Biosorption of Cr(VI) and Zn(II) ions from aqueous solution onto the solid biodiesel waste residue: mechanistic, kinetic and thermodynamic studies

In this present study, the biosorption of Cr(VI) and Zn(II) ions from synthetic aqueous solution on defatted J atropha oil cake (DJOC) was investigated. The effect of various process parameters such as the initial pH, adsorbent dosage, initial metal ion concentration and contact time has been studied in batch-stirred experiments. Maximum removal of Cr(VI) and Zn(II) ions in aqueous solution was observed at pH 2.0 and pH. 5.0, respectively. The removal efficiency of Cr(VI) and Zn(II) ions from the aqueous solution was found to be 72.56 and 79.81 %, respectively, for initial metal ion concentration of 500 mg/L at 6 g/L dosage concentration. The biosorbent was characterized by Fourier transform infrared, scanning electron microscopy and zero point charge. Equilibrium data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models and the best fit is found to be with the Freundlich isotherm for both Cr(VI) and Zn(II) metal ions. The kinetic data obtained at different metal ion concentration have been analysed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and were found to follow the pseudo-second-order kinetic model. The values of mass transfer diffusion coefficients (D _e) were determined by Boyd model and compared with literature values. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were analysed using the equilibrium constant values (K _e) obtained from experimental data at different temperatures. The results showed that biosorption of Cr(VI) and Zn(II) ions onto the DJOC system is more spontaneous and exothermic in nature. The results indicate that DJOC was shown to be a promising adsorbent for the removal of Cr(VI) and Zn(II) ions from aqueous solution.     

Mechanisms of chromium and arsenite adsorption by amino-functionalized SBA-15

The adsorption of Cr(VI) and As(III) by amino-functionalized SBA-15 (NH₂-SBA-15) from single and binary systems were investigated in this work. The effects of pH and temperature on the adsorption of NH₂-SBA-15 were studied. Adsorption kinetics, isotherm model, and thermodynamics were studied to analyze the experimental data. pH 2 was the optimum condition for the adsorption of Cr(VI) and pH 4 for As(III) adsorption. Increasing temperature had a positive effect on the removal of both Cr(VI) and As(III). The Freundlich isotherm model can depict the adsorption process best. The pseudo-second-order kinetic model fitted well with the kinetic data of Cr(VI) and As(III) in the single-component system. In the binary system, the adsorption of As(III) by NH₂-SBA-15 was slightly enhanced with the presence of Cr(VI); however, As(III) had no obvious effect on the removal of Cr(VI). Regeneration experiments indicated that 0.1 mol/L NaHCO₃ was an efficient desorbent for the recovery of Cr(VI) and As(III) from NH₂-SBA-15; the desorption rates for Cr(VI) and As(III) were 91.6 and 33.59 %, respectively. After five recycling cycles, the removal rates were 88 and 7 % for Cr(VI) and As(III) adsorption by NH₂-SBA-15, respectively.     

