Novel biochar and hydrochar for the adsorption of 2-nitrophenol from aqueous solutions: An approach using the PVSDM model.

Two new adsorbents, namely avocado-based hydrochar and LDH/bone-based biochar, were developed, characterized, and applied for adsorbing 2-nitrophenol. The pore volume and surface diffusion model (PVSDM) was numerically solved for different geometries and applied to interpret the adsorption decay curves. Both adsorbents presented interesting textural and physicochemical characteristics, which achieved maximum adsorption capacities of 761 mg/g for biochar and 562 mg/g for hydrochar. The adsorption equilibrium data were well fitted by Henry isotherm. Besides, thermodynamic investigation revealed endothermic adsorption with the occurrence of electrostatic interactions. PVSDM predicted the adsorption decay curves for different adsorbent geometries at different initial concentrations of 2-nitrophenol. The surface diffusion was the main intraparticle mass transport mechanism. Furthermore, the external mass transfer and surface diffusion coefficients increased with the increase of 2-nitrophenol concentration.

Conversion of MDF wastes into a char with remarkable potential to remove Food Red 17 dye from aqueous effluents.

Medium density fiberboard (MDF) wastes were converted into an efficient char able to uptake Food Red 17 dye (FR17) from colored effluents. The yield of the pyrolysis process, in terms of char, was 29%. The produced char presented micro and mesoporous, with surface area of 218.8 m2 g-1 and total pore volume of 0.122 cm3 g-1. Regarding to the FR17 adsorption, removal percentages of 90% were found at pH 2 and using 0.5 g L-1 of char. Pseudo-first and pseudo-second order models were adequate to represent the adsorption kinetic profile, being the equilibrium reached within 20 min. Freundlich model was selected to represent the equilibrium data. The maximum adsorption capacity was 210 mg g-1. The adsorption of FR17 on the char was endothermic and physical in nature. The char was efficient for 8 adsorption-desorption cycles, maintaining the same adsorption capacity. In brief, this work demonstrated a useful practice in terms of cleaner production. It was possible add value to MDF wastes, generating an efficient and reusable adsorbent to treat colored effluents containing FR 17 dye.

Single and competitive dye adsorption onto chitosan-based hybrid hydrogels using artificial neural network modeling.

Chitosan-based hybrid hydrogels such as chitosan hydrogel (CH), chitosan hydrogel with activated carbon (CH-AC), scaffold-chitosan hydrogel (SCH), scaffold-chitosan hydrogel with activated carbon (SCH-AC) and scaffold-chitosan hydrogel with carbon nanotubes (SCH-CN) were synthesized, characterized and applied to adsorb Acid Blue 9 (AB) and Allura Red AC (AR) from single and simultaneous binary liquid systems. Experimental results revealed competitive adsorption as the adsorption capacity was reduced in binary system for each dye. In addition, SCH-CN presented the highest adsorption capacity for both dyes, indicating that the modification increased the number of active sites and the functionalization with OH groups favored the interactions with sulfonated groups of the dyes. A predictive artificial neural network (ANN) was implemented to forecast the adsorption capacity for AB and AR dyes as a function of initial molar concentration of each dye, adsorption time, porosity and mass percentage of carbonaceous material on each hydrogel. The network was trained with the Levenberg-Marquardt back-propagation optimization, and according to the high correlation coefficient (R = 0.9987) and low values of root mean square error (RMSE = 0.0119), sum of the absolute error (SAE = 0.7541) and sum of squares error (SSE = 0.0132), the best topology was found to be 5-10-10-10-2. The ANN proved to be effective in predicting dye adsorption capacity of each hydrogel, even for the competitive adsorption, as the R values were close to unity for all simulation systems.

Adsorption of methylene blue on agroindustrial wastes: Experimental investigation and phenomenological modelling.

In this work, agro-wastes coming from soursop (peel, seeds and pulp fiber) and sugarcane (bagasse) are used as low-cost biosorbents to remove methylene blue (MB) from aqueous media. Batch experiments are performed under different experimental conditions investigating the effects of biosorbent amount, dye concentration and stirring rate. The best results were found using soursop wastes for a MB concentration of 100 mg L-1, using 0.75 g of residue and a stirring rate of 110 rpm, removing a percentage above 90%. Theoretically, adsorption kinetic can be successfully described by the pseudo-second order model. Redlich-Peterson and Sips models are adopted to interpret the equilibrium adsorption of MB on sugarcane bagasse and soursop residue, respectively. Interestingly, the monolayer model with single energy derived by statistical physics theory is also applied for a deeper explanation of the adsorption mechanism of MB on both the adsorbents. The application of this model allows defining the adsorption geometry of the investigated adsorbate and provides important information about the interactions between the adsorbate and sorbents. In particular, the modelling analysis by statistical physics allows defining that the dye molecules are adsorbed in vertical position and the adsorption process is multi-molecular (i.e. n > 1). Finally, the estimation of adsorption energy suggested that MB adsorption on biosorbent is a physisorption process.

