Comparative Study of Zn2+, Cd2+, and Pb2+ Removal From Water Solution Using Natural Clinoptilolitic Zeolite and Commercial Granulated Activated Carbon. Equilibrium of Adsorption

Abstract

The aim of this work is to study the effectiveness of regional, low-cost natural clinoptilolitic zeolite tuff in heavy metal ions removal from aqueous solution, through comparative study with commercial granulated activated carbon. The equilibrium of adsorption of Cd²⁺, Pb²⁺, and Zn²⁺ on both adsorbents have been determined at 25, 35, and 45°C in batch mode. The granulated activated carbon has shown around three times higher adsorption capacity for Cd²⁺ and Zn²⁺ than natural zeolite, and almost the same adsorption capacity for Pb²⁺ as the natural zeolite. The metal ion selectivity series Pb²⁺ > Cd²⁺ > Zn²⁺, on a mass basis, has been obtained on both adsorbents. The Langmuir and Freundlich model have been used to describe the adsorption equilibrium. The thermodynamic parameters were calculated from the adsorption isotherm data obtained at different temperatures. The study of the influence of the acidity of the metal ion aqueous solution has shown an increase of metal ion uptake with increase of the pH. The sorption mechanism of Cd²⁺, Pb²⁺, and Zn²⁺ on natural zeolite changes from ion-exchange to ion-exchange and adsorption of metal-hydroxide with increase of the pH from 2 to 6 (and 7 for Zn²⁺). The preliminary cost calculation, based on adsorbents maximum adsorption capacity and their price, have revealed the potential of natural zeolite as an economic alternative to the granulated activated carbon in the treatment of heavy metal polluted wastewater.     

Adsorption of lead and copper on bentonite and grapeseed activated carbon in single- and binary-ion systems

In this study, bentonite originating from Turkey (Eski?ehir province) and activated carbon obtained from grapeseed were used as adsorbents for the removal of lead (Pb²⁺) and copper (Cu²⁺) ions from aqueous solutions. Experiments were performed in single- and binary-ion systems at constant temperature of 298 K and pH value of 5. In order to describe the adsorption mechanism Langmuir, Freundlich and Temkin isotherms were used. The total adsorption capacity values of adsorbents were compared. It was observed that the total adsorption capacity values were changed depending on the type of adsorbent used, type of metal ion and interaction between metal ions.     

Adsorption equilibrium of copper ion and phenol by powdered activated carbon, alginate bead and alginate-activated carbon bead

The adsorption equilibrium characteristics for single and binary components of copper ion and phenol onto powdered activated carbon, alginate bead and alginate-activated carbon (AAC) bead were studied. Adsorption equilibrium data of phenol and copper ion onto the adsorbents could be represented by Langmuir equation. The adsorption capacity of Cu²⁺ onto different adsorbents was in the following order: alginate bead > AAC bead > powdered activated carbon (PAC). On the other hand, that of phenol was: PAC > AAC bead > alginate bead. Multi-component equilibrium data were correlated by three different models. Among them the ideal adsorbed solution theory (IAST) gave the best fit to our data. And the adsorption amount of Cu²⁺ onto AAC bead was greater than that of phenol in the binary components.     

Adsorption of Pb2+ and Cd2+ onto a Novel Activated Carbon‐Chitosan Complex

A novel activated carbon‐chitosan complex adsorbent (ACCA) was prepared via the crosslinking of glutaraldehyde and activated carbon‐(NH₂‐protected) chitosan complex under microwave irradiation. The surface morphology of this adsorbent was characterized. The adsorption of ACCA for Pb²⁺ and Cd²⁺ was investigated. The results demonstrate that ACCA has higher adsorption capacity than chitosan. The adsorption follows pseudo first‐order kinetics. The isotherm adsorption equilibria are better described by Freundlich and Dubinin‐Radushkevich isotherms than by the Langmuir isotherm. The adsorbent can be recycled. These results have important implications for the design of low‐cost and effective adsorbents in the removal of heavy metal ions from wastewaters.     

