Search Results (37)

The projected depletion of fossil resources has initiated research on new and sustainable fuels which can be utilized in combination with conventional fuels. Lignocellulosic biomass, and more specifically lignin, can be depolymerized towards phenolic and aromatic bio-oils which can be converted downstream into bunker fuel blending components. Within this study, solvolysis under critical ethanol conditions and mild catalytic hydrotreatment were applied to heavy fractions of lignin pyrolysis bio-oils with the aim of recovering bio-oils with improved properties, such as a lower viscosity, that would allow their use as bunker fuel blending components. The mild reaction conditions, i.e., low temperature (250 °C), short reaction time (1 h) and low hydrogen pressure (30–50 bar), led to up 65 wt.% recovery of upgraded bio-oil, which exhibited a high carbon content (63–73 wt.%), similar to that of the parent bio-oil (68.9 wt.%), but a lower oxygen content and viscosity, which decreased from ~298,000 cP in the parent lignin pyrolysis oil to 526 cP in the hydrotreated oil, with a 10%Ni/Beta catalyst in methanol, and which was also sulfur-free. These properties permit the potential utilization of the oils as blending components in conventional bunker fuels. Full article

Hydrogen and oxygen isotopes of ore-forming fluid of nephrite deposits have always been changing due to mixings between different fluids and oxygen isotope exchanges between the ore-forming fluid and country rocks, resulting in that the tremolite (or actinolite) has to constantly re-establish new isotope fractionation equilibriums with the dynamic fluid, which is of great significance to understand the genesis of hydrogen and oxygen isotopes of nephrite. Based on this, Taylor’s closed model and fluid mixing model are used to unravel the control of multi-stage evolution of ore-forming fluid on the δD and δ¹⁸O of nephrite. Although Taylor’s closed model is conducive to interpreting the genesis of nephrite with light δD and δ¹⁸O, such as Vitim nephrite, Russia, and Chuncheon nephrite, South Korea, it is unable to be effectively used in other nephrite. The fluid mixing model can quantitatively constrain proportions of different fluids during different ore-forming stages. Multiple solutions of ore-forming fluids of carbonate rock-related nephrite result from the absence of external constraints, such as isotope compositions of intrusive rocks, carbonate rocks, and meteoric water. Due to the generally heavy δ¹⁸O of country rocks, a small amount of meteoric water that enters the hydrothermal system in the later ore-forming stage is insufficient to offset the δ¹⁸O increment of nephrite caused by the oxygen isotope exchange between country rocks and water, which should be responsible for the abnormal heavy δ¹⁸O of Luodian nephrite, Dahua nephrite, Sanchakou nephrite, Xiaomeiling nephrite, etc., and not metamorphic water dominating their formation. Full article

The refining industry is shifting from decarbonization to hydrogenation for processing heavy fractions to reduce pollution and improve efficiency. However, the carbon footprint of hydrogen production presents significant environmental challenges. This study couples refinery linear programming models with life cycle assessment to evaluate, from a long-term perspective, the role of low-carbon hydrogen in promoting sustainable and profitable hydrogenation refining practices. Eight hydrogen-production pathways were examined, including those based on fossil fuels and renewable energy, providing hydrogen for three representative refineries adopting hydrogenation, decarbonization, and co-processing routes. Learning curves were used to predict future hydrogen cost trends. Currently, hydrogenation refineries using fossil fuels benefit from significant cost advantages in hydrogen production, demonstrating optimal economic performance. However, in the long term, with increasing carbon taxes, hydrogenation routes will be affected by the high carbon emissions associated with fossil-based hydrogen, losing economic advantages compared to decarbonization pathways. With increasing installed capacity and technological advancements, low-carbon hydrogen is anticipated to reach cost parity with fossil-based hydrogen before 2060. Coupling renewable hydrogen is expected to yield the most significant economic advantages for hydrogenation refineries in the long term. Renewable hydrogen drives the transition of refining processing routes from a decarbonization-oriented approach to a hydrogenation-oriented paradigm, resulting in cleaner refining processes and enhanced competitiveness under emission-reduction pressures. Full article