Adsorption of crystal violet dye onto a mesoporous ZSM-5 zeolite synthetized using chitin as template.

HYPOTHESIS: ZSM-5 zeolite is an efficient adsorbent for several compounds. However, is a microporous material, and consequently, is little efficient for large dye molecules. In order to make ZSM-5 zeolite a mesoporous material with ability to adsorb dyes, the use of chitin (low-cost biopolymer) as template in the synthesis route can be an alternative. EXPERIMENTS: ZSM-5 zeolites were synthetized using a nucleating gel as structure-directing agent for the material formation, followed by the chitin insertion (or not), homogenization and hydrothermal treatment. The obtained zeolites (ZSM-5 and chitin/ZSM-5) from these different methods were characterized. The potential of ZSM-5 and chitin/ZSM-5 zeolites to adsorb crystal violet dye (CV) was evaluated in batch mode, considering the effects of adsorbent dosage and pH. Equilibrium, thermodynamic and kinetic studies were also performed. FINDINGS: The use of chitin in the synthesis route provided the following improvements on the ZSM-5 structure: (i) the mesopores volume increased from 0.027 (ZSM-5) to 0.142cm3g-1 (chitin/ZSM-5); (ii) the pore diameter increased from 1.97 (ZSM-5) to 22.49nm (chitin/ZSM-5); (iii) the porosity was increased and the crystallinity was decreased. For both, ZSM-5 and chitin/ZSM-5, the CV adsorption was favored with adsorbent dosage of 2.0gL-1 and pH of 7.5. The pseudo-second order model was suitable to represent the adsorption kinetics and, the Langmuir model was adequate to represent the equilibrium. The maximum adsorption capacity increased from 141.8 (ZSM-5) to 1217.3mgg-1 (chitin/ZSM-5). The adsorption was spontaneous, favorable and endothermic.

Mesoporous Nb2O5/SiO2 material obtained by sol-gel method and applied as adsorbent of crystal violet dye.

In this work, SiO2/Nb2O5 (SiNb) material was prepared using sol-gel method and employed as adsorbent for removal of crystal violet dye (CV). The material was characterized using nitrogen adsorption-desorption isotherms, FTIR spectroscopy, pHpzc, and SEM-EDS. The analysis of N2 isotherms revealed the presence of micro- and mesopores in the SiNb sample with specific surface area as high as 747 m2 g-1. For the CV adsorption process, variations of several parameters such as of pH, temperature, contact time, and concentration of dye of the process were evaluated. The optimum initial pH of the CV dye solution was 7.0. The adsorption kinetic and equilibrium data for CV adsorption were suitably represented by the general-order and Liu models, respectively. The maximum adsorption capacity of the CV dye by SiNb was achieved at 303 K, which attained 116 mg g-1 at this temperaure. Dye effluents were simulated and used to check the applicability of the SiNb material for treatment of effluents - the material showed very good efficiency for decolorization of dye effluents.

Adsorption of Methylene Blue by ultrasonic surface modified chitin.

HYPOTHESIS: Chitin is a biopolymer which can be used as a low-cost and eco-friendly material for dyes adsorption. The use of chitin for dyes removal is little investigated, due its low surface area, porosity and high crystallinity. So, an ultrasonic surface modified chitin (USM-chitin) was prepared and used for Methylene Blue (MB) adsorption. EXPERIMENTS: Chitin was obtained from shrimp wastes and its surface was modified by an ultrasound-assisted treatment. USM-chitin was characterized by N2 adsorption/desorption isotherms (BET surface area, total pore volume), infrared spectroscopy, X-ray diffraction and scanning electron microscopy. The adsorption of MB on USM-chitin was studied by kinetic, equilibrium, thermodynamic, interactions analysis, desorption and mass transfer aspects. FINDINGS: USM-chitin presented surface area 25 times higher than raw chitin. The porosity was increased and the crystallinity was decreased. The general order model was suitable to represent the adsorption kinetics and the Langmuir model was adequate for the equilibrium. The maximum adsorption capacity was 26.69 mg g(-1). The adsorption was spontaneous, favorable and exothermic. USM-chitin can be used seven times maintaining the same adsorption capacity.

Microwave-assisted activated carbon from cocoa shell as adsorbent for removal of sodium diclofenac and nimesulide from aqueous effluents.

