Treatment of industrial glycerol from biodiesel production by adsorption operation: kinetics and thermodynamics analyses

Abstract

Equilibrium, thermodynamic, and kinetic analyses of the pigments adsorption of the industrial glycerol onto activated charcoal were performed. As the pigments concentration was not known, then, a relative adsorption capacity was defined using absorbance values measured in a spectrophotometer at a wavelength of 265?nm. Kinetic study showed that about 60?s were needed to reach equilibrium conditions. Relative adsorption capacity reached 8?g^?1 for 1% of adsorbent amount (w/w). Adsorption enthalpy was of –17.63?kJ mol^?1, while for isosteric heat values were obtained between –7.39 and –18.46?kJ mol^?1. The mathematical methodology used for the parameters determinations proved to be robust and able to express the relationships of kinetics, equilibrium and thermodynamics. Enthalpy values obtained by Van't Hoff method was confirmed by isosteric heat calculation, evidencing that this methodology can be used for systems whose compositions are unknown, but detectable by indirect form.     

Adsorption of Furfural from Aqueous Solution onto Activated Carbon: Kinetic,Equilibrium and Thermodynamic Study

Abstract

The present study aims to evaluate the influence of various experimental parameters viz. initial pH (pH ₀), adsorbent dose, contact time, initial concentration and temperature on the adsorptive removal of furfural from aqueous solution by commercial grade activated carbon (ACC). Optimum conditions for furfural removal were found to be pH ₀ ≈ 5.9, adsorbent dose ≈ 10 g/l of solution and equilibrium time ≈ 6.0 h. The adsorption followed pseudo‐second‐order kinetics. The effective diffusion coefficient of furfural was of the order of 10^?13 m²/s. Furfural adsorption onto ACC was found to be best represented by the Redlich‐Peterson isotherm. A decrease in the temperature of the operation favorably influenced the adsorption of furfural onto ACC. The positive values of the change in entropy (ΔS ⁰); and the negatived value of heat of adsorption (ΔH ⁰) and change in Gibbs free energy (ΔG ⁰) indicated feasible, exothermic, and spontaneous nature of furfural adsorption onto ACC.     

Adsorption of H2, CO2, CH4, CO,N2 and H2O in Activated Carbon and Zeolite for Hydrogen Production

Abstract

The design of a layered pressure swing adsorption unit to treat a specified off-gas stream is based on the properties of the adsorbent materials. In this work we provide adsorption equilibrium and kinetics of the pure gases in a SMR off-gas: H₂O, CO₂, CH₄, CO, N₂, and H₂ on two different adsorbents: activated carbon and zeolite. Data were measured gravimetrically at 303–343 K and 0–7 bar. Water adsorption was only measured in the activated carbon at 303 K and kinetics was evaluated by measuring a breakthrough curve with high relative humidity.     

Paddle cactus (Tacinga palmadora) as potential low-cost adsorbent to treat textile effluents containing crystal violet

Abstract

The powdered biomass of paddle cactus (Tacinga palmadora), a rustic plant of great occurrence in the driest regions of Brazil, was evaluated as a low-cost adsorbent to treat textile effluents containing crystal violet (CV) dye. The powdered paddle cactus (PPC) was mainly composed by lignin and holocellulose, as well as, a variety of functional groups. Best results for CV adsorption were found using an adsorbent dosage of 0.5?g L^?1 at solution pH equivalent to 10.0. Fast adsorption kinetics was verified, being the equilibrium reached within 100?min, and the curves were well modeled by the pseudo-first-order model. The isotherms were well-represented by the Langmuir model. The maximum adsorption capacity was 228.74?mg g^?1 at 328?K. The estimated thermodynamics parameters were ΔG⁰_T?=?328K of –9.08?kJ mol^?1, ΔH⁰ of 12.44?kJ mol^?1, and ΔS⁰ of 0.065?kJ mol^?1 K^?1. In addition, PPC was able to treat a simulated textile effluent containing organic and inorganic compounds, reaching 93% of color removal efficiency. These findings show that powdered paddle cactus can be applied as potential low-cost adsorbent to treat textile effluents containing CV.     