The main goal of this research is the production of e-fuels in gasoline- and diesel-range hydrocarbons via the hydrocracking of wax from Fischer–Tropsch (FT-wax) synthesis. The hydrogen for the hydrocracking process originated from solar energy via water electrolysis, thus, the produced fuels were called e-fuels. The FT-wax was produced via the Fischer–Tropsch synthesis of syngas stream from the chemical looping gasification (CLG) of biogenic residues. For the hydrocracking tests, a continuous-operation TRL3 (Technology Readiness Level) pilot plant was utilized. At first, hydrocracking catalyst screening was performed for the upgrading of the FT-wax. Three hydrocracking catalysts were investigated (Ni-W, Ni-W zeolite-supported, and Ni-W Al₂O₃-supported catalyst) via various operating conditions to identify the optimal operating window for each one. These three catalysts were selected, as they are typical catalysts that are used in the petroleum refinery industry. The optimal catalyst was found to be the NiW catalyst, as it led to high e-fuel yields (38 wt% e-gasoline and 47 wt% e-diesel) with an average hydrogen consumption. The optimum operating window was found at a 603 K reactor temperature, 8.3 MPa system pressure, 1 hr⁻¹ LHSV, and 2500 scfb H₂/oil ratio. In the next phase, the production of 5 L of hydrocracked wax was performed utilizing the optimum NiW catalyst and the optimal operating parameters. The liquid product was further fractionated to separate the fractions of e-gasoline, e-diesel, and e-heavy fuel. The e-gasoline and e-diesel fractions were qualitatively assessed, indicating that they fulfilled almost all EN 228 and EN 590 for petroleum-based gasoline and diesel, respectively. Furthermore, a 12-month storage study showed that the product can be stored for a period of 4 months in ambient conditions. In general, green transportation e-fuels with favorable properties that met most of the fossil fuels specifications were produced successfully from the hydrocracking of FT-wax. Full article

Natural products hold immense potential for drug discovery, yet many remain unexplored in vast libraries and databases. In an attempt to fill this gap and meet the growing demand for effective drugs, this study delves into the promising world of ent-kaurane diterpenoids, a class of natural products with huge therapeutic potential. With a dataset of 570 ent-kaurane diterpenoids obtained from the literature, we conducted an in silico analysis, evaluating their physicochemical, pharmacokinetic, and toxicological properties with a focus on their therapeutic implications. Notably, these natural compounds exhibit drug-like properties, aligning closely with those of FDA-approved drugs, indicating a high potential for drug development. The ranges of the physicochemical parameters were as follows: molecular weights—288.47 to 626.82 g/mol; number of heavy atoms—21 to 44; the number of hydrogen bond donors and acceptors—0 to 8 and 1 to 11, respectively; the number of rotatable bonds—0 to 11; fraction Csp3—0.65 to 1; and TPSA—20.23 to 189.53 Ų. Additionally, the majority of these molecules display favorable safety profiles, with only 0.70%, 1.40%, 0.70%, and 46.49% exhibiting mutagenic, tumorigenic, reproduction-enhancing, and irritant properties, respectively. Importantly, ent-kaurane diterpenoids exhibit promising biopharmaceutical properties. Their average lipophilicity is optimal for drug absorption, while over 99% are water-soluble, facilitating delivery. Further, 96.5% and 28.20% of these molecules exhibited intestinal and brain bioavailability, expanding their therapeutic reach. The predicted pharmacological activities of these compounds encompass a diverse range, including anticancer, immunosuppressant, chemoprotective, anti-hepatic, hepatoprotectant, anti-inflammation, antihyperthyroidism, and anti-hepatitis activities. This multi-targeted profile highlights ent-kaurane diterpenoids as highly promising candidates for further drug discovery endeavors. Full article

