A comparative adsorption study of β-naphthol on four polymeric adsorbents from aqueous solutions

Adsorptive removal of aromatic compounds from aqueous solutions by polymeric adsorbents has attracted many concerns in recent years. A comparative adsorption study including equilibria, kinetics and column dynamics of β-naphthol from aqueous solutions was carried out using two hypercrosslinked polymeric adsorbents (HJ-1 and TEPA) we developed and two commercial polymeric adsorbents (XAD-4 and XAD-7). The adsorption isotherms could be well described by the Freundlich equation, and the adsorption equilibrium capacities of β-naphthol followed an order of q(e)((TEPA))>q(e)((HJ-1))>q(e)((XAD-4))>q(e)((XAD-7)). The isosteric adsorption enthalpies on HJ-1 and TEPA decreased with increasing adsorption fractional loading, while a constant enthalpy was observed for XAD-4 and XAD-7, implying that HJ-1 and TEPA had a heterogeneous surface while XAD-4 and XAD-7 possessed a homogenous surface. The surface energetic heterogeneity of HJ-1 and TEPA could be well characterized by the Do's model. The adsorption kinetics were fitted by both pseudo-first-order and pseudo-second-order rate equations, and the intra-particle diffusion was found to be the rate-limiting step. The adsorption breakthrough data were well correlated by the Thomas and Clark models, and the dynamic capacities for TEPA, HJ-1, XAD-4 and XAD-7 adsorbents were calculated to be 341.7, 321.6, 268.0 and 173.8 mg/g dry resin, which were within 90% of the corresponding equilibrium capacities obtained in the batch experiments.     

ADSORPTION OF 2,4-DICHLOROPHENOL IN AQUEOUS SOLUTION ONTO ADSORPTION RESIN MODIFIED BY N-ACETYLANILINE

A hypercrosslinked adsorption resin （ZH-05） modified by N-acetylaniline in the post crosslinking process was prepared. The adsorption properties of ZH-05 toward 2,4-dichlorophenol in comparison with granular activated carbon （GAC） and Amberlite XAD-4 were observed. The present study mainly focuses on the static equilibrium adsorption behaviors, desorption profiles and the proof of chemisorption. The results show that the Langmuir equation can give a perfect fitting to experimental data, and high temperature was favorable for adsorption of 2,4-dichlorophenol on ZH-05. A related equation was used to correlate the amount of chemisorption and the suppositionai chemisorption equilibrium concentration of adsorbate in aqueous solution. The adsorption capacities from different ranges of temperature and the static desorption experiment both reveal the same conclusion, i.e., the adsorption of 2,4-dichlorophenol from water on ZH-05 is a coexistent process of physical adsorption and chemical transition as on GAC.     

Optimum isotherm equation and thermodynamic interpretation for aqueous 1,1,2-trichloroethene adsorption isotherms on three adsorbents

Aqueous 1,1,2-trichloroethene (TCE) adsorption isotherms were obtained on Ambersorb^1® 563 and 572 adsorbents and Filtrasorb^2® 400 granular activated carbon (GAC). The data for Ambersorb 563 adsorbent covers TCE concentrations from 0.0009 to 600 mg/L. The data for each adsorbent was fit to 15 isotherm equations to determine an optimum equation.The best equation for the TCE adsorption isotherms is the Dubinin-Astakov (DA) isotherm. The DA isotherm coefficients were used to estimate the TCE micropore volume and the adsorption potential distribution. For each adsorbent, the TCE micropore volume is equivalent to the N₂ porosimetry micropore volume. The mean adsorption potential is 18.8, 13.0, and 8.9 kJ/mol, with coefficients of variation of 0.37, 0.53, and 0.67, for Ambersorb 563 and 572 adsorbents and Filtrasorb 400 GAC, respectively. Thus, Ambersorb 563 adsorbent has the most energetic and most homogeneous adsorption volume, while Filtrasorb 400 GAC has the least energetic and most heterogeneous adsorption volume. For these reasons, Ambersorb 563 adsorbent has the highest TCE capacity at low concentrations, whereas Filtrasorb 400 GAC has the highest TCE capacity at high concentrations. The performance of Ambersorb 572 adsorbent is generally intermediate to the other two adsorbents.     

