Adsorption of malachite green onto bentonite: Equilibrium and kinetic studies and process design

The adsorption of malachite green onto bentonite in a batch adsorber has been studied. The effects of contact time, initial pH and initial dye concentration on the malachite green adsorption by the bentonite have been studied. Malachite green removal was seen to increase with increasing contact time until equilibrium and initial dye concentration, and the adsorption capacity of bentonite was independent of initial pH in the range 3–11. Four kinetic models, the pseudo first- and second-order equations, the Elovich equation and the intraparticle diffusion equation, were selected to follow the adsorption process. Kinetic parameters; rate constants, equilibrium adsorption capacities and correlation coefficients, for each kinetic equation were calculated and discussed. It was shown that the adsorption of malachite green onto bentonite could be described by the pseudo second-order equation. The experimental isotherm data were analyzed using the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich equations. Adsorption of malachite green onto bentonite followed the Langmuir isotherm. The thermodynamic parameters, such as ΔH, ΔS and ΔG, were also determined and evaluated. A single stage batch adsorber was designed for different adsorbent mass/treated effluent volume ratios using the Langmuir isotherm.     

Kinetic and Equilibrium Studies on the Adsorption of Crystal Violet Dye using Kaolin as an Adsorbent

Abstract

Experimental investigations are carried out to adsorb toxic crystal violet dye from aqueous medium using kaolin as an adsorbent. Characterization of kaolin is done by measuring

1. particle size distribution using particle size analyzer,

2. BET surface area using BET surface analyzer,

3. structural analysis using X ray diffractometer, and

4. microscopic analysis using scanning electron microscope.

The effects of initial dye concentration, contact time, kaolin dose, stirring speed, pH, and temperature are studied for the adsorption of crystal violet in batch mode. Adsorption experiments indicate that the extent of adsorption is strongly dependent on the pH of the solution. Free energy of adsorption (ΔG ^o ), enthalpy (ΔH ^o ), and entropy (ΔS ^o ) changes are calculated to know the nature of adsorption. The calculated values of ΔG ^o are ?4.11 and ?4.48 kJ/mol at 295 K and 323 K, respectively, for 20 mg/L of dye concentration, which indicates that the adsorption process is spontaneous. The estimated values of ΔH ^o and ΔS ^o show the negative and positive sign, respectively, which indicate that the adsorption process is exothermic and the dye molecules are organized on the kaolin surface in more random fashion than in solution. The adsorption kinetic has been described by pseudo first order, pseudo second order and intra‐particle diffusion models. It is observed that the rate of dye adsorption follows pseudo second order model for the dye concentration range studied in the present case. Standard adsorption isotherms are used to fit the experimental equilibrium data. It is found that the adsorption of crystal violet on kaolin follows the Langmuir adsorption isotherm.     

Removal of Crystal Violet Dye from Aqueous Solution Using Calcined and Uncalcined Mixed Clay Adsorbents

In this work, calcined and uncalcined mixed clays containing kaolin, ball clay, feldspar, pyrophyllite, and quartz are examined as a potential adsorbent for the removal of crystal violet dye from aqueous solution. These clays are characterized by nitrogen adsorption/desorption isotherms, X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and thermo gravimetric analysis (TGA). The kinetics and thermodynamic parameters as well as the effects of the pH, the temperature, and the adsorbent dosage have also been investigated. The experimental results indicate that the Langmuir model expresses the adsorption isotherm better than the Freundlich model. The obtained result showed a tremendous increase in the crystal violet adsorption capacity (1.9 × 10^?3 mol g^?1) after calcination, which is one order greater than that of the uncalcined mixed clay. The mechanism of the adsorption process is elucidated on the basis of experimental data. The percentage removal of crystal violet dye increases with increasing the pH, the temperature, and the adsorbent dosage. The investigation of kinetic studies indicates that the adsorption of crystal violet on calcined and uncalcined mixed clays could be described by the pseudo-second-order model. The negative Δ G ⁰ values obtained from the thermodynamic investigation confirm that the adsorption is spontaneous in nature. The adsorption results suggest that the calcined and uncalcined mixed clays can also be used as low cost alternatives to the expensive activated carbon for the removal of dyes from aqueous solution.     

Adsorption of methylene blue on kaolinite

Methylene blue was adsorbed on kaolin from a local deposit. The raw kaolin itself was a relatively good adsorbent. The adsorption capacity was improved by purification and by treatment with NaOH solution. Calcination of the kaolin reduced the adsorption capacity. The adsorption data could be fitted by the Freundlich and Langmuir equations. Also, the thermodynamic parameters such as ΔH⁰, ΔS⁰ and ΔG⁰ were determined.     

