Removal of Acidic and Basic Dyes from Water using Crosslinked Polystyrene Based Quaternary Ethyl Piperazine Resin

In this study, a beaded polymer with quaternary amine functions was prepared in two steps, starting from poly (vinyl benzyl chloride-ethylene glycol dimethacrylate) (PVBC) based beads, according to the synthetic protocol; modification of ethyl piperazine with PVBC (EP-PS), and quaternization of ethylpiperazine modified beads with chloroacetic acid (QEP-PS). The QEP-PS resin was used for the removal of reactive red 120 as an acidic dye and malachite green chloride as a basic dye. Dye extraction experiments were carried out simply by contacting wetted sorbent samples with aqueous dye solutions at room temperature. Capacities were determined by colorimetric analysis of the residual dye contents. The resin showed that reasonable high dye sorption capacity (0.34-0.41 g per gram of dry resin) was achieved. The adsorption conditions (initial dye concentration and pH) were varied to evaluate the mechanism of adsorption of both basic dyes and acidic dyes on the prepared resin. This material is also able to remove both the anionic dye and cationic dyes completely even from highly diluted aqueous dye solutions.     

Preparation of poly (acrylic acid) containing core‐shell type resin for removal of basic dyes

BACKGROUND: A core‐shell type carboxylic acid modified resin was prepared and dye sorption characteristics of the resin were investigated. The resulting grafted resin material has been shown to be an efficient sorbent for removal of basic dyes from water as a result of the carboxylic acid group's affinity towards basic dye molecules. RESULTS: The resin was characterized using Fourier transform infrared spectroscopy (FT‐IR) and titrimetric methods. The basic dyes (methylene blue and crystal violet) were removed by contacting the swollen resin with aqueous dye solutions at room temperature. The adsorption capacities of resin were determined by colorimetric analysis of the residual dye content in the adsorption medium, which gave capacities for methylene blue and crystal violet of 300 and 250 mg g^?1 resin, respectively. The prepared resin is also able to remove basic dyes completely from dilute aqueous dye solutions. Batch kinetic sorption experiments determined that a pseudo‐second‐order rate kinetic model was applicable. CONCLUSION: Flexibility of the polymer side chains is expected to provide pseudo‐homogeneous reaction conditions and easy accessibility of the functional groups involved. The adsorbents are expected to have the advantage of mobility of the grafted chains in the removal of basic dyes from aqueous mixtures. The resin has potential as an adsorbent for removal of basic dyes for use over a wide pH range. Copyright © 2011 Society of Chemical Industry     

NEW CATION EXCHANGE RESINS BASED ON POLYVINYL ALCOHOL CONTAINING CARBOXYL GROUPS FOR THE REMOVAL OF SOME TEXTILE CONTAMINANTS FROM AQUEOUS SOLUTIONS

Two cation exchange resins having carboxyl contents, 628 and 424 meq/100 g sample were prepared by free radical polymerization of acrylic acid in presence of polyvinyl alcohol aqueous solution using methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator. The prepared resins were characterized by investigation of their potentiometric titration, durability, water solubility, and swellability. The removal of Cu²⁺ ions (in the form of copper sulfate) from aqueous solution using these resins was studied under different conditions, including resin particle size, copper sulfate concentration, time, pH, liquor to resin ratio (LR), agitation speed, and resin capacity. A comparison was also held among the removal of other cations, namely Ni²⁺ and Co²⁺, in their sulfate forms. The resins were also utilized in the removal of some basic dyes from their aqueous solutions.     

EXPERIMENTAL INVESTIGATION ON ADSORPTION OF AMIDO BLACK 10B DYE ONTO ZEOLITE SYNTHESIZED FROM FLY ASH

This work presents experimental studies on adsorptive removal of Amido black 10B dye using a low-cost zeolite synthesized from fly ash to study the effect of various parameters, namely pH, temperature, agitation speed, adsorption time, zeolite loading, and dye concentration, on dye removal efficiency. Dye removal efficiency increased with increase in adsorbent dosage, adsorption time, and stirrer speed, and the optimal values of zeolite dose, adsorption time, and stirrer speed were found to be 10 g/L, 6 h, and 300 rpm respectively. On the other hand, dye removal efficiency decreased with increase in the initial dye concentration as well as temperature, indicating that the adsorption process is exothermic and is effective at low concentrations of adsorbate. Maximum dye removal was obtained at low pH values (between 2 and 5), indicating the fact that the zeolite surface is positively charged. Experimental data matched well with the pseudo-first-order kinetic model and the Freundlich equilibrium isotherm. The most important observation in this work is that zeolite synthesized from fly ash could act as a very effective adsorbent for the removal of amido black dye from its aqueous solutions.     