Removal of Cr(VI) onto Ficus carica biosorbent from water

The utilization of sustainable and biodegradable lignocellulosic fiber to detoxify the noxious Cr(VI) from wastewater is considered a versatile approach to clean up a contaminated aquatic environment. The aim of the present research is to assess the proficiency and mechanism of biosorption on Ficus carica bast fiber via isotherm models (Langmuir, Freundlich, Temkin, Harkin’s–Jura, and Dubinin–Radushkevich), kinetic models, and thermodynamic parameters. The biomass extracted from fig plant was characterized by scanning electron microscopy and Fourier-transform infrared spectroscopy. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and contact time were studied by batch method. The equilibrium data were best represented by the Langmuir isotherm model, and the maximum adsorption capacity of Cr(VI) onto biosorbent was found to be 19.68 mg/g. The pseudo-second-order kinetic model adequately described the kinetic data. The calculated values of thermodynamic parameters such as enthalpy change (?H ⁰), entropy change (?S ⁰), and free energy change (?G ⁰) were 21.55 kJ/mol, 76.24 J/mol?K, and ?1.55 kJ/mol, respectively, at 30 °C which accounted for spontaneous and endothermic processes. The study of adsorbent capacity for Cr(VI) removal in the presence of Na⁺, Mg²⁺, Ca²⁺, SO ₄ ^2? , HCO ₃ ^? and Cl^? illustrated that the removal of Cr(VI) increased in the presence of HCO^3? ions; the presence of Na⁺, SO ₄ ^2? or Cl^? showed no significant influence on Cr(VI) adsorption, while Ca²⁺ and Mg²⁺ ions led to an insignificant decrease in Cr(VI) adsorption. Further, the desorption studies illustrated that 31.10 % of metal ions can be removed from an aqueous system, out of which 26.63 % of metal ions can be recovered by desorption in first cycle and the adsorbent can be reused. The results of the scale-up study show that the ecofriendly detoxification of Cr(VI) from aqueous systems was technologically feasible.     

Synthesis of α-Fe2O3 nanofibers for applications in removal and recovery of Cr(VI) from wastewater

Purpose

Nanomaterials such as iron oxides and ferrites have been intensively investigated for water treatment and environmental remediation applications. The purpose of this work is to synthesize α-Fe₂O₃ nanofibers for potential applications in removal and recovery of noxious Cr(VI) from wastewater.

Methods

α-Fe₂O₃ nanofibers were synthesized via a simple hydrothermal route followed by calcination. The crystallographic structure and the morphology of the as-prepared α-Fe₂O₃ nanofibers were characterized by X-ray diffraction, scanning electron microscope, and transmission electron microscope. Batch adsorption experiments were conducted, and Fourier transform infrared spectra were recorded before and after adsorption to investigate the Cr(VI) removal performance and adsorption mechanism. Langmuir and Freundlich modes were employed to analyze the adsorption behavior of Cr(VI) on the α-Fe₂O₃ nanofibers.

Results

Very thin and porous α-Fe₂O₃ nanofibers have been successfully synthesized for investigation of Cr(VI) removal capability from synthetic wastewater. Batch experiments revealed that the as-prepared α-Fe₂O₃ nanofibers exhibited excellent Cr(VI) removal performance with a maximum adsorption capacity of 16.17 mg g^?1. Furthermore, the adsorption capacity almost kept unchanged after recycling and reusing. The Cr(VI) adsorption process was found to follow the pseudo-second-order kinetics model, and the corresponding thermodynamic parameters ΔG°, ΔH°, and ΔS° at 298 K were calculated to be ?26.60 kJ?mol^?1, ?3.32 kJ?mol^?1, and 78.12 J?mol^?1 K^?1, respectively.

Conclusions

The as-prepared α-Fe₂O₃ nanofibers can be utilized as efficient low-cost nano-absorbents for removal and recovery of Cr(VI) from wastewater.     

Determination of the Adsorption Isotherm of Vapor-Phase Mercury Chloride on Powdered Activated Carbon Using Thermogravimetric Analysis

Abstract

This study investigated the use of thermogravimetric analysis (TGA) to determine the adsorptive capacity and adsorption isotherm of vapor-phase mercury chloride on powdered activated carbon (PAC). The technique is commonly applied to remove mercury-containing air pollutants from gas streams emitted from municipal solid waste incinerators. An alternative form of powdered activated carbon derived from a pyrolyzed tire char was prepared for use herein. The capacity of waste tire-derived PAC to adsorb vapor-phase HgCl₂ was successfully measured using a self-designed TGA adsorption system. Experimental results showed that the maximum adsorptive capacities of HgCl₂ were 1.75, 0.688, and 0.230 mg of HgCl₂ per gram of powdered activated carbon derived from carbon black at 30, 70, and 150 °C for 500 µg/m³ of HgCl₂, respectively. Four adsorption isotherms obtained using the Langmuir, Freundlich, Redlich-Peterson, and Brunauer–Emmett–Teller (BET) models were used to simulate the adsorption of HgCl₂. The comparison of experimental data associated with the four adsorption isotherms indicated that BET fit the experimental results better than did the other isotherms at 30 °C, whereas the Freundlich isotherm fit the experimental results better at 70 and 150 °C. Furthermore, the calculations of the parameters associated with Langmuir and Freundlich isotherms revealed that the adsorption of HgCl₂ by PAC-derived carbon black favored adsorption at various HgCl₂ concentrations and temperatures.     

