Search Results (302)

Catalytic upgrading of pyrolysis oils is an important step for producing replacement hydrocarbon-rich liquid biofuels from biomass and can help to advance pyrolysis technology. Catalysts play a pivotal role in influencing the selectivity of chemical reactions leading to the formation of main compounds in the final upgraded liquid products. The present work involved a systematic study of solvent-free catalytic reactions of cyclohexanone in the presence of hydrogen gas at 160 °C for 3 h in a batch reactor. Cyclohexanone can be produced from biomass through the selective hydrogenation of lignin-derived phenolics. Three types of catalysts comprising undoped NbOPO₄, 10 wt% NiO/NbOPO₄, and 30 wt% NiO/NbOPO₄ were studied. Undoped NbOPO₄ promoted both aldol condensation and the dehydration of cyclohexanol, producing fused ring aromatic hydrocarbons and hard char. With 30 wt% NiO/NbOPO₄, extensive competitive hydrogenation of cyclohexanone to cyclohexanol was observed, along with the formation of C₆ cyclic hydrocarbons. When compared to NbOPO₄ and 30 wt% NiO/NbOPO₄, the use of 10 wt% NiO/NbOPO₄ produced superior selectivity towards bi-cycloalkanones (i.e., C₁₂) at cyclohexanone conversion of 66.8 ± 1.82%. Overall, the 10 wt% NiO/NbOPO₄ catalyst exhibited the best performance towards the production of precursor compounds that can be further hydrodeoxygenated into energy-dense aviation fuel hydrocarbons. Hence, the presence and loading of NiO was able to tune the activity and selectivity of NbOPO₄, thereby influencing the final products obtained from the same cyclohexanone feedstock. This study underscores the potential of lignin-derived pyrolysis oils as important renewable feedstocks for producing replacement hydrocarbon solvents or feedstocks and high-density sustainable liquid hydrocarbon fuels via sequential and selective catalytic upgrading. Full article

Adequate treatment of the organic fraction of municipal solid waste (OFMSW) in co-digestion with sewage sludge (SS) through dark fermentation (DF) technologies has been widely studied and recognized. However, there is little experience with a high-solids approach, where practical and scalable conditions are established to lay the groundwork for further development of feasible industrial-scale projects. In this study, the biochemical hydrogen potential of OFMSW using a 7 L batch reactor at mesophilic conditions was evaluated. Parameters such as pH, redox potential, temperature, alkalinity, total solids, and substrate/inoculum ratio were adjusted and monitored. Biogas composition was analyzed by gas chromatography. The microbial characterization of SS and post-reaction percolate liquids was determined through metagenomics analyses. Results show a biohydrogen yield of 38.4 NmLH₂/gVS OFMSW, which forms ~60% of the produced biogas. Aeration was proven to be an efficient inoculum pretreatment method, mainly to decrease the levels of methanogenic archaea and metabolic competition, and at the same time maintain the required total solid (TS) contents for high-solids conditions. The microbial community analysis reveals that biohydrogen production was carried out by specific anaerobic and aerobic bacteria, predominantly dominated by the phylum Firmicutes, including the genus Bacillus (44.63% of the total microbial community), Clostridium, Romboutsia, and the phylum Proteobacteria, with the genus Proteus. Full article

The application of fluidized bed reactors to biomass fast pyrolysis is regarded as a promising technology for enabling high-value utilization of biomass. This work established a three-dimensional numerical model of an industrial-scale fluidized bed reactor for biomass catalytic pyrolysis, employing the multiphase particle-in-cell method (MP-PIC) and coupling catalytic pyrolysis kinetics. Primary gas flow rate and biomass–catalyst injection modes were optimized to further improve the performance of the reactor. The model received additional validation from experimental data, primarily to ensure prediction accuracy. The results revealed that an optimal primary gas flow rate of 4 kg/s achieved a peak catalytic efficiency of 71.3%. Using maximum high-quality liquid fuels and adopting a relatively dispersed inlet mode with opposite jetting for biomass and catalyst promoted uniform particle distribution and thermal homogeneity in the dense phase zone, further increasing the catalytic efficiency to 75.6%. With the integration of the multiphase particle-in-cell (MP-PIC) method with catalytic pyrolysis kinetics at the industrial-scale, this work could provide theoretical guidance for designing fluidized bed catalytic pyrolysis reactors and optimizing biomass catalytic pyrolysis processes. Full article