Adsorption equilibrium and kinetic studies of strontium on Mg-bentonite, Fe-bentonite and illite/smectite

Radionuclide adsorption on clay rocks has in recent years been studied mainly in connection with their use as sealing barriers in nuclear waste and spent nuclear fuel repositories. In Slovakia we find deposits of bentonites which should be used for the above mentioned purpose. The usability of adsorbents in practical applications depends on the speed of the adsorption process of the adsorbate on the adsorbent surface and distribution ratio. The work objective was the study of the kinetics of Sr adsorption on clay adsorbents with different geological origin. The geological origin of bentonite significantly influences its mineralogical and chemical composition and therein its adsorption properties. The adsorption process of strontium was fast. Adsorption equilibrium was reached for all three samples studied within 1 min from the beginning of the contact between solid and liquid phases. After the adsorption equilibrium was reached there were no more changes in the values of distribution coefficients and the adsorption percentage, and comparable values were reached in the contact-phase time span studied within 10 days. The values of adsorbed strontium were decreasing in the following order: J250 > L250 > DV45. The pseudo second-order kinetic models was used to describe model the kinetic data and provided excellent kinetic data fitting (R ² > 0.999).     

EFFECT OF pH ON THE ADSORPTION OF p-AMINOBENZOIC ACID ON POLYSTYRENE-BASED ADSORBENTS

In the present study the adsorptive properties of p-aminobenzoic acid with hypercrosslinked and multi-functional polymeric adsorbents at different solution pHs were systematically investigated in accordance with the particular physicochemical characteristics of the aromatic amphoteric compound involving both Lewis acid and Lewis base functional groups. It was found that the equilibrium adsorption data of the three polymeric adsorbents fitted well in the Langmuir and Freundlich isotherm equations. Studies at various pH levels indicate that the capacity of the adsorbents for adsorption of the ionic forms of adsorbate is less than that for the corresponding neutral species. At pH 3.78, the adsorption capacities of the three adsorbents are the highest. Whereas the adsorption property of multi-functional polymeric adsorbent NJ-99 is the largest, which may be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of p-aminobenzoic acid. The trend of the adsorption capacities of the three adsorbents towards p-aminobenzoic acid with the solution pH is in accord with the dissociation curve of the neutral molecular p-aminobenzoic acid. The adsorption forces include π-π interaction, hydrogen-bonding interaction and electrostatic attraction or repulsion when there exist the molecular and ionic adsorbing species at different pHs in aqueous solution.     

不同基团修饰的吸附树脂对芳香两性化合物的吸附等温线研究

研究了带有不同功能基团的超高交联吸附树脂NG-10和NJ-99对水溶液中芳香两性化合物氨基苯甲酸的静态吸附性能,并与不带功能基团的吸附树脂CHA-111和XAD-4进行了比较.研究结果表明,树脂NJ-99对水溶液中氨基苯甲酸的吸附能力高于其他树脂.邻氨基苯甲酸在4种树脂上的吸附量均大于对氨基苯甲酸,主要原因是其溶解度小.吸附等温线采用经验的Freundlich方程和理论的Langmuir吸附方程来拟合,在实验所研究的浓度范围内,方程的拟合相关性均很好.     

Competitive adsorption isotherm modelling of heterocyclic nitrogenous compounds,pyridine and quinoline,onto granular activated carbon and bagasse fly ash

In the present study, simultaneous adsorption of quinoline and pyridine onto adsorbents such as granular activated carbon (GAC) and bagasse fly ash (BFA) from pyridine–quinoline binary aqueous solution was studied at various temperatures (288–318 K). Gathered equilibrium adsorption data were further analysed using various multicomponent competitive isotherm models such as non-modified and modified competitive Langmuir isotherms, extended-Langmuir isotherm, extended-Freundlich model, Sheindorf–Rebuhn–Sheintuch (SRS) model, and non-modified and modified competitive Redlich–Peterson isotherm model. It was observed that increase in pyridine concentration decreased the total adsorption yield and the individual adsorption yield for both the quinoline and pyridine for both the adsorbents GAC and BFA at all the temperatures studied. Identical trend was observed during the equilibrium uptake of pyridine on to GAC and BFA with an increase in quinoline concentration. The extended-Freundlich model satisfactorily represented the binary adsorption equilibrium data of quinoline and pyridine onto GAC and BFA.     

Enhanced adsorption of radioactive strontium ions from aqueous solution by H2O2-modified attapulgite

Effective adsorption of Sr(II) onto H₂O₂-modified attapulgite in aqueous solution was investigated about kinetics and isothermal equilibrium adsorption. The adsorption equilibrium process of Sr(II) on adsorbents reached about 8 h at 40 °C. The adsorption kinetics followed the pseudo-second order equation and the isothermal adsorption data were fit well with the Langmuir isotherm model. The enhanced adsorption mechanism of H₂O₂-modified attapulgite for Sr(II) in aqueous solution was expatiated in detail. The H₂O₂ treatment for attapulgite is effective and as-made adsorbents can be applied for removal of Sr(II) in radioactive waste water.