Adsorption of cationic dye from aqueous solutions by activated carbon

Batch sorption experiments were carried out to remove a cationic dye, methylene blue (MB), from its aqueous solutions using a commercial activated carbon as an adsorbent. Operating variables studied were pH, stirring speed, initial methylene blue concentration and temperature. Adsorption process was attained to the equilibrium within 5 min. The adsorbed amount MB dye on activated carbon slightly changed with increasing pH, and temperature, indicating an endothermic process. The adsorption capacity of methylene blue did not significantly change with increasing stirring speed. The experimental data were analyzed by various isotherm models, and found that the isotherm data were reasonably well correlated by Langmuir isotherm. Adsorption measurements showed that the process was very fast and physical in nature. Thermodynamic parameters such as the adsorption entropy (ΔS^o) and adsorption enthalpy (ΔH^o) were also calculated as 0.165 kJ mol⁻¹ K⁻¹ and 49.195 kJ mol⁻¹, respectively. The ΔG^o values varied in range with the mean values showing a gradual increase from −0.256 to −0.780 to −2.764 and −7.914 kJ mol⁻¹ for 293, 313, 323 and 333 K, respectively, in accordance with the positive adsorption entropy value of the adsorption process.     

Comparison of Basic Dye Crystal Violet Removal from Aqueous Solution by Low-Cost Biosorbents

Abstract

The removal of basic dye crystal violet by low-cost biosorbents was investigated in this study using a batch experimental system. The adsorption of crystal violet onto various adsorbents was solution pH-dependent and the maximum removal occurred at basic pH 10.0. The kinetic experimental data were analyzed using pseudo-first-order and pseudo-second-order equations to examine the adsorption mechanism and the intraparticle diffusion model to identify the potential rate controlling step. These results suggested that the adsorption of crystal violet onto various adsorbents was best represented by the pseudo-second-order equation. The suitability of the Langmuir and Freundich adsorption isotherms to the equilibrium data was also investigated at various temperatures for all four sorbents and the adsorption isotherms exhibited Freundlich behavior. The Freundlich constant K_f was 1.55 for alligator weed, 2.33 for Laminaria japonica, 9.59 for rice bran and 5.38 (mg/g)/(mg/L)^1/n for wheat bran, respectively at adsorbent concentration 5 g/L, pH 10.0 and 20°C. The thermodynamic parameters (ΔH, ΔG, and ΔS) were calculated and the results showed that the adsorption process for various adsorbents was spontaneous, endothermic, with an increased randomness, respectively. The particle size and the reaction temperature exhibited an insignificant impact on the adsorption equilibrium of crystal violet. The adsorbents investigated could serve as low-cost adsorbents for removing the crystal violet from aqueous solution.     

Adsorption studies on the removal of Malachite Green from aqueous solutions onto halloysite nanotubes

Halloysite nanotubes (HNTs) were used as nano-adsorbents for removal of the cationic dye, Malachite Green (MG), from aqueous solutions. The adsorption of the dye was studied with batch experiments. The natural HNTs used as adsorbent in this work were initially characterized by FT-IR and TEM. The effects of adsorbent dose, initial pH, temperature, initial dye concentration and contact time were investigated. Adsorption increased with increasing adsorbent dose, initial pH, and temperature. Equilibrium was rapidly attained after 30 min of contact time. Pseudofirst-order, pseudo-second-order and intraparticle diffusion models were considered to evaluate the rate parameters. The adsorption followed pseudo-second-order kinetic model with correlation coefficients greater than 0.999. The factors controlling adsorption process were also calculated and discussed. The maximum adsorption capacity of 99.6 mg g⁻¹ of MG was achieved in pH = 9.5. Thermodynamic parameters of ΔG°, ΔH° and ΔS° indicated the adsorption process was spontaneous and endothermic.     

Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite

The use of low-cost and ecofriendly adsorbents was investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater. Sepiolite was used as an adsorbent for the removal of methyl violet (MV) and methylene blue (MB) from aqueous solutions. The rate of adsorption was investigated under various parameters such as contact time, stirring speed, ionic strength, pH and temperature for the removal of these dyes. Kinetic study showed that the adsorption of dyes on sepiolite was a gradual process. Quasi-equilibrium reached within 3 h. Adsorption rate increased with the increase in ionic strength, pH and temperature. Pseudo-first-order, the Elvoich equation, pseudo-second-order, mass transfer and intra-particle diffusion models were used to fit the experimental data. The sorption kinetics of MV and MB onto sepiolite was described by the pseudo-second-order kinetic equation. Intra-particle diffusion process was identified as the main mechanism controlling the rate of the dye sorption. The diffusion coefficient, D, was found to increase when the ionic strength, pH and temperature were raised. Thermodynamic activation parameters such as ΔG¹, ΔS¹ and ΔH¹ were also calculated.     

