Alkyl lactates are green solvents that are successfully employed in several industries such as pharmaceutical, food and agricultural. They are considered prospective renewable substitutes for petroleum-derived solvents and the opportunity exists to obtain these valuable chemicals from the chemical recycling of waste poly(lactic acid). Alkyl lactates (ethyl lactate, propyl lactate and butyl lactate) were obtained from the catalysed alcoholysis reaction of poly(lactic acid) with the corresponding linear alcohol. Reactions were catalysed by a Zn complex synthesised from an ethylenediamine Schiff base. The reactions were studied in the 50−130 °C range depending on the alcohol, at autogenous pressure. Arrhenius temperature-dependent parameters (activation energies and pre-exponential factors) were estimated for the formation of the lactates. The activation energies (Ea1, Ea2 and Ea−2) for alcoholysis in ethanol were 62.58, 55.61 and 54.11 kJ/mol, respectively. Alcoholysis proceeded fastest... [more]

Air−light hydrocarbon mixing gas is a new type of city gas which is composed of light hydrocarbon with the main component of n-pentane and air mixed in a certain proportion. To explore the dominant reactions for CO production of air−light hydrocarbon mixing gas with different mixing degrees at the critical equivalence ratios, a computational study was conducted on the combustion characteristics, including the ignition delay time, laminar flame speed, extinction residence time, and emission of air−light hydrocarbon mixing gas at atmospheric pressure and room temperature in the present study. The calculated results indicate that the ignition delay time of air−light hydrocarbon mixing gas at temperatures of 1000−1118 K is greater than that of n-pentane, while the opposite at temperatures of 1118−1600 K. From the study of the laminar flame speed and ignition delay time, it was found that the essence of air−light hydrocarbon mixing gas is that its attribute parameter is determined by the ra... [more]

In this communication, we describe our preliminary results for the development of a new method of ethylene and propene (co)polymerization at low pressure at room temperature, using cyclodextrin-assisted aqueous radical polymerization for the first time. For polypropylene homopolymerization, the cyclodextrin was entirely removed, and the partially soluble polymer was characterized. The purification of polyethylene was not complete, since the threaded cyclodextrins remained on the polymer chain, enhancing its solubility and enable to analyze the sample. With this environmentally benign method, polyolefines could be produced, for the first time. The estimated yield was low, and therefore the conditions should be further tuned for industrial application. This straightforward approach could also be applied to synthesize poly(ethylene-co-vinyl acetate) copolymer with an ethylene content of 20 mol% and enhanced yield. Although the procedure in this stage of research has some limitations, the... [more]

In the recent two decades, graphene-based materials have achieved great successes in catalytic processes towards sustainable production of chemicals, fuels and protection of the environment. In graphene, the carbon atoms are packed into a well-defined sp2-hybridized honeycomb lattice, and can be further constructed into other dimensional allotropes such as fullerene, carbon nanotubes, and aerogels. Graphene-based materials possess appealing optical, thermal, and electronic properties, and the graphitic structure is resistant to extreme conditions. Therefore, the green nature and robust framework make the graphene-based materials highly favourable for chemical reactions. More importantly, the open structure of graphene affords a platform to host a diversity of functional groups, dopants, and structural defects, which have been demonstrated to play crucial roles in catalytic processes. In this perspective, we introduced the potential active sites of graphene in green catalysis and showca... [more]

Freshwater is only 2.5% of the total water on the Earth and rest is contaminated or brackish. Various physical and chemical techniques are being used to purify the contaminated water. This study deals with catalytic plasma treatment of contaminated water collected from different sites of Faisalabad-Pakistan. A non-thermal DC plasma jet technique was used to treat the water samples in the presence of TiO2 catalyst. The plasma-assisted catalytic treatment introduced some oxidative species (O3, H2O2, HO2−, OH−) in the water. These species reacted with pollutants and cause the degradation of harmful contaminants, especially dyes. The degradation of dye sample during plasma treatment was more pronounced as compared to other samples. pH, conductivity and TDS of dye containing sample decreased after catalytic plasma treatment. The degradation of organic pollutants increased due to presence of several oxidants, such as TiO2, ferrous ions and hydrogen peroxide. FT-IR analysis revealed the degra... [more]

