Thermochemical Characteristics Research Articles

Numerical simulation of gasifier optimization for combined hydrogen production and carbon reduction in a chemical looping gasification (CLG) system

Chemical looping gasification (CLG) for combined hydrogen production and carbon capture represents a significant pathway for the clean, low-carbon utilization of traditional fossil fuels. Currently, a significant knowledge gap remains concerning the interplay between reactor configuration optimization and the complex gas–solid interactions in the CLG systems. This study integrates reactive computational fluid dynamics-discrete element method (CFD-DEM) simulations with a coarse-grained model (CGM) to analyze 3D coal-based CLG systems. The spatiotemporal distributions of gas–solid flow dynamics and thermochemical characteristics are revealed. It is found that increasing the gasifier height enhances fuel conversion and hydrogen production but compromises CO2 absorption. Smaller reactor diameters induce excessively rapid gas–solid flows, leading to incomplete fuel conversion and reduced hydrogen yield, while larger diameters cause uneven flows, significantly deteriorating hydrogen production and carbon absorption efficiency. Based on the simulation findings, the optimal height-to-diameter ratio for the gasifier in a CLG system is approximately 28.8, optimizing H2 production while maintaining efficient CO2 absorption. Moreover, the superficial gas velocity has a multifaceted influence on the hydrogen production and carbon reduction performance in the CLG process, necessitating a comprehensive consideration of its effects on fuel reaction time, gas–solid interactions, and other factors.

Thermochemical conversion characteristics and kinetics of Cu- and Mn-contaminated biomass using a continuous pyrolysis-combustion method

Thermochemical conversion characteristics and kinetics of Cu- and Mn-contaminated biomass using a continuous pyrolysis-combustion method

Understanding Stabilization Factors in Heterodinuclear Ln-Al Complexes from DFT Simulations on Thermochemistry Data: A Counterintuitive Conclusion.

This study validates a computational protocol to predict the stability of heterodinuclear complexes by varying ligands on both moieties and analyzing the reaction Gibbs free energy (ΔGr) values. To this purpose, a series of Eu-Al complexes with the general formula [Eu(LEu)3Al(LAl)3], where LEu is the ligand of europium and LAl is an oxygen donor ligand of aluminum, is used. The nature of the bridging bonds and thermochemical characteristics (ΔGr, enthalpy, and entropy) of the complexes were evaluated via DFT calculations. We demonstrated that both entropic and enthalpic effects play a relevant role in the stability. The analysis of the series allows us to identify three ΔGr ranges where heterodinuclear complexes are (i) stable and easy to characterize, (ii) fragile and difficult to characterize, and (iii) not observed (unreacted precursors are recovered). To rationalize the trend of the stability and correlate it with the chemical nature of the ligands, we investigated the condensed Fukui function on the Al fragment. Results suggest that to obtain stable heteronuclear complexes, it is necessary to consider ligands with small condensed Fukui function values. This corresponds to a less nucleophilic oxygen site, yet counterintuitively, it allows the ligand to delocalize the received electronic charge and stabilize the complex.

Optimization of hydrogen-rich syngas from coal and sewage sludge co-gasification in supercritical water

Supercritical water gasification (SCWG) of coal and biomass waste complies with the structure of energy consumption and the targets for carbon peaking and carbon neutrality. In this work, the optimal blending ratio and thermochemical transformation characteristics of coal and sewage sludge (SS) co-gasification were explored experimentally at various temperatures (500–660 °C), residence time (0–40 min), feedstock concentrations (5–15 %), and catalyst utilization. The demethylation and dehydroxylation of intermediate products (aliphatic compounds, monocyclic aromatic hydrocarbons (MAHs)) improve the gasification performance under favorable experiment conditions (high temperature, long residence time, low feedstock concentration, and addition of catalysts). The optimal gasification results are an H2 yield of 38.36 mol/Kg and a 118.81 % increase of CGE (cold gas efficiency) in K2CO3-catalyzed gasification compared to the absence of the catalyst. Subsequently, the co-gasification mechanism of coal and SS was determined by the analysis of the three-phase product. Ultimately, a regression model was first established to obtain the practical optimization mechanism and yield prediction of hydrogen-rich syngas through response surface plots and regression equations. As verified in multiple experiments under varying situations, the regression model’s fitting accuracy yields an average relative error of 5.53 %.

