ABSTRACT
Adsorptive-photocatalytic composites based on activated carbon (AC) and α-ferrous oxalate dihydrate (α-FOD) were synthesized by an original two-step method and subsequently used for the removal of phenol from aqueous solutions. To obtain the composites, ferrotitaniferous black mineral sands (0.6FeTiO3·0.4Fe2O3) were first dissolved in an oxalic acid solution at ambient pressure, and further treated under hydrothermal conditions to precipitate α-FOD on the AC surface. The ratio of oxalic acid to the mineral sand precursor was tuned to obtain composites with 8.3 and 42.7 wt.% of α-FOD on the AC surface. These materials were characterized by X-ray powder diffraction, scanning electron microscopy, and the nitrogen adsorption-desorption method. The phenol removal efficiency of the composites was determined during 24 h of adsorption under dark conditions, followed by 24 h of adsorption-photocatalysis under visible light irradiation. AC/α-FOD composites with 8.3 and 42.7 wt.% of α-FOD adsorbed 60% and 51% of phenol in 24 h and reached a 90% and 96% removal efficiency after 12 h of irradiation, respectively. Given its higher photocatalytic response, the 42.7 wt.% α-FOD composite was also tested during successive cycles of adsorption and adsorption-photocatalysis. This composite exhibited a reasonable level of cyclability (~99% removal after four alternated dark/irradiated cycles of 24 h and ~68% removal after three simultaneous adsorption-photocatalysis cycles of 24 h). The promising performance of the as-prepared composites opens several opportunities for their application in the effective removal of organic micropollutants from water.
ABSTRACT
Catalytic biomass pyrolysis is one of the most promising routes for obtaining bio-sustainable products that replace petroleum derivatives. This study evaluates the production of aromatic compounds (benzene, toluene, and xylene (BTX)) from the catalytic pyrolysis of lignocellulosic biomass (Pinus radiata (PR) and Eucalyptus globulus (EG)). Chilean natural zeolite (NZ) was used as a catalyst for pyrolysis reactions, which was modified by double ion exchange (H2NZ) and transition metals impregnation (Cu5H2NZ and Ni5H2NZ). The catalysts were characterized by nitrogen adsorption, X-ray diffraction (XRD), ammonium programmed desorption (TPD-NH3), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). Analytical pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS) allowed us to study the influence of natural and modified zeolite catalysts on BTX production. XRD analysis confirmed the presence of metal oxides (CuO and NiO) in the zeolite framework, and SEM-EDS confirmed successful metal impregnation (6.20% for Cu5H2NZ and 6.97% for Ni5H2NZ). Py-GC/MS revealed a reduction in oxygenated compounds such as esters, ketones, and phenols, along with an increase in aromatic compounds in PR from 2.92% w/w (without catalyst) to 20.89% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/5, and in EG from 2.69% w/w (without catalyst) to 30.53% w/w with Ni5H2NZ at a biomass/catalyst ratio of 1/2.5. These increases can be attributed to acidic sites within the catalyst pores or on their surface, facilitating deoxygenation reactions such as dehydration, decarboxylation, decarbonylation, aldol condensation, and aromatization. Overall, this study demonstrated that the catalytic biomass pyrolysis process using Chilean natural zeolite modified with double ion exchange and impregnated with transition metals (Cu and Ni) could be highly advantageous for achieving significant conversion of oxygenated compounds into hydrocarbons and, consequently, improving the quality of the condensed pyrolysis vapors.
ABSTRACT
Peanut shells' adsorption performance in caffeine and triclosan removal was studied. Peanut shells were analyzed for their chemical composition, morphology, and surface functional groups. Batch adsorption and fixed-bed column experiments were carried out with solutions containing 30 mg/L of caffeine and triclosan. The parameters examined included peanut shell particle size (120-150, 300-600, and 800-2000 µm), adsorbent dose (0.02-60 g/L), contact time (up to 180 min), bed height (4-8 cm), and hydraulic loading rate (2.0 and 4.0 m3/m2-day). After determining the optimal adsorption conditions, kinetics, isotherm, and breakthrough curve models were applied to analyze the experimental data. Peanut shells showed an irregular surface and consisted mainly of polysaccharides (around 70% lignin, cellulose, and hemicellulose), with a specific surface area of 1.7 m2/g and a pore volume of 0.005 cm3/g. The highest removal efficiencies for caffeine (85.6 ± 1.4%) and triclosan (89.3 ± 1.5%) were achieved using the smallest particles and 10.0 and 0.1 g/L doses over 180 and 45 min, respectively. Triclosan showed easier removal compared to caffeine due to its higher lipophilic character. The pseudo-second-order kinetics model provided the best fit with the experimental data, suggesting a chemisorption process between caffeine/triclosan and the adsorbent. Equilibrium data were well-described by the Sips model, with maximum adsorption capacities of 3.3 mg/g and 289.3 mg/g for caffeine and triclosan, respectively. In fixed-bed column adsorption tests, particle size significantly influenced efficiency and hydraulic behavior, with 120-150 µm particles exhibiting the highest adsorption capacity for caffeine (0.72 mg/g) and triclosan (143.44 mg/g), albeit with clogging issues. The experimental data also showed good agreement with the Bohart-Adams, Thomas, and Yoon-Nelson models. Therefore, the findings of this study highlight not only the effective capability of peanut shells to remove caffeine and triclosan but also their versatility as a promising option for water treatment and sanitation applications in different contexts.
