Biomass pyrolysis and polypropylene (PP) pyrolysis in a stirred tank reactor exhibited different heat transfer phenomena whereby heat transfer in biomass pyrolysis was driven predominantly by heat radiation and PP pyrolysis by heat convection. Therefore, co-pyrolysis could exhibit be expected to display various heat transfer phenomena depending on the feed composition. The objective of the present work was to determine how heat transfer, which was affected by feed composition, affected the yield and composition of the non-polar fraction. Analysis of heat transfer phenomena was based on the existence of two regimes in the previous research in which in regime 1 (the range of PP composition in the feeds is 0−40%), mass ejection from biomass particles occurred without biomass particle swelling, while in regime 2 (the range of PP composition in the feeds is 40−100%), mass ejection was preceded by biomass particle swelling. The co-pyrolysis was carried out in a stirred tank reactor with heat... [more]

Innovative nanofibrous membranes based on Pd/Au catalysts immobilized via electrospinning onto different polymers were engineered and tested in the selective oxidation of 5-(hydroxymethyl)furfural in an aqueous phase. The type of polymer and the method used to insert the active phases in the membrane were demonstrated to have a significant effect on catalytic performance. The hydrophilicity and the glass transition temperature of the polymeric component are key factors for producing active and selective materials. Nylon-based membranes loaded with unsupported metal nanoparticles were demonstrated to be more efficient than polyacrylonitrile-based membranes, displaying good stability and leading to high yield in 2,5-furandicarboxylic acid. These results underline the promising potential of large-scale applications of electrospinning for the preparation of catalytic nanofibrous membranes to be used in processes for the conversion of renewable molecules.

Photoelectrochemical production of hydrogen peroxide was studied by using a cell functioning with a WO3 photoanode and an air breathing cathode made of carbon cloth with a hydrophobic layer of carbon black. The photoanode functioned in the absence of any sacrificial agent by water splitting, but the produced photocurrent was doubled in the presence of glycerol or ethanol. Hydrogen peroxide production was monitored in all cases, mainly in the presence of glycerol. The presence or absence of the organic fuel affected only the obtained photocurrent. The Faradaic efficiency for hydrogen peroxide production was the same in all cases, mounting up to 74%. The duplication of the photocurrent in the presence of biomass derivatives such as glycerol or ethanol and the fact that WO3 absorbed light in a substantial range of the visible spectrum promotes the presently studied system as a sustainable source of hydrogen peroxide production.

A titanium nitride (TiN) coating using microwaves can be accomplished in air, and satisfies the required conditions of an on-demand TiN coating process. However, the coating mechanism using microwaves is not completely clear. In this study, to understand the detailed mechanism of microwave titanium nitridation in air, the quantity of nitrogen and oxygen in reacted TiN powder has been investigated by an inert melting method. Titanium powders were irradiated with microwaves by a multi-mode type 2.45 GHz microwave irradiation apparatus, while also being held at various temperatures for two different dwell times. X-ray diffraction (XRD) results revealed that nitridation of the powder progressed with increasing process temperature, and the nitridation corresponds to the powder color after microwave irradiation. The nitrogen contents of the samples increased with increasing processing temperature and dwell time, unlike oxygen. It is postulated that the reaction of convected air with titanium... [more]

The yield and composition of the biocrude obtained by hydrothermal liquefaction (HTL) of Nannocloropsis gaditana using heterogeneous catalysts were evaluated. The catalysts were based on metal oxides (CaO, CeO2, La2O3, MnO2, and Al2O3). The reactions were performed in a batch autoclave reactor at 320 °C for 10 min with a 1:10 (wt/wt) microalga:water ratio. These catalysts increased the yield of the liquefaction phase (from 94.14 ± 0.30 wt% for La2O3 to 99.49 ± 0.11 wt% for MnO2) as compared with the thermal reaction (92.60 ± 1.20 wt%). Consequently, the biocrude yields also raised in the metal oxides catalysed HTL, showing values remarkably higher for the CaO (49.73 ± 0.9 wt%) in comparison to the HTL without catalyst (42.60 ± 0.70 wt%). The N and O content of the biocrude obtained from non-catalytic HTL were 6.11 ± 0.02 wt% and 10.50 ± 0.50 wt%, respectively. In this sense, the use of the metal oxides decreased the N content of the biocrude (4.62 ± 0.15−5.45 ± 0.11 wt%), although, the... [more]