Analysis of intraparticle diffusion on adsorption of crystal violet on bentonite

Abstract

In the present work, kinetics of crystal violet (CV) adsorption on bentonite was studied by pore volume and surface diffusion model (PVSDM), surface diffusion model (SDM), and pore volume diffusion model (PVDM). The adsorption decay curves were obtained in batch system using different adsorbent dosages. The PVDM model did not interpreted the kinetic adsorption since the calculated value of D_p equal to 5.64?×?10^?7 cm² s^?1 predicted a slower adsorption than that obtained by the experimental data. The PVSDM results indicates that the intraparticle diffusion is predominantly due to surface diffusion (93%) and the pore volume diffusion can be negligible. Once the surface diffusion was the limiting step, the estimation with one (D_s) and two (D_sq and α) parameters were tested in the SDM model. The statistical analysis revealed that the one-parameter SDM model was most appropriate to predict the CV adsorption on bentonite. The optimal values of Ds ranged from 6.19?×?10^?10 to 6.49?×?10^?10 cm² s^?1, and decrease with the adsorbent dosage.     

A Non-Conventional Adsorbent for the Removal of Clofibric Acid from Aqueous Phase

The adsorption of Clofibric acid, one of the most frequently prescribed high environmental risk drugs, was studied using H₃PO₄ activated Schumannianthus dichotomus (ASD). The chemical characteristics of the adsorbent were established by Bohem’s titration, pH_PZC, FTIR, SEM, XRD, porosity, and surface area analysis. It was observed that the adsorbent was microporous-mesoporous in nature with BET surface area of 1199.98 m².g^?1. The influence of temperature (303-323 K), pH (2-10), textural properties, adsorbent load, and contact time was studied. The Langmuir equation was found to best represent the equilibrium data for clofibric acid-adsorbent system, yielding monolayer adsorption capacity of 258.39 mg.g^?1 at 303 K. The pseudo-second order model best explained (R² > 0.999) the adsorption kinetics with rate constant 0.037 g.mg^?1min^?1. The thermodynamics parameters, ΔG°, ΔH°, and ΔS°, evaluated as ?8.14 kJmol^?1, ?34.07 kJmol^?1, and ?85.5 JK^?1mol^?1, respectively, revealed that the adsorption process is feasible, spontaneous, and exothermic in nature. In the column mode, the adsorption capacity of ASD (267.93 mg.g^?1) was found to be higher than the batch mode of operation (258.39 mg.g^?1). The cost incurred per kg of the developed adsorbent was USD 14.36.     

Removal of Cr(VI) From Aqueous Solution by Turkish Vermiculite: Equilibrium,Thermodynamic and Kinetic Studies

Abstract

The adsorption of Cr(VI) from aqueous solution by Turkish vermiculite were investigated in terms of equilibrium, kinetics, and thermodynamics. Experimental parameters affecting the removal process such as pH of solution, adsorbent dosage, contact time, and temperature were studied. Equilibrium adsorption data were evaluated by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Langmuir model fitted the equilibrium data better than the Freundlich model. The monolayer adsorption capacity of Turkish vermiculite for Cr(VI) was found to be 87.7 mg/g at pH 1.5, 10 g/L adsorbent dosage and 20°C. The mean free energy of adsorption (5.9 kJ/mol) obtained from the D–R isotherm indicated that the type of sorption was essentially physical. The calculated thermodynamic parameters (ΔG ^o , ΔH ^o and ΔS ^o ) showed that the removal of Cr(VI) ions from aqueous solution by the vermiculite was feasible, spontaneous and exothermic at 20–50°C. Equilibrium data were also tested using the adsorption kinetic models and the results showed that the adsorption processes of Cr(VI) onto Turkish vermiculite followed well pseudo-second order kinetics.     

