Effect of complexing agents on liquid‐phase adsorption and desorption of copper(II) using chitosan

The effect of complexing agents on adsorption and desorption of Cu(II) from aqueous solutions using chitosan was investigated. Three complexing agents were used including EDTA (ethylenediaminetetraacetic acid), citric acid, and tartaric acid. It was shown that the isotherm data could be fitted by the Langmuir equation under a limited concentration range. Furthermore, the adsorption processes were analyzed by an intraparticle diffusion model and the rate parameters of intraparticle diffusion for Cu(II) adsorption could be correlated with the initial Cu(II) concentrations. Finally, the desorption of Cu(II) and its complexes from the loaded chitosan was tested using complexing agent solutions. Under comparable conditions, tartaric acid solution gave the best desorption efficiency. © 1999 Society of Chemical Industry     

Interference of EDTA in the treatment of metal plating wastewater by biosorption

BACKGROUND: The applicability of biosorption for the treatment of metal plating wastewater is adversely affected by the presence of complexing agents. To investigate this limitation on the removal of copper(II) onto peat, batch and column experiments were carried out using EDTA as the model complexing agent. The influence of pH and copper(II):EDTA mass ratios were evaluated for copper(II) concentrations between 5 and 100 mg Cu(II) dm^?3. RESULTS: EDTA negatively affected the copper(II) uptake of peat for pH > 5. Batch and column experiments showed that copper(II)‐EDTA complexes were not sorbed by peat. The leaks of copper(II) detected from the beginning of the column operation matched the copper(II)‐EDTA concentration in the feed solutions. To overcome the interference of EDTA, a novel approach based on the combination of peat + activated carbon was proposed. Nearly complete removal of copper(II) was maintained over 70 h in the treatment of a solution containing 20 mg Cu(II) dm^?3 with 11% of copper(II)‐EDTA complexes. CONCLUSION: A new mass transport model coupling copper(II) speciation in the feed and mass transfer rate‐controlled process simulated the copper(II) breakthrough curves in the presence of EDTA and could be used to successfully predict the breakthrough point. This work demonstrated that biosorption can also be applied for the treatment of wastewater containing complexing agents with the proper combination of sorbent materials. © 2012 Society of Chemical Industry     

Extraction of Metal Ions with Task Specific Ionic Liquids: Influence of a Coordinating Anion

Hydrophobic ionic liquids (ILs) were generated by association between a cationic ester derivative of betaine and bis(trifluoromethylsulfonyl)imide (Tf₂N^?) or dicyanamide (Dca^?) anions. Extraction of Cu(II), Ni(II), Pb(II), and Cd(II) from water was performed with these ILs at room temperature. The use of Dca^? anion greatly enhances the extraction efficiency of IL phase towards metal ions extraction. The metal could be back-extracted from the ionic liquid phase with aqueous EDTA solutions. The metal extractability of the ionic liquid after the back-extraction is equivalent to that of the fresh mixture showing that ionic liquid can be reused for several extraction and back-extraction cycles.     

Lightweight hydrophobic cellulose foam material with low density and high porosity applications in Cu (II) adsorption

Cellulose foam, renowned for its lightweight properties and exceptional adsorption capacity, has emerged as a significant material of interest. In our study, a distinct functionalized cellulose foam adsorbent was developed using N,N-methylenebisacrylamide (MBA) as a cross-linker. This foam was further chemically tailored with 3-aminopropyltriethoxysilane (APTES) and tannic acid (TA) to optimize its affinity for Cu (II). Utilizing a green and efficient procedure at ambient temperature, MBA was directly crosslinked with MCC sol, the resultant foam features a distinguished three-dimensional, multi-walled porous configuration, marked by a strikingly low average density of 0.0306 g/cm³ and an impressive average porosity surpassing 97%. Subsequently, more amino and oxygen-containing groups were introduced by simple impregnation. The rich functional groups and unique structure enabled the adsorption of Cu (II) up to 93 mg/g, demonstrating an increasing trend in line with rising Cu (II) concentrations. Furthermore, this composite cellulose foam displayed commendable hydrophobic characteristics, evident from a hydrophobic angle surpassing 120°. From both environmental and economic perspectives, this chemically-modified cellulose material epitomizes an ideal adsorbent, showcasing unparalleled adsorption capacity coupled with robust chemical and structural integrity. As such, it presents a viable option for the efficient sequestration of Cu (II) in wastewater treatments.     