The aim of the work is a comparison of two combustion systems of fuels with different reactivity. The first is combustion of the fuel mixture and the second is combustion in a dual-fuel engine. Diesel fuel was burned with pure ethanol. Both methods of co-firing fuels have both advantages and disadvantages. Attention was paid to the combustion stability aspect determined by COVIMEP as well as the probability density function of IMEP. It was analyzed also the spread of the maximum pressure value, the angle of the position of maximum pressure. The influence of ethanol on ignition delay time spread and end of combustion process was evaluated. The experimental investigation was conducted on 1-cylinder air cooled compression ignition engine. The test engine operated with constant rpm equal to 1500 rpm and constant angle of start of diesel fuel injection. The engine was operated with ethanol up to 50% of its energy fraction.

This work investigated quality properties of pellets of raw cassava rhizome (P-RC), pellets of pelletized cassava rhizome followed by torrefaction (T-CP), and pellets of torrefied cassava rhizome followed by pelletizing (P-TC). Torrefaction was conducted at temperatures of 230, 250, and 280 °C for 30 min. Pyrolysis characteristics of T-CP and P-TC at torrefied temperatures of 230 and 250 °C were studied using thermogravimetric analysis. It was found that at the similar torrefied temperature, P-TC had a higher bulk density, energy density, and pellet durability than that of T-CP and P-RC while T-CP had a higher HHV and moisture absorption than P-TC and P-RC. The bulk density of P-TC was 1.13−1.19 and 1.33−1.52 times higher than that of P-RC and T-CP, respectively. The HHV of T-CP was 1.07 and 1.29 times higher than P-TC and P-RC, respectively. The energy density of P-TC was 1.24−1.56 and 1.20−1.41 times higher than that of P-RC and T-CP. In terms of Pellet Fuel Institute (PFI) standard,... [more]

Fenton reactions that involve nano zero-valent iron (nZVI) have shown high promise in the removal of organic pollutants. In this work, nZVI stabilized with carboxymethyl cellulose (CMC) was evaluated for drimaren red X-6BN (DRX-6BN, 10 mg/L) and bisphenol-a (BPA, 800 mg/L) removal. Oxidation reactions were conducted for removal of both compounds by varying nZVI/CMC concentration (0.01−5 g/L), hydrogen peroxide (H2O2, 0.01−0.1 g/L), and pH (3−9). DRX-6BN degradation rate was the highest (kinetic constant (kobs) = 4.622 h−1) when working at pH 3 and 3 g/L of nZVI/CMC. Increasing H2O2 concentration could not improve the reaction. For BPA, all the conditions tested showed removals of more than 96% with 0.02 g/L of H2O2. This result was compared with the activity of nZVI loaded in hydrophilic PVDF (Polyvinylidene fluoride) membranes by polyacrylic acid (PAA) to entrap nanoparticles to the membrane surface. As expected, the attachment of nZVI onto the membranes diminished nanoparticles’ acti... [more]

A kinetic model for the dithiolactone-mediated radical polymerization of vinyl monomers based on the persistent radical effect and reversible addition (negligible fragmentation) was used to calculate the polymerization rate and describe molar mass development in the polymerization of methyl methacrylate at 60 °C, using 2,2-azobisisobutyronitrile (AIBN) as an initiator, as well as dihydro-5-phenyl-2(3H)-thiophenethione (DTL1) and dihydro-2(3H)-thiophenethione (DTL2) as controllers. The model was implemented in the PREDICI commercial software. A good agreement between experimental data and model predictions was obtained.

Companies in the field of the collection and treatment of waste cooking oils (WCO) for subsequent biodiesel production usually have to cope with high acidity oils, which cannot be directly transformed into fatty acid methyl esters due to soap production. Since glycerine is the main byproduct of biodiesel production, these high acidity oils could be esterified with the glycerine surplus to transform the free fatty acids (FFA) into triglycerides before performing the transesterification. In this work, commercial glycerol was esterified with commercial fatty acids and commercial fatty acid/lampante olive oil mixtures over tin (II) chloride. In the first set of experiments, the esterification of linoleic acid with glycerol excess from 20 to 80% molar over the stoichiometric was performed. From 20% glycerol excess, there was no improvement in FFA reduction. Using 20% glycerol excess, the performance of a biochar obtained from heavy metal-contaminated plant roots was compared to that of SnCl... [more]