A method of thermal and chemical activation of waste bleaching earth for preparation of a low-cost carbon-mineral adsorbent for chromium(VI) removal

ABSTRACT

In this study, the use of a spent bleaching earth for removal of Cr(VI) ions from aqueous solutions was investigated. The waste material derived from the process of vegetable oil purification was subjected to thermal and chemical activation. The so-prepared carbon-mineral adsorbents were characterised by the uptake of chromium(VI) from synthetic solutions. The highest adsorption capacities were obtained for adsorbents carbonised at 400°C (15.9 mg?g^?1) and activated with H₂SO₄ (15.8 mg?g^?1). Based on the equilibrium and kinetic studies, it was concluded that the adsorption mechanism was based on chemisorption only since no correlation with the porous texture was found.     

Adaptive neuro-fuzzy inference system (ANIFS) and artificial neural network (ANN) applied for indium (III) adsorption on carbonaceous materials

Abstract

In this paper, we present an initial study relating the adsorption of indium (III) onto carbonaceous materials, namely the activated carbon (AC), multiwalled carbon nanotubes functionalized with OH (MWCNT–OH), and the multiwalled carbon nanotubes functionalized with COOH (MWCNT–COOH). The main objective of this study is the development of the adaptive neuro-fuzzy inference system (ANFIS) and an artificial neural network (ANN) for predicting the adsorption capacity in different operating conditions for different materials. Both models take into account the adsorbent type, adsorbent dosage (0.05, 0.25, 0.5, 1.0, 1.5, and 2.0?g L^?1), and the contact time (5, 20, 60, and 120?min) for predicting the adsorption capacity, which varied from 12.896 to 981.000?mg g^?1, a total record of 72 was used. Both modeling methodologies applied can represent the experimental data, taking into account the statistical values obtained. The ANFIS achieved the best performance when the hybrid method was selected, this leads into R of 0.9998, RMSE of 48,373 with 250 epochs. On the other hand, the ANN can represent the best performance when using the Levenberg–Marquardt algorithm, reaching an R of 0.9831, MSE of 0.0180 and 9 epochs. Considering the modeling and experimental aspects indicates that the increase of the adsorbent dosage diminished the adsorbent capacity. The increase of the contact time causes the effect to increase the adsorption capacity until its equilibrium. Lastly, it is possible to conclude that the MWCNT–COOH is the most suitable adsorbent to be used between the selected materials.     

Removal of Pb(II) from aqueous solutions by adsorption onto clayey soil of Indian origin: Equilibrium, kinetic and thermodynamic profile

The feasibility of applying natural, untreated clayey soil as low-cost alternative adsorbent for Pb(II) removal from aqueous solutions was investigated with a batch experimental set-up. Experiments were carried out as a function of initial solution pH (1?C8), contact time (10?C360 min), initial Pb(II) concentration (20?C100 mg L^?1), adsorbent dose (0.5?C5 g) and temperature (303?C333 K). Adsorption equilibrium data were well described by the Langmuir isotherm with maximum adsorption capacity of 121.86 mg g^?1 at 303 K. Adsorption of Pb(II) followed pseudo-second-order kinetics. Gibbs free energy (??G⁰) was spontaneous for all interactions, and the adsorption process exhibited exothermic enthalpy values. The adsorbent was easily regenerated by using 0.1M HNO₃ solution and was reused for five sorptiondesorption cycles without any considerable loss in adsorption capacity. It could be concluded that clayey soil may be used as an inexpensive and effective adsorbent without any treatment or any other modification for the removal of Pb(II) ions from aqueous solutions.     