Phosphates in wastewater at elevated concentrations cause eutrophication of water bodies and their removal from treated wastewater is essential before effluents are discharged to the environment. Phosphates are predominately removed during wastewater treatment by chemical precipitation which is usually expensive and has a significant environmental footprint. The purpose of this study was to investigate the effectiveness of waste recycled bricks as adsorbent for phosphate removal during wastewater treatment. The kinetics, isotherms, and thermodynamics of adsorption were investigated to establish the mechanisms of adsorption. The results showed that adsorption capacities increased with an increase in contact time, adsorbent dosage, and initial phosphate concentration. The kinetic study indicated that adsorption was governed by several mechanisms with various processes dominating different stages of the adsorption. The adsorption process was better represented by the pseudo-second-order k... [more]

TiO2 nanoparticles were prepared via an electrochemical method using pulse alternating current and applied in the photocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF). Its physicochemical properties were characterized by SEM, HRTEM, XRD, and BET methods. The effect of scavenger and UVA light intensity was studied. The results revealed that electrochemically synthesized TiO2 nanoparticles exhibit higher DFF selectivity in the presence of methanol (up to 33%) compared with commercial samples.

The isomerization of glucose-containing hydrolysates to fructose is a key step in the process from lignocellulosic biomass to the platform chemical hydroxymethylfurfural. We investigated the isomerization reaction of glucose to fructose in water catalyzed by hydrotalcite. Catalyst characterization was performed via IR, XRD, and SEM. Firstly, glucose solutions at pH-neutral conditions were converted under variation of the temperature, residence time, and catalyst loading, whereby a maximum of 25 wt.% fructose yield was obtained at a 38 wt.% glucose conversion. Secondly, isomerization was performed at pH = 2 using glucose solutions as well as glucose-containing hydrolysates from lignocellulosic biomass. Under acidic conditions, the hydrotalcite loses its activity for isomerization. Consequently, it is unavoidable to neutralize the acidic hydrolysate before the isomerization step with an inexpensive base. As a neutralizing agent NaOH is preferred over Ba(OH)2, since higher fructose yields... [more]

Rutile decomposition by sulfuric acid, including the formation of two salts, Ti(SO4)2/TiOSO4, is thermodynamically modelled. It is shown that TiO2 can spontaneously dissolve in H2SO4 solutions. However, titania is considered as an inert (ballast) phase component of titanium-containing raw materials due to the decelerated separate nature of such chemical transformations. It is concluded that the hampered related kinetics of dissolution can be attributed to the lability of Ti(IV) cations/the specific engineered features of the hierarchical crystalline structure. It is suggested that the breaking of Ti−O−Ti bonds without additional mechanical strains in crystal lattice geometry becomes more advantageous when smaller negative anions/fluoride ions can be used. The analysis of sulfate-fluoride extraction leaching of titanium confirmed that a decrease in the Gibbs energy in the presence of F occurs. It is indicated by kinetic research studies that the addition of corrosive sodium reagent (NaF... [more]

Highly active metal chlorides grafted on silicoaluminophosphate number 5, MClx/SAPO-5 (M = Cu, Co, Sn, Fe and Zn) catalysts via simple grafting of respective metal chlorides (MClx) onto SAPO-5 are reported. The study shows that thermochemical treatment after grafting is essential to ensure the formation of chemical bondings between MClx and SAPO-5. In addition, the microscopy, XRD and nitrogen adsorption analyses reveal the homogeneous distribution of MClx species on the SAPO-5 surface. Furthermore, the elemental microanalysis confirms the formation of Si−O−M covalent bonds in ZnClx/SAPO-5, SnClx/SAPO-5 and FeClx/SAPO-5 whereas only dative bondings are formed in CoClx/SAPO-5 and CuClx/SAPO-5. The acidity of MClx/SAPO-5 is also affected by the type of metal chloride grafted. Thus, their catalytic behavior is evaluated in the acid-catalyzed acylation of 2-methylfuran under novel non-microwave instant heating conditions (90−110 °C, 0−20 min). ZnClx/SAPO-5, which has the largest amount of... [more]

Formaldehyde is an important industrial chemical that is a strong-smelling and colorless gas. It is used in a number of processes such as making household products and building materials, glues and adhesives, resins, certain insulation materials, etc. Formaldehyde can be produced industrially using air and methanol as raw materials in the presence of metal oxide catalyst or silver-based catalyst. The operating conditions and requirements of the process depend on the type of catalyst used. Therefore, a comparative study of both processes was conducted, and the results were compared. It was observed that the silver-based catalyst process has a compact plant size since the amount of air required is halved as compared to the metal oxide process. Thus, it appears that the silver-based catalyst process is more suitable for small-scale production due to its compact size and reduced utility cost.

