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]

Microwave drying is a promising and effective way to drying and upgrading lignite. The influence of temperature (100⁻140 °C) and microwave power levels (500⁻800 W) on thin-layer drying characteristics of Zhaotong lignite under microwave irradiation were investigated. Fourteen thin-layer drying models were used to analyze the microwave drying process while six thin-layer drying models were used to analyze the hot-air drying process. The microwave drying processes at all temperature (100⁻140 °C) or low microwave power levels (500⁻700 W) exhibited four periods: a warm-up period, a short constant period, the first and second falling rate period, while one falling rate period was found during hot-air drying. The effective diffusion coefficient of lignite were calculated and it increases with increasing temperature and microwave power levels. During microwave drying, the two-term exponential model is the most suitable model for all applied conditions, while the Modified Page model is the mos... [more]

Mathematical modeling of olefin polymerization processes has advanced significantly, driven by factors such as the need for higher-quality end products and more environmentally-friendly processes. The modeling studies have had a wide scope, from reactant and catalyst characterization and polymer synthesis to model validation with plant data. This article reviews mathematical models developed for olefin polymerization processes. Coordination and free-radical mechanisms occurring in different types of reactors, such as fluidized bed reactor (FBR), horizontal-stirred-bed reactor (HSBR), vertical-stirred-bed reactor (VSBR), and tubular reactor are reviewed. A guideline for the development of mathematical models of gas-phase olefin polymerization processes is presented.

Polyimides with excellent physicochemical properties have aroused a great deal of interest as gas separation membranes; however, the severe performance decay due to CO₂-induced plasticization remains a challenge. Fortunately, in recent years, advanced plasticization-resistant membranes of great commercial and environmental relevance have been developed. In this review, we investigate the mechanism of plasticization due to CO₂ permeation, introduce effective methods to suppress CO₂-induced plasticization, propose evaluation criteria to assess the reduced plasticization performance, and clarify typical methods used for designing anti-plasticization membranes.

To solve the unwieldy problem of coal chemical wastewater reverse osmosis concentrate (ROC), a novel treatment method in which coking coal was used to adsorb the organic from ROC and the adsorption mechanism involved was investigated. The results showed that the organic components in the ROC of coal chemical industry can be effectively absorbed by the coking coal and the total organic carbon, UV254 and chromaticity of treated ROC reduced by 70.18%, 70.15% and 59.55%, respectively, at the coking coal dosage of 80 g/L. The isothermal adsorption data were fitted to the Langmuir model well. The kinetics were expressed well by the quasi-second-order kinetic model. The intragranular diffusion model and the BET (Acronym for three scientists: Brunauer⁻Emmett⁻Teller) test showed that the adsorption occurred mainly on the surface of the coking coal and its macropores and mesopores. When the pollutants further diffused to the mesopores and micropores, the adsorption rate decreased. The result of... [more]

Removal of hexavalent chromium had attracted much attention as it is a hazardous contaminant. An electrocoagulation-like technology electro-reduction was applied. The chromium (VI) in the wastewater was reduced to chromium (III) by the electron supplied by electricity power and Fe2+, formed from corrosion of steel electrodes in acidic conditions. The mechanism and parameters affecting the reaction were investigated. The results optimized by response surface methodology indicated that the influence of single factor on the reduction efficiency followed the order: A: dosage of H₂SO₄ > C: reaction time > D: reaction temperature > B: current intensity. The reduction efficiency was hardly affected by current intensity, while it was increased with the increasing of reaction time and acid concentration. The reducing agent, Fe2+ an and extra free electron, acted as a reducing agent and could easily reduce hexavalent chromium to trivalent chromium at high temperatures in an acidic medium.

Graphene oxide (GO) was used as a support for manganese oxide (MnO₂) for the preparation of a nanocomposite catalyst for the degradation of an azo dye, Reactive Black 5 (RB5). The nanocomposite was characterized for the structure by XRD, for the morphology with SEM, and for the surface chemistry with FTIR and potentiometric titration measurements. The GO-MnO₂ nanocomposite presented a high catalytic activity for the degradation/oxidation of RB5 at ambient conditions, which was higher than that of the pure MnO₂ and could be attributed to the beneficial contribution of the manganese oxide and the graphene oxide.