Nitrosymmetallochelates—I. Mechanism of FeNO—EDTA complex formation and its oxidation

A nitrosyliron(II) complex with EDTA was produced by reaction of the Fe(II)—EDTA complex and nitrous acid in citric acid—phosphate buffer solution. The experimental results pointed out that nitrous acid is reduced to nitrous oxide by Fe(II)—EDTA complex followed by the formation reaction of nitrosyliron(II) EDTA complex. The composition of this complex was determined to be Fe(II) (NO)₂EDTA by both electrochemical and spectroscopic methods.A mechanism of the oxidation of Fe(II) (NO)₂EDTA was proposed in which nitrous oxide breaks away from the iron ion. The photoeffect on this reaction is discussed.     

Polymer-Enhanced Crossflow Filtration for Removal of Fe(III), Cu(II), and Cd(II) Ions from Dilute Aqueous Solutions

Abstract

The removal of Fe(III), Cu(II), and Cd(II) ions from aqueous solutions was studied by polymer-enhanced crossflow filtration technique. Alginic acid polymer was used as complexing agents to enhance the retention. Alginic acid/cellulose composite membranes were used in the filtration. In the filtration of metal ion solutions the effects of alginic acid content of the membranes and pH on the percent retention and the permeate flux were examined. The maximum percent retention was found as 98% for 1 × 10^?4 M Fe(III) solution at the flow velocity of 100 mL/min, pH of 3.0, pressure of 60 kPa in the presence of alginic acid as complexing agent by using 0.25 (w/v)% alginic acid/cellulose composite membranes. For 1 × 10^?4 M Cu(II) and Cd(II) solutions the maximum percent retentions were found as 71% and 80% respectively using 0.50 (w/v)% Alginic acid/cellulose composite membranes when the filtration was carried out in the presence of alginic acid at pressure of 10 kPa, flow velocity of 100 mL/min and pH of 7.0.     

Cellulose-lanthanum hydroxide nanocomposite as a selective marker for detection of toxic copper

In this current report, a simple, reliable, and rapid method based on modifying the cellulose surface by doping it with different percentages of lanthanum hydroxide (i.e., 1% La(OH)₃-cellulose (LC), 5% La(OH)₃-cellulose (LC2), and 10% La(OH)₃-cellulose (LC3)) was proposed as a selective marker for detection of copper (Cu(II)) in aqueous medium. Surface properties of the newly modified cellulose phases were confirmed by Fourier transform infrared spectroscopy, field emission scanning electron microscope, energy dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopic analysis. The effect of pH on the adsorption of modified cellulose phases for Cu(II) was evaluated, and LC3 was found to be the most selective for Cu(II) at pH 6.0. Other parameters, influencing the maximum uptake of Cu(II) on LC3, were also investigated for a deeper mechanistic understanding of the adsorption phenomena. Results showed that the adsorption capacity for Cu(II) was improved by 211% on the LC3 phase as compared to diethylaminoethyl cellulose phase after only 2 h contact time. Adsorption isotherm data established that the adsorption process nature was monolayer with a homogeneous adsorbent surface. Results displayed that the adsorption of Cu(II) onto the LC3 phase obeyed a pseudo-second-order kinetic model. Selectivity studies toward eight metal ions, i.e., Cd(II), Co(II), Cr(III), Cr(VI), Cu(II), Fe(III), Ni(II), and Zn(II), were further performed at the optimized pH value. Based on the selectivity study, it was found that Cu(II) is highly selective toward the LC3 phase. Moreover, the efficiency of the proposed method was supported by implementing it to real environmental water samples with adequate results.     

