Synthesis of a new type of adsorbent containing carboxyl and amidoxime groups by preirradiation grafting and its absorption of metal ions

A new type of adsorbent containing amidoxime and carboxyl groups was synthesized by the preirradiation graft copolymerization of acrylonitrile (AN) and acrylic acid (AA) onto fibrous‐type poly(vinyl alcohol) followed by amidoximation with hydroxylamine. The radiation dose and ratio of AN and AA monomers influenced the degree of grafting, the content of the amidoxime group, and the adsorption capacity. The synthesis course, structure, and properties of the adsorbent were investigated with Fourier transform infrared, scanning electron microscopy, and thermogravimetry. The adsorption property of the adsorbent for palladium(II) ions was also studied systematically. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1986–1992, 2002     

Preparation of amidoximated polyester fiber and competitive adsorption of some heavy metal ions from aqueous solution onto this fiber

In this study, a fibrous adsorbent containing amidoxime groups was prepared by graft copolymerization of acrylonitrile (AN) onto poly(ethylene terephthalate) (PET) fibers using benzoyl peroxide (Bz₂O₂) as initiator in aqueous solution, and subsequent chemical modification of cyano groups by reaction with hydroxylamine hydrochloride in methanol. The grafted and modified fibers were characterized by FTIR, TGA, SEM, and XRD analysis. The crystallinity increased, but thermal stability decreased with grafting and amidoximation. The removal of Cu(II), Ni(II), Co(II), Pb(II), and Cd(II) ions from aqueous solution onto chelating fibers were studied using batch adsorption method. These properties were investigated under competitive conditions. The effects of the pH, contact time, and initial ion concentration on the removal percentage of ions were studied. The results show that the adsorption rate of metal ions followed the given order Co(II) > Pb(II) > Cd(II) > Ni(II) > Cu(II). The percentage removal of ions increased with initial ion concentration, shaking time, and pH of the medium. Total metal ion removal capacity was 49.75 mg/g fiber on amidoximated fiber. It was observed that amidoximated fibers can be regenerated by acid without losing their activity, and it is more selective for Pb(II) ions in the mixed solution of Pb‐Cu‐Ni–Co‐Cd at pH 4. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Development of novel adsorbent materials for recovery and enrichment of uranium from aqueous media

A new polymeric adsorbent bearing both hydrophilic groups providing swelling in water and amidoxime groups for chelating with uranyl ions (UO₂²⁺), has been developed and its adsorptive ability for recovering uranium from aqueous media has been investigated. The polymers obtained by irradiating the solution of polyethylene glycol (PEG) in acrylonitrile (AN) are defined as interpenetrating polymer networks (IPNs) and the adsorbent has been obtained by applying the amidoximation reaction to the IPNs with a conversion ratio of ∼ 60%. Kinetics of the conversion reaction of the cyano (CN) group to the amidoxime (HONCNH₂) group has been studied by reacting with hydroxylamine (NH₂OH) solution at a molar ratio of NH₂OH/CN = 1.25 in aqueous media at three different temperatures, 30, 40, and 50°C, for 3–4 days. The degree of amidoximation ratio was determined by UO₂²⁺ ion adsorption and FTIR spectrometry and the UO₂²⁺ ion adsorption values were found by both UV and gamma spectrometry and also by gravimetry. It was found that the polymeric adsorbent has a very high adsorption ability for uranium and quite a good stability in aqueous media. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2475–2480, 1997     

A New Type of Amidoxime-Group-Containing Adsorbent for the Recovery of Uranium from Seawater

Abstract

A new type of adsorbent containing amidoxime groups for the recovery of uranium from seawater was synthesized by the radiation-induced graft polymerization of acrylonitrile onto polymeric fiber followed by amidoximation with hydroxylamine. When amidoxime groups were introduced superficially on the fiber, the amount of uranium adsorbed by the amidoxime groups was higher than that with the amidoxime groups introduced homogeneously in the fiber. The introduction of the poly(acrylic acid) chain and the increase in temperature and flow rate in the adsorption process were effective in increasing the amount of adsorbed uranium. Although alkali metals and alkaline earth metals were found in the adsorbent, the concentration factors for these metals were less than 1/10³ of that for uranium. The present adsorbent had a high stability to various treatments such as contact with alkali and seawater.     

