Preparation and regeneration of a thermo-sensitive adsorbent material: methyl cellulose/calcium alginate beads (MC/CABs)

Polymer Bulletin - In this study, preparation and regeneration of methyl cellulose/calcium alginate beads (MC/CABs), a thermo-sensitive adsorbent material, have been introduced. The effects of...     

Novel type of alginate gel‐based adsorbents for heavy metal removal

Various alginate gel‐based adsorbents were investigated for the removal of heavy metals: alginate beads, alginate capsules, and alginate gel‐coated adsorbent. Of these, alginate capsules showed the greatest Pb²⁺ uptake capacity of 1560 mg g^?1 of dry sodium alginate, and the alginate gel‐coated adsorbent, prepared simply by forming a thin alginate film on an inert matrix, achieved rapid adsorption equilibrium within 10 min. Adsorbed metals were readily removed from the alginate gel‐based adsorbents using eluents such as HNO₃ and could be reused for up to 10 adsorption–desorption cycles without marked loss of metal uptake capacity. Alginate gel‐coated adsorbents could be prepared in a dried state and have great application potential for the removal of heavy metals from contaminated water. Copyright © 2004 Society of Chemical Industry     

Improved synthesis of a branched poly(ethylene imine)‐modified cellulose‐based adsorbent for removal and recovery of Cu(II) from aqueous solution

This study focuses on an improved synthesis of a branched poly (ethylene imine) (PEI)‐modified cellulose‐based adsorbent (Cell‐g‐PGMA‐PEI). We aim to improve the adsorbent capacity by reducing side reaction of epoxide ring opening during graft copolymerization of glycidyl methacrylate (GMA) onto cellulose which increases the content of epoxy groups, anchors to immobilize branched PEI moieties. FTIR spectra provided the evidence of successful graft copolymerization of GMA onto cellulose initiated by benzoyl peroxide (BPO) and modification with PEI. The amount of epoxy groups of Cell‐g‐PGMA was 4.35 mmol g^?1 by epoxy titration. Subsequently, the adsorption behavior of Cu(II) on cell‐g‐PGMA‐PEI in aqueous solution has been investigated. The data from the adsorption kinetic experiments agreed well with pseudo‐second‐order model. The adsorption isotherms can be interpreted by the Langmuir model with the maximum adsorption capacity of 102 mg g^?1 which was largely improved compared with the similar adsorbent reported. The dynamic adsorption capacity obtained from the column tests was 119 mg g^?1 and the adsorbent could be regenerated by HCl of 0.1 mol L^?1. Results indicate that the novel pathway for the synthesis of Cell‐g‐PGMA‐PEI exhibits significant potential to improve the performance of adsorbents in removal and recovery of Cu(II) from aqueous solution. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

CO2 sorption performance by aminosilane functionalized spheres prepared via co‐condensation and post‐synthesis methods

Amine functionalized silica microspheres were synthesised via a modified Stöber reaction for carbon dioxide (CO₂) adsorption. A number of adsorbents were synthesized by co‐condensation and post synthesis immobilization of amines on porous silica spheres. CO₂ adsorption studies were carried out on a fixed bed gas adsorption rig with online mass spectrometry. Amine co‐condensed silica spheres were found to adsorb up to 66 mg CO₂ g^?1 solid in a 0.15 atm CO₂ stream at 35°C. Simple post‐synthesis addition of aminopropyltriethoxysilane to amine co‐condensed silica was found to significantly increase the uptake of CO₂ to 211 mg CO₂ g^?1 under similar conditions, with CO₂ desorption commencing at temperatures as low as 60°C. The optimum temperature for adsorption was found to be 35°C. This work presents a CO₂ adsorbent prepared via a simple synthesis method, with a high CO₂ adsorption capacity and favorable CO₂ adsorption/desorption performance under simulated flue gas conditions. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2825–2832, 2016     

Adsorption characteristics of methylene blue onto the N-succinyl-chitosan-<Emphasis Type="Italic">g</Emphasis>-polyacrylamide/attapulgite composite