     

THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p-nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.     

Lanthanum ion–impregnated granular activated carbon for the removal of phenol from aqueous solution: Equilibrium and kinetic study

The current study discusses application of the lanthanum ions (La³⁺) as an activating agent incorporated /immobilized into coconut shell–based granular activated carbon (GAC) for porosity development; subsequently, the carbon material is used for the adsorption of phenol from aqueous solutions. The new carbons were characterized using FTIR, XRD, CHNO, burn off, and carbon yield. The surface functional groups were determined by Boehm titration. The Brunauer–Emmett–Teller (BET) surface area of the carbons is 953 m² g⁻¹ (GACLa1073), 997 m² g⁻¹ (GAC383), and 973 m² g⁻¹ (GACO383). Langmuir, Freundlich, Dubinin–Radushkevich, and John–Sivanandan Achari (J-SA) isotherm models on the equilibrium isotherm data were examined for the new carbon-phenol system. It is found that the Langmuir isotherm fits better with a monolayer adsorption capacity, highest for GACLa1073 (387.59 mg g⁻¹) followed by GAC383 (303.03 mg g⁻¹) and GACO383 (197.62 mg g⁻¹). Kinetic studies reveal that the adsorption system follows the pseudo–second-order kinetic model. Isotherm analysis by the phase change method of John-Sivanandan Achari (J-SA) isotherm gives a better insight into adsorption phenomena, which is accompanied by regeneration studies of carbon with >75% for GACLa1073 after three cycles.     

Modeling synergistic adsorption of phenol/aniline mixtures in the aqueous phase onto porous polymer adsorbents

The adsorption equilibria of phenol and aniline on nonpolar polymer adsorbents (NDA-100, XAD-4, NDA-16 and NDA-1800) were investigated in single- and binary-solute adsorption systems at 313 K. The results showed that all the adsorption isotherms of phenol and aniline on these adsorbents can be well fitted by Freundlich and Langmuir equations, and the experimental uptake of phenol and aniline in all binary-component systems is obviously higher than predicted by the extended Langmuir model, arising presumably from the synergistic effect caused by the laterally acid-base interaction between the adsorbed phenol and aniline molecules. A new model (MELM) was developed to quantitatively describe the synergistic adsorption behavior of phenol/aniline equimolar mixtures in the binary-solute systems and showed a marked improvement in correlating the binary-solute adsorption of phenol and aniline by comparison with the widely used extended Langmuir model. The newly developed model confirms that the synergistic coefficient of one adsorbate is linearly correlated with the adsorbed amount of the other, and the larger average pore size of adsorbent results in the greater synergistic effect of phenol/aniline equimolar mixtures adsorption.     

ADSORPTION OF BENZOIC ACID AND P-NITROBENZOIC ACID ON A NEW HYPERCROSSLINKED PHENOL GROUP PST ADSORBENT

1.INTRODUCTIONThepolymericadsorbentAmberliteXAD-4isconsideredoneofthemostsuitablepolymericadsorbentsforremovingphenoliccompoundsfromwaterstreams[1,2]becauseitischemicallystable,notsolubleinsolventsandmoreselectiveforaromaticringsduetoitshydrophobicproperties.However,methanol,acetoneoracetonitrile,hastobeusedtoenhancethesurfacecontactbetweenadsorbentandthesolute.DavankovandTsyurupadescribedanewseriesofadsorbents[3,4].Thistechniqueyieldedpolystyrenesorbentsofunusualhypercrosslinkedstructu…     

ADSORPTION OF BENZOIC ACID AND P-NITROBENZOIC ACID ON A NEW HYPERCROSSLINKED PHENOL GROUP PST ADSORBENT

A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-I, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, the dynamic adsorption behaviors through column and the adsorption thermodynamics were studied. Results show that Freundlich equation gives a fitting adsorption isotherm. The specific surface of AM-l is only 67% of that of Amberlite XAD-4, but the adsorption capacities on AM-1 are much higher about 125%～166% than that on Amberlite XAD-4,which is contributed to the micropore mechanism and polarity. The negative values of the adsorption enthalpy are indicative of an exothermic process. Enthalpy and free energy changes of adsorption both manifest a physic-sorption process. The negative values of the adsorption entropy indicate that the adsorption is well consistent with the restricted mobilities and the configurations of the adsorbed benzoic acid molecules on the surface of studied adsorbents with superficial heterogeneity. Both adsorbents were used in mini-column experiments for adsorbing benzoic acid expecting to elucidate the higher breakthrough adsorption capacity of the new hypercrosslinked polymeric adsorbent AM-1 as compared with that of Amberlite XAD-4.     