The commercial COCO simulation program was used to mimic the experimental slow pyrolysis process of five different biomasses based on thermodynamic consideration. The program generated the optimum set of reaction kinetic parameters and reaction stoichiometric numbers that best described the experimental yields of solid, liquid and gas products. It was found that the simulation scheme could predict the product yields over the temperature range from 300 to 800 °C with reasonable accuracy of less than 10% average error. An attempt was made to generalize the biomass pyrolysis behavior by dividing the five biomasses into two groups based on the single-peak and two-peak characteristics of the DTG (derivative thermogravimetry) curves. It was found that this approximate approach was able to predict the product yields reasonably well. The proposed simulation method was extended to the analysis of slow pyrolysis results derived from previous investigations. The results obtained showed that the p... [more]

Biomass pyrolysis and the valorization of co-products (biochar, bio-oil, syngas) could be a sustainable management solution for agricultural and forest residues. Depending on its properties, biochar amended to soil could improve fertility. Moreover, biochar is expected to mitigate climate change by reducing soil greenhouse gas emissions, if its C/N ratio is lower than 30, and sequestrating carbon if its O/Corg and H/Corg ratios are lower than 0.2 and 0.7, respectively. However, the yield and properties of biochar are influenced by biomass feedstock and pyrolysis operating parameters. The objective of this research study was to validate an approach based on the response surface methodology, to identify the optimal pyrolysis operating parameters (temperature, solid residence time, and carrier gas flowrate), in order to produce engineered biochars for carbon sequestration. The pyrolysis of forest residues, switchgrass, and the solid fraction of pig manure, was carried out in a vertical au... [more]

In this work, the liquid phase hydrogenation of furfural has been studied using a biochar-supported platinum catalyst in a batch reactor. Reactions were performed between 170 °C and 320 °C, using 3 wt % and 5 wt % of Pt supported on a maple-based biochar under hydrogen pressure varying from 500 psi to 1500 psi for reaction times between 1 h and 6 h in various solvents. Under all reactive conditions, furfural conversion was significant, whilst under specific conditions furfuryl alcohol (FA) was obtained in most cases as the main product showing a selectivity around 80%. Other products as methylfuran (MF), furan, and trace of tetrahydrofuran (THF) were detected. Results showed that the most efficient reaction conditions involved a 3% Pt load on biochar and operations for 2 h at 210 °C and 1500 psi using toluene as solvent. When used repetitively, the catalyst showed deactivation although only a slight variation in selectivity toward FA at the optimal experimental conditions was observed.

In this work, the characteristics of waste pig fat degradation using supercritical alcohols have been studied. Comparative analysis of the influence of supercritical methanol and supercritical ethanol as solvents on the transesterification was the primary focus of this research. The experiments were carried out with waste pig fat to alcohol weight ratios of 1:1.5 (molar ratio: 1:40.5 for methanol and 1:28 for ethanol), 1:2.0 (molar ratio: 1:54 for methanol and 1:37.5 for ethanol) and 1:2.5 (molar ratio: 1:67.5 for methanol and 1:47 for ethanol) at transesterification temperatures 250, 270 and 290 °C for holding time 0, 15, 30, 45 and 60 min. Increase in the transesterification and holding time increased the conversion while increase in alcohol amount from 1:1.5 to 1:2.0 and 1:2.5 had minimal effect on the conversion. Further, majority of the ester composition in using SCM as solvent falls in the carbon range of C17:0, C19:1 and C19:2 while that for SCE falls in the carbon range of C18:... [more]

Cocoa bean roasting allows for reactions to occur between the characteristic aroma and taste precursors that are involved in the sensory perception of chocolate and cocoa by-products. This work evaluates the moisture kinetics of cocoa beans during the roasting process by applying empirical and semi-empirical exponential models. Four roasting temperatures (100, 140, 180, and 220 °C) were used in a cylindrically designed toaster. Three reaction kinetics were tested (pseudo zero order, pseudo first order, and second order), along with 10 exponential models (Newton, Page, Henderson and Pabis, Logarithmic, Two-Term, Midilli, Verma, Diffusion Approximation, Silva, and Peleg). The Fick equation was applied to estimate the diffusion coefficients. The dependence on the activation energy for the moisture diffusion process was described by the Arrhenius equation. The kinetic parameters and exponential models were estimated by non-linear regression. The models with better reproducibility were the... [more]

