The Biginelli reaction is a multicomponent reaction for obtaining dihydropyrimidinthiones quickly, with multiple substitution patterns. The reaction mechanism remains unclear. Three possible pathways proposed for the reaction are the iminium route, an enamine intermediate, and the Knoevenagel pathway. However, when thiourea was used, no theoretical calculations were reported. Thus, based on the literature, the iminium pathway was used to obtain evidence explaining the lack of reactivity of 2,4-dihydroxybenzaldehyde towards the Biginelli adduct, compared with 4-hydroxybenzaldehyde. This computational study, carried out using the B3LYP/6-31++G(d,p) level of theory, showed an increment of 150 kJ/mol in the activation energy of the slowest pathway, due to the presence of a hydroxyl group in position 2 (ortho) of the aromatic aldehyde, decreasing its reactivity. Natural bond orbital (NBO) calculations suggest that the determinant steps are simultaneous, i.e., the polarization of the carbony... [more]

Due to the inherent difficulties in determination of the degree of branching for polymers produced in pulsed laser polymerization (PLP) experiments, the behavior of the degree of branching and backbiting reaction in high laser frequency and relatively high reaction temperatures have not been well-established. Herein, through a simulation study, the validity of different explanations on the recovery of PLP-molar mass distribution at high laser frequencies is discussed. It is shown that the reduction of the backbiting reaction rate at high laser frequency, and consequent decrease in the degree of branching, is not a necessary condition for recovering the PLP-molar mass distribution. The findings of this work provide simulation support to a previous explanation about the possibility of using high laser frequency for reliable determination of the propagation rate coefficient for acrylic monomers.

The almond cake is a protein- and oil-rich by-product of the mechanical expression of almond oil that has the potential to be used as a source of valuable proteins and lipids for food applications. The objectives of this study were to evaluate the individual and combined effects of solids-to-liquid ratio (SLR), reaction time, and enzyme use on oil and protein extraction yields from almond cake. A central composite rotatable design was employed to maximize the overall extractability and distribution of extracted components among the fractions generated by the aqueous (AEP) and enzyme-assisted aqueous extraction process (EAEP). Simultaneous extraction of oil and protein by the AEP was favored by the use of low SLR (1:12.82) and longer reaction times (2 h), where extraction yields of 48.2% and 70% were achieved, respectively. Increased use of enzyme (0.85%) in the EAEP resulted in higher oil (50%) and protein (75%) extraction yields in a shorter reaction time (1 h), compared with the AEP... [more]

Nowadays, the massive production of biodiesel leads to a surplus of glycerol. Thus, new applications of this by-product are being developed. In this study, glycerol steam reforming was carried out with Ni catalysts supported on Al2O3 rings and La-modified Al2O3. The catalysts were characterized by N2 physical adsorption, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and thermogravimetry. Both catalysts were effective in glycerol steam reforming. However, Ni/Al2O3 activity decreased over reaction time. Ni/La2O3/Al2O3 showed the best stability during the reaction. In addition, the activity of the modified support, La2O3/Al2O3, was evaluated. The modification of the support lent catalytic properties to the solid. Some conditions such as catalyst arrangement (catalyst in the first or second reactor), space velocity, and reaction temperature were studied. The highest hydrogen production was obtained when half the amount of the catalyst was located in bot... [more]

The use of nanostructure materials as heterogeneous catalysts in the synthesis of organic compounds have been receiving more attention in the rapid developing area of nanotechnology. In this review, we mainly focused on our own work on the synthesis of hybrid palladium−iron oxide nanoparticles. We discuss the synthesis of Pd−Fe3O4—both morphology-controlled synthesis of Pd−Fe3O4 and transition metal-loaded Pd−Fe3O4—as well as its application in various C−C coupling reactions. In the case of rose-like Pd−Fe3O4 hybrid nanoparticles, thermal decomposition can be used instead of oxidants or reductants, and morphology can be easily controlled. We have developed a method for the synthesis of nanoparticles that is facile and eco-friendly. The catalyst was recyclable for up to five continual cycles without significant loss of catalytic activity and may provide a great platform as a catalyst for other organic reactions in the near future.