Adsorption of Copper (II) onto Different Adsorbents

Removal of copper (II) from aqueous solution of CuCl₂·2H₂O by different adsorbents, namely, sissoo sawdust, activated carbon, and fly ash were investigated. Adsorption of copper (II) on sissoo sawdust, activated carbon, and fly ash has been studied using batch techniques. Kinetic and isotherm studies were determined as a function of the solution pH, temperature, contact time, adsorbent dosage, and initial adsorbate concentration. Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin isotherms were used to analyze the equilibrium data at different temperatures. The maximum adsorption capacities for copper (II) on sissoo sawdust, activated carbon, and fly ash adsorbents at 30, 40, and 50°C temperatures were found to be 263.2, 166.6, and 142.8; 125.0, 88.49, and 72.46; 69.93, 181.8, and 111.1 mg/g, respectively. The thermodynamics of copper (II) adsorption on sissoo sawdust, activated carbon, and fly ash indicates its spontaneous and endothermic nature. Kinetic studies showed that the adsorption followed a pseudo-second-order kinetic model.     

Use of oxide minerals to abate fluoride from water

The removal of fluoride from aqueous solutions has been investigated using various oxide ores such as refractory grade bauxite, feed bauxite, manganese ore, and hydrated oxides of manganese ores (WAD). The refractory grade bauxite showed promising results. The studies were carried out as functions of contact time, pH, concentration of adsorbents, concentration of adsorbate, and temperature. The adsorption was rapid during the initial 5 min but equilibrium was attained within 120 min. The adsorption followed first-order kinetics. The present system followed the Langmuir adsorption isotherm model. Various thermodynamic parameters such as free energy, enthalpy, entropy, and equilibrium constants were calculated. The isosteric heat calculations showed that the adsorption process followed a heterogeneous model.     

Optimized adsorption and effective disposal of Congo red dye from wastewater: Hydrothermal fabrication of MgAl-LDH nanohydrotalcite-like materials

The effectiveness of Congo red (CR) adsorption from aqueous solutions onto MgAl-layered double hydroxide (MgAl-LDH) nanosorbents was examined in this study. MgAl-LDH was synthesized using the hydrothermal method, and physicochemical characterization was performed via powdered X-ray diffraction, high-resolution transmission electron microscopy, Fourier transform infrared analysis, and zeta potential measurements. For optimum adsorption of CR onto the synthesized MgAl-LDH nanosorbent, the adsorption process was employed in batch experiments. Adsorption parameters, such as the adsorbent dosage, solution pH, contact time, and initial adsorbate concentration, vary with the adsorption kinetics and isotherm mechanism. The results of the batch experiments indicated rapid adsorption of CR dye from aqueous solutions onto MgAl-LDH during the first 30 min until equilibrium was achieved at 180 min with a dye concentration of 50 mg/100 mL and MgAl-LDH adsorbent dosage of 0.05 g. The experimental adsorption data fit adequately with the monolayer coverage under the Langmuir isotherm model (R² = 0.9792), and showed the best fit with the pseudo-second-order kinetic model (R² = 0.996). The change in zeta potential confirmed the effective adsorption interaction between the positively charged MgAl-LDH and the negatively charged CR molecules with electrostatic interactions. This work is distinguished by the successful hydrothermal preparation of MgAl-LDH in the form of homogenous nanoscale particles (～100 nm). The prepared MgAl-LDH showed a high adsorption capacity toward anionic CR dye with a maximum adsorption capacity of 769.23 mg/g. This capacity is higher than those reported for other adsorbents in previous research.     

Kinetics of adsorption and desorption of Pb(II) in aqueous solution on activated carbon by two-site adsorption model

The adsorption and desorption equilibrium and kinetics of lead ions from aqueous solutions on a granular activated carbon (GAC) were examined. Rapid increase followed by slow increase in Pb(II) amount on the GAC was observed as a function of time for the adsorption, while rapid decrease and consecutive very slow decrease was observed in desorption. Based on the experimental results, a two-site adsorption model was proposed for the adsorption and the desorption of Pb(II) under the study conditions. The Pb(II) adsorption on the GAC was estimated to have simultaneously occurred on the strong and the weak adsorption sites. Conventional Langmuir-type kinetic equations were introduced to quantitatively predict the adsorption and desorption with the two-site model by optimizing the parameters to fit the equilibrium and the kinetic experimental results. The equilibrium and kinetic experimental results could be represented by the equations by using one set of the common Langmuir parameters. Resultant kinetic parameters revealed that the adsorption equilibrium constant was two orders of magnitude greater for strong adsorption site than for weak adsorption site, though the maximum number of weak adsorption site was 1.5 times as great as that of strong adsorption site. The strong adsorption equilibrium constant resulted from a small desorption rate constant for the site. The equations were demonstrated to be applicable for predicting other desorption performances as well.     