Electron Beam Grafted Polymer Adsorbent for Removal of Heavy Metal Ion from Aqueous Solution

Abstract

An electron beam grafted adsorbent was synthesized by post irradiation grafting of acrylonitrile (AN) on to a non‐woven thermally bonded polypropylene (PP) sheet using 2 MeV electron beam accelerator. The grafted poly(acrylonitrile) chains were chemically modified to convert a nitrile group to an amidoxime (AMO) group, a chelating group responsible for metal ion uptake from an aqueous solution. The effect of various experimental variables viz. dose, dose rate, temperature, and solvent composition on the grafting extent was investigated. PP grafted with the amidoxime group (AMO‐g‐PP) was tested for its suitability as an adsorbent for removal of heavy metal ions such as Co²⁺, Ni²⁺, Mn²⁺, and Cd²⁺ from aqueous solution. Langmuir and Freundlich adsorption models were used to investigate the type of adsorption of these ions. The adsorption capacities of the adsorbent for the metal ions were found to follow the order Cd²⁺>Co²⁺>Ni²⁺>Mn²⁺. The kinetics of adsorption of these ions indicated that the rate of adsorption of Cd²⁺ was faster than that of other ions studied.     

Chelating polymer granules prepared by radiation‐induced homopolymerization. II. Characterizations

Characterizations of chelating polymer adsorbent granules, incorporating amidoxime groups based on polyacrylonitrile (PAN), prepared for selective adsorption of uranium and likely other transition metals were studied. PAN was prepared by radiation‐induced polymerization technique and followed by amidoximation reaction. Conversion of PAN into polyacrylamidoxime (PAO) was studied by fourier transform infrared (FTIR), X‐ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Morphology and thermal properties were also investigated. PAO was investigated in the separation of uranium from iron‐rich silicate rock samples and subjected to x‐ray fluorescence analysis (XRF). Selective adsorption for uranium and low affinity for alkali and alkaline earth metals were observed. The order of selectivity was found to be U ? Cu > Fe > Ni > Cr > V ? Ca > K. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1180–1187, 2006     

A New Type of Amidoxime-Group-Containing Adsorbent for the Recovery of Uranium from Seawater. III. Recycle Use of Adsorbent

Abstract

An amidoxime-group-containing adsorbent for recovering uranium from seawater was made by radiation-induced graft polymerization of acrylonitrile onto polymeric fiber, followed by amidoximation. Uranium adsorption of the adsorbent contacted with seawater in a column increased with the increase in flow rate, then leveled off. The relationship between uranium adsorption in a batch process and the ratio of the amount of seawater to that of adsorbent was found to be effective in evaluating adsorbent contacted with any amount of seawater. The conditioning of the adsorbent with an alkaline solution at higher temperature (80°C) after the acid desorption recovered the adsorption ability to the original level. This made it possible to apply the adsorbent to recycle use. On the other hand, the adsorbent conditioned at room temperature or that without conditioning lost adsorption ability during recycle use. The increase in water uptake was observed as one of the physical changes produced during recycle use of the alkaline-conditioned adsorbent, while the decrease in water uptake was observed with the unconditioned adsorbent. The IR spectra of the adsorbent showed a probability of reactions of amidoxime groups with acid and alkaline solutions, which can explain the change in uranium adsorption during the adsorption-desorption cycle.     