Unveiling the effects of thallium and bismuth p-n doping on germanium-based clusters (n5 to n12) for applications in semiconductor materials

We report a computational investigation utilizing density functional theory (DFT) concerning the pure Gen, as well as their doped analogues (BiGen-1, TlGen-1) and p-n doped BiTlGen-2 clusters with n ranging from 5 to 12. To get a deeper insight in their properties, we focus on the size dependency of these Gen, BiGen-1, TlGen-1, and BiTlGen-2 clusters as well as their shape, relative stabilities, and thermochemical characteristics including binding energy, fragmentation energy, second-order energy difference, and HOMO-LUMO energy gaps. The systematic observations from the data of binding energies indicate that BiGen-1, TlGen-1 and BiTlGen-2 cluster have more structural and thermodynamic stability when compared with the pure Gen clusters. To validate the electronic characteristics of these clusters, additional energy gap-related parameters such as chemical hardness, vertical ionization potentials (VIP), and vertical electron affinities (VEA) are also computed. The doping seems to stabilize the Gen clusters and the highest stability has been achieved for BiGe7, TlGe9, and BiTlGe7 clusters as suggested by the combined effect of all these parameters.

Effect of interaction between different plastics and polyvinyl chloride on the chlorine transformation behavior in volatiles during low-temperature pyrolysis

To reduce the pollution during the pyrolysis recovery of chlorine-containing plastic waste from different sources, effects of the interaction between different plastics and polyvinyl chloride (PVC) on the transformation of chlorine at low temperature were investigated by thermogravimetry-Fourier transform infrared (TG-FTIR) and fixed-bed pyrolysis experiments. Results showed that the proportions of chlorine in chars were all <0.04 %, indicating that almost all chlorine was released after pyrolysis. However, the chlorine forms in volatiles were significantly changed with mixing different plastics. HCl production was significantly inhibited due to the addition of other plastics, while the organic chlorinated compounds (OCCs) formation was promoted, which increased the distribution of chlorine in liquid products. During PVC pyrolysis, chlorine was mainly distributed in gas (93.09 %) in the form of HCl, only a small amount of aliphatic chlorides were generated and distributed in liquid (6.89 %). After the addition of polystyrene (PS), polyethylene (PE) and polyethylene terephthalate (PET), the chlorine distribution in liquid increased to 8.86 %, 11.98 % and 25.99 %, respectively. The formation of OCCs was significantly affected by the difference in thermochemical reaction characteristics of plastics. Specifically, the production of aromatic chlorides was promoted by PS, while the generation of aliphatic chlorides and aromatic chloroesters was significantly promoted by PE and PET, respectively. Therefore, the release form of chlorine could be significantly altered by the interaction between PVC and other waste plastics, which provides a reference for the regulation of chlorine-containing pollutants in the recovery and utilization of plastic waste.

Cellulose Acetate Microparticles Synthesized from Agave sisalana Perrine for Controlled Release of Simvastatin.

Simvastatin (SIM) is widely prescribed to treat hyperlipidemia, despite its limitations, such as a short half-life and low oral bioavailability. To overcome these drawbacks, the development of a controlled-release formulation is desirable. This study aims to develop a microparticulate system based on cellulose acetate (ACT) obtained from Agave sisalana Perrine to promote a controlled SIM release. SIM-loaded microparticles (SMP) were prepared using the solvent emulsification-evaporation method. Several parameters were evaluated, including particle size, surface charge, morphology, encapsulation efficiency, thermochemical characteristics, crystallinity, and in vitro release profile. ACT exhibited favorable flow properties after acetylation, with a degree of substitution values superior to 2.5, as confirmed by both the chemical route and H-NMR, indicating the formation of cellulose triacetate. The obtained SMP were spherical with an average size ranging from 1842 to 1857 nm, a zeta potential of -4.45 mV, and a high SIM incorporation efficiency (98%). Thermal and XRD analyses revealed that SIM was homogeneously dispersed into the polymeric matrix in its amorphous state. In vitro studies using dialysis bags revealed that the controlled SIM release from microparticles was higher under simulated intestinal conditions and followed the Higuchi kinetic model. Our results suggest that ACT-based microparticles are a promising system for SIM delivery, which can improve its bioavailability, and result in better patient compliance.