This study addresses the microbial corrosion of cement-based materials in coastal urban sewer networks, systematically investigating the kinetic mechanisms of sulfur biogeochemical cycling under seawater infiltration conditions. Through dynamic monitoring of sulfide concentrations and environmental parameter variations in anaerobic pipelines, a multiphase coupled kinetic model integrating liquid-phase, gas-phase, and biofilm metabolic processes was developed. The results demonstrate that moderate salinity enhances the activity of sulfate-reducing bacteria (SRB) and accelerates sulfate reduction rates, whereas excessive sulfide accumulation inhibits SRB activity. At 35 °C, the mathematical model coefficient “a” for sulfate reduction in the reactor with 3 g/L salinity was significantly higher than those in reactors with 19 g/L and 35 g/L salinities, with no significant difference observed between the latter two. Overall, high sulfate concentrations do not act as limiting factors for sulfide oxidation under anaerobic conditions; instead, they enhance the reaction within specific concentration ranges. The refined kinetic model enables prediction of sulfur speciation in tropical coastal urban sewer pipelines, providing a scientific basis for corrosion risk assessment. Full article

Catalytic methane decomposition offers an attractive and sustainable pathway for producing CO_x-free hydrogen and valuable carbon nanotubes. This work investigates the innovative use of liquid metals, particularly gallium and indium, as promoters for iron catalysts based on a titanium dioxide and alumina composite to improve this process even more. In a fixed-bed reactor operating at 800 °C and atmospheric pressure, all catalyst activities for methane decomposition were thoroughly assessed while keeping the gas hourly space velocity at 6 L/g h. Surface area and porosity, H₂-temperature programmed reduction/oxidation, X-ray diffraction, Raman spectroscopy, scanning transmission electron microscopy, and thermogravimetry analysis were utilized to investigate the physicochemical properties of the catalyst. The result showed that iron supported on a titanium-alumina catalyst exhibited higher activity, stability, and reproducibility with a methane conversion of 90% and hydrogen production of 81% after three cycles, with 240 min for each cycle and stability for 480 min. In contrast, the liquid metal-promoted catalysts improved the metal-support interaction and textural properties, such as surface area, pore volume, and particle dispersion of the catalysts. Still, the catalytic efficiency significantly improved. However, the gallium-promoted catalyst displayed excellent reusability. The characterization of the spent catalyst proved that both the iron supported on a titanium-alumina and its gallium-promoted derivative produced graphitic carbon; on the contrary, the indium-promoted catalyst produced amorphous carbon. These results demonstrate how liquid metal promoters can be used to adjust the characteristics of catalysts, providing opportunities for improved reusability and regulated production of carbon byproducts during methane decomposition. Full article

Polycyclic aromatic hydrocarbons (PAHs) in biochar, as opposed to those in pyrolysis liquid products that exit the reactor without adhering to the solid product, are particularly undesirable due to their environmental persistence and potential toxicity. When applied as a soil amendment, biochar containing PAHs poses risks to soil ecosystems and human health. Their formation during pyrolysis presents a significant challenge in biochar production, requiring the optimization of pyrolysis process parameters to minimize PAH content for safe soil amendment applications. This study explored the effects of particle size and heating rate on PAH formation during corn cob pyrolysis. Thermogravimetric analysis (TGA) was employed to heat corn cob powder of varying sample masses from ambient temperature to 550 °C at heating rates of 5, 10, and 20 °C/min. Simultaneously, the Chemical Reaction Engineering and Chemical Kinetics (CRECK) model simulated the pyrolysis of spherical corn cob biomass particles with a radius ranging from 1 to 40 mm, using feedstock chemical compositions as inputs. Tar species generated from the solid biomass model were introduced into a gas-phase batch reactor model to evaluate PAH formation. The results demonstrate that the particle size and heating rate significantly affect PAH formation, shedding light on the complex dynamics of biomass pyrolysis. A single spherical particle with a radius close to 1 mm approximates ideal TGA conditions by minimizing temperature and mass transfer limitations. The CRECK model suggested that a particle radius of 5–10 mm, combined with a low heating rate of 5 °C/min, optimally reduces PAH formation. Future research should focus on using thermogravimetric analysis coupled with gas chromatography–mass spectrometry (TGA-GC-MS) to comprehensively quantify PAH species formation. Full article