Crossflow filtration of iron(III), copper(II), and cadmium(II) aqueous solutions with alginic acid/cellulose composite membranes

The removal of Fe(III), Cu(II), and Cd(II) ions from aqueous solutions was investigated with a crossflow filtration technique. Alginic acid (AA)/cellulose composite membranes were used for retention. In the filtration of Fe(III) solutions, the effects of the crossflow velocity, applied pressure, AA content of the membranes, and pH on the retention percentage and the permeate flux were examined. The maximum retention percentage was found to be 89% for a 1 × 10^?4M Fe(III) solution at the flow velocity of 100 mL/min and the pressure of 60 kPa with 0.50% (w/v) AA/cellulose composite membranes at pH 3. Aqueous solutions of Cu(II) and Cd(II) were filtered at the flow velocity of 100 mL/min and pressure of 10 kPa. The effects of the AA content of the membranes and pH of the waste medium on the retention percentage and the permeate flux were determined. For 1 × 10^?4M Cu(II) and Cd(II) solutions, the maximum retention percentages were found to be 94 and 75%, respectively, at pH 7 with 0.50% (w/v) AA/cellulose composite membranes. When metal‐ion mixtures were used, the retention percentages of Fe(III), Cu(II), and Cd(II) were found to be 89, 48, and 10%, respectively, at pH 3 with 0.50% (w/v) AA/cellulose composite membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Silver–copper electrodeposition from ammonium hydroxide solution: influence of EDTA and HEDTA

The influence of EDTA (ethylenediaminetetraacetic acid, disodium salt) or HEDTA (N-(2-hydroxyethyl)ethylenediaminetriacetic acid, trisodium salt) on silver–copper electrodeposition from ammonium hydroxide solution was investigated. Voltammetric studies showed that silver was deposited at potentials more negative than +0.100 V, while the copper(II) ion was reduced to copper(I) ion and metallic copper at potentials more negative than +0.100 and −0.375 V, respectively. Chronoamperometry, scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDS) indicated that, for deposits obtained at −0.450 V, increasing either the silver content in the silver–copper deposit or the charge density of deposition led to dendritic growth. Moreover, dendritic growth decreased when either the EDTA or HEDTA concentration increased. EDS analysis of the deposits obtained at −0.200 V showed codeposition of copper with silver, which was attributed to Cu(I) ion disproportionation to Cu(0) and Cu(II). Moreover, the silver–copper deposits obtained at −0.200 V, from a solution containing EDTA or HEDTA, were non-dendritic in spite of the high silver content. The presence of EDTA and HEDTA improved the silver–copper morphology. X-ray diffraction analysis indicated that the silver–copper electrodeposit was a supersaturated solid solution.     

PSSMA修饰磁性氧化石墨烯对Pb2+、Cu2+ 的吸附性能

以氧化石墨烯(GO)、FeCl_3·6H_2O及聚(4-苯乙烯磺酸-共聚-马来酸)钠盐(PSSMA)为主要原料,通过简便一步溶剂热法制备了阴离子聚电解质修饰磁性氧化石墨烯(MGO@PSSMA),并将其用于水溶液中重金属Pb~(2+)、Cu~(2+)的吸附去除。采用FTIR、SEM、TEM、VSM和DLS对制备的MGO@PSSMA进行了表征。考察了溶液pH、吸附时间、溶液初始质量浓度对Pb~(2+)、Cu~(2+)在MGO@PSSMA及未经PSSMA修饰磁性氧化石墨烯(MGO)上吸附的影响。探讨了吸附等温过程、吸附动力学及吸附作用机理。结果表明:MGO表面引入PSSMA可有效增加其对Pb~(2+)、Cu~(2+)的吸附量。在pH=5,溶液初始质量浓度为300 mg/L时,MGO@PSSMA对Pb~(2+)和Cu~(2+)的实际吸附量达141.1和104.8 mg/g。当溶液初始质量浓度为150 mg/L时,MGO@PSSMA对Pb~(2+)和Cu~(2+)的吸附平衡时间分别为2和1.5 min。MGO@PSSMA对Pb~(2+)、Cu~(2+)的吸附动力学及吸附等温数据分别符合准二级吸附动力学模型和Langmuir吸附等温模型。使用乙二胺四乙酸(EDTA)和HCl可实现MGO@PSSMA的有效再生;通过外加磁场作用可实现MGO@PSSMA的回收再利用。     