Thermochemical and physical characteristics of isomeric tetracycloundecanes obtained from endo- and exo-dicyclopentadienes

By combining the cyclopropanation and hydrogenation processes of endo- and exo-isomers of dicyclopentadiene, two pairs of tetracycloundecane stereoisomers were obtained, differing in the position of a three-membered cycle. For the first time, under the same conditions for the exo,endo- and exo,exo-tetracyclo[5.3.1.02,6.08,10]undecanes and endo,anti- and exo,anti-tetracyclo[6.2.1.02,7.03,5]undecanes obtained the enthalpy of combustion and formation, saturated vapor pressure and enthalpy and entropy of vaporization were determined, and critical temperatures, pressures, volumes, Pitzer's acentric factors and critical compressibility factors were calculated. The isomers obtained have a higher energy density than JP-10.

Assessing the potential of functionalized cobalt-doped graphyne-like boron nitride as an efficient and accessible catalyst for oxygen reduction reaction in fuel cells

Due to its exorbitant expense and scarcity on Earth, there is a need to anticipate a cost-effective and widely accessible catalyst that can effectively replace platinum, which is known for its efficiency in fuel cells. In this context, catalysts such as OH, H, and COOH group-functionalized cobalt-doped Graphyne-like boron nitride (referred to as BNyen) are being examined to enhance the mechanism of oxygen reduction reaction (ORR) via direct 4e− reduction. According to findings derived from DFT, it has been observed that reactions predominantly take place above Co metal center rather than edge site of BNyen. Additionally, the thermochemical characteristics point to the fact that these reactions release a significant amount of heat, suggesting their feasibility. By examining reversible potential of products and intermediates on phthalocyanines as well as adsorption energy (Eads), it has been determined that Co-BNyen(OH) serves as a superior catalyst for ORR process. In conclusion, this research affirms that BNyen materials hold significant promise as catalysts for ORR, a crucial process in fuel cell applications.

STUDYING THE THERMOCHEMICAL CHARACTERISTICS OF SINTERING WITH ALKALI CONCENTRATE FROM WASTE COPPER TAILINGS

A long period of deposit development leads to a reduction in the volume of balance reserves of ores, while the volume of accumulation of waste (tailings) from mining and processing production increases. In connection with this, an urgent problem is the processing of waste tailings, which can serve as an additional source of commercial products of non-ferrous metals. The set objectives can be achieved by implementing comprehensive extraction of valuable components, reducing fuel, and energy costs at the stage of low-temperature sintering to produce white soot (grade BS-100). In order to determine the amount of heat of chemical reactions during sintering of rough copper concentrate with sodium hydroxide, thermochemical calculations were carried out. For the research, we used rough copper concentrate with a copper content of 4.40% and silver of 77.03 g/t. An equation has been obtained for calculating the heat of chemical reactions of rough concentrate sintering. According to this equation, the greatest contribution to the heat release is provided by the iron content (60%), three times less and equally (19%) - copper and silicon and about 0.2% is absorbed by aluminum. The thermal effect of sintering will be -920.45 kW·h/t of concentrate. From the heat balance of sintering it follows that with an alkali consumption of up to 200% of the mass of the concentrate. The heat of chemical reactions will be sufficient for the autogeneity of the process. Research has been carried out on sintering the concentrate with alkali in the temperature range of 250-500 °C and obtaining white soot from a productive leaching solution with the extraction of 60% silicon. White soot (mSiO2·nH2O) was isolated by two-stage carbonization of a silicate solution with carbon dioxide in a recirculation system with further washing of the precipitate with a solution of sulfuric acid. For citation: Karimova L.M., Kairalapov Ye.T., Makascheva G.K., Kharchenko Ye.M. Studying the thermochemical characteristics of sintering with alkali concentrate from waste copper tailings. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 7. P. 72-79. DOI: 10.6060/ivkkt.20246707.7004.