In this study, we investigated the kinetics of arsenic removal from waste acid by the combination of zero-valent iron (ZVI) and CuSO4. ZVI samples were characterized by X-ray diffraction and scanning electron microscopy before and after arsenic removal; the results showed that after the arsenic removal reaction, As2O3 and magnetite phases were detected on the surface of these samples. Kinetic studies were carried out under different reaction temperatures, with different CuSO4 concentrations, and with different iron to arsenic molar ratios (Fe/As). The kinetic data of the arsenic removal were fitted to different kinetic models. The fitting results showed that the arsenic removal process could be described by the shrinking core model, controlled by residual layer diffusion. The apparent activation energy of the reaction was 9.0628 kJ/mol, the reaction order with the CuSO4 concentrations was −0.12681, and the reaction order with the molar ratio of iron to arsenic (Fe/As) was 3.152.

Kinetic modeling of the bulk free radical copolymerizations of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (EHA); methyl methacrylate (MMA) and EHA; as well as BA, MMA and EHA was performed using the software PREDICI®. Predicted results of conversion versus time, composition versus conversion, and molecular weight development are compared against experimental data at different feed compositions. Diffusion-controlled effects and backbiting for BA were incorporated into the model as they proved to be significant in these polymerizations. The set of estimated global parameters allows one to assess the performance of these copolymerization systems over a wide range of monomer compositions.

Application of nanoparticles in aqueous base-fluids for intensification of absorption rate is an efficient method for absorption progress within the system incorporating bubble-liquid process. In this research, SO2 and CO2 were separately injected as single raising bubbles containing nanofluids to study the impact of nanoparticle effects on acidic gases absorption. In order to do this, comprehensive experimental studies were done. These works also tried to investigate the effect of different nanofluids such as water/Al2O3 or water/Fe2O3 or water/SiO2 on the absorption rate. The results showed that the absorption of CO2 and SO2 in nanofluids significantly increases up to 77 percent in comparison with base fluid. It was also observed that the type of gas molecules and nanoparticles determine the mechanism of mass transfer enhancement by nanofluids. Additionally, our findings indicated that the values of mass transfer coefficient of SO2 in water/Al2O3, water/Fe2O3 and water/SiO2 nanofluid... [more]

Four Cl/Me substituted [ONNO] Zr-catalysts have been tested in ethene/α-olefin polymerization. Replacing electron-donating methyl with isosteric but electron-withdrawing chlorine substituents results in a significant increase of comonomer incorporation. Exploration of steric and electronic properties of the ancillary ligand by DFT confirm that relative reactivity ratios are mainly determined by the electrophilicity of the metal center. Furthermore, quantitative DFT modeling of propagation barriers that determine polymerization kinetics reveals that electronic effects observed in these catalysts affect relative barriers for insertion and a capture-like transition state (TS).

Pyrimidine-nucleoside phosphorylases (Py-NPases) have a significant potential to contribute to the economic and ecological production of modified nucleosides. These can be produced via pentose-1-phosphates, an interesting but mostly labile and expensive precursor. Thus far, no dynamic model exists for the production process of pentose-1-phosphates, which involves the equilibrium state of the Py-NPase catalyzed reversible reaction. Previously developed enzymological models are based on the understanding of the structural principles of the enzyme and focus on the description of initial rates only. The model generation is further complicated, as Py-NPases accept two substrates which they convert to two products. To create a well-balanced model from accurate experimental data, we utilized an improved high-throughput spectroscopic assay to monitor reactions over the whole time course until equilibrium was reached. We examined the conversion of deoxythymidine and phosphate to deoxyribose-1-p... [more]

The utilization of coal-based activated carbons focuses on improving the physicochemical structure for achieving high-capacity. Herein, the catalytic effect of NaCl (1 and 3 wt%) in the presence of oxygen functional groups on the improvement of the physicochemical structure of coal-based activated carbons is studied in this work. A large quantity of Na can be retained in 1NaJXO and 3NaJXO with the presence of oxygen functional groups to promote further its catalytic characteristics during pyrolysis, resulting in the disordered transformation of the carbon structure. In addition, the development of micropores is mainly affected by the distribution and movement of Na catalyst, whereas the growth of mesopores is mainly influenced by the evolution of oxygen functional groups. Then, the active sites of 3NaJXO-800 can no longer be consumed preferentially in the presence of Na catalyst during subsequent CO2 activation to facilitate the sustained disordered conversion of the microstructure and... [more]