The gas-liquid sulfonation of α-olefin sulfonate (AOS) in falling film reactors faces significant limitations, primarily due to poor mass transfer efficiency and excessive byproduct formation. To overcome these challenges, a novel cross-shaped microchannel reactor was developed for the continuous gas-liquid sulfonation of α-olefin (AO) with gaseous sulfur trioxide (SO₃). The influence of key process parameters, including gas-phase flow rate, reaction temperature, SO₃/AO molar ratio, and SO₃ volume fraction, on product characteristics and their interactions was systematically investigated using the single-factor experiment and response surface methodology (RSM). A high-precision empirical model (coefficient of determination, R² = 0.9882) to predict product content was successfully constructed. To achieve multi-objective optimization considering product active substance content and energy efficiency, a strategy combining a two-population genetic algorithm with the entropy-weighted TOPSIS (Technique for Order of Preference by Similarity to Ideal Solution) method was implemented. Optimal conditions were determined as follows: gas-phase flow rate of 228 mL/min, reaction temperature of 52 °C, SO₃/AO molar ratio of 1.27, and SO₃ volume fraction of 4%. Compared to conditions optimized solely by RSM, this multi-objective approach achieved a significant 10% reduction in energy efficiency, with only a marginal 3.8% decrease in active substance content. This study demonstrates the feasibility and advantages of microreactors for the efficient and green synthesis of AOS. Full article

The co-pyrolysis of straw biomass and polyethylene film at different mass ratios was carried out in a small fixed-bed reactor with CaO as catalyst. The resulting synthesis gas production, liquid and solid products, and pyrolysis kinetics were studied by gas chromatography and thermogravimetric analysis. The results showed that with increasing proportion of plastic in the feedstock, co-pyrolysis had a synergistic effect on the CH₄ yield, reaching as high as 3.124 mol CH₄/kg feedstock, while the H₂ and CO yields continuously decreased. Comparing the experimental and theoretical yields of synthesis gas, the trends for CO and CH₄ were consistent, but those of H₂ and CO₂ differed widely. Examining the influence of element mass ratios in the feedstock on the synthesis gas composition, it was found that the biomass and plastics affected the formation of oxygen- and hydrogen-containing gases, respectively. The activation energy and pre-exponential factor showed increasing and decreasing trends, respectively, when the feedstock proportions and heating rate changed. Fitted linear correlation coefficients for all pyrolysis stages exceeded 0.99. Full article

This research delves into the co-pyrolysis of refuse-derived fuel (RDF) and oil shale (OS), utilizing a 50% weight ratio for each component. The study employs a fixed-bed reactor, augmented by electrical kiln heating, to conduct the co-pyrolysis process. A significant aspect of this research is the use of Aspen Plus software for process simulation, with the simulated results undergoing validation through experimental data. A commendable correlation was observed between the experimental outcomes and the model predictions, underscoring the reliability of the simulation approach. The investigation reveals distinct product yields from the pyrolysis of 100% RDF and 100% OS. Specifically, the pyrolysis of pure RDF yielded 45.26% gas, 20.67% oil, and 34.07% char by weight. In contrast, the pyrolysis of pure OS resulted in 14.51% gas, 8.32% liquid, and a significant 77.61% char by weight. The co-pyrolysis of RDF and OS in a 50% blend altered the product distribution to 31.98% gas, 12.58% liquid, and 55.09% char by weight. Furthermore, the Aspen Plus simulation model aligned closely with these findings, predicting yields of 31.40% gas, 11.9% oil, and 56.6% char by weight for the RDF-OS blend. This study not only elucidates the co-pyrolysis behavior of RDF and OS but also contributes valuable insights into the potential of these materials to address the pressing issue of plastic waste management and energy resource utilization. The findings underscore the efficacy of RDF and OS co-pyrolysis as a viable strategy for enhancing the value extraction from waste and underutilized energy resources, presenting a promising avenue for environmental and energy sustainability. Full article