Carbon dioxide (CO2) has been anticipated as an ideal carbon building block for organic synthesis due to the noble properties of CO2, which are abundant renewable carbon feedstock, non-toxic nature, and contributing to a more sustainable use of resources. Several green and proficient routes have been established for chemical CO2 fixation. Among the prominent routes, this review epitomizes the reactions involving cycloaddition of epoxides with CO2 in producing cyclic carbonate. Cyclic carbonate has been widely used as a polar aprotic solvent, as an electrolyte in Li-ion batteries, and as precursors for various forms of chemical synthesis such as polycarbonates and polyurethanes. This review provides an overview in terms of the reaction mechanistic pathway and recent advances in the development of several classes of catalysts, including homogeneous organocatalysts (e.g., organic salt, ionic liquid, deep eutectic solvents), organometallic (e.g., mono-, bi-, and tri-metal salen complexes a... [more]

We collected pine dust and Acacia tortilis samples from Zimbabwe and Botswana, respectively. We then pyrolyzed them in a bench-scale plant under varying conditions. This investigation aimed to determine an optimum temperature that will give result to maximum yield and quality of the bio-oil fraction. Our experimental results show that we obtain the maximum yield of the oil fraction at a pyrolysis temperature of 550 °C for the acacia and at 500 °C for the pine dust. Our results also show that we obtain an oil fraction with a heating value (HHV) of 36.807 MJ/kg using acacia as the feed material subject to a primary condenser temperature of 140 °C. Under the same pyrolysis temperature, we obtain an HHV value of 15.78 MJ/kg using pine dust as the raw material at a primary condenser temperature of 110 °C. The bio-oil fraction we obtain from Acacia tortilis at these condensation temperatures has an average pH value of 3.42 compared to that of 2.50 from pine dust. The specific gravity of the... [more]

Herein, the progress of nitrate removal by a heterotrophic culture in a batch reactor and continuous-flow fixed-biofilm reactor was examined. Two batch experiments for nitrate reduction with acetate degradation using 250 mL batch reactors with acclimated denitrifying biomass were conducted. The experimental results indicated that the nitrate was completely reduced; however, the acetate remained at a concentration of 280 mg/L from initial nitrate concentration of 100 mg/L. However, the acetate was fully biodegraded by the denitrifying biomass at an initial nitrate concentration of 300 mg/L. To evaluate the biokinetic parameters, the concentration data of nitrate, nitrite, acetate, and denitrifying biomass from the batch kinetic experiments were compared with those of the batch kinetic model system. A continuous-flow fixed-biofilm reactor was used to verify the kinetic biofilm model. The removal efficiency of nitrate in the fixed-biofilm reactor at the steady state was 98.4% accompanied... [more]

This paper investigates aquathermolysis of heavy oil in carbonate reservoir rocks from Boca de Jaruco, which is developed by the cyclic steam stimulation method. The nickel-based catalyst precursor was introduced in order to intensify the conversion processes of heavy oil components. The active form of such catalysts—nickel sulfides—are achieved after steam treatment of crude oil at reservoir conditions. The experiments were carried out on a rock sample extracted from the depth of 1900 m. Changes in composition and structure of heavy oil after the conversion were identified using SARA-analysis, Gas Chromatography-Mass Spectroscopy of saturated fractions, FTIR spectroscopy of saturated fractions, and MALDI of resins. It is revealed that catalyst particles provide a reduction in the content of resins and asphaltenes due to the destruction of carbon-heteroatom bonds. Moreover, the destruction of C=Carom. bonds and interactions with aromatic rings are heightened. In contrast, the results o... [more]