N-succinyl-chitosan-g-polyacrylamide/attapulgite (NSC-g-PAM/APT) composite was applied as adsorbent for the removal of methylene blue (MB) from aqueous solution. The initial pH value of the dye solutions, the contact temperature, the contact time and the concentration of the dye solutions on adsorption capacity of the composite for MB dye were investigated. The adsorption kinetics and isotherms were also studied. It was shown that all the sorption processes were better fitted by pseudo-second-order equation and the Langmuir equation. The results indicated that the adsorption capacity of the composite was higher than those of chitosan (CTS) and attapulgite (APT). The desorption studies revealed that the composite provided the potential for regeneration and reuse after MB dye adsorption, which implied that the composite could be used as quite effective adsorbent for the removal of MB from aqueous solution.     

High‐efficiency recovery of rare earth ions by hydrolyzed poly(styrene‐co‐maleic anhydride)

Hydrolyzed poly(styrene‐co‐maleic anhydride) (PSMA) as a high‐efficiency adsorbent is used for recovering La³⁺, Eu³⁺, Tb³⁺, and Yb³⁺ from the simulate wastewater of bastnaesite leach liquor. The pseudo‐first‐order and pseudo‐second‐order models are used to fit adsorption data in the kinetic studies and the results show good correlation with the pseudo‐second‐order model. The Langmuir model is found to fit for the isotherm data of all the rare earth ions (RE³⁺) and the maximum adsorption capacity of hydrolyzed PSMA is 285.79, 301.92, 305.46, and 336.65 mg g^?1 at 298 K for La³⁺, Eu³⁺, Tb³⁺, and Yb³⁺, respectively. The adsorption could be conducted in at pH 6.0 and the equilibrium is fast established in 30 min. Competition from coexisting ions (Ca²⁺, Mg²⁺) was proved to be insignificant. Moreover, the spent adsorbent could be well regenerated and kept above 80% of adsorption efficiency at the end of the fifth cycle. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43676.     

Enhanced swelling and methylene blue adsorption of polyacrylamide‐based superabsorbents using alginate modified montmorillonite

Polyacrylamide/sodium alginate modified montmorillonite (PAM/SA‐MMT) superabsorbent composites were synthesized by free‐radical polymerization under normal atmospheric conditions. They were characterized by X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy (FTIR). Their water absorbency and methylene blue (MB) adsorption behaviors were studied. Compared with PAM/MMT composites, PAM/SA‐MMT composites demonstrated greater water absorbency (863 g g^?1 in distilled water and 101 g g^?1 in 0.9 wt % NaCl solution) and higher adsorption capacity of 2639 mg g^?1 for MB. The adsorption behaviors of the composites showed that the isotherms and adsorption kinetics were in good agreement with the Langmuir equation and pseudo‐second‐order equation, respectively. FTIR analysis suggested that the MB adsorption of PAM/SA‐MMT composites via a mechanism combined electrostatic, H‐bonding and hydrophobic interaction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40013.     

Removal of methylene blue dyes from wastewater using cellulose‐based superadsorbent hydrogels

Superadsorbent cellulose‐graft‐acrylic acid (C‐g‐AA) hydrogels were successfully prepared via free radical polymerization in phosphoric acid solution. Phosphoric acid solution provides a homogeneous reaction system. The C‐g‐AA hydrogels have a porous network inner structure with cellulose as the backbone. The introduced carboxyl groups enable the C‐g‐AA hydrogels with good swelling property (swelling ratio 7327%) and excellent MB adsorption capacity (equilibrium adsorption amount 2197 mg g^?1). The dynamic swelling behaviors of the hydrogels were tested, water intake of hydrogels followed a non‐Fickian type diffusion. The effects of mole ratio of AA to cellulose, the pH of adsorption medium and the initial MB concentration on dye adsorption capacity of hydrogels were investigated. The adsorption isotherm and kinetics fit the Langmuir model and the Pseudo‐second‐order model well, respectively. Desorption was carried out in weak acid solution and 70% MB could be removed, suggesting the C‐g‐AA hydrogels had the potential for reuse. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Removal of ammonium cations from aqueous solution using arene‐sulphonic acid functionalised SBA‐15 as adsorbent