The removal of uranium (VI) from aqueous solutions onto activated carbon developed from grinded used tire

In this study, activated carbon was prepared from waste tire by KOH chemical activation. The pore properties including the BET surface area, pore volume, pore size distribution, and average pore diameter were characterized. BET surface area of the activated carbon was determined as 558 m²/g. The adsorption of uranium ions from the aqueous solution using this activated carbon has been investigated. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied by a batch method. The optimum pH for adsorption was found to be 3. The removal efficiency has also been determined for the adsorption system as a function of initial concentration. The experimental results were fitted to Langmuir, Freundlich, and Dubinin–Radushkevich (D-R) isotherm models. A comparison of best-fitting was performed using the coefficient of correlation and the Langmuir isotherm was found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of uranium ions onto waste tire activated carbon was 158.73 mg/g. The thermodynamic equilibrium constant and the Gibbs free energy were determined and results indicated the spontaneous nature of the adsorption process. Kinetics data were best described by pseudo-second-order model.     

Preparation of activated carbon from dried pods of Prosopis cineraria with zinc chloride activation for the removal of phenol

Utilization of agrowaste materials for the production of activated carbon, as an excellent adsorbent with large surface area, is well established industrially, for dephenolation of wastewater. In the present work, dried pods of Prosopis cineraria—a novel and low-cost agrowaste material—were used to prepare activated carbons by zinc chloride activation. Batch adsorption experiments were carried out to study the effects of various physicochemical parameters such as initial phenol concentration, adsorbent dose, initial solution pH, and temperature. Pseudo-first-order second-order and diffusion kinetic models were used to identify the possible mechanisms of such adsorption process. The Langmuir and Freundlich equations were used to analyze the adsorption equilibrium. Maximum removal efficiency of 86 % was obtained with 25 mg?L^?1 of initial phenol concentration. The favorable pH for maximum phenol adsorption was 4.0. Freundlich equation represented the adsorption equilibrium data more ideally than the Langmuir. The maximum adsorption capacity obtained was 78.32 mg?g^?1 at a temperature of 30 °C and 25 mg?L^?1 initial phenol concentration. The adsorption was spontaneous and endothermic. The pseudo-second-order model, an indication of chemisorption mechanism, fitted the experimental data better than the pseudo-first-order Lagergren model. Regeneration of spent activated carbon was carried out using Pseudomonas putida MTCC 2252 as the phenol-degrading microorganism. Maximum regeneration up to 57.5 % was recorded, when loaded phenol concentration was 25 mg?L^?1. The data obtained in this study would be useful in designing and fabricating an efficient treatment plant for phenol-rich effluents.     

Efficient removal of uranium(VI) from aqueous systems by heat-treated carbon microspheres

In this study, uranium(VI) was successfully removed from aqueous solutions using heat-treated carbon microspheres based on a batch adsorption technique. Influence of the parameters, such as solution pH, contact time, initial uranium(VI) concentration, and temperature on the removal efficiency have been investigated in detail. The results reveal that the maximum adsorption capacity of the heat-treated carbon microspheres toward uranium(VI) is 92.08 mg g^?1, displaying a high efficiency for the removal of uranium(VI) from aqueous solution. The experimental data are analyzed using sorption kinetic models. It is revealed that the process obey the pseudo-second-order kinetic model, the determining step might be chemical sorption. The thermodynamic parameters, such as ΔH°, ΔS°, and ΔG° show that the process is endothermic and spontaneous. This work provides an efficient, fast, and convenient approach for the removal of uranium(VI) from aqueous solutions.     