Use of Amidoxime-Group-Containing Adsorbent for the Recovery of Uranium and Other Elements from Phosphoric Acid Solution

Abstract

An amidoxime-group-containing fibrous adsorbent which was made by the radiation-induced grafting of acrylonitrile onto a synthetic fiber was applied to the recovery of uranium and other elements (V, Ti, Fe, etc.) from phosphoric acid solution of a fertilizer plant. The adsorption amount of these elements increased in proportion to the concentration of amidoxime groups introduced in the adsorbent. The distribution of the metals adsorbed in 24 h was homogeneous in the adsorbent containing more than 4.9 meq/g amidoxime groups while it was limited to the surface region of the adsorbent containing 1.5 meq/g amidoxime groups. The rise in the pH of the solution brought about by adding sodium hydroxide produced a maximum amount of adsorption at pH = 3. The concentration factors for U, V, Ti, and Fe were 2.8 × 10², 8.6 × 10³, 4.2 × 10³, and 6.1 × 10², respectively.     

Removal of Cu(II), Cr(III), and Cr(VI) from Aqueous Solution using a Novel Agricultural Waste Adsorbent

A novel adsorbent, chufa corm peels (CCP), is used for removing Cu(II), Cr(III), and Cr(VI) from aqueous solutions. The adsorption ability and characteristics of the CCP are thoroughly investigated. The adsorption capability for three heavy metal ions is in the order of Cu(II) > Cr(III) > Cr(VI). The morphology and elemental distribution on the biomass of CCP were evaluated by scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). Fourier-transform infrared spectroscopy (FTIR) analysis revealed that oxygen-containing functional groups, especially carboxylic and hydroxyl groups were responsible for chemical coordination between ionizable functional groups and metal ions. The adsorption features were evaluated based on the batch biosorption experiment. The results showed that the adsorption well meets the Freundlich adsorption isotherm models and pseudo-second-order kinetics model. In summary, this work demonstrated that CCP is an attractive, efficient, and low-cost adsorbent biomaterial that can be used for the removal of heavy metals from environmental contaminations.     

Synthesis of a polyacrylamidoxime chelating fiber and its efficiency in the retention of palladium ions

A chelating fibrous polymer with metal complexing ability was prepared by partial conversion of the nitrile groups of melana (an acrylonitrile‐based synthetic fiber) into amidoxime groups ? C(NH₂) = NOH using a solution of 3% hydroxylamine in methanol by refluxing at 80°C. The molar ratio of NH₂OH/CN and the reaction time were adjusted to values of 0.9 and 2 h, respectively. The amidoximated polyacrylonitrile fiber with a 2.89 meq/g ion‐exchange capacity functions as an efficient chelating adsorbent for palladium ions. The pH dependence, the contact time, and the temperature of palladium ion retention from a model solution on amidoximated acrylic fiber were studied. The fibrous chelating adsorbent exhibited high affinity for palladium ions in acidic solution (pH = 2–6) at high temperature (50–60°C). The values of parameters q_m and K_L (from the Langmuir equation) determined at different temperatures of adsorption and the thermodynamic quantities ΔG, ΔH, and ΔS were calculated. The adsorbed palladium ions can be quantitatively desorbed by elution with a 0.3% hydrochloric solution of thiourea. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3730–3735, 2004     

Studies on the Amidoximation of Polyacrylonitrile Films: Influence of Synthesis Conditions

Chemical transformation of acrylic membranes with hydroxylamine hydrochloride (HA) was carried out to introduce amidoxime groups. It was found that the reaction conditions, such as reaction time, HA concentration and temperature influence the amidoxime content, significantly. A sharp enhancement in the amidoximation at 80°C was observed. The FTIR studies showed a significant loss of nitrile groups during amidoximation process. Optimum conditions for the amidoximation process were investigated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of fibrous adsorbents containing amidoxime groups by radiation-induced grafting and application to uranium recovery from sea water