Adsorption of Methylene Blue on Poly (Methacrylic Acid) Modified Chitosan and Photocatalytic Regeneration of the Adsorbent

The preparation of poly(methacrylic acid) modified chitosan microspheres (PMAA-GLA-CTS) and its application for the removal of cationic dye, methylene blue (MB), in aqueous solution in a batch system were described. The modified chitosan was characterized using FTIR and XPS analysis. The effects of the pH of the solution, contact time, and initial dye concentration were studied. The adsorption capacity of the microspheres for MB increased significantly after the modification as a large number of carboxyl groups were introduced. The equilibrium process was better described by the Langmuir rather than the Freundlich isotherm. According to the Langmuir equation, the maximum adsorption capacity was 1 g · g^?1 for MB. Kinetic studies showed better correlation coefficients for a pseudo-second-order kinetic model, confirming that the sorption rate was controlled by a chemisorption process. Photocatalytic regeneration of spent PMAA-GLA-CTS using UV/TiO₂ is effective. Further, the regenerated PMAA-GLA-CTS exhibits 90% efficiency for a subsequent adsorption cycle with MB aqueous solutions.     

Adsorption Behavior of Cationic and Anionic Dyes onto Acid Treated Coconut Coir

The adsorption of Methylene Blue (MB) and Acid Orange 7 (AO7) from aqueous solutions by acid treated coconut coir was investigated under laboratory conditions to assess its potential in removing cationic and anionic dyes. The acid treated coconut coir exhibited better adsorption capacity in cationic dye MB than anionic dye AO7 and the data obtained can be well described by both Langmuir and Freundlich isotherm models. According to the Langmuir isotherm model, the maximum adsorption capacities of MB and AO7 onto acid treated coconut coir were 121 mg/g and 10 mg/g, respectively. The adsorption behavior of MB and AO7 onto acid treated coconut coir was analyzed with first-order Lagergren model and pseudo-second order model.     

SEPARATION OF MOLYBDENUM SPECIES BY ELECTRODIALYSIS

Lab-scale tests have been carried out in order to assess the possibility of separating molybdenum from aqueous solutions by means of electrodialysis (ED). Mo-containing sodium hydroxide, sulfuric acid, ammonium hydroxide, and hydrochloric acid solutions were tested at 25°C in a five-compartment ED cell. Cell voltages were markedly lower in ammonium hydroxide and chloride solutions, but separation in the latter electrolyte was limited by the low solubility of Mo species. Best results were achieved for Mo separation by ED from an aqueous alkaline solution with 21.8 g L^?1 Mo and 3.4 M ammonium hydroxide and a cell current density of 120 A m^?2. Under these conditions, the Mo transport rate from the working solution was 5.6 mol m^?2 h^?1 and the specific energy consumption for Mo separation was 2.2 kWh kg^?1. These results suggest that this operation should be further studied at pilot scale.     

Adsorption of phenazine dyes using poly(hydroxamic acid) hydrogels from aqueous solutions

Swelling and adsorption properties of poly(hydroxamic acid), (PHA) hydrogels in aqueous solutions of some phenazine dyes such as Neutral Red, Safranin T, and Janus Green have been investigated. PHA hydrogels containing N,N′ methylenebisacrylamide or ethyleneglycoldimethacrylate were used in experiments on swelling, diffusion and adsorption of the dyes. The equilibrium swelling (S_eq) values of PHA hydrogels in aqueous solutions of the phenazine dyes were calculated as 2.16–33.25 g g^?1. Swelling kinetic parameters such as initial swelling rate, swelling rate constant, and maximum swelling were found. Dye diffusion into hydrogels was found to be non‐Fickian in character. Diffusion coefficients are ranged 1.32 × 10^?6 cm² s^?1 ? 44.70 × 10^?6 cm² s^?1. Adsorption of the phenazine dyes onto PHA hydrogels was studied by batch technique. PHA hydrogels in the phenazine dye solutions showed the dark coloration. The data was found that Freundlich isotherm model fits. According the Freundlich constants, the adsorption isotherms are of S‐type in Giles classification. All swelling and binding parameters for PHA‐EGDMA were found to be higher than those for PHA‐NNMBA. The type of crosslinker influenced the swelling, binding, and sorption more than the type of dye. Finally, it can be said that PHA hydrogels may be used a sorbent for removal of dyes. POLYM. ENG. SCI., 58:310–318, 2018. © 2017 Society of Plastics Engineers     