Use of activated dry flowers (ADF) of Alstonia Scholaris for chromium (Vl) removal: equilibrium, kinetics and thermodynamics studies

In this study, a natural adsorbent (activated dry flowers (ADF)) was prepared from plant-derived waste biomass by chemical activation and employed for chromium (VI) removal from aqueous medium using experimental batch technique. Experiments were carried out as function of adsorbent dosage, pH, and contact time. The maximum chromium (Vl) removal was observed at initial pH 3 (~94 % removal). The equilibrium data was fitted well to Langmuir isotherm. The adsorption capacity of ADF was found to be 4.40 (mg chromium (Vl)/g) which was comparable to the adsorption capacity of some other adsorbents documented. Among various kinetic models applied, pseudo second-order model was found to explain the kinetics of chromium (VI) adsorption most effectively (R ² >0.99). Thermodynamic parameters such as ΔG, ΔS, and ΔH shows that adsorption process was spontaneous and endothermic at all the concentration ranges studied. Desorption of chromium (Vl) with 2 N NaOH was effective (~71 %) and, hence, there exists the possibility of recycling the ADF. The major advantages of using ADF as an adsorbent are due to its effectiveness in reducing the concentration of chromium (Vl) to very low levels. It requires little processing and is reversible as well as eco-friendly in contrast to traditional methods.     

Utilization of Arachis hypogaea hull,an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m²/g and 0.28 cm³/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

Kinetics and isotherm analysis of Tropaeoline 000 adsorption onto unsaturated polyester resin (UPR): a non-carbon adsorbent

The presence of dyes in water is undesirable due to the toxicological impact of their entrance into the food chain. Owing to the recalcitrant nature of dyes to biological oxidation, a tertiary treatment like adsorption is required. In the present study, unsaturated polyester resin (UPR) has been used as a sorbent in the treatment of dye-contaminated water. Different concentrations of Tropaeoline 000 containing water were treated with UPR. The preliminary investigations were carried out by batch adsorption to examine the effects of pH, adsorbate concentration, adsorbent dosage, contact time, and temperature. A plausible mechanism for the ongoing adsorption process and thermodynamic parameters have also been obtained from Langmuir and Freundlich adsorption isotherm models. Thermodynamic parameter showed that the sorption process of Tropaeoline 000 onto activated carbon (AC) and UPR were feasible, spontaneous, and endothermic under studied conditions. The estimated values for (ΔG) are ?10.48?×?10³ and ?6.098?×?10³ kJ mol^?1 over AC and UPR at 303 K (30 °C), indicating towards a spontaneous process. The adsorption process followed pseudo-first-order model. The mass transfer property of the sorption process was studied using Lagergren pseudo-first-order kinetic models. The values of % removal and k _ad for dye systems were calculated at different temperatures (303–323 K). The mechanism of the adsorption process was determined from the intraparticle diffusion model.     

改性蜂窝煤渣吸附Cr（VI）的动力学和热力学性能

利用碳酸钡对蜂窝煤渣进行改性，通过粉末X射线衍射光谱（XRD）和扫描电镜（SEM）对改性前后蜂窝煤渣的物质组成和形貌进行表征，研究了改性蜂窝煤渣吸附Cr（VI）的动力学和热力学性能。实验结果表明，改性蜂窝煤渣对Cr（VI）具有良好的吸附能力，吸附过程符合准二级吸附动力学模型。分别用Langmuir、Freundlich、D-R和Tempkin等4种吸附等温线模型对实验数据进行拟合，Langmuir方程拟合效果最好，25、35和45℃下的饱和吸附量分别为2．985、2．562和2．630mg／g。D—R和Tempkin模型研究表明，吸附过程属于物理吸附。热力学研究表明，改性蜂窝煤渣对Cr（VI）的吸附是一个自发的、放热过程。     

Biosorption of Cr(VI) by free and immobilized Pediastrum boryanum biomass: equilibrium, kinetic, and thermodynamic studies

Background and purpose

The biosorption of Cr(VI) from aqueous solution has been studied using free and immobilized Pediastrum boryanum cells in a batch system. The algal cells were immobilized in alginate and alginate?Cgelatin beads via entrapment, and their algal cell free counterparts were used as control systems during biosorption studies of Cr(VI).

