Electrochemical removal of boron from water: Adsorption and thermodynamic studies

The present work provides an electrochemical removal of boron from water and its kinetics, thermodynamics, isotherm using mild steel and stainless steel as anode and cathode respectively. The various operating parameters on the removal efficiency of boron were investigated, such as initial boron ion concentration, initial pH, current density and temperature. The results showed that the optimum removal efficiency of 93.2% was achieved at a current density of 0.2 A dm^?2 at pH of 7.0. First‐, second‐order rate equations, Elovich and Intraparticle models were applied to study adsorption kinetics. Adsorption isotherms of boron on Fe(OH)₃ were determined and correlated with isotherm equations such as Langmuir, Freundlich and D‐R models. Thermodynamic parameters, such as standard Gibb's free energy (ΔG°), standard enthalpy (ΔH°) and standard entropy (ΔS°), were also evaluated by Van't Hoff equation. The adsorption process follows second‐order kinetics. The adsorption of boron preferably fits with Langmuir adsorption isotherm suggesting monolayer coverage of adsorbed molecules. The adsorption of boron onto Fe(OH)₃ was found to be spontaneous and endothermic. © 2011 Canadian Society for Chemical Engineering     

Monodisperse‐porous N‐methyl‐D‐glucamine functionalized poly(vinylbenzyl chloride‐co‐divinylbenzene) beads as boron selective sorbent

To generate a new sorbent with high boron adsorption capacity, we synthesized monodisperse‐porous poly(vinylbenzyl chloride‐co‐divinylbenzene), poly(VBC‐co‐DVB), beads 8.5 μm in size by a new “modified seeded polymerization” technique. By using their chloromethyl functionality, the beads were derivatized by a simple, direct reaction with a boron‐selective ligand, N‐methyl‐D ‐glucamine (NMDG). The selection of poly(VBC‐co‐DVB) beads as a starting material allowed to obtain high boron sensitive‐ligand density on the beads depending on their high chloromethyl content. In the batch adsorption runs performed using NMDG‐attached poly(VBC‐co‐DVB) beads as sorbent, boron removal was efficiently performed in a wide pH range between 4 and 11. Quantitative boron removal was observed with the sorbent concentration of 4 g/L. In the same runs, plateau value of equilibrium adsorption isotherm was obtained as 14 mg boron/g beads. Relatively higher boron adsorption was explained by high ligand density and high specific surface area of the sorbent. Boron adsorption isotherms were analyzed using Langmuir and Freundlich models. In the kinetic runs performed for boron removal, the equilibrium was attained within 10 min at a value of 98%. The fast kinetic behavior was explained by the smaller particle size and enhanced porosity of the new sorbent. Infinite solution volume model and unreacted core model were used to evaluate boron adsorption onto the NMDG‐attached poly(VBC‐co‐DVB) beads. The results indicated that the adsorption process is controlled by the particle‐diffusion step. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Removal of Boron from Aqueous Solutions by Adsorption Using Fly Ash,Zeolite, and Demineralized Lignite

In the present study for the purpose of removal of boron from water by adsorption using adsorbents like fly ash, natural zeolite, and demineralized lignite was investigated. Boron in water was removed with fly ash, zeolite, and demineralized lignite with different capacities. Ninety-four percent boron was removed using fly ash. Batch experiments were conducted to test the removal capacity, to obtain adsorption isotherms, thermodynamic and kinetic parameters. Boron removal by all adsorbents was affected by pH of solution; maximum adsorption was achieved at pH 10. Adsorption of boron on fly ash was investigated by the Langmuir, Freundlich, and the Dubinin-Radushkevich models. Standard entropy and enthalpy changes of adsorption of boron on fly ash were, ΔS ⁰  = ?0.69 kJ/mol K and ΔH ⁰  = ?215.34 kJ/mol, respectively. The negative value of ΔS ⁰ indicated decreased randomness at the solid/solution interface during the adsorption boron on the fly ash sample. Negative values of ΔH ⁰ showed the exothermic nature of the process. The negative values of ΔG ⁰ implied that the adsorption of boron on fly ash samples was spontaneous. Adsorption of boron on fly ash occurred with a pseudo-second order kinetic model, and intraparticle diffusion of boron species had also some effect in adsorption kinetics.     