Polypropylene fibers and polyethylene hollow fibers were used as trunk polymers and were irradiated by electron beams with a dose of 200 kGy under N₂ atmosphere. Grafting of acrylonitrile to those irradiated fibers was carried out at 40°C for different periods of time. The degree of grafting was determined as a function of time. The fibrous adsorbents containing amidoxime groups were prepared by the reaction of acrylonitrile-grafted polymers with 3% hydroxylamine in a methanol–water mixture (1 : 1). Distribution of copper ions complexed with amidoxime groups at various adsorption times was obtained by electron-probe X-ray microanalysis. The amidoxime groups are homogeneously distributed in the cross section of fibrous adsorbents. The fibrous adsorbents based upon polypropylene fiber of 40 μm showed a remarkable kinetic behavior for Cu²⁺. Even after 15 min, the adsorption capacity was 2.32 mmol Cu²⁺ per gram of fiber. Also, the functionalization with hydroxylamine was carried out at different conditions to compare the adsorption characteristics of the resultant adsorbents. Despite having superficially different properties (elemental microanalysis, ion-exchange capacities, adsorption capacity for UO), the polypropylene-based fibrous adsorbents showed similar adsorption properties for uranium from sea water. The adsorption tests proved the performance of the polypropylene-based fibrous adsorbents as a promising material for uranium recovery from sea water. In addition, uranium uptake of fibrous adsorbents increased in proportion to the volume of sea water. © 1993 John Wiley & Sons, Inc.     

高氟高氯含铀废水中偕胺肟基改性聚丙烯腈纤维螯合铀的研究

以聚丙烯腈纤维（PANF）为基体与盐酸羟胺反应制得偕胺肟基改性纤维（AO-PANF）,并通过扫描电镜、红外光谱和批次吸附,探究了AO-PANF对高氟高氯含铀废水中铀的螯合行为。结果表明,偕胺肟化反应将PANF中的氰基成功转化为偕胺肟基团,转化率随盐酸羟胺浓度增加而增大,氰基转化率为22.34%时,AO-PANF对铀的吸附量最大。随废水pH增加,AO-PANF对铀的吸附量先增大后减小,pH为5时,其值最大。F^-和Cl^-浓度变化对AO-PANF的吸附量影响较小。当处理100 ml铀初始浓度为100 mg·L^-1,pH为5的废水,温度为45℃,吸附剂投加量为0.40 g时,转化率为22.34%的AO-PANF对铀的吸附量为19.53 mg·g^-1,3 h左右吸附达到平衡。AO-PANF通过偕胺肟基团中-NH₂与废水中UO₂F₄^2-螯合实现对铀的吸附。该吸附过程符合Freundlich等温吸附模型和准二级动力学方程。研究表明AO-PANF可以有效地螯合高氟高氯含铀废水中的铀,具有良好的应用前景。     

Introduction of amidoxime groups into cellulose and its ability to adsorb metal ions

Introduction of amidoxime groups into cellulose substrate was investigated by reaction of cyano-group-containing celluloses such as cyanoethylcellulose (CE-Cell) and acrylonitrilegrafted cellulose (G-Cell) with hydroxylamine at 70°C in water medium (pH = 7.0). Dissolving pulp from softwood was used as the cellulose sample, and photografting was applied to the preparation of G-Cell, where hydrogen peroxide was used as a photoinitiator. Degree of substitution (DS) of CE-Cell and percent grafting of G-Cell employed were less than 1.5 and 40, respectively. The amidoximation of CE-Cell proceeded easily, and the amidoxime content increased with increasing the reaction time and increasing the concentration of hydroxylamine, but the amidoxime content of G-Cell decreased significantly at longer reaction time. The amidoximated samples prepared by CE-Cell exhibited an ability to adsorb metal ions such as Cu²⁺, Ni²⁺, and Co²⁺, and the adsorbed amount of Cu²⁺ was highest among the three metal ions. Moreover, the adsorption of Cu²⁺ varied depending on the DS of CE-Cell. That is, the absorption ability was reduced when the sample was prepared using CE-Cell with higher DS. The amidoximated samples prepared from G-Cell showed adsorption of Cu²⁺ similar to samples prepared by CE-Cell with lower DS, irrespective of percent grafting. © 1995 John Wiley & Sons, Inc.     

