Breakthrough of natural organic matter from fixed bed adsorbers: investigations based on size-exclusion HPLC

Fixed bed adsorption experiments were performed using four granular activated carbon (GAC) columns designed by packing two size ranges of pulverized and sieved Filtrasorb 400 (d=0.5-0.59 and 1.0-1.19 mm) to two bed depths (L=10 and 20 cm), respectively. Continuous supplying of river water containing a lower content of natural organic matter (NOM) allowed investigation of the breakthrough of aqueous natural organic matrices assessed with lumped quality indices of total dissolved organic carbon (DOC) and ultraviolet absorbance at 260 nm (UV260). The capability of GAC columns in dealing with sudden rise in the load of influent NOM was also displayed by intermittently adding to the influent river water a peaty field groundwater that contained a higher content of NOM. Besides, assisted by the size-exclusion HPLC (SEHPLC), changes in the apparent molecular weight distribution of NOM along the bed depth of GAC columns were evaluated, and an important finding revealing relatively even adsorption for adsorbable NOM constituents within the entire molecular weight range of 1000-5200 g mol⁻¹ as PSS (polystyrene sulfonates) detected for the river and groundwater NOM was obtained. Furthermore, using a previously proposed hypothetical multi-component approach incorporating the ideal adsorbed solution theory and a plug flow homogeneous surface diffusion model, the observed concentration profiles of the river water NOM were predicted.     

Adsorbents from Waste materials

The possibility of using pyrolyzed wastes produced in already working incineration plants, as adsorbents for waste water treatment, was studied. Showing very poor adsorption properties, they were improved by steam activation technique used in the conventional activated carbon manufacturing. It is concluded that various organic waste materials can be converted to carbonaceous final products with a character similar to activated carbon. Their adsorption properties and pore size distribution are determined by the structure of the starting material. Although most of these samples have a low specific surface area, their pore volume is not negligible in the meso-and micropore range. Adsorption tests with model waste waters confirmed that adsorption properties are strongly influenced by the character of the suface. The adsorption capacity of these samples can be utilized for the treatment of strongly polluted industrial waste waters. Considering that the raw material ‘needed’ to manufacture these adsorbent is produced permanently and the adsorbents do not have to be regenerated, it might be worthwhile using these kinds of adsorbents in the primary treatment of industrial waste waters.     

Effect of quenching time and quenching agent dose on total organic halogen measurement

Total organic halogen (TOX) is a collective parameter and a toxicity indicator for all the halogenated organic disinfection byproducts (DBPs) in a water sample. TOX measurement involves concentration of halogenated organic DBPs by adsorption onto activated carbon. Prior to activated carbon adsorption, quenching the chlorine residual in a water sample is an indispensable step to eliminate the positive interference resulting from continued chlorination with organic compounds adsorbed on the activated carbon surface or with the activated carbon surface itself. Arsenite is generally applied as the quenching agent. In this study, the arsenite quenching agent dose that was 100% of the stoichiometric amount of the chlorine residual in a water sample was demonstrated to be most appropriate. In practice, to ensure complete reduction of chlorine residual, slight overdose of arsenite is often recommended, but this was found to cause negative interferences in the TOX measurement due to two reasons. First, the competitive adsorption existed between halogenated organic DBPs and the excessive arsenite on the activated carbon. This competitive adsorption effect was pronounced within a quenching time of 15?min. After 15?min of quenching, a large fraction of arsenite might have reacted with some easily-reduced halogenated DBPs to become arsenate, which is partially ionized at pH 2 and less likely adsorbed on the activated carbon. In this case, more halogenated organic DBPs could be adsorbed on the activated carbon, resulting in the measured TOX concentrations to be much closer to the actual one contained in the sample. Second, excessive arsenite might lead to reduction or decomposition of halogenated organic DBPs with a prolonged quenching time (>60?min). Thus, to avoid the negative interferences, the appropriate quenching time should be 15–60?min.     

Adsorption of vapor mixtures of water and organic substance on activated carbons

The isotherms of water adsorption in the presence of an organic substance vapor with a specified concentration are calculated from experimental data on the joint frontal dynamics of adsorption of water vapor and several organic substances (benzene, hexane, cyclohexane, tetrachloromethane, and perfluorotripropylamine) on two samples of activated carbons. The influence of the organic substances on the equilibrium water adsorption decreases with an increase in the molecule size.     

Activated carbon cloth as adsorbent and oxidation catalyst for the removal of amitrole from aqueous solution

Removal of amitrole from water was studied by adsorption on an activated carbon cloth and by oxidation with hydrogen peroxide using the same activated carbon cloth as catalyst. Study variables included the solution pH, ionic strength, and temperature in the adsorption process and the solution pH and the surface chemistry of the activated carbon cloth in the oxidation process. Results showed that amitrole adsorption on activated carbon cloth was not adequate to remove amitrole from water due to the high solubility and low aromaticity of the herbicide, which reduced its adsorption on the carbon. A higher amitrole removal rate was obtained with the activated carbon/H₂O₂ system. The best results were obtained on basic activated carbon surfaces at pH 7–10, when hydroxyl radical formation is favored, achieving the removal of 35–45% of the AMT, compared with 20–25% under the best adsorption conditions. Importantly, oxygen fixed on the carbon surface during AMT oxidation must be removed by heat treatment in order to regenerate the surface basicity of the carbon before its reutilization in another oxidation cycle.     