Research on the synergistic high-value reuse of waste tires and used catalysts in spent fluid catalytic cracking (FCC) catalysts was carried out in this study to address the serious ecological and environmental problems caused by waste tires and spent FCC catalysts. The experiment, in which a spent FCC catalyst was applied to the catalytic cracking of waste tires, fully utilized the residual activity of the spent FCC catalyst and was compared with a waste tire pyrolysis experiment. The comparative experimental results indicated that the spent FCC catalyst could improve the cracking efficiency of waste tires, increase the output of light oil in pyrolysis products, and improve the quality of pyrolysis oil. It could also be used for the conversion of sulfur compounds during cracking. The content of 2-methyl-1-propylene in catalytic cracking gas was found to be up to 65.59%, so a new method for producing high-value chemical raw materials by the catalytic cracking of waste tires with spent... [more]

At present, the preparation of highly porous graphitic activated carbons (HPGACs) using the usual physical and chemical activation methods has met a bottleneck. In this study, HPGACs are directly synthesized from lignite at 900 °C. The whole process is completed by a microwave pretreatment, a graphitization conversion of the carbon framework at a low temperature using a small amount of FeCl3 (10−30 wt%), and a subsequent physical activation using CO2. Consequently, the dispersed and mobile iron species, in the absence of oxygen functional groups (removed during the microwave pretreatment), can greatly promote catalytic graphitization during pyrolysis, and, as an activating catalyst, can further facilitate the porosity development during activation. The as-obtained AC-2FeHLH-5-41.4(H) presents a low defect density, high purity, and specific surface area of 1852.43 m2 g−1, which is far greater than the AC-HLH-5-55.6(H) obtained solely by physical activation. AC-2FeHLH-5-41.4(H) as a supe... [more]

Replacing petro-based materials with renewably sourced ones has clearly been applied to polymers, such as those derived from itaconic acid (IA) and its derivatives. Di-n-butyl itaconate (DBI) was (co)polymerized via nitroxide mediated polymerization (NMP) to impart elastomeric (rubber) properties. Homopolymerization of DBI by NMP was not possible, due to a stable adduct being formed. However, DBI/styrene (S) copolymerization by NMP at various initial molar feed compositions fDBI,0 was polymerizable at different reaction temperatures (70−110 °C) in 1,4 dioxane solution. DBI/S copolymerizations largely obeyed first order kinetics for initial DBI compositions of 10% to 80%. Number-average molecular weight (Mn) versus conversion for various DBI/S copolymerizations however showed significant deviations from the theoretical Mn as a result of chain transfer reactions (that are more likely to occur at high temperatures) and/or the poor reactivity of DBI via an NMP mechanism. In order to suppre... [more]

Permittivity is a vitally important parameter for the description of the absorption and heating characteristics of materials under microwave irradiation. In this paper, the permittivity of nickel-containing sludge (NCS), which is created during battery production as a cheap secondary resource, was measured at temperatures from 20 °C to 600 °C at 2.45 GHz using the cavity perturbation method. In addition, the loss tangent (tanδ) and penetration depth (Dp) of microwaves into the material were calculated. The results of the permittivity study show that the dielectric constant (ε′) and dielectric loss factor (ε″) of the NCS increase with increasing temperature. The variations of the loss tangent (tanδ) and penetration depth (Dp) with the temperature can be divided into two parts at 200 °C. The effect of the initial moisture content on the dielectric properties of the material is notably greater than that of the temperature, which was confirmed by the heating curve. After microwave pretreat... [more]