Removal of ammonium cations from aqueous solution was investigated using an arene‐sulphonic acid functionalised mesostructured SBA‐15 material as adsorbent. Arene‐sulphonic acid‐SBA‐15 (AS‐SBA‐15) was prepared via a co‐condensation strategy using tetraethylorthosilicate (TEOS) and 2‐(4‐chlorosulphonylphenyl)ethyltrimethoxysilane (CSPTMS) as framework precursors under acidic conditions. The material exhibited high surface area (680 m²/g) and total pore volume (0.84 mL/g). The effects of adsorbent loading, initial ammonium concentration, temperature, pH and the presence of competitive ions on the adsorption performances were investigated. The ammonium removal increased with the increase of the adsorbent loading and the decrease of the initial concentration. The adsorption capacity decreased with increasing the temperature. Maximum adsorption capacity obtained at 5°C was ca. 19 mg NH/g adsorbent. The isotherms data were studied using different adsorption models and thermodynamic parameters were calculated. Competitive ions such K⁺ and Na⁺ slightly affected the ammonium adsorption. After six adsorption–desorption cycles, the adsorbent retained its adsorption capacity.     

Efficient removal of Cu(II) using amino‐functionalized superparamagnetic nanoparticles prepared via SI‐ATRP

An amino‐functionalized nano‐adsorbent (DETA‐MNPs) was prepared by a process involving: (1) synthesis of superparamagnetic Fe₃O₄ nanoparticles; (2) introduction of amino groups after which ATRP initiator was anchored; (3) grafting of glycidyl methacrylate (GMA) via SI‐ATRP; and (4) ring‐opening reaction of epoxy groups with diethylenetriamine (DETA). The nano‐adsorbent was characterized by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM) and applied to remove Cu(II) in batch experiments. The effects of pH, Cu(II) concentrations, solution ionic strength, and contact time were investigated. The results show that the DETA‐MNPs are spherical with cubic spine structure, high saturation magnetization (41.9 emu g^?1), and an average diameter of 10 nm. The maximum Cu(II) adsorption capacity achieves 83.33 mg g^?1 at pH 5.0 by Langmuir model. The adsorption process is highly pH‐dependent and reaches equilibrium within 20 min. Furthermore, the DETA‐MNPs exhibit excellent dispersibility and reusability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42859.     

CO2 capture efficiency in post‐combustion using MWNT‐PAA in a packed bed column

The adsorption capacity of polyaspartamide (PAA) and multi‐wall carbon nanotubes with polyaspartamide (MWNT‐PAA) was investigated through a packed bed column with the flowing of flue gas composed of 15 % CO₂, 5 % O₂ and the balance N₂. The adsorption performed at 25 °C, 110 kPa and inlet gas flow rate of 60 mL/min resulted in high CO₂ adsorption capacity of 5.70 and 10.20 mmol‐CO₂/g for PAA and MWNT‐PAA, respectively. The adsorption kinetics was very high, so 7 min were enough for the effluent gas to reach the breakthrough after saturation. The consistency of adsorbents in recurring regeneration was successful through a continuous TSA system of 10 cycle adsorption‐desorption with temperatures of 25–100 °C. The evaluation of heat through differential scanning calorimetry (DSC) resulted in exothermic adsorption with heat release of 45.14 kJ/mol and 124.38 kJ/mol for PAA and MWNT‐PAA, respectively. The heat release was found favourable to promote the desorption as the temperature could rise after adsorption. This is an advantage for energy efficiency, as it depicts the potential of energy recovery. Thus, both adsorbent PAA and MWNT‐PAA were demonstrated to be promising for CO₂ adsorption capture in post‐combustion.     