Synthesis of chitosan beads as boron sorbents

Parameters, such as pH, temperature, initial boron concentration, adsorbent dosage, and ionic strength, affecting boron adsorption onto chitosan beads were examined in this study. The following values were obtained as the optimum conditions in our studied ranges: pH 8.0, temperature = 308 K, amount of chitosan beads = 0.15 g, initial boron concentration = 4 mg L⁻¹, and ionic strength = 0.1 M NaCl]. The adsorption kinetics were also examined in terms of three kinetic models: the pseudo‐first‐order, pseudo‐second‐order, and intraparticle diffusion models. The pseudo‐second‐order kinetic model showed very good agreement with the experimental data. Intraparticle plots seemed to have two steps and indicated multilinearity. Equilibrium data were evaluated with nonlinear and linear forms of the Langmuir and Freundlich equations. The experimental data conformed to the Freundlich equation on the basis of the formation of multilayer adsorption. To characterize the synthesized chitosan beads, we used Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) analyses. As shown by FTIR analysis, the boron species may have interacted with the NH₂ groups on chitosan. Microparticles of about 5 μm appeared in the SEM micrographs of the chitosan beads. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fly ash as a sorbent for boron removal from aqueous solutions: Equilibrium and thermodynamic studies

ABSTRACT

This study presents the application of fly ash from brown coal and biomass burning power plant as a sorbent for the removal of boron ions from an aqueous solution. The adsorption process efficiency depended on the parameters, such as adsorbent dosage, pH, temperature, agitation time and initial boron concentration. The experimental data fitted well with the Freundlich isotherm model and the maximum capacity was found to be 16.14 mg g^?1. The adsorption kinetics followed the pseudo-second-order model. Also, the intra-particle diffusion model parameters were calculated. Thermodynamic parameters such as change in free energy (ΔG°), enthalpy (ΔH°), entropy (ΔS°) revealed on exothermic nature of boron adsorption onto the fly ash.     

新型壳聚糖/锆复合球的制备及硼吸附性能

通过氧氯化锆与壳聚糖的配位反应以及Zr （OH）4在壳聚糖内的原位沉淀,制备了一种新型壳聚糖-锆复合球（CTS-Zr）并用于硼的吸附分离。采用扫描电子显微镜（SEM）和傅里叶红外光谱（FTIR）对CTS-Zr进行了表征,系统考察了溶液pH、硼初始浓度、接触时间、温度及共存阴离子Cl^-、NO₃^-和SO₄^2-对CTS-Zr吸附性能的影响。结果表明：pH=2～7时,CTS-Zr对硼的吸附效率较高;吸附平衡行为符合Langmuir等温吸附模型;pH=7时,最大吸附量计算值为21.1 mg·g^-1;吸附动力学符合准二级动力学模型;常见的共存阴离子对硼的吸附影响很小;吸附热力学研究表明,CTS-Zr对硼的吸附过程为放热的非自发过程;使用pH=12的NaOH水溶液,对吸附剂CTS-Zr进行了洗脱,洗脱效率为96.3%,且经过3次吸附-解吸循环后,CTS-Zr的吸附效率没有明显降低。     

Synthesis of N-methylglucamine modified macroporous poly(GMA-co-TRIM) and its performance as a boron sorbent