Precipitate Flotation Studies with Monolauryl Phosphate and Monolauryldithiocarbamate

Abstract

Monolauryl phosphate has been employed for the removal of copper(II), manganese(II), and zinc(II) by foam flotation at various pH's and ionic strengths. Good removals of all three metal ions were obtained in the basic pH range and in the presence of up to 0.2 M sulfate. Coprecipitation of Zn(II) with ferric hydroxide was essential to attain good removal of Zn(II). The removal of Cu(II) was also good from solutions containing oxalate, silicate, phosphate, and metaphosphate; however, the presence of EDTA hinders the removal of Cu(II). The potential of lauryldithiocarbamate as a chelating surfactant for the removal of Cu(II) was explored at various pH's and in the presence of various anions. We conclude that lauryldithiocarbamate is a weak chelating agent, unable to compete efficiently for Cu(II) with anions such as CO₃ ^2?, HPO₄ ^2?, SiO₃ ^2?, and EDTA. The relatively rapid decomposition of lauryldithiocarbamate in solution coupled with its weakness as a chelating surfactant make it unsuitable for the removal of Cu(II) by foam flotation.     

Polyethylenimine-modified sugarcane bagasse cellulose as an effective adsorbent for removing Cu(II) from aqueous solution

Polyethylenimine-modified sugarcane bagasse cellulose (SBCMP), as a new adsorbent, was synthesized by the reaction of polyethylenimine (PEI) with sugarcane bagasse cellulose and glutaraldehyde. The adsorption of Cu(II) by SBCMP was pH-dependent, and the higher removal efficiency of Cu(II) appeared in the range of pH 3.0–6.0. The adsorption isothermal data fitted well with the Langmuir model, and the maximum adsorption capacity of SBCMP was up to 107.5 mg/g. The adsorption kinetics was best described by the pseudo-second-order kinetic. The adsorption of Cu(II) by SBCMP was unfavorable at high temperatures, and thermodynamic analyses implied that the adsorption of Cu(II) by SBCMP was an exothermic reaction. Fourier transform infrared spectroscopy (FT-IR) combined with X-ray photoelectron spectroscopy (XPS) revealed that Cu(II) adsorption on SBCMP mainly controlled by the nitrogen atoms of  NH group in PEI. The results of regeneration cycles showed that SBCMP was suitable for reuse in the adsorption of Cu(II) from aqueous solution. These experimental results suggested that SBCMP is expected to be a new biomass adsorbent with high efficiency in removing Cu(II) from wastewater.     

Structure and properties of Cu(II) complex bamboo pulp fabrics

Cu(II) complex bamboo pulp fabric (CBPF) was prepared by treating bamboo pulp fabric with the copper liquor. Washing fastness and the releases of Cu(II) were measured by the washing test. Antibacterial performance of CBPF against Escherichia coli and Staphylococcus aureus was evaluated. The morphology of Cu(II) on the fiber surface was characterized with scanning electron microscope. FTIR spectroscopy and X‐ray photoelectron spectrometry were used to detect the chemical bonding between Cu(II) and cellulose. X‐ray diffraction, thermogravimetry and mechanical test were used to investigate the effect of Cu(II) on the crystallinity, thermal stability, and mechanical property of bamboo fabric. The results showed that Cu(II) ion was bonded to fiber surface, especially via forming metal complex with hydroxyl of cellulose, and the resultant complex CBPF demonstrated excellent antibacterial activity and good thermal stability. In comparison with those of the bamboo pulp fabric in the condition that mechanical properties have no significant change, the crystallinity was decreased from 44.8% to 40.5% after treatment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Adsorption of copper(II) and chromium(III) ions onto amidoximated cellulose