Removal of basic dyes from aqueous solution by low-cost adsorbent: Wood apple shell (Feronia acidissima)

The adsorption of two basic dyes, methylene blue (MB) and crystal violet (CV) on wood apple shell (WAS) were investigated using a batch adsorption technique. A series of experiments were undertaken in an agitated batch adsorber to assess the effect of the system variables such as solution pH, dye concentration and temperature. Removal of dyes was observed to be most effective at higher pH. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The results showed that Langmuir equation fits better than the Freundlich equation. It was observed that the WAS adsorbent showed higher adsorption capacity for crystal violet (130 mg/g) than methylene blue (95.2 mg/g). The FTIR studies indicate that the interaction of dye and WAS surface is via the nitrogen atoms of the adsorbate and oxygen groups of the adsorbent. The adsorption of dyes onto WAS proceeds according to a pseudo-second-order model. Thermodynamic parameters such as free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were also calculated. The studies show that WAS, a lignocellulosic inexpensive material, can be an alternative to other expensive adsorbents used for dye removal in wastewater treatment.     

Biosorption of Pb(II) ions from aqueous solution by pine bark (Pinus brutia Ten.)

The biosorption potential of pine (Pinus brutia Ten.) bark in a batch system for the removal of Pb(II) ions from aqueous solutions was investigated. The biosorption characteristics of Pb(II) ions on the pine bark was investigated with respect to well-established effective parameters including the effects of solution pH, initial Pb(II) concentration, mass of bark, temperature, and interfering ions present, reusability, and desorption. Initial solution pH and contact time were optimized to 4.0 and 4 h, respectively. The Langmuir and Freundlich equilibrium adsorption models were studied and observed to fit well. The maximum adsorption capacity of the bark for Pb(II) was found to be 76.8 mg g⁻¹ by Langmuir isotherms (mass of bark: 1.0 g L⁻¹). The kinetic data fitted the pseudo-second-order model with correlation coefficient greater than 0.99. The thermodynamic parameters Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes were also calculated, and the values indicated that the biosorption process was spontaneous. Reutilization of the biosorbent was feasible with a 90.7% desorption efficiency using 0.5 M HCl. It was concluded that pine bark can be used as an effective, low cost, and environmentally friendly biosorbent for the removal of Pb(II) ions from aqueous solution.     

Magnetic and K+-cross-linked kappa-carrageenan nanocomposite beads and adsorption of crystal violet

Biopolymer-based magnetic beads, composed of kappa-carrageenan (κ-Car) and Fe₃O₄ nanoparticles, were synthesized. The magnetic beads were prepared through in situ precipitation of Fe²⁺/Fe³⁺ ions in the presence of carrageenan and subsequently treating with K⁺ solution. The structure of magnetic kappa-carrageenan beads (mκ-Carb) was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometer, and thermal gravimetric analysis techniques. According to SEM micrographs, an undulant and coarse structure with cubic-shaped sections was obtained when the magnetic nanoparticles were incorporated in composition of beads. The TEM image confirmed the formation of magnetic nanoparticles with an average size of 3–7 nm. The synthesized beads were examined as adsorbent to remove crystal violet dye from aqueous solutions. It was found that due to coarse surface, the rate of dye adsorption on magnetic beads can be improved slightly. The experimental adsorption kinetics was analyzed according to pseudo-first-order and pseudo-second-order kinetic models and the adsorption kinetics followed well the pseudo-second-order model. Isotherm adsorption data of dye on beads were modeled according to Langmuir and Freundlich isotherm models. The results revealed that the experimental data have the best fit to Langmuir isotherm model, and maximum adsorption capacity of beads for dye obtained was 84.7 mg/g. The influence of pH on the variation of adsorption capacity of beads for crystal violet was not considerable. The thermodynamic parameters indicated that the adsorption of CV dye on beads is spontaneous.     

Adsorption of Pb(II) from aqueous solution to MX-80 bentonite: Effect of pH, ionic strength, foreign ions and temperature

The adsorption of Pb(II) from aqueous solution to MX-80 bentonite was studied using batch technique under ambient conditions. Removal percent (%) and distribution coefficient (K_d) were determined as a function of shaking time, pH, ionic strength and temperature. The results showed that the adsorption behavior of Pb(II) on bentonite was strongly dependent on pH and ionic strength. The presence of complementary cations depressed the adsorption of Pb(II) on bentonite in the order of Li⁺ ≈ Na⁺ > K⁺ at pH 2–5. The adsorption isotherms were simulated by the Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) models very well. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) for the adsorption of Pb(II) were determined at three different temperatures of 291 K, 308 K and 328 K. The adsorption reaction was exothermic and the process of adsorption was favored at low temperature. The results suggest that bentonite is suitable as a sorbent material for the recovery and adsorption of Pb(II) from aqueous solution.     