In this study, through RH water model simulation experiments, the effects of precipitation bubbles on the two-phase flow pattern, liquid steel flow behavior, and flow characteristics in an RH reactor during the whole decarburization process were comparatively investigated and analyzed by using quasi-counts that reflected the similarity of the precipitation bubble phenomenon. The experimental results show that an increase in precipitation bubbles is positively related to an increase in circulating flow rate, a reduction in mixing time, and an increase in gas content and negatively related to the residence time of liquid steel in the vacuum chamber. The two-phase flow pattern of the rising tube under the influence of precipitation bubbles includes bubble flow, slug flow, mixing flow, and churn flow. Under the influence of precipitation bubbles, the liquid surface spattering inside the vacuum chamber is reduced, the fluctuation amplitude is reduced, the efficiency of liquid steel processing is improved, it is not easy for cold steel to form, and the fluctuation frequency is increased, which is conducive to increasing the surface area of the vacuum chamber; the bubbles’ rising, aggregating, and crushing behavior increases the stirring effect inside the vacuum chamber, which is conducive to improving the decarburization and mass transfer rate. Under the influence of the precipitated bubbles, the concentration gradient between the ladle and the vacuum chamber is increased, which accelerates the mixing speed of the liquid steel in the ladle, and the volume of the dead zone is reduced by 50%. The lifting gas flow rate can be appropriately reduced in the plant. Full article

The exploitation of fusion energy in tokamak reactors relies on efficient and reliable tritium management. The tritium needed to sustain the deuterium–tritium fusion reaction is produced in the Li-based blanket surrounding the plasma chamber, and, therefore, the effective extraction and purification of the tritium bred in the Li-blankets is needed to guarantee the tritium self-sufficiency of future fusion plants. This work introduces a new technology for the extraction of tritium from the Pb–Li eutectic alloy used in liquid blankets. Process units based on the concept of Membrane Gas–Liquid Contactor (MGLC) have been studied for the extraction of tritium from the Pb–Li in the Water Cooled Lithium Lead blankets of the DEMO reactor. MGLC units have been preliminarily designed and then compared in terms of the permeation areas and sizes with the tritium extraction technologies presently under study, namely the Permeator Against Vacuum (PAV) and the Gas–Liquid Contactors (GLCs). The results of this study show that the DEMO WCLL tritium extraction systems using MGLC require smaller permeation areas and quicker permeation kinetics than those based on PAV (Permeator Against Vacuum) devices. Accordingly, the MGLC extraction unit exhibits volumes smaller than those of both PAV and GLC. Full article

Increasing the efficiency and capacity of nuclear power units is a promising direction for the development of power generation systems. Unlike thermal power plants, nuclear power plants operate at relatively low temperatures of the steam working fluid. Due to this, the thermodynamic efficiency of such schemes remains relatively low today. The temperature of steam and the efficiency of nuclear power units can be increased by integrating external superheating of the working fluid into the schemes of steam turbine plants. This paper presents the results of a thermodynamic analysis of thermal schemes of NPPs integrated with hydrocarbon-fueled plants. Schemes with a remote combustion chamber, a boiler unit and a gas turbine plant are considered. It has been established that superheating fresh steam after the steam generator is an effective superheating solution due to the utilization of heat from the exhaust gases of the GTU using an afterburner. Furthermore, there is a partial replacement of high- and low-pressure heaters in the regeneration system, with gas heaters for condensate and steam superheating after the steam generator for water-cooled and liquid-metal reactor types. An increase in the net efficiency of the hybrid NPP is observed by 8.49 and 5.11%, respectively, while the net electric power increases by 93.3 and 76.7%. Full article