Subject(s)
Arachis , Caffeine , Triclosan , Caffeine/chemistry , Caffeine/isolation & purification , Triclosan/chemistry , Triclosan/isolation & purification , Arachis/chemistry , Adsorption , Kinetics , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Particle Size , Water Purification/methodsABSTRACT
This article presents a set of experimental data on the mechanical and physical properties of the Ecuadorian endemic bamboo species Guadua angustifolia kunth (Guadua a.k.), specifically the "Caña Mansa" biotype. The data on compressive, shear, tensile and bending strength, as well as the moisture content and density, were obtained by carrying out the corresponding tests following the ISO 22157:2019 standard. For this purpose, each bamboo culm examined was divided along its height into three sections that were thoroughly characterized. The equations used for the calculations of the mechanical and physical properties are described in detail for each test. Besides, the main mechanical properties of the characterized bamboo were compared to those of similar species reported in the literature. Property charts (compressive/tensile strength and modulus of rupture vs. density) were built to compare the Ecuadorian biotype evaluated with other classical and green materials by using appropriate software. These data give an insight into the valorization of natural structural materials harvested in the Americas for potential applications in different engineering fields, particularly for sustainable building.
ABSTRACT
Pinus radiata (PR) and Eucalyptus globulus (EG) are the most planted species in Chile. This research aims to evaluate the pyrolysis behaviour of PR and EG from the Bío Bío region in Chile. Biomass samples were subjected to microwave pretreatment considering power (259, 462, 595, and 700 W) and time (1, 2, 3, and 5 min). The maximum temperature reached was 147.69 °C for PR and 130.71 °C for EG in the 700 W-5 min condition, which caused the rearrangement of the cellulose crystalline chains through vibration and an increase in the internal energy of the biomass and the decomposition of lignin due to reaching its glass transition temperature. Thermogravimetric analysis revealed an activation energy (Ea) reduction from 201.71 to 174.91 kJ·mol-1 in PR and from 174.80 to 158.51 kJ·mol-1 in EG, compared to the untreated condition (WOT) for the 700 W-5 min condition, which indicates that microwave pretreatment improves the activity of the components and the decomposition of structural compounds for subsequent pyrolysis. Functional groups were identified by Fourier transform infrared spectroscopy (FTIR). A decrease in oxygenated compounds such as acids (from 21.97 to 17.34% w·w-1 and from 27.72 to 24.13% w·w-1) and phenols (from 34.41 to 31.95% w·w-1 and from 21.73 to 20.24% w·w-1) in PR and EG, respectively, was observed in comparison to the WOT for the 700 W-5 min condition, after analytical pyrolysis. Such results demonstrate the positive influence of the pretreatment on the reduction in oxygenated compounds obtained from biomass pyrolysis.
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The study of new materials formulated using recycled polymers offers an ecological and sustainable alternative for the construction industry. In this work, we optimized the mechanical behavior of manufactured masonry veneers made from concrete reinforced with recycled polyethylene terephthalate (PET) from discarded plastic bottles. For this purpose, we used the response surface methodology to evaluate the compression and flexural properties. PET percentage, PET size and aggregate size were used as input factors in a Box-Behnken experimental design resulting in a total of 90 tests. The fraction of the commonly used aggregates replaced by PET particles was 15%, 20% and 25%. The nominal size of the PET particles used was 6, 8 and 14 mm, while the size of the aggregates was 3, 8 and 11 mm. The function of desirability was used to optimize response factorials. The globally optimized formulation contained 15% of 14 mm PET particles in the mixture, and 7.36 mm aggregates, obtaining important mechanical properties of this characterization of masonry veneers. The flexural strength (four-point) was 1.48 MPa, and the compression strength was 3.96 MPa; these values show property improvements of 110% and 94%, respectively, compared to commercial masonry veneers. Overall, this offers the construction industry a robust and environmentally friendly alternative.