Polyethylenimine‐grafted and HSA‐immobilized poly(GMA–MMA) affinity adsorbents for bilirubin removal

The epoxy‐group‐containing microspheres from cross‐linked glycidyl methacrylate and methyl methacrylate, poly(GMA–MMA), were prepared by suspension polymerisation. The epoxy groups of the poly(GMA–MMA) microspheres were used for grafting with an anionic polymer polyethylenimine (PEI) to prepare non‐specific affinity adsorbents (poly(GMA–MMA)–PEI) for bilirubin removal. The specificity of the poly(GMA–MMA)–PEI adsorbent to bilirubin was further increased by immobilization of human serum albumin (HSA) via adsorption onto PEI‐grafted poly(GMA–MMA) adsorbent. Various amounts of HSA were immobilized on the poly(GMA–MMA)–PEI adsorbent by changing the medium pH and initial HSA concentration. The maximum HSA content was obtained at 68.3 mg g^?1 microspheres. The effects of pH, ionic strength, temperature and initial bilirubin concentration on the adsorption capacity of both adsorbents were investigated in a batch system. Separation of bilirubin from human serum was also investigated in a continuous‐flow system. The bilirubin adsorption on the poly(GMA–MMA)–PEI and poly(GMA–MMA)–PEI–HSA was not well described by the Langmuir model, but obeyed the Freundlich isotherm model. The poly(GMA–MMA)–PEI affinity microspheres are stable when subjected to sanitization with sodium hydroxide after repeated adsorption–desorption cycles. Copyright © 2004 Society of Chemical Industry     

Human serum albumin adsorption on poly[(glycidyl methacrylate)‐co‐(methyl methacrylate)] beads modified with a spacer‐arm‐attached L‐histidine ligand

Poly(GMA/MMA) beads were synthesized from glycidyl methacrylate (GMA) and methyl methacrylate (MMA) in the presence of a cross‐linker (i.e. ethyleneglycol dimethacrylate) (EGDMA) via suspension polymerization. The epoxy groups of the poly(GMA/MMA) beads were converted into amino groups with either ammonia or 1,6‐diaminohexane (i.e. spacer‐arm). An L ‐histidine ligand was then covalently immobilized on the aminated (poly(GMA/MMA)‐AH) and/or the spacer‐arm attached (poly(GMA/MMA)‐SAH) beads using glutaric dialdehyde as a coupling agent. Both affinity adsorbents were used in human serum albumin (HSA) adsorption/desorption studies under defined pH, ionic strength or temperature conditions in a batch reactor. The spacer‐arm attached affinity adsorbent resulted in an increase in the adsorption capacity to HSA when compared to the aminated counterpart (i.e. poly(GMA/MMA)‐AH). The maximum adsorption capacities of the affinity adsorbents were found to be significantly high, i.e. 43.7 and 80.2 mg g^?1 (of the beads), while the affinity constants, evaluated by the Langmuir model, were 3.96 × 10^?7 and 9.53 × 10^?7 mol L^?1 for poly(GMA/MMA)‐AH and poly(GMA/MMA)‐SAH, respectively. The adsorption capacities of the affinity adsorbents were decreased for HSA by increasing the ionic strength, adjusted with NaCl. The adsorption kinetics of HSA were analysed by using pseudo‐first and pseudo‐second‐order equations. The second‐order equation fitted well with the experimental data. Copyright © 2005 Society of Chemical Industry     

Removal of methylene blue from coloured effluents by adsorption onto SBA‐15

Adsorption has been proven to be the most efficient method for quickly lowering the concentration of dissolved dyes in an effluent. In this regard, activated carbon is the most widely used adsorbent for removal of dyes from aqueous solution. However, the high cost of production and regeneration make it uneconomical. Therefore, inorganic adsorbents (e.g. zeolites) with high surface areas have been used as alternatives to carbon adsorbents. Microporous zeolites ZSM‐5, NH₄‐Beta, MCM‐22 and mesoporous materials MCM‐41 have been investigated for the removal of dyes from aqueous solutions and they show effective adsorption performance. SBA‐15 possesses a larger pore size and pore wall thickness than MCM‐41. As a result, SBA‐15 has greater potential for the adsorption of methylene blue with larger molecule size and higher hydrothermal stability than the M41S family. SBA‐15 is an excellent adsorbent for methylene blue (MB), exhibiting 280 mg g^?1 adsorption capacity and about 100% fading rate for MB. The adsorptive process is so fast that adsorption equilibrium is achieved in 5 min. In addition, SBA‐15 can be effectively recovered by calcination and reused 10 times without significant loss in removal of MB from aqueous solution. The efficient adsorption of MB molecules onto SBA‐15 was ascribed to MB adsorbed into the pore channels of SBA‐15, which was confirmed by nitrogen physisorption analysis of the adsorbent before and after adsorption. The long reuse life of the adsorbent suggests a high potential for application in industry. Copyright © 2010 Society of Chemical Industry     