The laws of thermal degradation of the mixture of the heavy fraction of low-temperature coal tar and coal shale were investigated using dynamic thermogravimetry. The kinetic characteristics of the process were determined using various methods, including the Ozawa–Flynn-Wall, Friedman, non-parametric kinetics and Šesták–Berggren methods. It is shown that coal shale initiated changes in the kinetic parameters and decomposition rate of the heavy fraction of coal tar. It was found that a 13% content of coal shale in the mixture led to the maximum rate of weight loss of the heavy fraction of coal tar. A hydrodemetallization kinetic model of the mixture of the heavy fraction of low-temperature coal tar and coal shale is proposed. The kinetic parameters of the hydrodemetallization process were determined; in addition, the rate constants at various temperatures were estimated. The study shows that the distribution of trace elements in the hydrogenate from the initial mixture and in the hydrogenate from the solid residue was characterized by relatively low values of reaction rate constants. The maximum microelement distribution rate was achieved in the hydrogenate solid residue. Energy indicators of activation processes indicated that hydrodemetallization at low temperatures is advantageous from an energy point of view. Full article

The Paris Agreement aims to limit global warming, and one of the most polluting sectors is heavy industry, where cement production is a significant contributor. This work briefly explores some alternatives, recycling, reducing clinker content, waste heat recovery, and carbon capture, discussing their advantages and drawbacks. Then, it examines the economic viability and benefits of increasing oxygen concentration in the primary burning air from 21 to 27 vol.%, which could improve clinker production by 7%, and the production of hydrogen through PEM electrolysis to make up 5% of the fuel thermal fraction, considering both in a cement plant producing 3000 tons of clinker per day. This analysis used reference values from Secil, an international company for cement and building materials, to determine the required scale of the oxygen and hydrogen production, respectively, and calculate the CAPEX of each approach. It is concluded that oxygen enrichment can provide substantial fuel savings for a relatively low cost despite a possible significant increase in NO_x emissions. However, hydrogen production at this scale is not currently economically viable. Full article

Cadmium (Cd), being a highly toxic heavy metal, significantly impacts plant growth and development by altering nutrient uptake and causing oxidative and structural damage, resulting in reduced yield. To combat Cd toxicity and accumulation in wheat, it was hypothesized that co-application of Selenium (Se) and Silicon (Si) can reduce the adverse effect of Cd and regulate Cd resistance while improving Se fortification in wheat. Therefore, this study evaluated the comparative effect of Se and Si on the growth and antioxidant defense systems of wheat plants grown in a hydroponic setup. Briefly, the plants were acclimatized to the hydroponic solution for 1 week and then exposed to 10 µmol Cd. Afterwards, the treatments, including 0.2 mmol Si and 1.5 µmol Se, were applied as a root and foliar application, respectively. Plants supplemented with both Se and Si showed improved biomass and other physiological growth attributes, and this response was associated with improved activity/contents of antioxidants, including glutathione (GSH) content, glutathione reductase (GR), ascorbate peroxidase (APX), and catalase (CAT), with related lowering of hydrogen peroxide, malondialdehyde content, and structural damages. Moreover, by Se + Si supplementation, a decrease in total S levels in plant tissues was observed, whereas an increase in total protein concentration and GSH indicated a different and novel mechanism of Cd tolerance and S homeostasis in the plant. It was observed that Si was more involved in significantly reducing Cd translocation by stabilizing Cd in the root and reducing its content in the soluble fraction in both the root and shoot. Whereas Se was found to play the main role in reducing the oxidative damage caused by Cd, and the effect was more profound in the shoot. In addition, this study also observed a positive correlation between Si and Se for relative uptake, which had not been reported earlier. Our findings show that the Se and Si doses together benefit growth regulation and nutrient uptake; additionally, their combinations support the Cd resistance mechanism in wheat through upregulation of the antioxidant system and control of Cd translocation and subcellular distribution, ultimately contributing to the nutritional quality of wheat produced. Thus, it is concluded that the co-application of Se and Si has improved the nutritional quality while reducing the Cd risk in wheat and therefore needs to be employed as a potential strategy to ensure food safety in a Cd-contaminated environment. Full article