Benzene,toluene and o-xylene (BTX) removal from aqueous solutions through adsorptive processes

In this study, the monocomponent adsorption of benzene, toluene and o-xylene (BTX) compounds, as model contaminants present in the petrochemical wastewaters, was investigated using three types of adsorbents: activated carbon (Carbon CD 500), a polymeric resin (MN-202) and a modified clay (Claytone-40). Langmuir and Freundlich models were able to fit well the equilibrium experimental data. The BTX adsorption capacity increased in the following order: Claytone-40 < CD 500 < MN-202. The maximum uptake capacity of MN-202, given by the Langmuir fitting parameter, for benzene, toluene and o-xylene was 0.8 ± 0.1, 0.70 ± 0.08 and 0.63 ± 0.06 mmol/g at 26 °C. Desorption kinetics for polymeric resin with 50 % methanol solution were fast being able to reuse the resin in consecutive adsorption/desorption cycles without loss of sorption capacity. The adsorptive behaviour at batch system was modelled using a mass transfer kinetic model, considering that the sorption rate is controlled by a linear driving force model, which successfully predicts benzene, toluene and o-xylene concentration profiles, with homogeneous diffusivity coefficients, D _h , between 3.8 × 10^?10 and 3.6 × 10^?9 cm²/s. In general, benzene diffuses faster than toluene and o-xylene, which is in agreement with molecular diffusivity in water.     

Adsorption behavior of phenolic compounds onto polymeric adsorbents modified with 2-carboxybenzoyl groups

<正>Two hypercrosslinked polymeric adsorbents(ZH-01 and Amberlite XAD-4 resin) were employed to remove three kinds of phenolic compounds including phenol,4-nitrophenol and 2,4-dinitrophenol from aqueous solutions.The study was focused on the static equilibrium adsorption behavior,the column dynamic adsorption and desorption profiles.The Freundlich model gave a perfect fitting to the isotherm data.The adsorbing capacities for these three compounds on ZH-01 were higher than those on Amberlite XAD-4 within the temperature range 288-318 K,which was attributed to the large micropore area and 2-carboxybenzoyl functional groups on the network of ZH-01 resin.The adsorption for phenol and 4- nitrophenol on ZH-01 was a physical adsorption process,while for 2,4-dinitrophenol it was a coexistence process of physical adsorption and chemisorption's transitions.The column test showed the advantages of ZH-01 in the dynamic adsorption processes of phenolic compounds.Being used as the desorption reagent,sodium hydroxide solution showed an excellent performance.     

Thermodynamic study of fatty acids adsorption on different adsorbents

This work has as objective the study about the adsorption behavior of fatty acids (acetic, propionic, and butyric) on activated carbon and on modified and unmodified montmorillonite clays as a function of temperature and initial concentration of the adsorbate, through adsorption isotherms and their thermodynamic parameters (ΔG, ΔH, and ΔS). The activated carbon presented a higher adsorption capacity due to its relatively large surface area, compared to others adsorbents. The polar characteristic of fatty acids decreased with the increase in the length of non-polar hydrocarbon chain, improving the affinity between the activated carbon (non-polar adsorbent) and the acids. The adsorption capacity of modified montmorillonite (polar adsorbent) was favored due to the presence of the organic cation among its layers, which make the surface more hydrophobic and organophilic when compared to the unmodified montmorillonite surface. The amount of fatty acids adsorbed in the adsorbents surface increased with the concentration, at constant temperature, and decreased with the increase of temperature, at constant concentration. The amount of fatty acids adsorbed in the three adsorbents was related to the surface area and polarity of the adsorbent, concentration and solubility of the adsorbate and temperature of the solution. The negative values of ΔG and ΔH showed that the adsorption on activated carbon and on modified and unmodified montmorillonite clays was a spontaneous and an exothermic process. The decrease in the values of ΔG, with the increase of temperature, demonstrated that the adsorption was benefited by the high temperature and the positive values of ΔS showed that the fatty acids molecules were in a more randomic condition in the adsorbed state than in solution. The experimental results obtained at the temperatures of (298, 303, 313, and 323) K showed that experimental data were well represented by the Langmuir and Freundlich isotherms models.