Microwave-induced chemical activation process was used to prepare an activated carbon from cocoa shell for efficient removal of two anti-inflammatories, sodium diclofenac (DFC) and nimesulide (NM), from aqueous solutions. A paste was obtained from a mixture of cocoa shell and inorganic components; with a ratio of inorganic: organic of 1 (CSC-1.0). The mixture was pyrolyzed in a microwave oven in less than 10 min. The CSC-1.0 was acidified with a 6 mol L(-1) HCl under reflux to produce MWCS-1.0. The CSC-1.0 and MWCS-1.0 were characterized using FTIR, SEM, N2 adsorption/desorption curves, X-ray diffraction, and point of zero charge (pHpzc). Experimental variables such as initial pH of the adsorbate solutions and contact time were optimized for adsorptive characteristics of MWCS-1.0. The optimum pH for removal of anti-inflammatories ranged between 7.0 and 8.0. The kinetic of adsorption was investigated using general order, pseudo first-order and pseu do-second order kinetic models. The maximum amounts of DCF and NM adsorbed onto MWCS-1.0 at 25 °C are 63.47 and 74.81 mg g(-1), respectively. The adsorbent was tested on two simulated hospital effluents. MWCS-1.0 is capable of efficient removal of DCF and NM from a medium that contains high sugar and salt concentrations.

Preparation of nanoemulsions containing unsaturated fatty acid concentrate-chitosan capsules.

HYPOTHESIS: Fish oil is rich in unsaturated fatty acids (ω-3), which are highly susceptible to oxidative degradation. The use of encapsulation process to retard the fatty acid oxidation is an interesting alternative. In this work, nanoemulsions containing capsules of unsaturated fatty acids concentrate (UFAC) using chitosan as wall material were prepared and characterized. EXPERIMENTS: The UFAC were obtained from carp viscera and chitosan was obtained from shrimp wastes. The nanocapsules were prepared by the emulsion method. Four formulations were tested, using different combinations of chitosan concentration and homogenization times. In the more suitable conditions, the emulsion was freeze-dried to obtain a microstructure with capacity to increase the capsules stability. FINDINGS: The results showed that the nanocapsules presented a spherical shape. The use of low wall material concentration and high homogenization time provided nanocapsules with smallest size (332 nm) and lowest polydispersity index (0.214). The microstructure obtained by freeze drying was irregular and porous. The peroxide values demonstrated that the microstructure was able to protect the UFAC regarding to primary oxidation. The encapsulation efficiency was 74.1%, showing that chitosan has potential to be used as encapsulating agent for unsaturated fatty acid concentrate (UFAC).

New physicochemical interpretations for the adsorption of food dyes on chitosan films using statistical physics treatment.

In this work, statistical physics treatment was employed to study the adsorption of food dyes onto chitosan films, in order to obtain new physicochemical interpretations at molecular level. Experimental equilibrium curves were obtained for the adsorption of four dyes (FD&C red 2, FD&C yellow 5, FD&C blue 2, Acid Red 51) at different temperatures (298, 313 and 328 K). A statistical physics formula was used to interpret these curves, and the parameters such as, number of adsorbed dye molecules per site (n), anchorage number (n'), receptor sites density (NM), adsorbed quantity at saturation (N asat), steric hindrance (τ), concentration at half saturation (c1/2) and molar adsorption energy (ΔE(a)) were estimated. The relation of the above mentioned parameters with the chemical structure of the dyes and temperature was evaluated and interpreted.

Chitosan scaffold as an alternative adsorbent for the removal of hazardous food dyes from aqueous solutions.

HYPOTHESIS: The dye adsorption with chitosan is considered an eco-friendly alternative technology in relation to the existing water treatment technologies. However, the application of chitosan for dyes removal is limited, due to its low surface area and porosity. Then we prepared a chitosan scaffold with a megaporous structure as an alternative adsorbent to remove food dyes from solutions. EXPERIMENTS: The chitosan scaffold was characterized by infrared spectroscopy, scanning electron microscopy and structural characteristics. The potential of chitosan scaffold to remove five food dyes from solutions was investigated by equilibrium isotherms and thermodynamic study. The scaffold-dyes interactions were elucidated, and desorption studies were carried out. FINDINGS: The chitosan scaffold presented pore sizes from 50 to 200 µm, porosity of 92.2±1.2% and specific surface area of 1135±2 m(2) g(-1). The two-step Langmuir model was suitable to represent the equilibrium data. The adsorption was spontaneous, favorable, exothermic and enthalpy-controlled process. Electrostatic interactions occurred between chitosan scaffold and dyes. Desorption was possible with NaOH solution (0.10 mol L(-1)). The chitosan megaporous scaffold showed good structural characteristics and high adsorption capacities (788-3316 mg g(-1)).

Statistical optimization, interaction analysis and desorption studies for the azo dyes adsorption onto chitosan films.