Investigation on the thermochemical characteristics, kinetics and evolved gases for typical kitchen waste pyrolysis

Kitchen waste is a complex biomass waste, whose composition and properties vary with factors such as source, season and region. It is challenging to classify and characterize it. A thermogravimetric and kinetic study was performed to estimate pyrolysis characteristics and gas emissions of starch, peel, nut shell, and vegetables. Samples underwent pyrolysis in the Simultaneous Thermal Analysis from room temperature to 1200 K at different heating rates of 10, 20, 30 and 50 K/min. The starch had the narrowest pyrolysis temperature range, while nut shell exhibited the highest residual rate. The average activation energy for pyrolysis process calculated using Coats–Redfern method was in order of starch > vegetable ≈ nut shell > peel. The gaseous products and typical functional groups of the released volatiles were identified using specific information from Fourier Transform Infrared Spectroscopy (FTIR) and Mass Spectrometry (MS). These primarily included small inorganic molecules, aldehydes, aromatics, ethers, furans, ketones, organic acids, and phenols. Aliphatic hydrocarbons significantly contributed to the total gas yield and were the most abundant for all samples. The characteristic ion fragment with m/z = 60 was only observed in peel and nut shell, while m/z = 58 ion fragments were exclusive to starch and vegetables. The practical research can provide theoretical basis for the resource utilization and environmental management of kitchen waste.

Nitramino-polymer with ether bridges and 1,2,3-triazole subunits incorporated into the polymer chain

The creation of novel energetic polymers for future advanced solid composite propellants and gunpowder is an urgent area of modern research. A simple and effective waste-free cycloaddition reaction between dialkyne and diazide comonomers, both bearing nitramine groups, for the synthesis of an energetic polymer containing explosophoric units in the polymer chain has been described. Neither solvent nor catalyst is required for the production of this polymer, the comonomers used are readily available, and the product does not need any purification, and, importantly, this protocol scales well. The resulting polymer, C1Z1, (C14H22N12O8)n, was comprehensively characterized by spectral and physico-chemical methods. Compatibility with energetic plasticizers (NG, DNDEG, DANPE), thermochemical characteristics and combustion features indicate the prospects of target polymer C1Z1 (density, ρ = 1.484 g/cm3; onset temperatures is 230 °C; positive enthalpy of the formation, ΔHf0 = +636 kJ/kg; burning rate at 10 MPa is 9.5 mm/s) as a binder base for energetic materials. Comparison of C1Z1 with nitrocellulose (NC) and their compositions with plasticizers revealed the advantages of C1Z1.

Study on CO2 co-gasification of cellulose and high-density polyethylene via TG-FTIR and ReaxFF MD

CO2 co-gasification of solid waste and biomass presents an approach for the comprehensive utilization of waste materials, biomass and carbon dioxide. In this study, the CO2 co-gasification of cellulose and high-density polyethylene was explored utilizing TG-FTIR method and ReaxFF MD simulation. The thermal behavior, synergistic effect, volatile release characteristics, activation energy and reaction mechanism were thoroughly analyzed. The experimental findings indicated that CO2 co-gasification involved four stages: drying, cellulose pyrolysis, polyethylene pyrolysis and semi-coke gasification. Co-gasification inhibited cellulose pyrolysis but promoted polyethylene pyrolysis, with the most pronounced promoting effect occurring at 40% polyethylene content. The absorbance curve suggested that CO release was associated with cellulose pyrolysis and the reaction between cellulose coke and CO2, and C-H release was related to the pyrolysis of cellulose and polyethylene. Co-gasification alleviated the energy barrier, with the greatest effect occurring at 40% polyethylene content. The simulated results confirmed that the promotion of polyethylene pyrolysis was attributed to the connection of radicals from cellulose with polyethylene. Additionally, the combination of hydrocarbon radicals and hydrogen from polyethylene and cellulose contributed to gas production. This investigation provides insights into the thermochemical conversion characteristics for CO2 co-gasification of biomass and high-density polyethylene.