Swelling Characterization of Polyelectrolyte Poly(Hydroxamic Acid) Hydrogels in Aqueous Thiazin Dye Solutions

In this study, swelling behavior of polyelectrolyte poly(hydroxamic acid) (PHA) hydrogels have been investigated in aqueous thiazin dye solutions. PHA hydrogels were prepared by free radical polymerizations of acrylamide with some cross-linkers such as N,N′ methylenebisacrylamide (NBisA) and ethylene glycol dimethacrylate (EGDMA); then they were used in experiments on swelling and diffusion of some water-soluble cationic dyes such as methylene blue (MB), thionin (T), and toluidin blue (TB). Swelling experiments were performed in water at 25°C, gravimetrically. The equilibrium swelling percent (S%) values of PHA hydrogels were calculated as 238–2705%. Some swelling kinetic parameters such as initial swelling rate, swelling rate constant, and maximum (theoretical) swelling percent were found. Diffusional behavior of dye solutions was investigated. Dye diffusion into hydrogels was found to be non-Fickian in character. Diffusion exponent (n) is over 0.50. For sorption of thiazin cationic dyes, MB, T, and TB to PHA hydrogels were studied by batch sorption technique at 25°C. PHA hydrogels in the dye solutions showed the dark coloration. In the experiments of the adsorption, S-type adsorption in the Giles classification system was found.     

Biosorption of Direct Red 28 (Congo Red) from Aqueous Solutions by Eggshells: Batch and Column Studies

The feasibility of using eggshells as a low-cost biosorbent for the removal of Direct Red 28 (DR 28) from aqueous solutions was studied in batch and dynamic flow modes of operation. The effect of biosorption process variables such as particle size, solution pH, initial dye concentration, contact time, temperature, feed flow rate, and bed height were investigated. Both the Langmuir and Freundlich isotherm models exhibited excellent fit to the equilibrium biosorption data. Optimum pH (6.0), particle size (<250 µm), initial dye concentration (50 mg g^?1), temperature (313 K), and contact time (240 min) gave maximum monolayer biosorption capacity of 69.45 mg g^?1 which was higher than those of many sorbent materials. Pseudo-second-order kinetic model depicted the biosorption kinetics accurately. Thermodynamic study confirmed the spontaneous and endothermic nature of the biosorption process. Breakthrough time increased with increase in the bed height but decreased with increase in flow rate. Overall, batch and continuous mode data suggest the applicability of eggshells as an environment friendly and efficient biosorbent for removal of DR 28 from aqueous media.     

Synthesis and characterization of PET fibers grafted with binary mixture of 2-methylpropenoic acid and acrylonitrile by free radical: its application in removal of cationic dye

Grafting of binary vinyl monomer mixtures such as 2-methylpropenoic acid (MPA) and acrylonitrile (AN) onto poly (ethylene terephthalate) fibers (PET) was achieved in an aqueous medium with using benzoyl peroxide like free radical initiator. A new reactively fibrous adsorbent was used for removal of dye such as methylene blue (MB) from aqueous media through batch sorption method. Fibers adsorbent was swelled in solution to support the graft and the subsequent polymerization of MPA/AN onto polyester fibers. Optimum conditions for grafting were discovered and reactive fiber were characterized. Variations of graft yield with time, temperature, initiator concentration and monomer mixture ratio were investigated. The optimum initiator concentration was found to be 8 × 10^?3 mol/L. The percentage of grafting rose steadily with the vinyl monomer mixture monomer concentration (50 %). The optimum temperature and polymerization time were found to be 80 °C and 120 min, respectively. The use of AN and MPA monomers together in grafting produce a significant increased in the graft yield. Experimental studies showed that the percentage removal of MB was a great higher on the MPA/AN grafted PET (MPA/AN-g-PET) fibers than on the original PET fibers. The adsorbed quantity of MB improved with pH and basic pH was appropriate for the elimination of MB. MPA/AN-g-PET fibers removed 98 % of cationic dye when initial concentration diverse from 10 to 80 mg L^?1 at pH 9.0. Almost all of the adsorbed cationic dye was eluted by ethanoic acid in methanol. Ten removal–desorption cycles indicated that the reactive fibers were favorable for repetitive use without notable change in removal capacity. Consequently, the MPA/AN-g-PET fibers have demonstrated potential as an effective adsorbent for the extremely effective removal of cationic dyes from aqueous media.     