A chelating polymeric sorbent was developed by functionalizing poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate), poly(GMA-co-TRIM), with N-methylglucamine (MG) via a simple post-grafting route. The resulting well-defined millimeter-sized spheres of poly(GMA-co-TRIM)–MG had permanent macropore structures and low swelling degree, with accessible ligands of 1.84 mmol/g. The boron adsorption behavior of the sorbent was studied in batch mode by varying different parameters like the pH value, the initial concentration of boron and the adsorption time under noncompetitive conditions. It was found that the sorbent always maintained the high capacity between pH 2.6 and 8.6, in which the optimum pH was 7.5. The adsorption behavior of the sorbent obeyed the Langmuir isotherm well. The adsorption capacity of the sorbent for boron was in the same level as that of a commercially available N-methylglucamine-type polystyrene resin. However, it adsorbed boron more quickly. The sorbent also showed good durability and reusability through the fixed-bed adsorption tests. The study on the separation of boron from brine of salt lake showed a high selectivity of the sorbent, though the capacity for boron decreased due to the interference of diverse ions in brine.     

Synthesis and Characterization of PEG-Modified Polystyrene Particles and Isothermal Equilibrium Adsorption of Bovine Serum Albumin on these Particles

A series of monodisperse submicron polystyrene (PS) particles with different surface monomethoxy poly(ethylene glycol) (mPEG) densities were prepared and characterized. The effects of the chemically grafted mPEG chains (MW = 2,000) on the adsorption of bovine serum albumin (BSA) molecules onto these negatively charged particles at pHs 5 and 3 were investigated. The native particles at both pH values showed the largest values of q _max (maximum amount of BSA adsorbed on the particle surface). The surface mPEG chains were very effective in retarding the BSA adsorption and q _max decreased significantly with increasing surface mPEG density. The values of q _max were greater for both the native and mPEG-modified particles at pH 5 compared to those counterparts at pH 3, due to the different adsorption mechanisms. Hydrophobic interaction predominated in the adsorption of BSA molecules on the particles at pH 5, whereas electrostatic interaction had a crucial influence on the BSA adsorption at pH 3. At pH 5, the adsorption behaviors were qualitatively explained by the calculated values of the free energy barrier against the BSA adsorption. A schematic model was also proposed to qualitatively describe the conformations of BSA molecules adsorbed on the particle surfaces.     

Boron removal from water and its recovery using iron (Fe) oxide/hydroxide-based nanoparticles (NanoFe) and NanoFe-impregnated granular activated carbon as adsorbent

This study presents information obtained by the synthesis of Fe(3) oxide/hydroxide nanoparticles sol (NanoFe) and NanoFe-impregnated granular activated carbon as adsorbents for boron removal from solutions. The research describes an adsorption method for cleaning a solution containing boron contaminants followed by recovery of the adsorbent and the adsorbed material for safe removal or further reuse. The technology provides an efficient method of boron removal from water. A marked effect of NanoFe and NanoFe-impregnated GAC adsorbents concentration and pH level on boron removal efficiency was demonstrated. At least 95–98% boron recovery efficiency is possible using NanoFe sol and Fe-impregnated GAC that in fact also recover the adsorbent for reuse. Boron adsorption onto the NanoFe-impregnated GAC adsorbent may be described by pseudo-second-order reaction kinetics and the Langmuir isotherm model. The boron adsorption capacity on iron (3) oxide nanoparticles and Fe-impregnated GAC at an equilibrium concentration of 0.3 mg/dm³ as B in the solution is much higher than these values for similar adsorbents reported in the literature.     

Mechanism of copper(II) adsorption by polyvinyl polyacrylate

The mechanism of copper adsorption by polyvinyl polyacrylate (PVPA) was examined using ESR and magnetic measurements. The copper adsorption by PVPA obeyed Langmuir adsorption isotherm with the maximum adsorption amounts of 4.17 mmol g^?1 adsorbent, being larger than those of uranium adsorption. Though copper in the solution was completely adsorbed by the resin above pH 4, the ESR intensity was remained low level and only increased above pH 8. The ESR spectrum of Cu(II) ion in PVPA are axial type with tetragonally distorted octahedral symmetry, having parameters of g_⊥ = 2.361, g_? = 2.057, |A_⊥| = 14.0 m cm^?1 (pH 5), and g_⊥ = 2.329, g_? = 2.058, |A_⊥| = 16.2 m cm^?1, |A_?| = 2.7 m cm^?1 (pH 9). The absorption peaks originated from Cu(II)–Cu(II) dimer was also observed (pH 5). The paramagnetic susceptibility of PVPA adsorbed Cu(II) ion at pH 5 explained by the dimer model with |J| = 220 K. These results suggested that most of copper was adsorbed and formed dimer in PVPA, being similar to that in Cu(II)‐acetate monohydrate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5372–5377, 2006     