Activation of carbon nanofibres for hydrogen storage

The present study was aimed to investigate different methods of activation of carbon nanofibres, CNF, in order to determine the beneficial effect on the hydrogen sorption capacities of increasing the surface area. Two activation systems were used: physical activation with CO₂ and chemical activation with KOH. A range of potential adsorbents were thus prepared by varying the temperature and time of activation. The structure of the CNF proved more suitable to activation by KOH than by CO₂, with the former yielding higher surface area carbons (up to 1000 m² g⁻¹). The increased surface area, however, did not correspond directly with a proportional increase in hydrogen adsorption capacity. Although high surface areas are important for hydrogen storage by adsorption on solids, it would appear that it is essential that not only the physical, but also the chemical, properties of the adsorbents have to be considered in the quest for carbon based materials, with high hydrogen storage capacities.     

Removal of Lead Ions from Aqueous Solutions by Different Types of Industrial Waste Materials: Equilibrium and Kinetic Studies

Abstract

A comparative study of the adsorbents prepared from several industrial wastes for the removal of Pb²⁺ has been carried out. Fertilizer industry waste viz. carbon slurry and steel plant wastes viz. blast furnace (B.F.) slag, dust, and sludge were investigated as low‐cost adsorbents after proper treatment in the present study. The adsorption of Pb²⁺ on different adsorbents has been found in the order: B.F. sludge>B.F. dust>B.F. slag>carbonaceous adsorbent. The least adsorption of Pb²⁺ on carbonaceous adsorbent even having high porosity and consequently greater surface area as compared to other three adsorbents, indicates that surface area and porosity are not important factors for Pb²⁺ removal from aqueous solutions. The adsorption of Pb²⁺ has been studied as a function of contact time, concentration, and temperature. The adsorption has been found to be exothermic, and the data conform to the Langmuir equation. The kinetic results reveal that the present adsorption system follows Lagergren's first order rate equation. Since all three waste products from the steel industry show higher potential to remove lead from water, therefore, it is suggested that these metallurgical wastes can be fruitfully employed as low‐cost adsorbents for effluent treatment containing toxic metal ions.     

Characteristics of Cobalt Adsorption on Prepared TiO2 and Fe-Ti-O Adsorbents in High Temperature Water

Abstract

TiO₂ and Fe-Ti-O adsorbents were prepared by hydrolysis of Ti(OC₃H₇)4 and by alkalizing an equimolar mixed solution of TiCl₄ and FeCl₂, followed by heat treatment of their hydroxides. Their structures were studied by x-ray diffractometry and TG-DTA. The Co²⁺ adsorption characteristics of the adsorbent in high temperature water were investigated in a stirred autoclave. The prepared Fe-Ti-O adsorbent was found to be a stable nonstoichiometric ferrous/ferric titanium oxide with pseudobrookite and rutile structures. The Co²⁺ adsorption capacity of the Fe-Ti-O adsorbent was determined to be larger (0.38 meq Co²⁺/g adsorbent at 280[ddot]C) than that of TiO₂ at high temperature. The enthalpy changes (ΔH[ddot]) of about 34 and 49 kJ·mol^?1 due to the adsorption of Co²⁺ on the TiO₂ and Fe-Ti-O adsorbents, respectively, indicates that the adsorption is endothermic in the experimental temperature range (150–280[ddot]C). It is shown that the specific surface areas of these adsorbents are not dominant factors for Co²⁺ adsorption on oxides at high temperature.     

Experimental study and artificial neural network simulation of methane adsorption on activated carbon

The adsorption of methane on two activated carbons with different physical properties was measured. Adsorption isotherms were obtained by static volumetric method at different temperatures and pressures. The experimental results sow the best gas storage capacity was 113.5 V/V at temperature 280 K and pressure 8.5MPa on an activated carbon with surface area 1,060 m²/gr. An artificial neural network (ANN) based on genetic algorithm (GA) was used to predict amount of adsorption. The experimental data including input pressure, temperature and surface area of adsorbents as input parameters were used to create a GA-ANN simulation. The simulation results were compared with the experimental data and a good agreement was observed. The simulation was applied to calculate isosteric heat of adsorption by using the Clausius-Clapeyron equation. Comparison of the calculated adsorption heat showed different surface heterogeneity of the adsorbents.     