Investigation on thermochemical characteristics and pyrolysis kinetics of lignocellulosic biomass for biofuel production feasibility

Investigation on thermochemical characteristics and pyrolysis kinetics of lignocellulosic biomass for biofuel production feasibility

Thermogravimetric Analysis of Eucalyptus Leaves as An Alternative Fuel for Rural Areas

The utilization of biomass waste as a substitute for conventional energy sources has gained popularity, and one possible source is the litter generated by eucalyptus plantations. The present study used thermogravimetric analysis (TGA) gain insight into the thermochemical characteristics of eucalyptus leaves. It was identified by heating the sample in a nitrogen environment from ambient temperature to 850oC at a rate of 10 oC/minute. Eucalyptus leaves have a high volatile matter (VM) content and a calorific value (CV) of 17.26 MJ/kg, according to the ultimate and proximate analysis. Additionally, the TGA results showed that eucalyptus leaves had a lower ignition temperature than other biomasses. Eucalyptus leaves began to devolatilize at 119 oC, reaching a peak temperature of 326 oC, and losing 68% of their weight as a result.

Grindability of Torrefied Camelina Straw and Microparticle Evaluation by Confocal Laser Scanning Microscopy for Use as Biofuel

This study examined the combined effect of torrefaction and microwave absorbers on improving biomass thermochemical characteristics and grindability for heat, power, and value-added products. Camelina straw in two grinds, ground (6.4 mm screen size) and chopped with biochar addition (0%, 10% and 20%), was torrefied in a bench-scale microwave reactor at torrefaction temperatures of 250 °C and 300 °C with residence times of 10, 15 and 20 min under inert conditions and nitrogen-activated. After torrefaction, the geometric mean particle and size distribution, moisture content, ash content, bulk and particle densities were determined, and the grinding performance values of torrefied ground and chopped with and without biochar were determined and compared with the raw camelina straw. The results showed that the geometric diameter decreased after torrefaction in both grinds. The specific energy required for grinding torrefied biomass decreased significantly with biochar addition, longer residence times, and increased torrefaction temperatures. Torrefied ground camelina straw with biochar after grinding had the lowest grinding energy of 34.30 kJ at 300 °C/20 min. The surface morphology by confocal laser scanning microscopy of torrefied camelina straw particles indicated that biochar addition (&gt;10%) and a torrefaction temperature at 250 °C can create profound surface distortion, and beyond 300 °C, colossal surface damage and carbonized weight fractions were produced.

Microwave heating of oil shale based on multiphysics field coupling: Positioning of the waveguide

Microwave heating has proven widespread applications in oil shale pyrolysis; however, the impact of waveguide port positioning on the microwave reactor's thermal performance remains underexplored. This work establishes a 3D coupled model that incorporates electromagnetic, thermochemical, and fluid dynamics effects employing multiphysics modeling methodology. The thermochemical characteristics of an oil shale sample under microwave irradiation are quantified for a broad range of waveguide port positions, specified via Latin hypercube sampling, which ensures the randomness of the port coordinates. The cavity field strength exhibits markedly high sensitivity to the waveguide positioning: the standard deviation of the cavity-averaged electromagnetic intensities for all considered positions is found to be 30.42% greater compare to the associated mean. The best port position yields a temperature rising rate an order of magnitude higher than the worst positioning, for which kerogen pyrolysis does not appear to be even activated in the same initial stage. The ranking of waveguide positions identified based on the temperature rising rate aligns well with the analysis of microwave utilization efficiency. The study offers insights for optimized microwave reactor design with enhanced oil shale thermal treatment.

