA-based solid phase desulfurization agents. [ABSTRACT FROM AUTHOR]

The primary objective of this work was to investigate the simultaneous removal of refractory sulfur (dibenzothiophene, DBT) and nitrogen compounds (indole, IND) from model gasoline. This research aimed to develop an efficient adsorption process to mitigate the emission of sulfur oxide and nitrogen oxides, which pose direct threats to human health and the environment. Additionally, the study focused on addressing technical challenges encountered in the refinery process, particularly the poisoning of catalysts due to the presence of these compounds. To achieve the study's goals, granular activated carbon (GAC) was subjected to acid treatment for modification. Molybdenum species were then incorporated into the acid‐treated GAC using the wet impregnation technique. The composition and distribution of elements on the surface of the modified GAC (Mo‐AAC) were analyzed via X‐ray photoelectron spectroscopy (XPS). Various characterization techniques were employed to confirm the uniform dispersion of molybdenum species on the GAC surface. The specific surface area of the adsorbent was increased from 257 m2/g to 316 m2/g following the acid treatment and molybdenum modification. The study explored the impact of several key parameters on the removal of DBT and IND using central composite design (CCD). A regression model was derived using CCD through hybrid central composite design, and its adequacy was verified with the means of tests such as analysis of variance (ANOVA), a lack of fit test, and residuals distribution consideration. Experimental results match well with the results obtained by CCD model, justifying the accuracy of models. The results showed that all four parameters have a significant impact on removal of DBT and IND. Increasing temperature and the adsorbent dose positively affected the removal of both DBT and IND, indicating that higher temperatures and greater adsorbent dosages improved removal efficiency. On the other hand, the concentration of DBT and IND had a negative impact, signifying that higher initial contaminant concentrations hindered removal efficiency. The study determined the optimum initial contaminant concentrations for DBT and IND, temperature, and adsorbent dose to be 186 mg/L, 50 mg/L, 25.5°C, and 32 g/L, respectively. These conditions yielded the highest removal efficiency. The research demonstrated that Mo‐AAC has the capability to effectively reduce the sulfur and nitrogen content of model gasoline, making it a promising solution for addressing environmental and refinery challenges associated with these compounds. [ABSTRACT FROM AUTHOR]