Thermochemical process of biomass is being considered as a latest technique for the restoration of energy source and biochemical products. In this study, the influence of the different heating rates on pyrolysis behaviors and kinetic of jute stick were investigated to justify the waste jute stick biomass as a potential source of bioenergy. Pyrolysis experiments were carried out at four several heating rates of 10, 20, 30 and 40 °C/min, by utilizing the thermogravimetric analyzer (TG-DTA) and a fixed-bed pyrolysis reactor. Two different kinetic methods, Kissinger−Akahira−Sunose (KAS) and Ozawa−Flynn−Wall (OFW) were used to determine the distinct kinetic parameters. The experimental results showed that, the heating rates influenced significantly on the position of TG curve and maximum Tm peaks and highest decomposition rate of the jute stick biomass. Both the highest point of TG and the lowest point of Derivative thermogravimetry (DTG) curves were shifted towards the maximum temperature.... [more]

A computational methodology based on inverse modeling and metaheuristics is presented for determining the best parameters of kinetic models aimed to predict the behavior of biomass depolymerization processes during size scaling up. The Univariate Marginal Distribution algorithm, particle swarm optimization, and Interior-Point algorithm were applied to obtain the values of the kinetic parameters (KM and Vmax) of four mathematical models based on the Michaelis−Menten equation: (i) Traditional Michaelis−Menten, (ii) non-competitive inhibition, (iii) competitive inhibition, and (iv) substrate inhibition. The kinetic data were obtained from our own experimentation in micro-scale. The parameters obtained from an optimized micro-scale experiment were compared with a bench scale experiment (0.5 L). Regarding the metaheuristic optimizers, it is concluded that the Interior-Point algorithm is effective in solving inverse modeling problems and has the best prediction power. According to the result... [more]

Pyrolysis process has been considered to be an efficient approach for valorization of lignocellulosic biomass into bio-oil and value-added chemicals. Bio-oil refers to biomass pyrolysis liquid, which contains alkanes, aromatic compounds, phenol derivatives, and small amounts of ketone, ester, ether, amine, and alcohol. Lignocellulosic biomass is a renewable and sustainable energy resource for carbon that is readily available in the environment. This review article provides an outline of the pyrolysis process including pretreatment of biomass, pyrolysis mechanism, and process products upgrading. The pretreatment processes for biomass are reviewed including physical and chemical processes. In addition, the gaps in research and recommendations for improving the pretreatment processes are highlighted. Furthermore, the effect of feedstock characterization, operating parameters, and types of biomass on the performance of the pyrolysis process are explained. Recent progress in the identificat... [more]

The need for miniaturised reaction systems has led to the development of various microreactor platforms, such as droplet-based microreactors. However, these microreactors possess inherent drawbacks, such as rapid evaporation and difficult handling, that limit their use in practical applications. Liquid marbles are droplets covered with hydrophobic particles and are a potential platform that can overcome the weaknesses of bare droplets. The coating particles completely isolate the interior liquids from the surrounding environment, thus conveniently encapsulating the reactions. Great efforts have been made over the past decade to demonstrate the feasibility of liquid marble-based microreactors for chemical and biological applications. This review systemically summarises state-of-the-art implementations of liquid marbles as microreactors. This paper also discusses the various aspects of liquid marble-based microreactors, such as the formation, manipulation, and future perspectives.

Methane is activated at ambient conditions in a dielectric barrier discharge (DBD) plasma reactor packed with Pd/γ-alumina catalyst containing different loadings of Pd (0.5, 1, 5 wt%). Results indicate that the presence of Pd on γ-alumina substantially abates the formation of deposits, leads to a notable increase in the production of alkanes and olefins and additionally improves the energy efficiency compared to those obtained for the non-packed reactor and the bare γ-alumina packed reactor. A low amount of Pd (0.5 and 1 wt%) favors achieving a higher production of olefins (mainly C2H4 and C3H6) and a higher yield of H2. Increasing Pd loading to 5 wt% promotes the interaction of H2 and olefins, which consequently intensifies the successive hydrogenation of unsaturated compounds, thus incurring a higher production of alkanes (mainly C2H6 and C3H8). The substantial abatement of the deposits is ascribed to the role of Palladium in moderating the strength of the electric and shifting the r... [more]

In this study, electro-oxidation (EOx) and in situ generation of ferrate ions [Fe(VI)] were tested to treat water contaminated with Blue BR dye (BBR) using a boron-doped diamond (BDD) anode. Two electrolytic media (0.1 M HClO4 and 0.05 M Na2SO4) were evaluated for the BDD, which simultaneously produced oxygen radicals (•OH) and [Fe(VI)]. The generation of [Fe(VI)] was characterized by cyclic voltammetry (CV) and the effect of different current intensity values (e.g., 7 mA cm−2, 15 mA cm−2, and 30 mA cm−2) was assessed during BBR degradation tests. The discoloration of BBR was followed by UV-Vis spectrophotometry. When the EOx process was used alone, only 78% BBR discoloration was achieved. The best electrochemical discoloration conditions were found using 0.05 M Na2SO4 and 30 mA cm−2. Using these conditions, overall BBR discoloration values up to 98%, 95%, and 87% with 12 mM, 6 mM, and 1 mM of FeSO4, respectively, were achieved. In the case of chemical oxygen demand (COD) reduction, th... [more]

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]