Synthesis,Characterization, and Some Utilization of Cellulose/Melamine Formaldehyde/Methylamine Anion Exchange Resin

Cellulose, melamine formaldehyde precondensate (MF), and methylamine hydrochloride (MA.HCl) were reacted in aqueous medium at different conditions, including time, temperature, MF/MA.HCl molar ratio, and liquor-to-cellulose ratio (LR). Reaction conditions were selected to prepare a cellulose/MF/MA anion exchanger having a total nitrogen and an amino nitrogen of 23.1% and 131 mEq/100 g, respectively. Potentiometric titration showed that the strength, pK_b , of this resin was 7.2. The resin lost about 3% and 9% of its total and amino nitrogen, respectively, during the first five cycles of the durability test, after which it suffered no losses up to 25 cycles. The resin was utilized in the removal of three anionic dyestuffs (direct, acid, and reactive) as well as permanganate and dichromate anions from aqueous solutions at different pH values ranging from 3 to 12. Maximum extents of removal were manifested at a pH value of 3, at which they followed the descending order: (permanganate ～ acid dye) > (reactive dye ～ dichromate) » direct dye.     

The Fenton Chemistry and Its Combination with Coagulation for Treatment of Dye Solutions

Abstract

Aqueous solutions of Acid Blue 74, Acid Orange 10, and Acid Violet 19 were subjected to Fenton/Fenton‐like oxidation and its combination with lime coagulation. The analysis indicated no dependence of chemical oxidation efficacy on dye concentration in the range of 0.1–1 g L^?1. Complete or nearly complete (higher than 95%) color removal of all treated samples was observed. Dye:H₂O₂ weight ratio of 1∶2 proved optimal for treatment of all dye solutions by means of Fenton/Fenton‐like oxidation. Moderate doses of hydrogen peroxide led to the improvement of biodegradability of dye solutions. No formation of any toxic intermediates during the oxidation of Acid Orange 10 and Acid Violet 19 was detected. Only a slight toxicity increase was observed after Acid Blue 74 degradation by Fenton chemistry. H₂O₂/Fe³⁺ system with pH adjusted to 3 proved the most effective oxidation process. The combination of Fenton chemistry and subsequent lime coagulation was the most feasible treatment method of removing COD and UV₂₅₄ and UV_max absorbance of dye solutions. Combined oxidation and coagulation was more effective for Acid Blue 74 and Acid Orange 10 elimination than for Acid Violet 19.     

Molecularly Imprinted Ion-Exchange Resin for Fe3+

Abstract

Ion exchange resins selective for the sequestration of Fe³⁺ from aqueous solutions containing citrate were prepared by the molecular imprinting technique. Sorption characteristics of imprinted resins prepared with high (85 mole%) and low (3 mole%) amounts of covalent cross‐linking were examined. Experiments to determine loading capacity and selectivity, relative to several metal ions of physiological significance, were performed. The Fe³⁺ capacity of the highly cross‐linked resin was larger but the selectivity was lower.     

Dye Adsorption on Cubic Polyhedral Oligomeric Silsesquioxane-Based Poly(acrylamide-<Emphasis Type="Italic">co</Emphasis>-itaconic acid) Hybrid Nanocomposites: Kinetic,Thermodynamic and Isotherms Studies

In the present study, poly(acrylamide-co-itaconic acid) hybrid nanocomposites were synthesized via free radical copolymerization method. Octavinyl polyhedral oligomeric silsesquioxane (OV-POSS) with different weight ratio (0, 4, 8, 12 and 14 wt%) was utilized as a cross-linker. Dye adsorption properties of the as-prepared hybrid nanocomposites were investigated for crystal violet (CV) elimination from aqueous solution. The effect of various parameters, such as OV-POSS content, adsorbent amount, pH, temperature, contact time and initial dye concentration, on the adsorption of CV was studied. Moreover, adsorption kinetic, isotherm and the thermodynamic of the CV adsorption on the so-called hybrid nanocomposites were studied.     

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.     

Mechanistic,Kinetic, and Thermodynamic Evaluation of Adsorption of Hazardous Malachite Green onto Conch Shell Powder

The present study explores the ability of a new adsorbent—conch shell powder (CSP) in removing Malachite Green from aqueous solutions. The effect of various process parameters, namely initial solution pH, temperature, initial dye concentration, adsorbent dose, and contact time was investigated. Adsorption equilibrium data were well described by the Langmuir isotherm with maximum adsorption capacity of 92.25 mg g^?1 at 303 K. The kinetic data conformed to the pseudo-second-order kinetic model. A thermodynamic study showed the spontaneous nature and feasibility of the adsorption process. The results provide strong evidence to support the hypothesis of adsorption mechanism.     