辐射交联聚丙烯腈偕胺肟纤维的制备及其对钒(Ⅲ)的吸附研究

采用60Coγ射线对聚丙烯腈纤维进行预辐射交联,并经偕胺肟化反应,制备了含有偕胺肟基的聚丙烯腈螯合纤维,用于钒(Ⅲ)离子的吸附行为研究。结果表明,辐射交联可以有效提高聚丙烯腈纤维的肟胺化反应速率;经肟胺化和吸附之后的纤维力学性能良好;较高的肟胺化程度导致聚丙烯腈纤维对三氯化钒具有很高的吸附容量。     

Adsorption of Cr(III), Ni(II), Zn(II), Co(II) ions onto phenolated wood resin

In this study, phenolated wood resin was used an adsorbent for the removal of Cr(III), Ni(II), Zn(II), Co(II) ions by adsorption from aqueous solution. The adsorption of metal ions from solution was carried at different contact times, concentrations and pHs at room temperature (25°C). For individual metal ion, the amount of metal ions adsorbed per unit weight of phenolated wood resin at equilibrium time increased with increasing concentration and pH. Also, when the amounts of metal ions adsorbed are compared to each other, it was seen that this increase was order of Cr(III) > Ni(II) > Zn(II) > Co(II). This increase was order of Cr(III) > Ni(II) > Co(II) > Zn(II) for commercial phenol–formaldehyde resin. Kinetic studies showed that the adsorption process obeyed the intraparticle diffusion model. It was also determined that adsorption isotherm followed Langmuir and Freundlich models. Adsorption isotherm obtained for commercial phenol–formaldehyde resin was consistent with Freundlich model well. Adsorption capacities from Langmuir isotherm for commercial phenol–formaldehyde resin were higher than those of phenolated wood resin, in the case of individual metal ions. Original adsorption isotherm demonstrated the monolayer coverage of the surface of phenolated wood resin. Adsorption kinetic followed the intraparticle diffusion model. The positive values of ΔG° determined using the equilibrium constants showed that the adsorption was not of spontaneous nature. It was seen that values of distribution coefficient (K_D) decreasing with metal ion concentration in solution at equilibrium (C_e) indicated that the occupation of active surface sites of adsorbent increased with metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2838–2846, 2006     

Parametric studies on the synthesis of amidoximated adsorbent resins

The main goal of this study was to obtain acrylonitrile (AN)‐divinylbenzene (DVB) copolymer beads that can serve as the matrix for preparation of amidoxime resins. AN‐DVB amidoxime resin was synthesized via suspension polymerization and the effect of different parameters such as the speed of stirrer, the amounts of suspending agent, hydrophilic agent, diluent agent, and initiator on its properties was investigated by fractional factorial (Taguchi) experimental design method. This method gives much‐reduced variance for the experiments with optimum control parameters setting and provides a set of minimum experiments compared to the conventional methods. The results showed that the most effective parameters on the amidoximation of resins were hydrophilic agent content, speed of stirrer, and the amount of suspending agent, respectively. Furthermore, anion‐exchange capacity of the amidoxime resins was utilized as a criterion for the evaluation of amidoxime adsorbent groups and the adsorption potential of the synthesized resins was determined by cation‐exchange capacity. The amount of methylacrylate as a hydrophilic agent had the most significant effect on the ion‐exchange capacity of the final product. Swelling ratio was also measured to evaluate the adsorption capacity of the synthesized resin. The results showed that the amounts of hydrophilic and diluent agents had significant effects on swelling ratio of resin. Finally, cation‐exchange capacity and swelling ratio of amidoxime resin were changed greatly because of alkaline treatment, but it had no significant effect on the anion‐exchange capacity of the synthesized resin. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Uranyl ion adsorptivity of N-vinyl 2-pyrrolidone/acrylonitrile copolymeric hydrogels containing amidoxime groups