Dry reforming of CH4 was conducted over promoted Ni catalysts, supported on mesoporous gamma-alumina. The Ni catalysts were promoted by various metal oxides (CuO, ZnO, Ga2O3, or Gd2O3) and were synthesized by the incipient wetness impregnation method. The influence of the promoters on the catalyst stability, coke deposition, and H2/CO mole ratio was investigated. Stability tests were carried out for 460 min. The H2 yield was 87% over 5Ni+1Gd/Al, while the CH4 and CO2 conversions were found to decrease in the following order: 5Ni+1Gd/Al > 5Ni+1Ga/Al > 5Ni+1Zn/Al > 5Ni/Al > 5Ni+1Cu/Al. The high catalytic performance of 5Ni+1Gd/Al, 5Ni+1Ga/Al, and 5Ni+1Zn/Al was found to be closely related to their contents of NiO species, which interacted moderately and strongly with the support, whereas free NiO in 5Ni+1Cu/Al made it catalytically inactive, even than 5Ni/Al. The 5Ni+1Gd/Al catalyst showed the highest CH4 conversion of 83% with H2/CO mole ratio of ~1.0.

In this paper, the most important methods of thermal conversion of biomass, such as: hydrothermal carbonization (180−250 °C), torrefaction (200−300 °C), slow pyrolysis (carbonization) (300−450 °C), fast pyrolysis (500−800 °C), gasification (800−1000 °C), supercritical steam gasification, high temperature steam gasification (>1000 °C) and combustion, were gathered, compared and ranked according to increasing temperature. A comprehensive model of thermal conversion as a function of temperature, pressure and heating rate of biomass has been provided. For the most important, basic process, which is pyrolysis, five mechanisms of thermal decomposition kinetics of its components (lignin, cellulose, hemicellulose) were presented. The most important apparatuses and implementing devices have been provided for all biomass conversion methods excluding combustion. The process of combustion, which is energy recycling, was omitted in this review of biomass thermal conversion methods for two reasons.... [more]

The catalytic activity of the partial oxidation reforming reaction for hydrogen production over 10% Ni supported on high and low surface area alumina and zirconia was investigated. The reforming reactions, under atmospheric pressure, were performed with a feed molar ratio of CH4/O2 = 2.0. The reaction temperature was set to 450−650 °C. The catalytic activity, stability, and carbon formation were determined via TGA, TPO, Raman, and H2 yield. The catalysts were calcined at 600 and 800 °C. The catalysts were prepared via the wet-impregnation method. Various characterizations were conducted using BET, XRD, TPR, TGA, TPD, TPO, and Raman. The highest methane conversion (90%) and hydrogen yield (72%) were obtained at a 650 °C reaction temperature using Ni-Al-H-600, which also showed the highest stability for the ranges of the reaction temperatures investigated. Indeed, the time-on-stream for 7 h of the Ni-Al-H-600 catalyst displayed high activity and a stable profile when the reaction tempera... [more]

To improve the prevention of spontaneous coal combustion, reduced iron powder and other ingredients should be added together to form an iron-based deoxidizing inhibitor, with the dual effect of oxygen consumption and inhibition. The oxygen consumption rate of the inhibitor was studied through experiments. According to the theory of coordination resistance, the coordination resistance of Fe3+ was studied via the density functional method. Subsequently, a comparative experiment of the effects on spontaneous coal combustion was conducted. The research shows that several kinds of common resistance agents that are added to the reduced iron powder can consume oxygen. However, the rate of oxygen consumption varies. Fe3+ produced by the reduced iron powder indicates a strong coordination resistance. When compared with traditional inhibitors of Mg2+, Fe3+ has a stronger inhibition effect on the N, P, and S reactive groups in coal. The overall inhibitory effect is better than that of traditional... [more]

The small-scale rotating drum reactor (SS-RDR) was designed and constructed without using purge gas for the purpose of household application. The thermal and torrefaction characteristics of SS-RDR were studied and compared with other reactor types. It was found that the heat loss at the reactor wall and heat loss from exhaust gas of the SS-RDR were in the range of 6.3−12.4% and 27.9−42.8%, respectively. The increase of flue gas temperature resulted in the decrease of heat loss at the reactor wall and the increase of heat loss from exhaust gas. The heating rate of the SS-RDR was in the range of 7.3−21.4 °C/min. The higher heating value (HHV) ratio, mass yield, and energy yield ofthe SS-RDR were in the range of 1.2−1.6, 35.0−81.0%, and 56.2−96.5%, respectively. A comparison of torrefaction characteristics of various reactor types on HHV ratio-mass yield-iso-energy yield diagram indicated that the torrefaction characteristics of the SS-RDR were better than that of the rotating drum reacto... [more]