Commercial Diatomite for Adsorption of Tetracycline Antibiotic from Aqueous Solution

Extensive use of antibiotics in human therapy and farming industry has resulted in their accumulation and potential hazards to the environment. In this study, diatomite, which is a siliceous rock with large surface area and high adsorptivity towards organic compounds, was used to adsorb the antibiotic tetracycline (TC) from aqueous media. The adsorption kinetics, isotherms, thermodynamics, and effects of the adsorbent amount and ionic strength were evaluated in batch adsorption experiments. The adsorption of TC onto diatomite followed the pseudo-second-order kinetics model, and the sorption equilibrium was reached in 120 min. The perfect adsorbent amount could be selected within the range of 1 ? 20 g·L^?1. The equilibrium data at different temperatures was satisfactorily fitted to the Langmuir isotherm equation with high R² above 0.999, and the maximum monolayer adsorption capacity of 303.03 mg·g^?1 was obtained at 318 K using 1 g·L^?1 diatomite. Thermodynamic parameters showed that the adsorption reaction was spontaneous and endothermic. Moreover, the adsorption of TC was insignificantly affected by the ionic strength of 0.05-1% NaCl and CaCl₂, indicating that diatomite has a potential practical application as adsorbent media for removing TC from real water.     

Modeling of Adsorptive Filtration of a Leather Dye in a Fixed Bed Column

Abstract

Activated carbons offer an efficient option for the removal of organic and inorganic contaminants from water. However, due to its high costs and difficulty in the regeneration, other low cost adsorbents have been used. In this work, the adsorption capacity of an adsorbent carbon with high iron oxides concentration was compared with that of a commercial activated carbon in the removal of a leather dye from an aqueous solution. The adsorbents were characterized using SEM/EDAX analysis and BET surface area. The capacity of adsorption of the adsorbents was evaluated through the static method at 25°C. The results showed that the color removal was due to the adsorption and precipitation of the dye on the surface of the solids. The adsorption equilibrium was described according to the linear model for the adsorbent carbon and the equilibrium constant was 0.02 L g^?1. The equilibrium of adsorption on activated carbon exhibited a behavior typical of the Langmuir isotherm and the monolayer coverage was 24.33 mg g^?1. A mathematical model was proposed to describe the dynamics of the color removal using a fixed bed considering that the color removal is due to the adsorption and the precipitation of the dye on the adsorbent.     

Adsorptive removal of fluoride from water by activated carbon derived from CaCl2-modified Crocus sativus leaves: Equilibrium adsorption isotherms,optimization, and influence of anions

A central composite design using response surface methodology was applied for the experimental design and optimization of fluoride adsorption on an activated carbon derived from calcium chloride-modified Crocus sativus leaves (AC-CMCSL). Fluoride removal efficiency as function of independent variables, such as initial fluoride concentration, pH, adsorbent dose, and time has been investigated. The maximum percentage removal of fluoride at optimum conditions (initial fluoride concentration?=?6.5?mg?L^?1, pH?=?4.5, adsorbent dose?=?15?g?L^?1 and time?=?70?min) was 85.43%. By comparing adsorption isotherm, the Freundlich model provided the best correlation (R²?=?0.99) for the adsorption of fluoride on AC-CMCSL. The maximum adsorption capacity from the Langmuir model (q_max) was 2.01?mg?g^?1. The influence of the co-existing anions on fluoride adsorption was in the following order: PO₄^3??>?SO₄^2??>?Cl^??>?NO₃^?. The results of the present study showed that activated carbon derived from the leaves of calcium chloride-modified Crocus sativus has a good potential for fluoride removal from aqueous solution.     