The reactive crystallization of lithium carbonate (Li2CO3) from lithium sulfate (Li2SO4) and sodium carbonate (Na2CO3) solutions is a key process in harvesting solid lithium, whether from ores, brines, or clays. However, the process kinetics and mechanism remain poorly understood and the modelling of the reactive crystallization of Li2CO3 is not available. Hence, this work aims to determine the kinetics and mechanisms of the nucleation and growth of Li2CO3 reactive crystallization by induction time measurements and to model and optimize the crystallization process using response surface methodology. Induction time measurements were carried out as functions of initial supersaturation and temperature using a laser method. It was found that the primary nucleation mechanism of Li2CO3 varies with solution supersaturations, in which, expectedly, the heterogenous nucleation mechanism dominates at low supersaturations while the homogeneous nucleation mode governs at high supersaturations. The... [more]

As kerogen is the main organic component in shale, the adsorption capacity, diffusion and permeability of the gas in kerogen plays an important role in shale gas production. Based on the molecular model of type II kerogen, an organic nanoporous structure was established. The Grand Canonical Monte Carlo (GCMC) and Molecular Dynamics (MD) methods were used to study the adsorption and diffusion capacity of mixed gas systems with different mole ratios of CO₂ and CH₄ in the foregoing nanoporous structure, and gas adsorption, isosteric heats of adsorption and self-diffusion coefficient were obtained. The selective permeation of gas components in the organic pores was further studied. The results show that CO₂ and CH₄ present physical adsorption in the organic nanopores. The adsorption capacity of CO₂ is larger than that of CH₄ in organic pores, but the self-diffusion coefficient of CH₄ in mixed gas is larger than that of CO₂. Moreover, the self-diffusion coefficient in the horizontal directi... [more]

As byproducts of the combustion process of hydrocarbon fuels, soot particles are difficult to remove, and they can greatly harm human health and pollute the environment. Therefore, the formation and growth processes of the soot particles has become a study focus of researchers. In this paper, the nanostructure and oxidation reactivity of carbonaceous particles collected from ethylene inverse diffusion flames with or without the additions of three pentanol isomers (1-pentanol, 3-methyl-1-butanol, and 2-methyl-1-butanol) were investigated in detail. The nanostructure and oxidation characteristics of nascent soot particles were characterized using high resolution transmission electron microscopy (HRTEM), X-ray diffractometry (XRD) and thermogravimetric analysis (TGA). It was found that the nascent soot cluster of pure ethylene flame had a loose structure, while the additions of pentanol isomers made the soot agglomerates more compact and delayed the growth of graphitic structures. The pen... [more]

Tetraethylenepentamine (TEPA)-based mesoporous MCM-41 is used as the adsorbent to determine the CO₂ desorption kinetics of amine-modified materials after adsorption. The experimental data of CO₂ desorption as a function of time are derived by zero-length column at different temperatures (35, 50, and 70 °C) and analyzed by Avrami’s fractional-order kinetic model. A new method is used to distinguish the physical desorption and chemical desorption performance of surface-modified mesoporous MCM-41. The activation energy Ea of CO₂ physical desorption and chemical desorption calculated from Arrhenius equation are 15.86 kJ/mol and 57.15 kJ/mol, respectively. Furthermore, intraparticle diffusion and Boyd’s film models are selected to investigate the mechanism of CO₂ desorption from MCM-41 and surface-modified MCM-41. For MCM-41, there are three rate-limiting steps during the desorption process. Film diffusion is more prominent for the CO₂ desorption rates at low temperatures, and pore diffusio... [more]

In the next few years, even though there will be a continuous growth of renewables and a loss of the share of fossil fuel, energy production will still be strongly dependent on fossil fuels. It is expected that coal will continue to play an important role as a primary energy source in the next few decades due to its lower cost and higher availability with respect to other fossil fuels. However, in order to improve the sustainability of energy production from fossil fuels, in terms of pollutant emissions and energy efficiency, the development of advanced investigation tools is crucial. In particular, computational fluid dynamics (CFD) simulations are needed in order to support the design process of low emission burners. Even if in the literature several combustion models can be found, the assessment of their performance against detailed experimental measurements on full-scale pulverized coal burners is lacking. In this paper, the numerical simulation of a full-scale low-NO x , ae... [more]