Reversible addition−fragmentation chain−transfer (RAFT) polymerization of methyl methacrylate (MMA) is modeled and monitored using a multi-rate multi-delay observer in this work. First, to fit the RAFT reaction rate coefficients and the initiator efficiency in the model, in situ 1 H nuclear magnetic resonance (NMR) experimental data from small-scale (400 mL) reflux reactions is then used to validate the fitted model. The fitted model accurately predicts the polymer properties of the large-scale reactions with slight discordance at late reaction times. Based on the fitted model, a multi-rate multi-delay observer coupled with an inter-sample predictor and dead time compensator is designed, to account for the asynchronous multi-rate measurements with non-constant delays. The multi-rate multi-delay observer shows perfect convergence after a few sampling times when tested against the fitted model, and is in fair agreement with the real data at late reaction times when implemented ba... [more]

The present work discusses the adsorptive removal of a phenolic pollutant, i.e., 2,4,6-trichlorophenol (TCP), using low cost untreated agricultural waste pine cone powder (PCP). The present biosorbent was thoroughly characterized with the help of FTIR, SEM, XRD, and CHN analysis. The presence of amine (-NH2), hydroxyl (-OH) and carbonyl (C=O) functional groups was detected by the FTIR analysis. The important biosorption factors like agitation time, biomass dosage, initial adsorbate concentration, and the initial pH were examined by batch studies. The biosorption kinetic process was fast, reaching equilibrium in 75 min. The experimental kinetic data revealed an excellent agreement with the pseudo second order (PSO) model. On the other hand, the Langmuir isotherm model best described the equilibrium data with the maximum biosorption capacity (qmax) of 243.90 mg/g. These values are better than the adsorption capacities of most agro-based untreated adsorbents previously reported in the lit... [more]

The effects of ultrasonic and ozonation pretreatments on organic solubilization, anaerobic biodegradability, and biogas production were elucidated in this study. Two pretreatment methods for batch anaerobic digestion for biogas recovery with the same material and experimental conditions were the focus for comparison. Anaerobic digestion experiments were conducted at ambient temperature with the solid retention time set to 25 days. The obtained results indicated that the soluble chemical oxygen demand increased from 0.344 without pretreatment to 1.023 and 1.228 g/L with ultrasound and ozone pretreatments, respectively, whereas the yields of biogas production in the 25 days increased by 32.3 and 52.9% via ultrasonic irradiation and ozonation relative to the control case, respectively. The biodegradability of the organic compounds of the samples for the cases of ultrasound, ozone pretreatments, and control achieved 55.9, 64.31, and 39.18%, respectively, in terms of chemical oxygen demand... [more]

Iron ore was studied as a CO2 absorbent. Carbonation was carried out by mechanochemical and high temperature−high pressure (HTHP) reactions. Kinetics of the carbonation reactions was studied for the two methods. In the mechanochemical process, it was analyzed as a function of the CO2 pressure and the rotation speed of the planetary ball mill, while in the HTHP process, the kinetics was studied as a function of pressure and temperature. The highest CO2 capture capacities achieved were 3.7341 mmol of CO2/g of sorbent in ball milling (30 bar of CO2 pressure, 400 rpm, 20 h) and 5.4392 mmol of CO2/g of absorbent in HTHP (50 bar of CO2 pressure, 100 °C and 4 h). To overcome the kinetics limitations, water was introduced to all carbonation experiments. The calcination reactions were studied in Argon atmosphere using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis. Siderite can be decomposed at the same temperature range (100 °C to 420 °C) for the samples... [more]

Sugarcane juice is a perishable food with a good nutritional profile. Thus, there is a need to increase its shelf life by reducing water content which facilitates storage and transportation. In this study, process conditions were optimized to concentrate the sugarcane juice at various microwave powers (30, 50, 80, 100 W). A central composite design was applied to optimize the process conditions (power and time). The overall evaporation time depends on microwave powers; increase in power reduced the processing time. The results showed that at 100 W sugarcane juice was concentrated to 75° brix for 15 min which reduced the energy consumption to 1.3 times compared to other powers. Moreover, microwave processing better retained the sensory properties of concentrate and preserved its antioxidant activity. Thus, 100 W was most energy efficient in concentrating sugarcane juice. In general, microwave processing reduced the processing time and cost making it a sustainable approach to concentrate... [more]