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The development of sustainable, cost-efficient, and high-performance nanofluids is one of the current research topics within drilling applications. The inclusion of tailorable nanoparticles offers the possibility of formulating water-based fluids with enhanced properties, providing unprecedented opportunities in the energy, oil, gas, water, or infrastructure industries. In this work, the most recent and relevant findings related with the development of customizable nanofluids are discussed, focusing on those based on the incorporation of 2D (two-dimensional) nanoparticles and environmentally friendly precursors. The advantages and drawbacks of using 2D layered nanomaterials including but not limited to silicon nano-glass flakes, graphene, MoS2, disk-shaped Laponite nanoparticles, layered magnesium aluminum silicate nanoparticles, and nanolayered organo-montmorillonite are presented. The current formulation approaches are listed, as well as their physicochemical characterization: rheology, viscoelastic properties, and filtration properties (fluid losses). The most influential factors affecting the drilling fluid performance, such as the pH, temperature, ionic strength interaction, and pressure, are also debated. Finally, an overview about the simulation at the microscale of fluids flux in porous media is presented, aiming to illustrate the approaches that could be taken to supplement the experimental efforts to research the performance of drilling muds. The information discussed shows that the addition of 2D nanolayered structures to drilling fluids promotes a substantial improvement in the rheological, viscoelastic, and filtration properties, additionally contributing to cuttings removal, and wellbore stability and strengthening. This also offers a unique opportunity to modulate and improve the thermal and lubrication properties of the fluids, which is highly appealing during drilling operations.
ABSTRACT
Magnetic composites obtained by impregnation of lignocellulosic biomass with magnetite nanoparticles were used for zinc(II) removal from aqueous synthetic solutions. Laurel, canelo and eucalyptus sawdust, with a particle size between 74 and 150 µm were used as support. Structural and morphological examinations of the composites confirmed the presence of magnetite nanoparticles in the lignocellulosic support. Transmission Electron Microscopy showed nanoparticles with diameters of about 20 nm. The maximum removal efficiencies for 7 g L-1 of modified adsorbent were increased to 98.9, 98.8 and 97.6% for laurel, canelo and eucalyptus magnetic composites, respectively, in comparison to 60.9, 46.0 and 33.3%, for corresponding unmodified adsorbents. Adsorption data was analyzed using pseudo-first, pseudo-second order and intra-particle diffusion kinetic models and various isotherm models. The results determined that Freundlich isotherm fits the Zn ions adsorption on magnetite modified adsorbents while chemisorption and boundary diffusion were dominating the process.
ABSTRACT
The performance of fibrous membrane composites fabricated via electrospinning is strongly influenced by the solution's properties, process variables and ambient conditions, although a precise mechanism for controlling the properties of the resulting composite has remained elusive. In this work, we focus on the fabrication of electrospun poly(vinylpyrrolidone) (PVP) fibers, by varying both the polymer concentration and the mixture of ethanol (EtOH) and dimethylformamide (DMF) used as solvent. The impact of the solvent composition on the structural properties is assessed by a combined experimental and theoretical approach, employing scanning electron microscopy (SEM), differential scanning calorimetry (DSC), rheology, Fourier-transform infrared spectroscopy (FTIR) and stress-strain curves obtained from tensile tests to characterize the fibrous membranes produced, and density functional theory (DFT) calculations to explain the solvent's affect on PVP crystallization. We establish a morphological phase diagram, and propose a possible mechanism based on the measured fiber diameter distribution, the viscoelastic properties of the precursor solution, the correlation between the functional groups and the mechanical properties, the thermal transitions and the degree of crystallinity. We also employ DFT calculations to model the polymer coverage at equilibrium of a PVP polymer chain in the presence of EtOH/DMF solvent mixtures to corroborate the crucial role their îO or -OH groups play in achieving high PVP coverages and promoting the stability of the resulting fiber. These findings will be valuable to researchers interested in predicting, modulating, and controlling both a fiber's morphology and its concomitant physico-chemical properties.
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Persistent Organic Pollutants (POPs) have become a very serious issue for the environment because of their toxicity, resistance to conventional degradation mechanisms, and capacity to bioconcentrate, bioaccumulate and biomagnify. In this review article, the safety, regulatory, and remediation aspects of POPs including aromatic, chlorinated, pesticides, brominated, and fluorinated compounds, are discussed. Industrial and agricultural activities are identified as the main sources of these harmful chemicals, which are released to air, soil and water, impacting on social and economic development of society at a global scale. The main types of POPs are presented, illustrating their effects on wildlife and human beings, as well as the ways in which they contaminate the food chain. Some of the most promising and innovative technologies developed for the removal of POPs from water are discussed, contrasting their advantages and disadvantages with those of more conventional treatment processes. The promising methods presented in this work include bioremediation, advanced oxidation, ionizing radiation, and nanotechnology. Finally, some alternatives to define more efficient approaches to overcome the impacts that POPs cause in the hydric sources are pointed out. These alternatives include the formulation of policies, regulations and custom-made legislation for controlling the use of these pollutants.