Vehicular Tire as Potential Adsorbent for the Removal of Polycyclic Aromatic Hydrocarbons

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants, entering into various water and wastewater systems through various natural and anthropogenic activities. The aim of the work is to convert vehicular tires, a highly available waste material, into potential adsorbent for the removal of PAHs from aqueous solutions. The BET surface area of the prepared vehicular tire activated carbon is 643.86 m²/g. Removal of PAHs using activated carbons and the effect of various parameters such as contact time, adsorbent dose, temperature, and pH on the adsorption have been evaluated. The data were fitted to Freundlich and Langmuir isotherms and values of various constants were evaluated. In all the cases, Freundlich model was found to be better fitted. The equilibrium time for adsorption of PAHs was 120 min. The values of thermodynamic parameters, such as Gibb's free energy change ΔG°, enthalpy change ΔH°, and entropy change ΔS°, were calculated using adsorption equilibrium constants obtained from Langmuir isotherm. The thermodynamic data for adsorption of PAHs revealed spontaneity and endothermic nature of the adsorption process. The samples were analyzed using a UV–vis spectrophotometer for PAH determination. Mixture of sodium hydroxide and ethanol in different proportions was tried for desorption of PAHs and 50% ethanolic NaOH solution was most effective. The developed activated carbon demonstrates good adsorption and desorption capabilities for PAHs, indicating towards its suitability for use in the treatment processes of various industrial effluents or water streams containing PAHs.     

Adsorption of Pb2+ and Cd2+ onto a Novel Activated Carbon‐Chitosan Complex

A novel activated carbon‐chitosan complex adsorbent (ACCA) was prepared via the crosslinking of glutaraldehyde and activated carbon‐(NH₂‐protected) chitosan complex under microwave irradiation. The surface morphology of this adsorbent was characterized. The adsorption of ACCA for Pb²⁺ and Cd²⁺ was investigated. The results demonstrate that ACCA has higher adsorption capacity than chitosan. The adsorption follows pseudo first‐order kinetics. The isotherm adsorption equilibria are better described by Freundlich and Dubinin‐Radushkevich isotherms than by the Langmuir isotherm. The adsorbent can be recycled. These results have important implications for the design of low‐cost and effective adsorbents in the removal of heavy metal ions from wastewaters.     

Influence of Magnetic Nanoparticles on Surface Changes in CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Nerium Oleander Leaf Waste Activated Carbon Nanocomposite for Water Treatment

The paper reports on the successful use of the nano crystalline cobalt ferrite doped Nerium oleander leaf waste activated carbon (CoFe₂O₄/NOAC) synthesized by an urea assisted auto combustion technique to assess accurate kinetics and equilibrium parameters regarding the investigation of adsorption. The specific features of nano composite were investigated by various analytical techniques such as Scanning electron microscope with EDAX, powder X-ray diffraction study, BET surface area analysis, TG and DSC, Vibrating Sample Magnetometer. The BET analysis indicates that CoFe₂O₄ nano particles embedded in NOAC have increased the pore diameter for better adsorption. TG and DSC show the thermal stability of composite. The VSM study shows the Ferro magnetic behavior of nano composite which revealed that CoFe₂O₄/NOAC could be separated and retrieved easily by an external magnet after adsorption of AV49. The efficiency of adsorption of AV49 from aqueous solution was investigated through a series of batch experiments by using CoFe₂O₄/NOAC. The batch adsorption experiments showed the efficient removal on CoFe₂O₄/NOAC under optimum conditions such as pH 6.5, contact time-55 min and adsorbent dosage-50 mg. Adsorption kinetics—Pseudo first order and second order, Isotherms—Langmuir and Freundlich have been adapted to analyze the adsorption capacity. The results showed that the adsorption followed the pseudo second order kinetics and Langmuir isotherm equation is the best to describe the adsorption process. According to the thermodynamic study, it was very effective at higher temperatures also. The thermodynamic parameters ?G^o, ?H^o and ?S^o were also evaluated for this adsorption.     