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.     

A method of thermal and chemical activation of waste bleaching earth for preparation of a low-cost carbon-mineral adsorbent for chromium(VI) removal

ABSTRACT

In this study, the use of a spent bleaching earth for removal of Cr(VI) ions from aqueous solutions was investigated. The waste material derived from the process of vegetable oil purification was subjected to thermal and chemical activation. The so-prepared carbon-mineral adsorbents were characterised by the uptake of chromium(VI) from synthetic solutions. The highest adsorption capacities were obtained for adsorbents carbonised at 400°C (15.9 mg?g^?1) and activated with H₂SO₄ (15.8 mg?g^?1). Based on the equilibrium and kinetic studies, it was concluded that the adsorption mechanism was based on chemisorption only since no correlation with the porous texture was found.     

Adsorption of chromium(VI) and nickel(II) ions on acid- and heat-activated deoiled spent bleaching clay

De-oiled spent bleaching clay was activated either by acid treatment followed by heat activation or by heat activation alone at temperatures between 200 and 800°C. The surface area of the heat-activated clay attained a maximal value of ≈120 m² g⁻¹ at temperatures between 400 and 500°C while the acid-heat-treated clay attained maximal surface area of ≈140 m² g⁻¹. The adsorption capacities of chromium [Cr(VI)] for both series studied increased as the activation temperature increased until 300°C and decreased again at higher temperatures. At lower pH, more than 95% of the Cr(VI) was absorbed in a solution with initial concentration of 1 mg L⁻¹ per gram of adsorbent activated at 300°C. The adsorption patterns followed Freudlich's isotherms. Two maximal values of adsorption capacities of nickel [Ni(II)] were observed at activation temperatures of 200 and 500°C for acid-treated samples, whereas these were at 200 and 700°C for the nonacid-treated samples. The amount of Ni(II) adsorbed increased with the pH of the solution for all samples studied. The maximal adsorption capacities of the adsorbents in solution containing initial Ni(II) concentration of 5 mg L⁻¹ per 0.5 g of adsorbent and at pH 6 were found to be 44 and 42%, respectively, for the acid-treated sample activated at 500°C and for the nonacid-treated sample activated at 700°C. They all obeyed both the Langmuir's and Freundlich's isotherms.     

In situ detection and removal of metal ion by porous gold electrode

A sensing electrode for the detection of heavy metal ions in aqueous solution selectively measured the concentrations of target materials on its functionalized surface, which has affinity to target metal ions. Target ions were adsorbed simultaneously on the functionalized electrode during the sensing process. Therefore, to understand this, experiments on the amperometric response and isotherms with an initial concentration of Hg²⁺ were tested. Detection current was dependent on the concentration of Hg²⁺, and the equilibrium concentration of Hg²⁺ adsorbed to the electrode showed a Langmuirian shape. Correlation between the detection current and removal capacity for Hg²⁺ revealed that it is possible to estimate the adsorbed concentration on the electrode during the sensing step. Although the macroporous gold electrode prepared herein showed relatively low adsorption performance compared to conventional adsorbents, when we prepare nanoporous gold electrodes with a uniform nanopore structure and large surface area, in situ detection and simultaneously removal of metal ions by nanoporous gold electrode will be possible.     

Column studies on metal ion removal by dyed cellulosic materials

Cellulosic materials, namely bleached bamboo pulp, jute fibers, and sawdust dyed with a reactive dye of monochlorotriazine type were used in the column studies for removal of different metal ions. The use of an adsorption column makes the process continuous, so that it is economically viable on an industrial scale. After the adsorption of metal ions such as Cu²⁺, Pb²⁺, Hg²⁺, Fe²⁺, Fe³⁺, Zn²⁺ and Ni²⁺, the adsorbents were successfully regenerated by using dilute acids. These columns were then used repeatedly for adsorption either of the same salt for more than ten times or of different salts in succession. No loss in adsorption power was observed.     