由飞灰合成的沸石吸附废水中染料的动态平衡

The removal performance of a basic dye, methylene blue (MB), in aqueous solution was investigated by adsorption process on single-phase and high-crystalline zeolite A (FA-ZA) and X (FA-ZX). Both adsorbents FA-ZA and FA-ZX were synthesized from fly ash prepared aluminosilicate gel followed by the hydrothermal treatment at 100°C with the control of Si/Al molar ratio, respectively. The properties of the synthetic zeolites and commercial grade zeolites, such as thermal stability, elemental composition, and cation exchange capacity, were investigated for comparison. Batch method was used to study the influential parameters, such as initial pH value of the solution, temperatures, and adsorbents dosage, on the adsorption process. The experimental data were well fitted by Ho’ pseudo-second-order model and liquid film diffusion model. The suitability of Langmuir and Freundlich isotherms to the equilibrium data was investigated in the solid-liquid system while the Langmuir model produces the best re-sults. Thermodynamic data (ΔH, ΔS, and ΔG) corresponding to the MB uptake were evaluated from the Langmuir model. In all the adsorption experiments, the adsorption capacity followed the order as follows: FA-ZX > FA-ZA. In addition, attempts were also made to regenerate the adsorbents.     

Thermodynamics of hydrogen adsorption on the zeolite Ca-Y

Variable-temperature infrared spectroscopy was used for a thermodynamic study on hydrogen adsorption on the zeolite Ca-Y. Adsorption renders the H–H stretching mode infrared active, at 4078 cm⁻¹; and simultaneous measurement of IR absorbance and hydrogen equilibrium pressure, over a range of temperature, allowed standard adsorption enthalpy and entropy to be determined. They resulted to be ΔH°= −15.0(±1.0) kJ mol⁻¹ and ΔS° = −127(±10) J mol⁻¹ K⁻¹, respectively. These relatively high values of adsorption enthalpy and entropy are discussed in the broader context of corresponding data for other hydrogen adsorbents.     

Adsorption Characteristics of Congo Red from Aqueous Solution onto Tea Waste

The feasibility of using tea waste (TW) as a low-cost adsorbent for the adsorption of an anionic dye (Congo red) from aqueous solution has been investigated. Adsorption in a batch process was conducted to study the effect of adsorbent dosage, initial dye concentration, contact time, pH, and temperature. The experimental data were analyzed by the Langmuir, Freundlich, and Temkin models. The adsorption system was best described by the Langmuir isotherm (R ² > 0.99). Adsorption kinetics followed a pseudo-second-order model (R ² > 0.99). The effect of mechanical treatment (vibratory mill) was also studied. The experimental results showed that using this physical treatment leads to an increase in the adsorption capacity of TW from 32.26 to 43.48 mg/g. Thermodynamic analyses revealed that the adsorption of Congo red on TW was endothermic and spontaneous in nature. The results indicated that TW can be employed as a potential low-cost adsorbent for the removal of Congo red from aqueous solution.     

Use of CaCl2 modified bentonite for removal of Congo red dye from aqueous solutions

CaCl₂ modified bentonite (BCa²⁺), a clean and cost-effective adsorbent with a basal spacing of 15.43 Å, was prepared for the removal of Congo red dye from water. It was effective for the removal of Congo red with a high adsorption capacity, and the adsorption was favored over a broad pH range (5-10). The pseudo-second-order kinetic model provided the best correlation of the experimental data. Adsorption isotherms indicated that sorption took place at specific homogeneous sites within the adsorbent. Furthermore, BCa²⁺ showed higher sorption capacity compared with other common materials used as adsorbents for Congo red dye. The results showed that BCa²⁺ could be employed as a low-cost material for the removal of Congo red from aqueous solutions.     