Kinetics,Thermodynamics, and Isothermic Evaluation in Sorption Study of Hazardous Dye Using Sodium Dodecylsulfate Physically Impregnated in Polyester‐Type Polyurethane Foam

Use of polyester‐type polyurethane foam (PUF) is an effective adsorbent for the removal of hazardous dye: crystal violet (CV) from an aqueous solution. In this adsorption study, the formation of hydrophobic ion pair (opposite charge attraction) between the charged species, i.e., cationic (basic) dye CV and anionic surfactant sodium dodecylsulfate (SDS) sorbed onto PUF. Chemical calculations were performed using quantum simulation to understand ion‐pair formation for CV–SDS at the semiempirical PM6 level. Adsorption studies were performed using 200 mg cylindrical PUF with an overhead stirrer in solutions containing varying compositions of the dye–surfactant mixture. The equilibrium thermodynamics and kinetics of the adsorption process were studies by measuring CV dye removal as a function of time and temperature. Results show that the formation of the dye–surfactant ion pair is necessary for effective adsorption onto PUF. Various adsorption isotherms, viz., Langmuir, Freundlich, Temkin, Dubinin–Radushkevich (DRK), Harkin‐Jura, and several kinetic models, viz., pseudo‐first order, pseudo‐second order, Elovich, and Intraparticle diffusion were used to fit the spectrophotometric result. The equilibrium adsorption data fit to the Langmuir isotherm gives the maximum adsorption of PUF as 33.39 mg g^?1 from 200 mL 5.0 × 10^?5 mol L^?1 CV solution at 298.15 K. The kinetics study showed that the overall adsorption process follows pseudo‐second‐order kinetics. The Morris–Weber model suggests that an intraparticle diffusion process is active in controlling the adsorption rate. The Freundlich, Temkin, DRK adsorption isotherms showed that solute dye transfers from solution to the PUF adsorbent surface through physical adsorption. The Langmuir and Harkin‐Jura adsorption isotherms suggest that the adsorbent surface is homogeneous in nature. The thermodynamic data showed that the adsorption process is spontaneous and endothermic with a positive enthalpy change and a negative change in Gibb's energy.     

Defluoridation performance and mechanism of nano‐scale aluminum oxide hydroxide in aqueous solution

BACKGROUND: The present study has concentrated on investigating the fluoride removal potential of nano‐scale aluminum oxide hydroxide (nano‐AlOOH). A series of batch adsorption experiments were carried out to assess parameters that influence the adsorption process. The different parameters investigated include the effect of contact time, initial fluoride concentration, adsorbent dose, pH of the solution and co‐existing anions. RESULTS: Most of the adsorption took place during the first 30 min and kinetic and equilibrium adsorption data show that the process obeys a pseudo‐second‐order kinetic equation and the Langmuir adsorption model. The fluoride removal efficiency is greater than 90% between pH 6 and 8 and decreases as pH values increase to 11. The presence of SO₄^2? or PO₄^3? in aqueous solution was found to reduce the fluoride uptake. Desorption studies showed that the fluoride can easily be desorbed at pH 13. CONCLUSION: Nano‐AlOOH possesses a maximum fluoride capacity of 3259 mg F^? kg^?1, which is comparable with that of activated alumina. Maximum adsorption occurred at around pH 7, which makes nano‐AlOOH a potential adsorbent for drinking water treatment. Copyright © 2009 Society of Chemical Industry     

Adsorptive removal of dye from real textile wastewater using graphene oxide produced via modifications of hummers method

Abstract

This work focused on producing different graphene oxide (GO) samples for further application in the adsorptive removal of dyes from real textile wastewater. Among all conditions tested, the sample produced using KMnO₄ and no sonication bath exhibited the best performance. Before the experiments using wastewater, kinetics and equilibrium of adsorption studies were performed with Methylene Blue (MB) dye. Experimental data showed the isotherm fitted the Freundlich model, and kinetic results fitted the pseudo-second order model. Theoretical q_max was 308.11?mg.g^?1 and over 90% removal of MB was reached in approximately 5?min. Although GO has been widely applied to remove cationic and anionic dyes from water, not many studies have presented GO as an adsorbent for real textile wastewater treatment. In 30?min, GO removed nearly 85% of turbidity and over 60% of color from a real sample, indicating that GO might be an excellent alternative to treat textile wastewater.