Energy potential of biomass from rice husks in bangladesh: An experimental study for thermochemical and physical characterization

Rice husks, abundant leftovers from rice production, offer immense potential as a renewable energy source through thermochemical conversion processes. However, their efficient utilization hinges on understanding their unique thermal properties and reaction kinetics. This study addresses a critical gap by meticulously analyzing four prominent Bangladeshi rice husk varieties: BR22, BRRI Dhan46, BRRI Dhan47, and BRRI Dhan49. Through rigorous experimentation, we unveil a comprehensive dataset encompassing their physical, chemical, and thermochemical characteristics. Our investigation reveals favorable alignment of moisture content with various conversion technologies, alongside suitable bulk density for efficient handling. Proximate analysis sheds light on crucial components like ash, volatile matter, and fixed carbon, vital for optimizing combustion efficiency. Furthermore, elemental analysis not only highlights the presence of ash-forming elements but also assures low nitrogen and sulfur content, suggesting potential environmental benefits compared to conventional fuels. Delving into thermochemical characteristics, we measured higher heating values ranging from 13.31 MJ/kg to 14.42 MJ/kg, confirming the viability of these rice husk varieties for energy conversion. Thermogravimetric and kinetic analyses further illuminate their unique decomposition behavior, with BRRI Dhan47 exhibiting the highest decomposition rate, emphasizing the distinct reactivity profiles of different varieties. This extensive dataset empowers researchers and industry professionals with valuable insights for informed decision-making. By understanding the unique attributes of each rice husk variety and their behavior during conversion, we can optimize operational parameters for various thermochemical methods. Ultimately, this study bridges a critical research gap and paves the way for more efficient and sustainable utilization of rice husks as a renewable energy source, contributing to a greener future.

Insights into the gas-solid hydrodynamics and thermochemical characteristics in a pilot-scale chemical looping combustion unit using MP-PIC

Chemical looping combustion (CLC) emerges as an efficient pathway for CO2 capture and storage, yet complex in-furnace phenomena are still far from being understood. Accordingly, the multiphase reactive flow during the CLC process in a pilot-scale dual circulation fluidized bed (DCFB) is numerically investigated by the multi-phase particle-in-cell method considering thermochemical sub-models. After model validations, the thermochemical behaviors and the impact of operating parameters on CLC performance are explored, followed by unveiling the underlying mechanisms of heat and mass transfer characteristics. The pressure gradient is explicitly correlated with the solid holdup in two reactors. Gas-solid flow in the fuel reactor (FR) is more heterogeneous than that in the air reactor (AR) due to complex reactions and large amounts of gas/particle exchanges with other parts of the DCFB, and the whole CLC unit shows good circulating and heat transfer performance. Higher temperatures improve fuel conversion and increase CO2 yield. Elevating the air/fuel ratio (ψ) significantly enhances CLC performance at ψ ≤ 1.0 but it insignificantly affects the CLC performance at ψ > 1.0. A higher total inlet flow rate leads to suppressed fuel conversion and a subsequent decline in CO2 yield. The particle heat transfer coefficient (HTC) in the AR is approximately 450 W/(m2·K), significantly higher than that in the FR of about 300 W/(m2·K).

Effects of multi-strain pretreatment on thermochemical properties and component structure of paulownia

This study aims to delve into the impact of long-term multi-strain pretreatment on the thermochemical characteristics of paulownia. The nine-month experimental analysis reveals that the fourth month marks a crucial turning point in the pretreatment process. From Stage I (0–4 months) to Stage II (4–9 months), the pyrolysis temperature range continuously narrows, reducing a maximum of 31.47%. The char yield initially increased by 10.25% and then decreased by 6.95%. Calorific value showed a slow initial decline of 3.98–4.08%, followed by a subsequent increase of 7.66%. The ignition point continued to rise by 5.61%− 5.78%. The compositional experimental results indicate that in the first stage, strain primarily depolymerize the high-polymer lignin, resulting in a decrease in calorific value. The increase in the relative content of syringyl lignin (S) contributes to the rise in char yield. In Stage II, the S units are converted into guaiacyl lignin (G), which has a lower char yield, while the exposed hemicellulose and cellulose undergo severe erosion. The relative content of lignin and enzymatic products with stubborn structures increases, leading to an increase in calorific value. However, the higher breaking temperature of bonds in these structures results in a continuous increase in the ignition point. This study clearly establishes that after nine months of pretreatment, the paulownia exhibits characteristics of rapid pyrolysis, high calorific value and ignition point, which provides a reliable basis for uncovering the potential reuses of paulownia.