Summary N-vinyl 2-pyrrolidone (VP) / Acrylonitrile (AN) copolymeric hydrogels were synthesized by using γ-radiation and amidoximated for the purpose of uranyl ion adsorption. Optimum amidoximation time was determined by following the uranyl ion, UO₂ ²⁺, adsorption capacity. The adsorption of amidoximated copolymers was studied from different uranyl ion solutions (1000–1850 ppm). The results of all adsorption studies showed that the interaction between UO₂ ²⁺ and amidoxime groups comply with Langmuir type isotherm. The adsorption capacity was found as 0.54 g UO₂ ²⁺ /g dry amidoximated copolymeric hydrogels. From the stoichiometric calculations, it was found that the bonding between UO₂ ²⁺ and amidoxime groups is 1 to 4. Received: 7 September 1999/Revised version: 21 February 2000/Accepted: 18 March 2000     

Polymer brushes on graphene oxide for efficient adsorption of heavy metal ions from water

The pollution of heavy metal ions in water poses a serious threat to human being and ecosystems. Here, we report polyamidoxime (PAO) brush grafted graphene oxide (GO) as a highly efficient adsorbent for extraction of toxic metal cations from water. Surface-initiated atom transfer radical polymerization was used to grow polyacrylonitrile (PAN) brushes on GO, followed by conversion of the nitrile groups in PAN into amidoxime groups, which had high binding affinity toward heavy metal cations. The PAO brush grafted GO demonstrated significantly fast adsorption kinetics and large adsorption capacity. At optimal pH 5, the PAO brush grafted GO can achieve maximum adsorption capacities of 116.7 mg g⁻¹ for Pb(II), 258.6 mg g⁻¹ for Ag(I), 192.2 mg g⁻¹ for Cu(II), and 167.9 mg g⁻¹ for Fe(III), which were significantly larger than those of small molecule functionalized GO. Mechanism analysis suggested that the enhanced adsorption performance was due to the myriads of functional groups in PAO brushes that were easily accessible to metal ions because of the swelling of the polymer brushes in water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48156.     

Amidoximated poly(acrylonitrile) particles for environmental applications: Removal of heavy metal ions,dyes, and herbicides from water with different sources

Monodispersed poly(acrylonitrile) [p(AN)] particles were prepared by surfactant free emulsion polymerization and the hydrophobic nitrile groups were converted to hydrophilic amidoxime groups by treatment with hydroxylamine hydrochloride (NH₂OH.HCl) in water. The p(AN) and amidoximated p(AN) [amid‐p(AN)] particles were characterized by Fourier transformation infrared (FT‐IR) spectroscopy, thermal gravimetric analysis (TGA), and scanning electron microscopy (SEM). The prepared particles were used as adsorbents in the removal from aqueous media of three different types of pollutants; organic dyes methylene blue (MB), and rhodamine 6 G (R6G), a heavy metal ion Cd (II), and a herbicide paraquat (PQ). The effects of various parameters such as amidoximation, pH of solution, amount of particles, and the initial concentration of solution were investigated. Upon amidoximation, a great increase in the adsorption capacity of the prepared particles was observed as the adsorbed amounts were increased to 87, 91, 74, and 91 mg/g from 5, 1.54, 1.06, and 1.22 mg/g for Cd (II), MB, R6G, and PQ, respectively. The amid‐p(AN) particles were also able to remove considerable amounts of these pollutants from tap, river, and sea water. Langmuir, Freundlich, and Temkin adsorption isotherms were applied and it was found that the adsorption of Cd (II) and PQ followed the Langmuir adsorption model, whereas the adsorption of MB was found to obey the Freundlich adsorption isotherm. Pseudo first‐order and pseudo second‐order kinetics were also applied and the results showed that the adsorption processes of Cd (II), PQ, MB, and R6G follow pseudo second‐order kinetics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43032.