In this study, Ni, Co and Ni−Co catalysts supported on binary oxide ZrO2−Al2O3 were synthesized by sol-gel method and characterized by means of various analytical techniques such as XRD, BET, TPR, TPD, TGA, SEM, and TEM. This catalytic system was then tested for syngas respective H2 production via partial oxidation of methane at 700 °C and 800 °C. The influence of calcination temperatures was studied and their impact on catalytic activity and stability was evaluated. It was observed that increasing the calcination temperature from 550 °C to 800 °C and addition of ZrO2 to Al2O3 enhances Ni metal-support interaction. This increases the catalytic activity and sintering resistance. Furthermore, ZrO2 provides higher oxygen storage capacity and stronger Lewis basicity which contributed to coke suppression, eventually leading to a more stable catalyst. It was also observed that, contrary to bimetallic catalysts, monometallic catalysts exhibit higher activity with higher calcination temperatur... [more]

The current research presents an experimental approach on the mechanism, kinetic and decay of industrial Pd-Ag supported α-Al2O3 catalyst used in the acetylene hydrogenation process. In the first step, the fresh and deactivated hydrogenation catalysts are characterized by XRD, BET (Brunauer−Emmett−Teller), SEM, TEM, and DTG analyses. The XRD results show that the dispersed palladium particles on the support surface experience an agglomeration during the reaction run time and mean particle size approaches from 6.2 nm to 11.5 nm. In the second step, the performance of Pd-Ag supported α-Al2O3 catalyst is investigated in a differential reactor in a wide range of hydrogen to acetylene ratio, temperature, gas hourly space velocity and pressure. The full factorial design method is used to determine the experiments. Based on the experimental results ethylene, ethane, butene, and 1,3-butadiene are produced through the acetylene hydrogenation. In the third step, a detailed reaction network is pr... [more]

Carbon capture and sequestration (CCS) is taking the lead as a means for mitigating climate change. It is considered a crucial bridging technology, enabling carbon dioxide (CO₂) emissions from fossil fuels to be reduced while the energy transition to renewable sources is taking place. CCS includes a portfolio of technologies that can possibly capture vast amounts of CO₂ per year. Mineral carbonation is evolving as a possible candidate to sequester CO₂ from medium-sized emissions point sources. It is the only recognized form of permanent CO₂ storage with no concerns regarding CO₂ leakage. It is based on the principles of natural rock weathering, where the CO₂ dissolved in rainwater reacts with alkaline rocks to form carbonate minerals. The active alkaline elements (Ca/Mg) are the fundamental reactants for mineral carbonation reaction. Although the reaction is thermodynamically favored, it takes place over a large time scale. The challenge of mineral carbonation is to offset this limitat... [more]

The motivation of this work is to investigate experimentally the influence of nonthermal plasma (NTP) application on the reaction kinetics of atmospheric pressure steam gasification of charcoal using a thermostatically controlled drop tube reactor. A gliding-arc generator provides about 1 kW electrical power NTP. For comparison thermal gasification is investigated under comparable flow and specific energy input conditions providing additional heat to the steam. Optical temperature measurement 20 cm flow down of the NTP zone is utilized to characterize the specific enthalpy of the reactive flow. The composition of produced syngas is measured by a gas analyzer and used for the calculation of gas flow rates. The results show a NTP-enhancement on the production of individual syngas components (H₂, CO, CH₄), especially on hydrogen production by around 39%. The syngas-based carbon conversion and hydrogen release are calculated from the carbon and hydrogen balance between the correspondent co... [more]

Reduction of carbon dioxide emission from natural and industrial flue gases is paramount to help mitigate its effect on global warming. Efforts are continuously deployed worldwide to develop efficient technologies for CO₂ capture. The use of environment friendly amino acids as rate promoters in the present amine systems has attracted the attention of many researchers recently. In this work, the reaction kinetics of carbon dioxide with blends of N-methyldiethanolamine and L-Arginine was investigated using stopped flow technique. The experiments were performed over a temperature range of 293 to 313 K and solution concentration up to one molar of different amino acid/amine ratios. The overall reaction rate constant (kov) was found to increase with increasing temperature and amine concentration as well as with increased proportion of L-Arginine concentration in the mixture. The experimental data were fitted to the zwitterion and termolecular mechanisms using a nonlinear regression techniqu... [more]