Chitosan films (CF) were applied to remove azo dyes (tartrazine and amaranth) from aqueous solutions by adsorption. CF were prepared by casting technique and characterized. Response surface methodology was employed to optimize the adsorption process as a function of pH (2, 3 and 4) and CF concentration (100, 150 and 200 mg L(-1)). The possible interactions CF-dyes were investigated by Fourier transform infrared spectroscopy, dispersive energy X-ray spectroscopy, thermogravimetric analysis and color parameters. Adsorption-desorption cycles were also performed. The more appropriate conditions for the adsorption of both dyes were pH of 2 and CF concentration of 100 mg L(-1). Under these conditions, the tartrazine and amaranth adsorption capacities were 413.8 and 278.3 mg g(-1), respectively. The interactions between the CF protonated amino groups and anionic form of the dyes at pH 2 were confirmed. Desorption experiments showed that the CF can keep its adsorption capacity maximum for two cycles.

Biosorption of phenol onto bionanoparticles from Spirulina sp. LEB 18.

The biosorption of phenol onto bionanoparticles from Spirulina sp. LEB 18 was studied. Firstly, the bionanoparticles were prepared from Spirulina sp. strain LEB 18 and characterized. After, response surface methodology was employed to optimize the biosorption process as a function of pH (3.2-8.8) and bionanoparticles dosage (0.15-1.85 g L(-1)). Finally, equilibrium and thermodynamic studies were performed at different temperatures (298-328 K). The bionanoparticles presented hydrodynamic diameter of 232±3 nm and polydispersity index of 0.150. It was found that the more adequate condition for the phenol biosorption was pH of 6.0 and bionanoparticles dosage of 1.85 g L(-1). The Langmuir model presented satisfactory fit with the equilibrium experimental data. The maximum biosorption capacity was 159.33 mg g(-1), obtained at 298 K. The thermodynamic parameters showed that the biosorption was a spontaneous, favorable and exothermic process. Based on these results, it can be affirmed that the bionanoparticles are an alternative, renewable and eco-friendly biosorbent to removal phenol from aqueous solutions.

Optimization and kinetic analysis of food dyes biosorption by Spirulina platensis.

The biosorption of food dyes acid blue 9 and FD&C red no. 40 onto Spirulina platensis was studied. A full factorial design was used to analyze the effects of pH (2-4), stirring rate (50-400 rpm) and contact time (20-100 min) on biosorption capacity. In the best conditions, biosorption kinetics was analyzed and the experimental data were fitted with four kinetic models. The best conditions were: pH 2, 400 rpm and 100 min for acid blue 9, and pH 2, 225 rpm and 100 min for FD&C red no. 40. In these conditions, the biosorption capacities were 1653.0 mg g(-1) for acid blue 9 and 400.3 mg g(-1) for FD&C red no. 40. For both dyes, the Avrami kinetic model was the more appropriate to represent the experimental data. These results showed that the S. platensis is a suitable biosorbent for removal of food dyes from aqueous solutions.

Biosorption of food dyes onto Spirulina platensis nanoparticles: equilibrium isotherm and thermodynamic analysis.

The biosorption of food dyes FD&C red no. 40 and acid blue 9 onto Spirulina platensis nanoparticles was studied at different conditions of pH and temperature. Four isotherm models were used to evaluate the biosorption equilibrium and the thermodynamic parameters were estimated. Infra red analysis (FT-IR) and energy dispersive X-ray spectroscopy (EDS) were used to verify the biosorption behavior. The maximum biosorption capacities of FD&C red no. 40 and acid blue 9 were found at pH 4 and 298 K, and the values were 468.7 mg g(-1) and 1619.4 mg g(-1), respectively. The Sips model was more adequate to fit the equilibrium experimental data (R2>0.99 and ARE<5%). Thermodynamic study showed that the biosorption was exothermic, spontaneous and favorable. FT-IR and EDS analysis suggested that at pH 4 and 298 K, the biosorption of both dyes onto nanoparticles occurred by chemisorption.

Adsorption of food dyes acid blue 9 and food yellow 3 onto chitosan: stirring rate effect in kinetics and mechanism.

Adsorption of food dyes acid blue 9 and food yellow 3 onto chitosan was studied. Stirring rate influence on kinetics and mechanism was verified. Infra-red analysis was carried out before and after adsorption in order to verify the adsorption nature. Adsorption experiments were carried out in batch systems with different stirring rates (15-400 rpm). Kinetic behavior was analyzed through the pseudo-first-order, pseudo-second-order and Elovich models. Adsorption mechanism was verified according to the film diffusion model and HSDM model. Pseudo-second-order and Elovich models were satisfactory in order to represent experimental data in all stirring rates. For both dyes, adsorption occurred by film and intraparticle diffusion, and the stirring rate increase caused a decrease in film diffusion resistance. Therefore, the film diffusivity increased the adsorption capacity and, consequently, intraparticle diffusivity increased. In all stirring rates, the rate-limiting step was film diffusion. Adsorption of acid blue 9 and food yellow 3 onto chitosan occurred by chemiosorption.