Fuel resource diversification is a global effort to deviate from non-renewable fossil fuels. Biomass has been identified as an alternative solid biofuel source due to its desirable properties and carbon neutrality. As reported in the literature, biomass can positively contribute towards combating climate change while providing alleviation for energy security issue. As part of efforts to diversify biomass resources, this work intends to explore the potential of Napier grass, one type of energy crop, for the production of renewable syngas via gasification. This energy crop is originally from Africa, which is highly productive with low cost (40 tonnes per year per hectare). Limited studies were conducted to analyze the potential of such an energy crop as a fuel source, which is the subject of this work. In order to analyze the full potential of such energy crop, the physical and chemical characteristics of this biomass was first analyzed. To determine the productivity of syngas from this... [more]

Styrene is one of the most important monomers utilized in the synthesis of various polymers. Nevertheless, during distillation, storage, and transportation of ST, undesired polymer (i.e., UP) formation can take place. Thus, the control of undesired polymerization of styrene is a challenging issue facing industry. To tackle the mentioned issue, the antipolymer and antioxidant activity of stable nitroxide radicals (i.e., SNRs) and phenolics in styrene polymerization were studied by density functional theory (DFT) calculation and experimental approach. The electrophilicity index and growth percentage have been determined by DFT calculation and experimental approach, respectively. It is depicted that 2,6-di-tert-butyl-4-methoxyphenol (DTBMP) and 2,6-di-tert-butyl-4-methylphenol (BHT) from phenolics, and 4-hydroxy-2,2,6,6-tetramethyl piperidine 1-Oxyl (4-hydroxy-TEMPO) and 4-oxo-2,2,6,6-tetramethylpiperidine 1-Oxyl (4-oxo-TEMPO) from stable nitroxide radicals were the most effective inhibit... [more]

Microwave-assisted pyrolysis is a promising thermochemical technique to convert waste polymers and biomass into raw chemicals and fuels. However, this process involves several issues related to the interactions between materials and microwaves. Consequently, the control of temperature during microwave-assisted pyrolysis is a hard task both for measurement and uniformity during the overall pyrolytic run. In this review, we introduce some of the main theoretical aspects of the microwaves−materials interactions alongside the issues related to microwave pyrolytic processability of materials.

The in-depth understanding of the gas−solid flow and reaction behaviors, and their coupling characteristics during the chemical looping combustion (CLC) process has the guiding significance for the operation and optimization of a chemical looping combustor. A three-dimensional numerical model is applied to investigate the char-fueled CLC characteristics in a fuel reactor for efficient CO2 separation and capture. Simulations are carried out in a bubbling fluidized bed fuel reactor with a height of 2.0 m and a diameter of 0.22 m. The initial bed height is 1.1 m, and hence the height−diameter ratio of the slumped bed is five. The oxygen carrier is prepared with 14 wt% of CuO on 86 wt% of inert Al2O3. In the process of mathematical modeling, a Eulerian-Eulerian two-fluid model is adopted for both of the gas and solid phases. Gas turbulence is modeled on the basis of a k−ε turbulent model. The reaction kinetics parameters are addressed based upon previous experimental investigations from li... [more]

Sodium dodecyl sulfate (SDS) is a well-known surfactant, which can accelerate methane hydrate formation. In this work, methane hydrate formation kinetics were studied in the presence of SDS using a rocking cell apparatus in both temperature-ramping and isothermal modes. Ramping and isothermal experiments together suggest that SDS concentration plays a vital role in the formation kinetics of methane hydrate, both in terms of induction time and of final gas uptake. There is a trade-off between growth rate and gas uptake for the optimum SDS concentration, such that an increase in SDS concentration decreases the induction time but also decreases the gas storage capacity for a given volume. The experiments also confirm the potential use of the rocking cell for investigating hydrate promoters. It allows multiple systems to run in parallel at similar experimental temperature and pressure conditions, thus shortening the total experimentation time. Understanding methane hydrate formation and st... [more]