Chemical modification of cellulose powder is performed by successive reactions with acrylonitrile in an alkaline medium followed by aqueous hydroxylamine to prepare amidoximated cellulose. Due to complexation, the amidoxime groups immobilize heavy cations from buffered solutions at various pH values. The capacity of adsorption for Cu(II) and Cr(III) ions is related to the amount of amidoxime groups in the support and to the metal concentration of the polluted solution. The formation of a 1/1 complex is proved by the adsorption limit values. Desorption of the cations is possible by treatment with a stronger complexing agent such as ethylenediaminetetracetic acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1624–1631, 2000     

Effect of Compound Surface Treatment on the Performance of Poly(butylene succinate)/Chemithermomechanical Pulp Fiber Composites

Chemithermomechanical pulp fiber was pretreated by alkali solution to alter the surface characteristics of fibers. The untreated and treated fibers were used to prepare poly(butylene succinate)/chemithermomechanical pulp fiber composites with or without the incorporation of cellulose fatty acid ester (hydroxyethyl cellulose lauric acid ester). X-ray photoelectron spectrum analysis shows that the O/C ratio on the fiber surface increased after alkali treatment, indicating that part of lignin was removed during alkali treatment process. Scanning electron microcopy images indicate that the fiber surface was changed to rough after alkali treatment. The modification effect of hydroxyethyl cellulose lauric acid ester reflects as the improvement of fiber order in matrix, together with the enhancement of interfacial bonding, whereas, the modification effect of alkali treatment is mainly due to the enhancement of interfacial bonding. The integrated mechanical properties of composite prepared by alkali-treated fibers are superior to those of composite prepared by hydroxyethyl cellulose lauric acid ester-treated fibers. The combination of these two modification methods favors the enhancement of tensile and impact strengths of composite. However, in comparison with the composite prepared only by alkali treatment, the flexural strength and modulus would be despaired in a certain degree. When fibers were alkali treated, the shear viscosity of composite exhibited a larger increase, whereas the shear viscosity of composite prepared fibers with hydroxyethyl cellulose lauric acid ester treatment exhibits a slight decrease.     

Removal of Cu(II) and Zn(II) Using Lignocellulosic Fiber Derived from Citrus reticulata (Kinnow) Waste Biomass

Abstract

The biosorption of Cu(II) and Zn(II) using dried untreated and pretreated Citrus reticulata waste biomass were evaluated. The Cu(II) and Zn(II) sorption were found to be dependent on the solution pH, the biosorbent dose, the biosorbent particle size, the shaking speed, the temperature, the initial metal ions (800 mg/L), and the contact time. Twenty-eight physical and chemical pretreatments of Citrus reticulata waste biomass were evaluated for the sorption of Cu(II) and Zn(II) from aqueous solutions. The results indicated that biomass pretreated with sulphuric acid and EDTA had maximum Cu(II) and Zn(II) uptake capacity of 87.14 mg/g and 86.4 mg/g respectively. Moreover, the Langmuir isotherm model fitted well than the Freundlich model with R ² > 0.95 for both metal ions. The sorption of Cu(II) and Zn(II) occurred rapidly in the first 120 min and the equilibrium was reached in 240 min. FTIR and SEM studies were also carried out to investigate functional groups present in the biomass and the surface morphological changes of biomass.     

The inhibited reduction of different copper(II) complexes by phosphine oxides

The influence of hexyldiethyl- and octyldimethylphosphine oxide on the reduction of different Cu (II) complexes (ligands: oxalate, glycinate, EDTA, tartrate, malonate, citrate and alanin anion) was investigated by dc polarography. The mode of inhibition is changing as a function of the ligand. While the [Cu(EDTA)]²⁻, [Cu(ox)₂]²⁻, [Cu(gly)₂] and [Cu(ala)₂] complexes seem to cross the adsorption layer at the non-fully and fully covered electrode in the same way, all other complexes seem to change their structure before they are discharged, provided the electrode is fully covered with the surfactant. Both reaction channels were described by inhibition models, valid at the fully surfactant covered electrode.     