Kinetics and isotherm studies for the adsorption of boron from water using titanium dioxide

Boron is a necessary element for plants that are generally found in the ground and seawater, but it can also be poisonous in large doses. Contamination of water with boric acid or borate ions is a global concern. Due to the absence of the chemical charge that boron possesses, its removal is often difficult. To investigate boron's adsorption characteristics, kinetic, isotherm, and isothermal studies were performed. The adsorption of boron was shown to be a pH-dependent mechanism, with the best results at around pH 9.0. About 47% of the boron from a solution of 50 mg L⁻¹ was removed using 5 g titanium dioxide in 30 min. It was also demonstrated that boron adsorption kinetics increased with temperature, which is best described by the pseudo-second-order kinetic model (R² > 0.98) and also fits well with Elovich and pseudo-first-order models (R² > 0.94) at pH 9.0. Equilibrium was reached in about 40 min for all the samples. The film boundary layer diffusion step limits the rate. Experimental results correspond well to the Freundlich isotherm (R² = 0.95–0.99). Langmuir and Temkin's isotherms also fitted reasonably well (R² = 0.94–0.98). The Freundlich and Langmuir constants indicate favourable adsorption. The Gibbs free energy (ΔG) values increased negatively (from −11.47 to −15.63 kJ mol⁻¹) with increasing temperature, signifying a feasible and spontaneous process. The enthalpy change (ΔH) value of about 30.35 kJ mol⁻¹ indicated endothermic physical adsorption. The results indicate that titanium dioxide is an excellent and safe adsorbent for the removal of boron from water.     

Boron removal by liquid‐phase polymer‐based retention technique using poly(glycidyl methacrylate N‐methyl D‐glucamine)

The removal of boron was analyzed by liquid‐phase polymer based retention (LPR) technique using washing and enrichment method. The extracting reagents were water‐soluble polymers (WSPs) containing quaternary ammonium salts and N‐methyl‐D ‐glucamine (NMG) groups. The removal experiments of boron using the washing method were conducted at 1 bar of pressure by varying pH, polymer:boron molar ratio, and concentrations of interfering ions (chloride and sulfate). The results showed higher retention capacity for boron (60%) at pH 10 with the polymer containing NMG group. The optimal polymer:boron molar ratio was 40 : 1. Selectivity experiments showed that the presence of interfering ions did not affect the boron removal capacity. The maximal boron retention capacity was determined by the enrichment method, obtaining a value of 12 mg B/g‐polymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adsorption of thorium(IV) on MX-80 bentonite: Effect of pH, ionic strength and temperature

The adsorption of Th(IV) on MX-80 bentonite as a function of pH, ionic strength, Th(IV) concentration and temperature was studied by using batch technique. The results indicated that the adsorption of Th(IV) on bentonite depended on pH, ionic strength and temperature. The adsorption of Th(IV) decreased with increasing temperature, indicating that the adsorption process of Th(IV) on bentonite was exothermic. The experimental data of Th(IV) adsorption isotherms were obtained at T = 293, 303, 313, and 323K, and were analyzed with the Langmuir and Freundlich models, showing that the Langmuir model fitted the adsorption data better than the Freundlich model. Thermodynamic parameters, such as ΔH^o, ΔS^o, and ΔG^o, were calculated from the slope and intercept of the linear plot of lnK_d against 1000/T.     