Removal of Basic Dye from Aqueous Solution using Cinnamomum camphora Sawdust: Kinetics,Isotherms, Thermodynamics,and Mass-Transfer Processes

Cinnamomum camphora sawdust (CCS) was employed as a cheap and effective biosorbent to remove basic dye from aqueous solutions. The biosorbent was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Adsorption experiments were carried out in a batch system as a function of initial pH, adsorbent dose and particle size, ionic strength, initial dye concentration, and reaction temperature. The selected basic dye (malachite green) adsorption onto CCS significantly depended on these factors. By comparative kinetic analysis, the rate of sorption was conformed with good correlation to pseudo-second-order kinetics. Equilibrium data were fitted well by Langmuir isotherm with the maximum adsorption capacity of 155.0 mg/g at the temperature of 318 K and pH 7.0 ± 0.1. Thermodynamic parameters proved that malachite green dye biosorption process was spontaneous and endothermic within the investigated temperature range. The mechanism of adsorption was also studied. It was found that the adsorption of malachite green onto CCS was mainly governed by film diffusion. The electrostatic attractions and ionic interactions between malachite green dye and CCS might be responsible for the adsorption process. The comparative investigation suggested that the sawdust could be considered as a potential adsorbent for malachite green dye removal from wastewater.     

The chemical bonding of copper ions on kaolin from Suzhou, China

Reactions of copper with kaolin are important in determining copper fate in the environment. Adsorption characteristics of Cu by the kaolin from Suzhou, China were investigated at varying Cu concentrations (0 to 100 mg/l), pH values (approximately 2 to 11) and temperature (25, 40 and 50 °C). Cu adsorption by the kaolin was well described by the Langmuir and Freundlich adsorption equations. The kaolin did not exhibit the adsorption maximum, 666.67 mg/kg, as determined by the linearized form of the Langmuir equation. The k_d values decreased exponentially with increasing initial Cu concentrations in the solution. A unit increase in pH resulted in approximately 8.47, 9.61 and 10.82% increase in Cu adsorption by the kaolin at the initial Cu concentration 5, 50, 100 mg/l, respectively. The pH₅₀ values increase with increasing initial Cu concentration. Desorption of Cu was well described by the linear model (y = 0.0917x + 0.7136) with correlation coefficient R² = 0.9994. Most of the adsorbed Cu is nonspecific adsorption; the mobility of Cu in the kaolin from Suzhou, China is high under low pH conditions.     

Removal of Orange II by Phosphonium-modified Algerian Bentonites

An Algerian montmorillonite was modified with two organic surfactants, methyltriphenyl phosphonium bromide and n-hexyltriphenyl phosphonium bromide. The solids obtained were used as adsorbents to remove Orange II, an anionic dye from aqueous solutions. Batch experiments were conducted to study the effects of temperature (20–60°C), initial concentration of adsorbate (50–150 mg L^?1) and pH of solution 6.5 on dye adsorption. Due to their organophilic nature, exchanged montmorillonites were able to adsorb Orange II at a very high level. Adsorption of Orange II for B-NHTPB and B-MTPB at different pH show that the adsorption capacity clearly decreases with an increase in pH of the initial solution from 2 to 8, this decrease being dramatic for pH > 8. This may be due to hydrophobic interactions of the organic dye with both phosphonium molecules and the remaining non-covered portion of siloxane surface. The kinetics of the adsorption was discussed on the basis of three kinetic models, i.e., the pseudo-first-order, the pseudo-second-order, and the intraparticle diffusion models. Equilibrium is reached after 30 min and 60 min for B-MTPB and B-NHTPB, respectively; the pseudo-second-order kinetic model described very well the adsorption of Orange II on modified bentonites. The non-linear Langmuir model provided the best correlation of experimental data, maximum adsorption of Orange II is 53.78 mg g^?1 for B-NHTPB and 33.79 mg g^?1 for B-MTPB. The thermodynamic parameters, such as free energy of adsorption (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were also determined and evaluated. From thermodynamic studies, it was deduced that the adsorption was spontaneous and exothermic.     

Sol–gel-immobilized recombinant E. coli for biosorption of Cd

Recombinant Escherichia coli engineered with a metal-binding peptide was immobilized by entrapment in SiO₂ gel beads using the sol–gel method. Biosorption of Cd²⁺ ions by the immobilized cells was studied in both batch and continuous systems. Adsorption equilibrium could be established within 3 h and the kinetics was well described by the pseudo-second-order kinetic model. The equilibrium data were best described by the Langmuir isotherm with the maximum uptake capacity being 79.9 mg/g cell at 25 °C. More than 95% of the adsorbed Cd²⁺ could be removed with 0.1 M CaCl₂ during desorption. No loss in adsorption capacity was found up to five repeated adsorption/desorption cycles. From mass transfer analysis, only intraparticle diffusion effect was found to be important at low Cd²⁺ concentration (50 mg/dm³), while at high concentration (250 mg/dm³), both intraparticle and external mass transfer affected biosorption. Continuous removal and recovery of Cd²⁺ could be carried out by the immobilized cells in a packed-bed reactor.