Sorption of heavy metal ions from aqueous solutions in the presence of EDTA on monodisperse anion exchangers

Conventional precipitation methods of industrial sewage and wastewater purification are not very effective and are insufficient in many cases. This implies the necessity of searching new, effective methods exploiting cheap, accessible and ecologically safe ion exchangers and sorbents. The paper presents the studies on removal of heavy metal ions — Cu(II), Zn(II), Co(II), Ni(II) and Fe(III) — from aqueous solutions in the presence of EDTA carried out on commercially available, strongly basic monodisperse anion exchangers with the polystyrene skeleton gel, Lewatit MonoPlus M 500; and the macroporous, Lewatit MonoPlus MP 500, which are more widely applied in water purification processes. The research results indicate a high affinity of the Lewatit MonoPlus M 500 and Lewatit MonoPlus MP 500 anion exchangers in the chloride form for copper(II), nickel(II), cobalt(II) and zinc(II) complexes with EDTA. The affinity series for the heavy metal complexes in the 0.001 M M(II)/(III)–0.001 M EDTA and 0.001 M M(II)/(III)–0.001M EDTA–0.001 M–0.002 M NaOH systems were found for the Lewatit MonoPlus M 500 anion exchanger in the chloride form to be as follows: Cu(II) > Ni(II) > Co(II) > Zn(II) Fe(III). In the case of the Lewatit MonoPlus MP 500 anion exchanger in the chloride form there was found the following affinity series: Cu(II) > Co(II) > Ni(II) > Zn(II) Fe(III). These anion exchangers can be applied in the removal of copper(II) complexes from waters and wastewaters.     

Cellulose bound chlorophenols II: Preparation and characterization of phenyloxycarbonylpentanoyl celluloses dependence of substitution on chlorophenol structure

New types of polymeric phenols (including the fungicide PCP) are prepared by linking phenol and different chlorophenols to cellulose via ester bonds using adipic acid as bridging molecule. Monophenylesteracid chlorides of adipic acid are prepared as intermediates. The yield of esterification of cellulose with these compounds depends in a complicated manner on size and chlorosubstitution pattern of the phenolic substituents. It is tentatively assumed that hydrogen bonding between chlorophenol and cellulose is an important factor. The polymeric PCP ester showed fungicidal activity in an agar plate test.     

Synthesis,Characterization, and Applications of a New Chelating Resin Containing 4-2-(Thiazolylazo) Resorcinol (TAR)

A new phenol–formaldehyde based chelating resin containing 4-(2-thiazolylazo) resorcinol (TAR) functional groups has been synthesized and characterized by Fourier transform infrared spectroscopy and elemental analysis. Its adsorption behavior for Cu(II), Pb(II), Ni(II), Co(II), Cd(II), and Mn(II) has been investigated by batch and column experiments. The chelating resin is highly selective for Cu(II) in the pH range 2 ～ 3, whereas alkali metal and alkaline earth metal ions such as Na(I), Mg(II), and Ca(II) are not adsorbed even at pH 6. Quantitative recovery of most metal ions studied in this work except Co(II) is achieved by elution with 2M HNO₃ at a flow rate of 0.2 mL min^?1. A similar trend is observed for distribution coefficient values. The quantitative separations achieved on a mini-column of chelating resin include Cd(II) – Cu(II), Mn(II) – Pb(II), Co(II) – Cu(II), Mn(II) – Ni(II), and Mn(II) – Co(II) – Cu(II). The recovery of copper(II) is quantitative (98.0–99.0%) from test solutions (10–50 mg/L) by 1 mol/L HNO₃-0.01 mol/L EDTA. The chelating resin is stable in acidic solutions below 2.5 M HNO₃ or HCl as well as in alkaline solution below pH 11. The adsorption behavior of the resin towards Cu(II) was found to follow Langmuir isotherm and second order rate.