This study presents the Computational Fluid Dynamics (CFD) thermal design and experimental tests results for a multi-tubular solar reactor for hydrogen production based on the ferrite thermochemical cycle in a pilot plant in the Plataforma Solar de Almería (PSA). The methodology followed for the solar reactor design is described, as well as the experimental tests carried out during the testing campaign and characterization of the reactor. The CFD model developed for the thermal design of the solar reactor has been validated against the experimental measurements, with a temperature error ranging from 1% to around 10% depending on the location within the reactor. The thermal balance in the reactor (cavity and tubes) has been also solved by the CFD model, showing a 7.9% thermal efficiency of the reactor. CFD results also show the percentage of reacting media inside the tubes which achieve the required temperature for the endothermic reaction process, with 90% of the ferrite pellets inside... [more]

Mixing is considered as a critical process parameter (CPP) during process development due to its significant influence on reaction selectivity and process safety. Nevertheless, mixing issues are difficult to identify and solve owing to their complexity and dependence on knowledge of kinetics and hydrodynamics. In this paper, we proposed an optimization methodology using Computational Fluid Dynamics (CFD) based compartmental modelling to improve mixing and reaction selectivity. More importantly, we have demonstrated that through the implementation of surrogate-based optimization, the proposed methodology can be used as a computationally non-intensive way for rapid process development of reaction unit operations. For illustration purpose, reaction selectivity of a process with Bourne competitive reaction network is discussed. Results demonstrate that we can improve reaction selectivity by dynamically controlling rates and locations of feeding in the reactor. The proposed methodology inco... [more]

The present work gives a critical overview of the recent progresses and new perspectives in the field of photocatalytic membranes (PMs) in photocatalytic membrane reactors (PMRs), thus highlighting the main advantages and the still existing limitations for large scale applications in the perspective of a sustainable growth. The classification of the PMRs is mainly based on the location of the photocatalyst with respect to the membranes and distinguished in: (i) PMRs with photocatalyst solubilized or suspended in solution and (ii) PMRs with photocatalyst immobilized in/on a membrane (i.e., a PM). The main factors affecting the two types of PMRs are deeply discussed. A multidisciplinary approach for the progress of research in PMs and PMRs is presented starting from selected case studies. A special attention is dedicated to PMRs employing dispersed TiO₂ confined in the reactor by a membrane for wastewater treatment. Moreover, the design and development of efficient photocatalytic membran... [more]

Inference of biochemical network models from experimental data is a crucial problem in systems and synthetic biology that includes parameter calibration but also identification of unknown interactions. Stochastic modelling from single-cell data is known to improve identifiability of reaction network parameters for specific systems. However, general results are lacking, and the advantage over deterministic, population-average approaches has not been explored for network reconstruction. In this work, we study identifiability and propose new reconstruction methods for biochemical interaction networks. Focusing on population-snapshot data and networks with reaction rates affine in the state, for parameter estimation, we derive general methods to test structural identifiability and demonstrate them in connection with practical identifiability for a reporter gene in silico case study. In the same framework, we next develop a two-step approach to the reconstruction of unknown networks of inte... [more]

The kinetics of hydrogen absorption/desorption can be improved by decreasing particle size down to a few nanometres. However, the associated evolution of activation energy remains unclear. In an attempt to clarify such an evolution with respect to particle size, we electrochemically deposited Mg nanoparticles on a catalytic nickel and noncatalytic titanium substrate. At a short deposition time of 1 h, magnesium particles with a size of 68 ± 11 nm could be formed on the nickel substrate, whereas longer deposition times led to much larger particles of 421 ± 70 nm. Evaluation of the hydrogen desorption properties of the deposited magnesium nanoparticles confirmed the effectiveness of the nickel substrate in facilitating the recombination of hydrogen, but also a significant decrease in activation energy from 56.1 to 37.8 kJ·mol−1 H₂ as particle size decreased from 421 ± 70 to 68 ± 11 nm. Hence, the activation energy was found to be intrinsically linked to magnesium particle size. Such a re... [more]

Gas hydrate growth kinetics was studied at a pressure of 90 bars to investigate the effect of temperature, initial water content, stirring rate, and reactor size in stirred semi-batch autoclave reactors. The mixing energy during hydrate growth was estimated by logging the power consumed. The theoretical model by Garcia-Ochoa and Gomez for estimation of the mass transfer parameters in stirred tanks has been used to evaluate the dispersion parameters of the system. The mean bubble size, impeller power input per unit volume, and impeller Reynold’s number/tip velocity were used for analyzing observed trends from the gas hydrate growth data. The growth behavior was analyzed based on the gas consumption and the growth rate per unit initial water content. The results showed that the growth rate strongly depended on the flow pattern in the cell, the gas-liquid mass transfer characteristics, and the mixing efficiency from stirring. Scale-up effects indicate that maintaining the growth rate per... [more]