Subject(s)
Environmental Pollutants , Pesticides , Food Chain , Humans , Persistent Organic Pollutants , Pesticides/analysis , SoilABSTRACT
The caffeine adsorptive performance and compatibility characteristics (Eisenia foetida Savigny) of rice husk, peanut shell, corn cob and coconut fiber were studied, aiming to assess the suitability of these residues for vermifilter beds. For this purpose, the agro-industrial residues were characterized and the E. foetida Savigny compatibility was determined by acute and chronic toxicity tests. Batch adsorption tests were performed using caffeine solutions. Optimal adsorption conditions, kinetic models, isotherm type and the influence of three particle sizes (120-150, 300-600, 800-2000 µm) in the caffeine removal were determined. Coconut fiber (120-150 µm) proved to be the most efficient residue for the caffeine removal (94.2%), requiring 4 g/L for 30 min. However, coconut fiber was the less compatible for earthworms (14d-LC50 = 82%). The results obtained allow to define adequate strategies, such as mixing highly adsorptive residues with the more compatible ones, to choose the most effective materials for vermifiltration technologies.
Subject(s)
Oligochaeta , Adsorption , Animals , Caffeine , Cocos , KineticsABSTRACT
Contamination of water by heavy metals is a major environmental concern due to the potential ecological impact on human health and aquatic ecosystems. In this work, we studied the chemical modification of various fruit peels such as banana (BP), granadilla (GP), and orange ones (OP) in order to obtain novel bio-adsorbents to improve the removal of Zn(II) ions from 50 mg·L-1 synthetic aqueous solutions. For this purpose, sodium hydroxide and calcium acetate were employed to modify the fruit peels. The moisture, extractives, lignin, hemicellulose, and cellulose contents of the raw materials were determined according to ASTM standards. The obtained bio-adsorbents were characterized by scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). The results showed the OP bio-adsorbents performed better, especially when the concentration of the modifier solutions increased, e.g., the OP particles modified using 0.8 M NaOH and Ca(CH3COO)2 solutions resulted in 97% removal of Zn(II) contaminating ions and reached a maximum adsorption capacity of 27.5 mg Zn per gram of bio-adsorbent. The adsorption processes were found to follow a pseudo-second order model. The error function sum of square error indicated the Freundlich isotherm (non-linear regression) as best fit model. The obtained results are particularly interesting for material selection in wastewater treatment technologies based on contaminant adsorption.
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Data revealing the phase and chemical compositions of natural black sands from "El Ostional" beach, located in the northern Ecuadorian Pacific coast have been presented. The samples were collected from six points over the shore area of approximately 500â¯×â¯40 m2. The data on crystalline phases (iron titanium oxide, orthoclase feldspar and zircon) were determined by X-ray powder diffraction (XRPD), while semi-quantitative chemical analyses of major (Fe and Ti) and trace elements were obtained by X-ray fluorescence spectroscopy (XRF). The phase composition was verified by scanning electron microscopy (SEM), using backscattered electron (BSE) mode and energy dispersive spectroscopy (EDS). These comprehensive data are a contribution to valorize ilmenite-hematite solid solutions from natural resources towards the identification of novel technological applications.
ABSTRACT
Aldehydes are commonly encountered Volatile Organic Compounds (VOCs) released to the atmosphere from a variety of anthropogenic sources. Based on the increasing interest in developing sustainable and environmentally friendly materials for the decontamination of VOCs, cellulose particles have emerged as one possible candidate, but there is a lack of understanding of the physicochemical properties affecting the adsorption of VOCs, and the effect of the extraction source on these intrinsic features. The present study was focused on the evaluation of unmodified cellulose particles extracted from biodiverse sources in Ecuador as potential VOC decontaminants. Modifications of the natural fibers with polyethylenimine (PEI) coating were performed to enhance the adsorption effectiveness. Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) measurements, and scanning electron microscopy (SEM) methods were used to characterize the physicochemical properties of the isolates. Gas chromatography assays demonstrated that unmodified cellulose can adsorb an aldehyde VOC, hexanal, reaching up to a 56.42 ± 7.30% reduction. Electrostatic coating of the cellulose particles with small quantities of PEI enhanced the VOC remediation capacities (i.e. 98.12 ± 1.18%). Results demonstrated that the biodiverse plant source of the cellulose isolate can affect the gas capturing properties, and that these particles can be an environmentally friendly solution for effective adsorption of VOC pollutants.