This article discusses the problem of numerically solving the Navier–Stokes equations, the heat conduction equation, and the transport equation in the orthogonal coordinates of a free curve. Since the numerical solution domain is complex, the curvilinear mesh method was used. To do so, first, a boundary value problem was posed for the elliptic equation to automate the creation of orthogonal curved meshes. By numerically solving this problem, the program code for the curvilinear mesh generator was created. The motion of a liquid or gas through a porous medium was described by numerically solving the Navier–Stokes equations in freely curvilinear orthogonal coordinates. The transformation of the Navier–Stokes equation system, written in the stream function, vorticity variables, and cylindrical coordinates, into arbitrary curvilinear coordinates, was considered in detail by introducing metric coefficients. To solve these equations, the coefficients of which vary rapidly, a three-layer differential scheme was developed. The approximation, stability, and compactness of the differential scheme were previously studied. The considered problem was considered to be the mathematical model of a car catalytic converter, and computational experiments were conducted. Calculations were performed with the developed program code in different geometries of the computational domain and different values of grid size. The Reynolds number was changed from 100 to 10,000, and its effect on the size of the backflow in front of the porous medium was discussed. The software code, which is based on the differential equation of the Navier–Stokes equations written in the orthogonal coordinates of a curved line, and its calculation algorithm can be used for the mathematical and computer modeling of automobile catalytic converters and chemical reactors. Full article

The monitoring of contaminants in imitation jewelry has become important nowadays due to the high amount of products sold worldwide. Due to the complexity of the sample matrix (composed mainly of metals in high concentration), sample analysis can be very challenging. One interesting alternative for this purpose is the use of photochemical vapor generation coupled to inductively coupled plasma optical emission spectrometry (PVG-ICP-OES) due to the ability of separating the analytes from the sample solution prior to analysis; additionally, it is considered an eco-friendly approach if compared to other vapor generation techniques. Thus, this work presents the development and application of a PVG-ICP-OES system for the determination of Hg and Pb in imitation jewelry after sample dissolution in hydrochloric acid. The PVG system was built with two UV lamps (254 nm), a quartz capillary reactor, and a glass gas-liquid separator. Acetic acid concentration and UV exposure time were optimized using a central composite design, as well as the carrier gas flow rate and the radiofrequency (RF) power for the ICP-OES. The optimum conditions were achieved at 30% v/v acetic acid, 60 s reaction time, 0.035 L min⁻¹ carrier gas flow rate, and 1310 W for RF power. The influence of the sample matrix and chemical modifiers were studied, where it was found that the presence of the sample matrix may cause suppression of the analytical signal. The accuracy of the method was evaluated by recovery tests, which ranged from 88 to 102%. The detection limits ranged from 1 to 3 mg g⁻¹, allowing the monitoring of Hg and Pb in imitation jewelry. Full article

This study investigates the transformation of biogas (methane and carbon dioxide) into high-value liquid products using Ni/Al₂O₃, Fe/Al₂O₃, and Ni-Fe/Al₂O₃ catalysts in a non-thermal plasma (NTP)-assisted process within a dielectric barrier discharge (DBD) reactor, operating at room temperature and atmospheric pressure. We compared the effectiveness of these three catalysts, with the Ni-Fe/Al₂O₃ catalyst showing the highest enhancement in conversion rates, achieving 34.8% for CH₄ and 19.7% for CO₂. This catalyst also promoted the highest liquid yield observed at 38.6% and facilitated a significant reduction in coke formation to 10.4%, minimizing deactivation and loss of efficiency. These improvements underscore the catalyst’s pivotal role in enhancing the overall process efficiency, leading to the production of key gas products such as hydrogen (H₂) and carbon monoxide (CO), alongside valuable liquid oxygenates including methanol, ethanol, formaldehyde, acetic acid, and propanoic acid. The findings from this study highlight the efficacy of combining NTP with the Ni-Fe/Al₂O₃ catalyst as a promising approach for boosting the production of valuable chemicals from biogas, offering a sustainable pathway for energy and chemical manufacturing. Full article