To achieve the efficient utilization of low-concentration mine gas, reduce resource waste and alleviate environmental pollution, the high-temperature oxidation of low-concentration gas at a concentration range of 1.00% to 1.50%, which is directly discharged into the atmosphere during coal mine production, was carried out to recover heat for reuse. The gas oxidation equipment was improved for the heating process and the safety of low-concentration gas oxidation under a high-temperature environment was evaluated. The experimental results showed that the reactor could provide a 1000 °C high-temperature oxidation environment for gas oxidation after installing high-temperature resistant ceramics. The pressure variation curves of the reactor with air and different concentrations of gas were similar. Due to the thermal expansion, the air pressure slightly increased and then returned to normal pressure. In contrast, the low-concentration gas exhibited a stable pressure response in the high-tem... [more]

In order to systematically elucidate the combustion performance of fuel during sintering, this paper explores the influence of three factors, namely coal substitution for coke, quasi-particle structure and the coupling effect with reduction and oxidation of iron oxide, on fuel combustion characteristics, and carries out the kinetic calculation of monomer blended fuel (MBF) and quasi-granular fuel (QPF). The results show that replacing coke powder with anthracite can accelerate the whole combustion process. MBF and QPF are more consistent with the combustion law of the double-parallel random pore model. Although the quasi-particle structure increases the apparent activation energy of fuel combustion, it can also produce a heat storage effect on fuel particles, improve their combustion performance, and reduce the adverse effect of diffusion on the reaction process. In the early stage of reaction, the coupling between combustion of volatiles and reduction of iron oxide is obvious. The oxi... [more]

This work reports the synthesis of natural zeolite-based silver and magnetite nanocomposites and their application for the catalytic oxidation of methylene blue in water. The zeolite was impregnated with 5.5 wt.% Fe in the form of magnetite nanoparticles with size of 32 nm, and with 6.4 wt.% Ag in the form of silver oxide and metallic silver nanoparticles with sizes of 42 and 20 nm, respectively. The results showed that physical adsorption contributed to the removal of methylene blue by 25−36% and that Fe3O4@NZU is superior to Ag2O@NZU and Ag0@NZU, leading to 55% removal without oxidant and 97% in the presence of H2O2. However, there is no evidence of significant mineralization of methylene blue. The application of reaction rate models showed that the reaction order changes from zero to first and second order depending on the H2O2 concentration.

Biomass is currently one of the world’s major renewable energy sources. Biomass in a powder form has been recently proposed as the most encouraging of biomass contours, especially because it burns like a gas. In the current study, biomass powder was examined, for the first time, as a direct solid fuel in internal combustion engines. The aim of the current study was to investigate modeling tools for simulation of biomass powder in combustion engines (CE). The biomass powder applied was in a micro-scale size with a typical irregular shape; the powder length was in the range of 75−5800 μm, and the diameter was in the range 30−1380 μm. Different mechanisms for biomass powder drying and devolatilization/gasification were proposed, including different schemes’ and mechanisms’ rate constants. A comparison between the proposed models and experiments was carried out and results showed good matching. Nevertheless, it is important that a biomass powder simulation addresses overlapping/complicated... [more]

The effect of magnesium chloride as an additive of hydrothermal carbonization (HTC) of lignocellulosic biomass (Pinus radiata sawdust) was studied. The HTC tests were carried out at fixed conditions of temperature and residence time of 220 °C and 1 h, respectively, and varying the dose of magnesium chloride in the range 0.0−1.0 g MgCl2/g biomass. The carbonized product (hydrochar) was tested in order to determine its calorific value (HHV) while using PARR 6100 calorimeter, mass yield by gravimetry, elemental analysis using a LECO TruSpec elemental analyzer, volatile matter content, and ash content were obtained by standardized procedures using suitable ovens for it. The results show that using a dose of 0.75 g MgCl2/g biomass results in an impact on the mass yield that was almost equal to change operating conditions from 220 to 270 °C and from 0.5 to 1 h, without additive. Likewise, the calorific value increases by 33% for this additive dose, resulting in an energy yield of 68%, thus g... [more]