Self‐assembly of alginate/polyethyleneimine multilayer onto magnetic microspheres as an effective adsorbent for removal of anionic dyes

A novel magnetic adsorbent alginate/polyethyleneimine (ALG/PEI)_n/MN was developed for removal of anionic dyes from aqueous solution in this study. (ALG/PEI)_n/MN was prepared by depositing ALG/PEI multi‐layers onto amine‐modified Fe₃O₄ microspheres through layer‐by‐layer method. The morphologies and structures of the adsorbent were characterized by scanning electron microscopy, X‐ray diffractometer, and Fourier transform infrared spectrometer, respectively, and its performance in adsorption of anionic dye (acid orange 10, AO10) under varied experimental conditions were also investigated. The results revealed that the uptake capacity of AO10 by (ALG/PEI)_n/MN increased with the number of coated (ALG/PEI) bilayer on the adsorbents, and the maximum adsorption capacity for AO10 by (ALG/PEI)₄MN was 246.3 mg g^?1 at 25 °C. The adsorption process was exothermic and well described by the pseudo‐second order kinetic model and the Langmuir isothermal model. Moreover, (ALG/PEI)₄/MN showed good reusability and excellent magnetic separability. All the results demonstrate that (ALG/PEI)₄/MN is a potential recyclable adsorbent for removal of anionic dyes from wastewater. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45876.     

Removal of methylene blue (aq) using untreated and acid‐treated eucalyptus leaves and GA‐ANN modelling

In the present batch study, eucalyptus leaves (EUL), H₂SO₄‐treated eucalyptus leaves (SEUL), and H₃PO₄‐treated eucalyptus leaves (PEUL) are used as bio‐adsorbents for the removal of methylene blue (MB). The bio‐adsorption is executed to inspect the results of the variation between different experimental variables such as pH (2–10), adsorbent dose (1–10 g/L), contact time (5–360 min), and temperature (298–318 K) on the bio‐adsorption of MB. The Langmuir isotherm (R² = 0.99) fitted adequately to the bio‐adsorption data for the initial MB concentrations of 10–300 mg/L. It is also necessary to mention that the MB bio‐adsorption occurred in the order of a monolayer on the EUL, SEUL, and PEUL. The bio‐adsorption kinetics have been fitted by the pseudo‐second‐order model (R² ≥ 0.99) for various MB concentrations. The maximum bio‐adsorption capacity was 194.34 mg/g and was achieved for the H₃PO₄‐treated eucalyptus leaves (PEUL). These results showed that EUL, SEUL, and PEUL may be utilized as a favourable low‐cost bio‐adsorbent to eliminate MB from aqueous solutions. With safe disposal methods in mind, this investigation has revealed the eco‐friendliness of the bio‐adsorbents. A prediction of the removal percentage of methylene blue using a genetic algorithm (GA) from the data collected from the experiment has also been tested. The results related to the prediction using the GA‐ANN are accurate.     