Aquathermolysis is a promising process for improving the quality of heavy oil under reservoir conditions. However, the application of catalysts during the process can significantly promote the transformation of the heavy fragments and heteroatom-containing compounds of crude oil mixtures into low-molecular-weight hydrocarbons. This research paper conducted a comparative analysis of the catalytic effectiveness of water-soluble metal salts like NiSO₄ and FeSO₄ in the process of aquathermolysis to upgrade heavy oil samples extracted from the Ashal’cha reservoir. The temperature of the experiment was 300 °C for a duration of 24 h. Compared to the viscosity of the native crude oil, the Fe nanoparticles contributed to a 60% reduction in viscosity. The viscosity alteration is explained by the chemical changes observed in the composition of heavy oil after catalytic (FeSO₄) aquathermolysis, where the asphaltene and resin contents were altered by 7% and 17%, accordingly. Moreover, the observed aquathermolytic upgrading of heavy oil in the presence of FeSO₄ led to an increase in the yield of gasoline fraction by 13% and diesel fraction by 53%. The H/C ratio, which represents the hydrogenation of crude oil, increased from 1.52 (before catalytic upgrading) to 1.99 (after catalytic upgrading). The results of Chromatomass (GC MS) and Fourier-transform infrared spectroscopy (FT-IR) show the intensification of destructive hydrogenation reactions in the presence of water-soluble catalysts. According to the XRD and SEM-EDX results, the metal salts are thermally decomposed during the aquathermolysis process into the oxides of corresponding metals and are particularly sulfided by the sulfur-containing aquathermolysis products. Full article

The current study was performed for the experimental modeling of cyclic steam-air injection in a heavy oil reservoir model of dual porosity in the presence of a nickel-based catalyst for in situ oil upgrading enhanced by simultaneous hydrogen generation. The research was realized in the combustion tube setup with a sandpack core model under reservoir conditions due to the consistent injection of air followed by oil in situ combustion (ISC) and steam (water) injection. As a result, the original oil was upgraded regarding fractional composition and oil properties. In addition, simulated reservoir heterogeneity and cyclic stimulation intensified the hydrogen synthesis, which, in turn, could also contribute to oil upgrading. Full article

In 2009–2018, the isotopic composition of oxygen and hydrogen in the atmospheric precipitation, groundwater and river and lake water of Lake Onega basin was studied. The weighted annual isotope composition of precipitation at Petrozavodsk was δ¹⁸O = −11.7‰ and δ²H = −84‰ and varied from −30.9 to −4.1‰ for δ¹⁸O and from −23 to −22‰ for δ²H. The isotopic composition of the water in Lake Onega was relatively uniform from −11.5 to −9.3‰ for δ¹⁸O and from −85 to −71‰ for δ²H. In the bays, the isotopic composition of the water varied more substantially than in the central part of the lake due to the river runoff during springtime flooding. In late summer, the concentrations of deuterium and oxygen-18 increased in the lake water, and figurative points on the δ²H vs. δ¹⁸O diagram shifted above the meteoric line. The absorption of the isotopically heavy summer precipitation and disequilibrium isotope fractionation during evaporation led to the enrichment of the lake water by heavy isotopes. Experiments were conducted to estimate the evaporation influence on the isotope enrichment of the residual water, and a comparison of the obtained isotope data with the experimental function showed that commonly, about 4% and up to 12% of water was lost during the spring and summer, respectively. In the water of the tributaries, the abundance of the deuterium and oxygen-18 varied in a wider scale than in the lakes, from −14.4 to −9.1‰ for δ¹⁸O and from −102 to −73‰ for δ²H. An evaporation loss of up to 35% was found for the rivers in late summer, and this value was proportional to the area of lakes and wetlands in the elementary watershed. The initial isotope composition of the water in the tributaries prior to evaporation was estimated to be δ¹⁸O ≈ −14.1‰ and δ²H ≈ −103‰ on average and crossed the approximation and meteoric lines. This estimation was close to the average composition of the groundwater, i.e., δ¹⁸O ≈ −13.4‰ and δ²H ≈ −94‰ on the Lake Onega catchment. The slightly increased isotope depletion of the calculated composition in the initial river water in comparison with the groundwater was the result of the contribution of the spring snowmelt water, which had a significant influence on the lake water balance. Full article