氨基丙二醇功能化硼螯合树脂的制备及其硼酸吸附性能

分别用3-氨基-1,2-丙二醇（3-APD）和2-氨基-1,3-丙二醇（2-APD）对多孔氯甲基聚苯乙烯树脂（CMPS）进行修饰,制备得到含邻、间位二羟基官能团的硼螯合树脂：PS-3-APD和PS-2-APD。用傅里叶红外光谱仪（FTIR）、元素分析仪（EA）、压汞仪（MIP）和激光粒度仪（LPS）对材料进行表征,确认功能单体成功接枝于氯球上。对两种树脂进行了静态提硼性能研究,分别考察了原料液pH、初始硼酸浓度、外来金属离子对硼酸吸附量的影响,当溶液pH为9.15～9.20时,两种树脂对硼酸吸附量最大;溶液中Na⁺、Mg²⁺、Ca²⁺的存在会一定程度削弱树脂对硼酸吸附性能。吸附动力学表明其吸附速率较快,且均满足准二级动力学模型。与Freundlich相比,吸附等温线更符合Langmuir模型,拟合得到的理论最大吸附量分别为0.730mmol/g和0.868mmol/g。本文对未来新型硼螯合树脂的开发及工业化应用提供参考和指导。     

Sorption of boron on calcium alginate gel beads

In this work, the removal of boron by a biopolymer of alginate was studied in an aqueous solution. The effects of pH, initial boron concentration, alginate concentration in the beads and stirring time were evaluated. The ratio of mannuronic acid to guluronic acid (M/G) in the alginic acid used in this study was determined by NMR. FTIR spectroscopy was used to characterize the alginate and to observe the interactions produced by the boron adsorbed onto the beads. The maximum boron removal observed was 94 mg/g; this rate was obtained with a high initial boron concentration in an alkaline medium. A study of the isotherms established that the experimental data conform better to the Langmuir than the Freundlich isotherm model. The results obtained in the kinetic studies showed that the pseudo-second-order adsorption model is predominant and that the overall rate of boron adsorption appears to be controlled by chemisorptions.     

Adsorption behavior of β-lactoglobulin onto polyethersulfone membrane surface

The adsorption of whey protein onto polyethersulfone (PES) membrane was investigated by static adsorption experiments to understand fouling mechanism and optimize the process condition to minimize the membrane fouling. Adsorption isotherm was applied to calculate the isotherm parameters such as adsorption capacity (K_F) and surface heterogeneity (1/n). The K_F values increased about 3.7 times at pH 3.0, 1.5 times at pH 5.2, and 2.3 times at pH 9.0 compared to that at pH 7.0. The hydrophobic interaction by dissociation of dimer structure of β-lactoglobulin to monomer structure at acidic and alkaline conditions showed the greatly increasing of the amount of protein adsorption by the protein and membrane interaction which might form the strong and rigid protein layer on the polymeric membrane surface. The addition of salt reduced the protein adsorption on PES membrane because of the interactions between charged protein molecules and salt ions.     

Removal of basic and acid dyes from aqueous solutions by a waste containing boron impurity

In this study, batch experiments were carried out for the sorption of basic blue 41 (BB 41), and acid blue 225 (AB 225) onto boron waste (BW) from boron enrichment plant. The operating variables studied are the initial dye concentration, contact time, solution pH, and adsorbent dosage. The experimental equilibrium data were analyzed by using various adsorption isotherm models and the results have shown that the adsorption behavior of AB 225 and BB 41 could be described well reasonably by Langmuir and Temkin isotherms, respectively. Kinetics studies indicated that the adsorption of both dyes follow pseudo-second-order kinetics. The sorption of basic dye increased at high pH values, whereas the opposite was true for acidic dye. The results indicate that BW could be employed as low-cost alternatives to the commercially available adsorbents in wastewater treatment for the removal of acid and basic dyes.     