Preparation of a surface molecular‐imprinted adsorbent for Ni2+ based on Penicillium chrysogenum

A new chitosan molecular‐imprinted adsorbent was prepared from the mycelium of waste biomass. The results showed that an adsorbent using Penicillium chrysogenum mycelium as the core material was better than one derived from peanut coat. The adsorption capacity of the surface‐imprinted adsorbent for Ni²⁺ was enhanced by increasing the chitosan concentration in the imprinting process. Epichlorohydrin was better than glutaraldehyde as a cross‐linking agent; the optimal imprinted Ni²⁺ concentration for preparing the surface‐imprinted adsorbent was 2 mg (Ni²⁺) g^?1 of mycelium. The adsorption capacity of the surface‐imprinted adsorbent was 42 mg g^?1 (at 200 mg dm^?3 initial metal ions concentration) and twice that of the mycelium adsorbent. The surface‐imprinted adsorbent can be reused for up to 15 cycles without loss of adsorption capacity. Copyright © 2005 Society of Chemical Industry     

Poly(benzoxazine‐co‐sulfur): An efficient sorbent for mercury removal from aqueous solution

A novel sulfur‐rich adsorbent, poly(BA‐ala‐co ‐sulfur), was synthesized by reacting allyl functional benzoxazine (BA‐ala) and elemental sulfur. Simultaneous inverse vulcanization and ring‐opening reactions of benzoxazine generated copolymers in several feed ratios. The adsorption behavior of these copolymers was investigated in aqueous solutions containing Hg²⁺. A three level Box–Behnken design with four factors was applied in order to examine the interactive effect of Hg²⁺ concentration (ppm), S % in adsorbent, temperature, and pH. The optimum adsorption conditions were determined as: 10.33 ppm Hg²⁺, 68% S content, 329 K, and pH 6.3. Common isotherm and kinetic models were applied to the experimental data, where the Langmuir isotherm provided the better fit (q _max = 79.36 mg g^?1) and the pseudo‐second order fit indicated chemisorption as the process‐controlling step. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45306.     

Rubidium and Cesium Ion Adsorption by a Potassium Titanium Silicate-Calcium Alginate Composite Adsorbent

In this work, a composite spherical adsorbent, which employs potassium titanium silicate as an adsorption active component, and calcium alginate as a carrier, was successfully prepared. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were used to characterize the adsorbent. The kinetics and thermodynamics of rubidium and cesium ions adsorption were investigated comprehensively, by considering the effects of initial concentration, temperature, solution pH, and coexisting NaCl. According to the determination coefficients, the pseudo second-order kinetic model provided an impressive and comparable correlation, and the second-order rate constant and the initial adsorption rate increase with increasing temperature. In general, the equilibrium adsorption amount increases with the increasing initial metal ion concentration, but decreases with increasing coexisting NaCl. The adsorption capacity keeps constant in the pH value range 3-12 and slightly fades when the temperature increases from 25 to 55°C. Under similar conditions, rubidium and cesium show the similar adsorption amount. The adsorbent has a fast adsorption rate and an adsorption capacity of about 1.55 mmol g^?1 for rubidium and 1.47 mmol g^?1 for cesium when the initial metal ion concentration is 0.10 mol L^?1. The composite adsorbent is effective for the adsorption of rubidium or cesium ions from simulated brines.     

Stability constants of amidoximated chitosan‐g‐poly(acrylonitrile) copolymer for heavy metal ions

Amidoximated chitosan‐g‐poly(acrylonitrile) (PAN) copolymer was prepared by a reaction between hydroxylamine and cyano group in chitosan‐g‐PAN copolymer prepared by grafting PAN onto crosslinked chitosan with epychlorohydrine. The adsorption and desorption capacities for heavy metal ions were measured under various conditions. The adsorption capacity of amidoximated chitosan‐g‐PAN copolymer increased with increasing pH values, and was increased for Cu²⁺ and Pb²⁺ but a little decreased for Zn²⁺ and Cd²⁺ with increasing PAN grafting percentage in amidoximated chitosan‐g‐PAN copolymer. In addition, desorption capacity for all metal ions was increased with increasing pH values in contrast to the adsorption results. Stability constants of amidoximated chitosan‐g‐PAN copolymer were higher for Cu²⁺ and Pb²⁺ but lower for Zn²⁺ and Cd²⁺ than those of crosslinked chitosan. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 469–476, 1999