Methods

The changes in the functional groups of the biosorbents formulations were confirmed by Fourier transform infrared spectra. The effect of pH, equilibrium time, initial concentration of metal ions, and temperature on the biosorption of Cr(VI) ion was investigated.

Results

The maximum Cr(VI) biosorption capacities were found to be 17.3, 6.73, 14.0, 23.8, and 29.6?mg/g for the free algal cells, and alginate, alginate?Cgelatin, alginate?Ccells, and alginate?Cgelatin?Ccells at pH?2.0, which are corresponding to an initial Cr(VI) concentration of 400?mg/L. The biosorption of Cr(VI) on all the tested biosorbents (P. boryanum cells, alginate, alginate?Cgelatin, and alginate?Ccells, alginate?Cgelatin?Ccells) followed Langmuir adsorption isotherm model.

Conclusion

The thermodynamic studies indicated that the biosorption process was spontaneous and endothermic in nature under studied conditions. For all the tested biosorbents, biosorption kinetic was best described by the pseudo-second-order model.     

Adsorption of Cu2+ and methyl orange from aqueous solutions by activated carbons of corncob-derived char wastes

Corncob-derived char wastes (CCW) obtained from biomass conversion to syngas production through corncob steam gasification, which were often discarded, were utilized for preparation of activated carbon by calcination, and KOH and HNO₃ activation treatments, on the view of environment protection and waste recycling. Their adsorption performance in the removal of heavy metal ions and dye molecules from wastewater was evaluated by using Cu²⁺ and methyl orange (MO) as the model pollutant. The surface and structure characteristics of the CCW-based activated carbons (CACs) were investigated by N₂ adsorption, CO₂ adsorption, FT-IR, and He-TPD. The adsorption capacity varied with the activation methods of CACs and different initial solution concentrations, indicating that the adsorption behavior was influenced by not only the surface area and porosity but also the oxygen functional groups on the surface of the CACs. The equilibrium adsorption data were analyzed with the Langmuir, Freundlich, and Temkin isotherm models, and the adsorption kinetics was evaluated by the pseudo-first-order and pseudo-second-order models.     

Removal of arsenic species from water by batch and column operations on bagasse fly ash

Bagasse fly ash (BFA, a sugar industrial waste) was used as low-cost adsorbent for the uptake of arsenate and arsenite species from water. The optimum conditions for the removal of both species of arsenic were as follows: pH 7.0, concentration 50.0 μg/L, contact time 50.0 min, adsorbent dose 3.0 g/L, and temperature 20.0 °C, with 95.0 and 89.5 % removal of arsenate and arsenite, respectively. The Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich adsorption isotherms were used to analyze the results. The results of these models indicated single-layer uniform adsorption on heterogeneous surface. Thermodynamic parameters, i.e., ΔG°, ΔH°, and ΔS°, were also calculated. At 20.0 to 30.0 °C, the values of ΔG° lie in the range of ?4,722.75 to ?4,878.82 and ?4,308.80 to ?4,451.73 while the values of ΔH° and ΔS° were ?149.90 and ?121.07, and 15.61 and 14.29 for arsenate and arsenite, respectively, indicating that adsorption is spontaneous and exothermic. Pseudo-first-order kinetics was followed. In column experiments, the adsorption decreased as the flow rate increased with the maximum removal of 98.9 and 95.6 % for arsenate and arsenite, respectively. The bed depth service time and Yoon and Nelson models were used to analyze the experimental data. The adsorption capacity (N _o) of BFA on column was 3.65 and 2.98 mg/cm³ for arsenate and arsenite, respectively. The developed system for the removal of arsenate and arsenite species is economic, rapid, and capable of working under natural conditions. It may be used for the removal of arsenic species from any contaminated water resources.     