The adsorption behaviors of the multiple stimulus‐responsive poly(ethylene glycol)‐based hydrogels for removal of RhB dye

In this article, the multiple stimulus‐responsive organic/inorganic hybrid hydrogels by combining poly(2‐(2‐methoxyethoxy) ethyl methacrylate‐co‐oligo (ethylene glycol) methacrylate‐co‐acrylic acid) (PMOA) hydrogel with magnetic attapulgite/Fe₃O₄ (AT‐Fe₃O₄) nanoparticles were applied to the removal of Rhodamine B (RhB) dye from wastewater. The adsorption of RhB by the hydrogels was carried out under different external environmental, such as pH, temperature and magnetic‐field. The results showed that the hydrogels still possessed temperature, pH and magnetic‐field sensitivity during the adsorption process, which indicated that the adsorption could be controlled by the hydrogels responsive. The dye adsorption had a significant increment at 30°C and the removal of RhB could reach to over 95%. Besides, the low pH values were also favorable for the RhB adsorption, the removal was over 90% at pH = 4.56. Kinetic studies showed that the pseudo‐second order kinetic model well fitted the experimental data. The rate constant of adsorption was 0.0379 g/mg min. Langmuir and Freundlich isotherm models were applied to the equilibrium adsorption for describing the interaction between sorbent and adsorbate. The maximum K_L and K_F were 2.23 (L/g) and 0.87 (mg/g) at 30°C, respectively. Under the external magnetic‐field, the adsorption rate significantly increased within 250 min and the hydrogels could be separated easily from wastewater. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42244.     

Adsorption of Bovine Serum Albumine Onto Poly (<Emphasis Type="Italic">N</Emphasis>-<Emphasis Type="Italic">t</Emphasis>-Butylacrylamide-co-Acrylamide/Maleic Acid) Hydrogels

In the present study, a series of ionic poly(N-t-butylacrylamide-co-acrylamide) [P(NTBA-co-AAm)] hydrogels were synthesized by free-radical crosslinking copolymerization of N-t-butylacrylamide (NTBA) and acrylamide (AAm) monomers in fixed amount, but changing amount of maleic acid (MA) comonomer in methanol using N,N-methylene-bis-acrylamide (BAAm) as the crosslinker, ammonium persulfate (APS) as the initiator, and N,N,N′,N′-tetramethylethylenediamine (TEMED) as the activator. The swelling behavior of these hydrogels was analyzed in buffer solutions at various pHs. The prepared hydrogels also were investigated swelling-deswelling transition in water depending on the temperature. For the bovine serum albumin (BSA) adsorption, the effect of pH, temperature, initial protein concentration and adsorption rate were investigated. Maximum BSA adsorption was observed at pH 5.0 which is close to the isoelectric pH of BSA (pH 4.8). The highest adsorption rate was achieved in about 12 h. and also, maximum BSA adsorption was found at +5°C.     

Synergistic removal of Cu(II) and nitrazine yellow dye using an eco‐friendly chitosan‐montmorillonite hydrogel: Optimization by response surface methodology

A comprehensive feasibility study on adsorption of Cu(II) and a water‐soluble nitrazine yellow (NY) dye by chitosan‐montmorillonite (CS‐MMT) hydrogel as the biosorbent was investigated as a function of biosorbent dosage, initial concentration, pH, temperature, and the presence of salts. Box–Behnken methodology was applied to optimize the adsorption experiments. Maximum adsorption values were determined as 132.74 mg/g and 144.41 mg/g at pH = 5.0, for Cu(II) and NY dye, respectively. Equilibrium isotherms of Langmuir and Freundlich were analyzed by the non‐linear regression model. The equilibrium data were well described by Freundlich model and the adsorption process well fitted pseudo‐second order kinetics. The enthalpy change of adsorption (ΔH°) were calculated as ?3.78 kJ/mol and ?5.75 kJ/mol for Cu(II) and NY dye, respectively, indicating that the adsorption processes were exothermic. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43664.