Desorption Kinetics of A N,N-Dimethylformamide Vapor from Granular Activated Carbon and Hydrophobic Zeolite

Abstract

Such thermodynamic properties as enthalpy, free energy, and entropy of adsorption have been computed for N,N-dimethylformamide (DMF) vapor on two commercial adsorbents: coconut shell Type PCB of activated carbon and Type DAY of hydrophobic zeolite. The computation is based on the Langmuir adsorption isotherms obtained at 293, 303, and 313 K as reported by Tsai et al. The laden adsorbents were regenerated with hot inert nitrogen gas and studied by thermal gravimetric analysis at three different heating rates. The apparent activation energies (E _des) of thermal desorption were determined by using the Friedman method. The zeolite DAY has an adsorption potential higher than that of activated carbon PCB as indicated by the more negative value of the adsorption enthalpy of DMF vapor. The average value of E _des of zeolite DAY is larger than that of activated carbon PCB.     

Combined processes of glycerol polymerization/carbonization/activation to produce efficient adsorbents for organic contaminants

BACKGROUND: Glycerol was used to produce efficient adsorbents with a high surface area for organic contaminants by a combined process based on polymerization, carbonization and activation. RESULTS: Glycerol and sulfuric acid catalyst at concentrations of 0, 0.5, 1, 2 and 5 mol% were heated to 150 °C to form polyglycerol, which was then decomposed at 580 °C and activated with CO₂ at 850 °C. The resulting activated carbons had a high specific area (1630 m²g^?1) and high adsorption capacity of methylene blue used as a model organic contaminant. This process was also used to produce a special composite adsorbent based on expanded vermiculite (EV) coated with activated carbon. These composites were produced by impregnation of EV with glycerol followed by polymerization, thermal decomposition and activation with CO₂ to produce up to 25 wt% carbon and a surface area of 835 m²g^?1. CONCLUSIONS: The carbon layer present in the EV composite/activated carbon (GVE4CA2) produces a remarkable increase in the methylene blue adsorption capacity of the expanded vermiculite and strongly decreases undesirable water absorption. Copyright © 2012 Society of Chemical Industry     

Nano-sized carbon hollow spheres for abatement of ethylene

In this paper, the ethylene adsorption capacities of the nano-sized carbon hollow spheres (CNB) and active carbon (AC), the Pd (PdCl₂) impregnated CNB or AC (Pd/CNB, Pd/AC) and heat treatment under various conditions, were studied at different ethylene concentrations from 64 to 1060 ppm. The results indicated that AC had a good ethylene adsorption capacity at high ethylene concentration. Pd impregnation decreased the ethylene adsorption capacity of AC. Heat treatment and H₂ activation could increase the ethylene adsorption capacity, but also lowered than AC itself. CNB had lower ethylene adsorption capacity than AC, but heat treatment and H₂ activation could increase its ethylene adsorption capacity markedly. With activating condition from heat treatment in N₂ at 300 °C to activation in H₂/N₂ at 100 °C, to activation in H₂ at 200 °C, and to activation in H₂ at 300 °C, the ethylene adsorption capacity of Pd/CNB was increased regularly. At low ethylene concentration, viz., 64 ppm, the ethylene adsorption quantities (q _a) by Pd/CNB activated in H₂ at 200 or 300 °C were higher than any other adsorbents. So, activated in H₂ atmosphere at higher than 100 °C, Pd/CNB is particularly advantaged for adsorbing low concentration of ethylene. Amongst all the adsorbents used, Pd/CNB activated in H₂ atmosphere at 300 °C for 2 h has the highest ethylene adsorption capacity at lower concentration than 125 ppm. In addition, all the CNB, Pd/CNB, AC, and Pd/AC samples can be easily regenerated in airflow for more than 3 h.     