Sorption of carbendazim and linuron from aqueous solutions with activated carbon produced from spent coffee grounds: Equilibrium,kinetic and thermodynamic approach

Spent coffee grounds (SCG) have been used for the production of activated carbon (AC) by impregnation with different ratios of phosphoric acid at 600?°C, Xp (H₃PO₄/coffee): 3:1^30%, 4:1^30%, 3:1^50% and 4:1^50%. The obtained AC was characterized by BET, FTIR and SEM. BET surface area corresponds to 803.422 m² g^?1. The influences of the main parameters such as contact time, the pesticides initial concentration, adsorbent dose, pH and temperature on the efficiency of separation process were investigated during the batch operational mode. Results were modeled by adsorption isotherms: Langmuir, Freundlich and Temkin isotherms, which gave satisfactory correlation coefficients. The maximum adsorption capacities calculated from the Langmuir isotherms were 11.918?mg g^?1 for carbendazim and 5.834?mg g^?1 for linuron at room temperature. Adsorption kinetics of carbendazim and linuron have been studied by the pseudo-first-order, the pseudo-second-order and the intraparticle diffusion model. The results of adsorption kinetics have been fitted the best by pseudo-second-order model. The resulted data from FTIR characterization pointed to the presence of many functional groups on the AC surface. SCG adsorbent, as an eco-friendly and low-cost material, showed high potential for the removal of carbendazim and linuron from aqueous solutions.     

Potential use of Caulerpa fastigiata biomass for removal of lead: kinetics, isotherms, thermodynamic, and characterization studies

The present study attempts to analyze the biosorption trend of biosorbent Caulerpa fastigiata (macroalgae) biomass for removal of toxic heavy metal ion Pb (II) from solution as a function of initial metal ion concentration, pH, temperature, sorbent dosage, and biomass particle size. The sorption data fitted with various isotherm models and Freundlich model was the best one with correlation coefficient of 0.999. Kinetic study results revealed that the sorption data on Pb (II) with correlation coefficient of 0.999 can best be represented by pseudo-second-order. The biosorption capacity (q _e ) of Pb (II) is 16.11?±?0.32 mg g^?1 on C. fastigiata biomass. Thermodynamic studies showed that the process is exothermic (ΔH° negative). Free energy change (ΔG°) with negative sign reflected the feasibility and spontaneous nature of the process. The SEM studies showed Pb (II) biosorption on selective grains of the biosorbent. The FTIR spectra indicated bands corresponding to –OH, COO^?, –CH, C?=?C, C?=?S, and –C–C– groups were involved in the biosorption process. The XRD pattern of the C. fastigiata was found to be mostly amorphous in nature.     

聚丙烯酸水凝胶对氯化-1-丁基-3-甲基咪唑离子液体的吸附热力学和动力学研究

通过水溶液聚合法制备了聚丙烯酸水凝胶（polyacrylic acid,PAA）,研究了溶液酸碱度和温度对聚丙烯酸水凝胶吸附氯化1-丁基3-甲基咪唑离子液体的影响。结果表明,水凝胶对氯化1-丁基3-甲基咪唑离子液体的吸附量随溶液pH值增大而逐渐增大,pH=2～4时增幅明显,而pH大于4时变化趋于缓慢;随温度的升高而逐渐降低。该等温吸附行为基本符合Langmuir吸附等温式,由二级吸附动力学模型获得的吸附过程活化能（Ea=52.470 kJ/mol）可以看出,PAA对氯化1-丁基3-甲基咪唑的吸附属于化学吸附范畴。