Microwave-assisted green synthesis of hybrid nanocomposite: removal of Malachite green from waste water

Gum xanthan/psyllium-based nanocomposite was prepared by microwave-assisted synthetic method for the removal of toxic Malachite green (MG) dye from aqueous solutions. The nanocomposite was prepared by in situ incorporation of the K₂Zn₃[Fe(CN)₆]·9H₂O nanoparticles into the semi-IPN matrix in the presence of ammonium persulphate and glutaraldehyde as initiator-crosslinker system. Liquid uptake efficacy of the hybrid superabsorbent was enhanced through the optimization of different reaction conditions, including APS = 0.027 mol L^?1; glutaraldehyde = 0.053 × 10^?3 mol L^?1; solvent = 8.0 mL; acrylic acid = 10.928 mol L^?1; pH 7.0; reaction time = 60 s and microwave power = 100 % and its thermal behavior was evaluated using TGA-DTG-DTA technique. Candidate nanocomposite was characterized by FTIR, SEM, XRD and UV–visible spectroscopic methods. Various optimized parameters for the efficient removal (83 %) of the Malachite green were adsorbent dose of 800 mg, 14 mg L^?1 initial dye concentration and contact time of 28 h. Further, Langmuir and Freundlich adsorption isotherms showed good applicability in adsorption process of MG onto the nanocomposite with maximum adsorption efficiency of 3.21 mg g^?1. However, for Freundlich isotherm, R ² was around 0.9947 and value of 1/n was less than 1 for the synthesized nanocomposite which indicated that the Freundlich isotherm was more favorable than Langmuir isotherm model along with its usability for wide range of dye concentrations. The nanocomposite was found to be a potential product for dye removal from waste water and could prove to be a boon for textile sector.     

A Novel Pinus Tabulaeformis Based Adsorbent for the Removal of Malachite Green

Pyrolytic char treated with muffle furnace (TPC), a novel adsorbent, were investigated to enhance its adsorption capacity of malachite green (MG) dye. In addition, the dye adsorption behavior of the TPC in aqueous solution was investigated. The treatment temperature, treatment time, and the particle size of PC had a positive effect on the dye adsorption capacity of TPC. Equilibrium data was fitted well with Langmuir and Redlich-Peterson models with maximum adsorption capacity of 91.24, 111.27, and 119.01 mg g^?1 at 293, 303, and 313 K, respectively. The kinetic of adsorption was found to confirm to the Elovich equation with good correlation and the overall rate of MG uptake was found to be controlled by film diffusion, pore diffusion and particle diffusion. The Boyd plot confirmed that the external mass transfer was the rate-limiting step in the adsorption process. Different thermodynamic parameters have also been evaluated and it was found that the adsorption was spontaneous, feasible, and endothermic in nature. Adsorbents could be regenerated using 0.1 mol L^?1 NaOH solution at least three cycles, with up to 90% recovery. The TPC used in this work proved to be an effective material for the treatment of MG bearing aqueous solutions.     

Separation and Recovery of Cs from High Active Waste Simulant using Resorcinol Formaldehyde Polycondensate Resin: Batch and Column Studies

Resorcinol formaldehyde polycondensate resin has been extensively used for the separation of ¹³⁷Cs from low and medium active alkaline waste solutions. The present study examines the suitability of the resin for separation of Cs from high active solutions. Batch uptake of Cs by RFPR has been evaluated from test solutions containing varying Na (0.6–3.0 M) and Cs (1.00 × 10^?4 to 0.10 M) concentrations. Batch results have been used to establish Cs exchange isotherms of the resin and were found to follow Freundlich as well as Dubinin-Radushkevich (D-R) isotherm equations. The loading behavior of Cs on RFPR column has been evaluated by conducting five column runs using different Cs bearing solutions. Based on these results, it is concluded that the D-R equation can be used to predict saturated loading of Cs in the column. The saturation loading of Cs on 1 L bed was estimated to be as high as 13 g and 34 g from feed solution containing Cs concentration 2.57 × 10^?4 and 4.30 × 10^?3 mol/L respectively. Sequential elution of Na and Cs resulted in a high Cs bearing concentrate containing very low concentration of sodium. This study is relevant in the preparation of gamma source for radiation technology applications after immobilization of the concentrate in glass.