Aquathermolysis is one of the crucial processes being considered to successfully upgrade and irreversibly reduce the high viscosity of heavy crude oil during steam enhanced oil recovery technologies. The aquathermolysis of heavy oil can be promoted by transition metal-based catalysts. In this study, the catalytic performance of two water-soluble catalysts Ni(CH₃COO)₂ and Zn(CH₃COO)₂ on the aquathermolytic upgrading of heavy oil at 300 °C for 24 h was investigated in a high pressure–high temperature (HP-HT) batch reactor. The comparison study showed that nickel acetate is more effective than zinc acetate in terms of viscosity reduction at 20 °C (58% versus 48%). The viscosity alteration can be mainly explained by the changes in the group composition, where the content of resins and asphaltenes in the upgraded heavy crude oil sample in the presence of nickel catalyst was reduced by 44% and 13%, respectively. Moreover, the nickel acetate-assisted aquathermolysis of heavy oil contributed to the increase in the yield of gasoline and diesel oil fractions by 33% and 29%, respectively. The activity of the compared metal acetates in hydrogenation of the crude oil was judged by the results of the atomic H/C ratio. The atomic H/C ratio of crude oil upgraded in the presence of Ni(CH₃COO)₂ was significantly increased from 1.52 to 2.02. In addition, the catalyst contributed to the desulfurization of crude oil, reducing the content of sulfur in crude oil from 5.55 wt% to 4.51 wt% The destructive hydrogenation of resins and asphaltenes was supported by the results of gas chromatography-mass spectroscopy (GC-MS) and Fourier-transform infrared (FT-IR) spectroscopy analysis methods. The obtained experimental results showed that using water-soluble catalysts is effective in promoting the aquathermolytic reactions of heavy oil and has a great potential for industrial-scale applications. Full article

In this study, Nickel oxide-based catalysts (Ni_xO_x) were synthesized and used for the in-situ upgrading process of heavy crude oil (viscosity 2157 mPa·s, and API gravity of 14.1° at 25 °C) in aquathermolysis conditions for viscosity reduction and heavy oil recovery. All characterizations of the obtained nanoparticles catalysts (Ni_xO_x) were performed through Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), X-Ray and Diffraction (XRD), and ASAP 2400 analyzer from Micromeritics (USA), methods. Experiments of catalytic and non-catalytic upgrading processes were carried out in a discontinuous reactor at a temperature of 300 °C and 72 bars for 24 h and 2% of catalyst ratio to the total weight of heavy crude oil. XRD analysis revealed that the use of nanoparticles of NiO significantly participated in the upgrading processes (by desulfurization) where different activated form catalysts were observed, such as α-NiS, β-NiS, Ni₃S₄, Ni₉S₈, and NiO. The results of viscosity analysis, elemental analysis, and ¹³C NMR analysis revealed that the viscosity of heavy crude oil decreased from 2157 to 800 mPa·s, heteroatoms removal from heavy oil ranged from S—4.28% to 3.32% and N—0.40% to 0.37%, and total content of fractions (ΣC₈–C₂₅) increased from 59.56% to a maximum of 72.21%, with catalyst-3 thank to isomerization of normal and cyclo-alkanes and dealkylation of lateral chains of aromatics structures, respectively. Moreover, the obtained nanoparticles showed good selectivity, promoting in-situ hydrogenation-dehydrogenation reactions, and hydrogen redistribution over carbons (H/C) is improved, ranging from 1.48 to a maximum of 1.77 in sample catalyst-3. On the other hand, the use of nanoparticle catalysts have also impacted the hydrogen production, where the H₂/CO provided from the water gas shift reaction has increased. Nickel oxide catalysts have the potential for in-situ hydrothermal upgrading of heavy crude oil because of their great potential to catalyze the aquathermolysis reactions in the presence of steam. Full article