Removal of Lead (II) Ions from Aqueous Solution Using Eggplant Peels Activated Charcoal

The eggplant peel activated charcoal (EPPAC) was investigated as an adsorbent for the removal of lead II ions from aqueous solution. Three methods were tested for the production of eggplant peel activated charcoal (EPPAC) from eggplant peel charcoal (EPPC), yielding three different products; EPPAC-1, EPPAC-2, and EPPAC-3. The difference among the three methods lies in the primary physical mixing of the EPPC with the activating agent (potassium hydroxide) before heating the mixture in a furnace for activation. The removal efficiency of lead II ions by the three adsorbents was 57.7%, 70.0%, and 60.0% for EPPAC-1, EPPAC-2, and EPPPAC-3, respectively. The optimized activation parameters for EPPAC-2 were: activation time 2 hours, activation temperature 700°C, and activation ratio 1:2 (EPPAC: KOH). Scanning electron microscopy (SEM) revealed that EPPAC-2 has the most porous structure. The surface area of EPPAC-2 was measured to be 739 m²/g. Adsorption kinetics of lead (II) is best described by the pseudo-second-order kinetic model with second order rate constant of 1.70 × 10^?3 g/mg.h at room temperature. The adsorption of lead on EPPAC-2 is found to follow the Langmuir isotherm with a maximum adsorption capacity of 1.4 × 10² mg/g.     

The heavy metal adsorption characteristics on metakaolin-based geopolymer

Since porous materials often function as adsorbents, this study chose to investigate the adsorption of heavy metals by geopolymers. The geopolymer was made by condensing a mixture of metakaolin and alkali solution at a fixed ratio at room temperature and then pre-crashed to a fixed-radius size. This paper examined the adsorption efficiency of the geopolymer for different heavy metals (i.e., Pb²⁺, Cu²⁺, Cr³⁺, and Cd²⁺) in aqueous solutions under discrete experimental parameters. The experimental results verified that the geopolymer could adsorb heavy metals. Of the metals tested, optimal adsorption with the implementation of the geopolymer occurred with Pb²⁺. The data fit both the pseudo-second-order and the Langmuir equations. This discovery may facilitate the development of optimized procedures for wastewater treatment, thus providing an alternative solution to environmental damages caused by heavy metal pollutants.     

Preparation of Activated Carbons from Tobacco Stems by Potassium Hydroxide Activation and Phosphine Adsorption

Activated carbon preparation from tobacco stems by KOH activation at different activation temperatures and KOH/char mass ratios were investigated in this study. The effects of preparation parameters on activated carbon pore structure, morphometrics, microcrystallinities, and surface functional groups were characterized by N₂ adsorption, SEM, XRD, and FTIR technologies, respectively. The optimum preparation condition of activated carbon was activation temperature of 850°C, and KOH/char mass ratio of 2. Under this condition, the BET surface area of 2215 m²/g, and the pore volume of 1.343 cm³/g can be obtained. Prepared activated carbon showed clearly honeycomb holes, and a predominated amorphous structure. With increase of activation temperature and KOH/char mass ratio, decrease of surface oxygen functional group, and aromatization of the carbon structure was found. The activated carbon was subject to PH₃ purification, and the maximum PH₃ adsorption capacity of 253 mg/g can be realized based on well prepared KOH-AC with modification of 2.5% Cu. It seems that the activated carbon produced from chemical activation of tobacco stem would be an effective and alternative adsorbent for PH₃ adsorption because of its high surface area, adsorption capacity, and low cost.     

Arsenate and arsenite adsorbents composed of nano-sized cerium oxide deposited on activated alumina

Cerium oxide composited activated alumina was prepared and used as arsenate and arsenite adsorbents by oxidation of cerium chloride in H₂O₂ solution. The preparation conditions affected arsenic adsorption capabilities in the Al₂O₃–CeO₂. Efficient adsorption of arsenic was achieved when CeO₂ was deposited on 6.0 g of powdered activated alumina at 0.01 M Ce³⁺ concentration and H₂O₂/Ce = 0.5. The arsenic adsorption was particularly enhanced in the presence of the nano-size CeO₂ on the Al₂O₃ support, obeying the Langmuir adsorption isotherm model with maximum adsorption capacities of 13.6 and 10.5 mg/g, respectively, for arsenate and arsenite.