In this study, for the first time we investigated the in situ upgrading performance of Na metal nanoparticles, which were obtained by dispersing small pieces of sodium in liquid paraffin up to certain dispersity. In situ aquathermolytic reactions were modeled in a high pressure–high temperature reactor coupled with a Gas Chromatography (GC) system at a temperature of 250 °C for 24 h using a heavy oil sample, produced from the Ashal’cha reservoir, Republic of Tatarstan (Russia). The mean particle size of Na nanoparticles was 6.5 nm determined by the Dynamic Light Scattering (DLS) method. The nanoparticles were introduced to the reaction medium with a concentration of 2 wt.% The upgrading performance of Na nanoparticles was evaluated by several analytical methods such as Gas Chromatography (GC), elemental analysis (CHNS), SARA, Gas Chromatography–Mass Spectroscopy (GC-MS), FT-IR spectroscopy and viscosity measurements. It was revealed that Na nanoparticles interact with water to yield hydrogen gas, the concentration of which increases from 0.015 to 0.805 wt.% Moreover, the viscosity of upgraded heavy oil was reduced by more than 50% and the content of low-molecular-weight hydrocarbons in saturated and aromatics fractions was increased. The Na nanoparticles contributed to the utilization of hydrogen sulfide and carbon dioxide by 99 and 94 wt.%, respectively. Full article

Late Mesozoic and Cenozoic geodynamics of the Arctic region is discussed in the context of possible mechanisms which provide multistage cyclic transformations and transport of carbon through crust and mantle. Geodynamic processes control the abiogenic generation of hydrocarbons and the patterns of their localization. Possible mechanisms of abiotic hydrocarbon generation are explained in the context of carbon transport from subduction zones to rifts and serpentinization of ultramafic rocks in the rifts in the case of the Laptev Sea and Gakkel Ridge areas. The carbon of shallow crust origin migrates with encapsulated fragments of marine sediments which are consumed in the Pacific subduction zone where they become destroyed and transformed by different chemical and physical processes. The resulting C-species are involved in mantle convection flows and reach the continental rifts of the Laptev Sea and the Gakkel mid-ocean ridge. Thus, the hydrocarbons formed in the crust and in the mantle acquire signatures of abiotic origin. According to the authors, the scale of manifestation of abiogenic methanogenesis in the lower parts of the lithosphere and in the upper mantle is not so wide. Numerous small (mm and fractions of the mm) particles of exogenous matter and dispersed carbon pulled into the mantle can only form a stable crustal geochemical plume that propagates in the plane of movement of convective flows. Indirectly, the scale of manifestation of this process can be judged by the volumes of degassing of hydrocarbon and carbon dioxide gases, as well as hydrogen and its compounds in the rift systems of the earth’s crust, which are extremely insignificant. However, in the cold seas of the Eastern Arctic, massive emissions of bubble methane of mixed genesis were found. As shown in the literature, the range of variability of stable isotopes of carbon and ¹⁴C of methane in certain areas of discharge associated with rifting demonstrates values (anomalously heavy ¹³C, and young ¹⁴C) that can be considered as examples of presumably abiogenic origin. Our work is mostly theoretical and suggests further discussion and improvement of the mechanism of formation of abiogenic hydrocarbons and the processes of their transformation. Full article