Multicomponent Adsorption of Pesticides onto Activated Carbon Fibers

The adsorption equilibria of pesticides and metabolites (atrazine, deethylatrazine, deisopropylatrazine and simazine) are studied onto activated carbon fibers –ACF– with a broad pore size distribution (32% mesopore volume, 68% micropore volume). Mono-and multi-component isotherms have been determined for low concentrations, from 0.23×10⁻⁶ to 9.52×10⁻⁶ mol L⁻¹. Single solute isotherms, modeled by Freundlich and Langmuir models, tend to prove the influence of the adsorbate's solubility in the adsorption capacity of activated carbon fibers. Binary solute isotherms confirm the strong influence of pesticide solubility on the competitive adsorption mechanism: the competition is higher in the case of adsorbates of different solubilities (atrazine and DEA or DIA for example). Multicomponent experimental data were modeled by extended Langmuir-based equations and the Ideal Adsorbed Solution theory. Whereas the first ones failed to model accurately binary adsorption due to restrictive hypothesis, the IAS model showed a good agreement between experimental and predicted data. It emphasised also the difficulty in satisfying the hypothesis of the model in the case of highly adsorbed compounds. Finally, the simultaneous adsorption of atrazine and NOM (in a natural water, DOC = 18.2 mg L⁻¹) shows no adsorption competition effects between natural organic matter and atrazine. This is due to the presence of secondary micropores (0.8–2 nm) and mesopores in the ACF, which limit a pore blockage phenomenon by NOM.     

Adsorption heats of phenol on activated carbon using adapted method of immersion calorimetry

Simple adaptation of the technique of immersion calorimetry enables determining both integral and differential adsorption heats as well as the course of the adsorption isotherm of phenol on activated carbon. The innovative aspect of the applied procedure consists in bringing the phenol aqueous solution to contact with the suspension of carbon with water. Thus, the “interfering” heat effect of carbon interaction with water is eliminated, and only the net adsorption heat of phenol is monitored. The value of −52.5 kJ mol⁻¹ was ascertained as the molar differential adsorption heat at the low surface coverage (cca 0.2 mmol g⁻¹) of the sample of microporous carbon. As the adsorption process continues, for adsorption uptakes exceeding the value of about 1 mmol g⁻¹, molar differential adsorption heats appear to be established at a level of about −20 + 5 kJ mol⁻¹.     

Removal and recovery of vanadium(V) by adsorption onto ZnCl2 activated carbon: Kinetics and isotherms

Adsorption of vanadium(V) from aqueous solution onto ZnCl₂ activated carbon developed from coconut coir pith was investigated to assess the possible use of this adsorbent. The influence of various parameters such as agitation time, vanadium concentration, adsorbent dose, pH and temperature has been studied. First, second order, Elovich and Bangham’s models were used to study the adsorption kinetics. The adsorption system follows second order and Bangham’s kinetic models. Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherms have been employed to analyze the adsorption equilibrium data. Equilibrium adsorption data followed all the four isotherms—Langmuir, Freundlich, D-R and Temkin. The Langmuir adsorption capacity (Q ₀) was found to be 24.9 mg g^{− 1} of the adsorbent. The per cent adsorption was maximum in the pH range 4.0–9.0. The pH effect and desorption studies showed that ion exchange mechanism might be involved in the adsorption process. Thermodynamic parameters such as ΔG ⁰, ΔH ⁰ and ΔS ⁰ for the adsorption were evaluated. Effect of competitive anions in the aqueous solution such as PO₄ ^{3 −}, SO₄ ²⁻, ClO₄ ⁻, MoO₄ ²⁻, SeO₃ ²⁻, NO₃ ⁻ and Cl⁻ was examined. SEM and FTIR were used to study the surface of vanadium(V) loaded ZnCl₂ activated carbon. Removal of vanadium(V) from synthetic ground water was also tested. Results show that ZnCl₂ activated coir pith carbon is effective for the removal of vanadium(V) from water.     

Preparation and characterization of activated carbon from <Emphasis Type="Italic">Amygdalus Scoparia</Emphasis> shell by chemical activation and its application for removal of lead from aqueous solutions

Two series of activated carbon have been prepared by chemical activation of Amygdalus Scoparia shell with phosphoric acid or zinc chloride for the removal of Pb(II) ions from aqueous solutions. Several methods were employed to characterize the active carbon produced. The surface area was calculated using the standard Brunauer-Emmet-Teller method. The microstructures of the resultant activated carbon were observed by scanning electron microscopy. The chemical composition of the surface resultant activated carbon was determined by Fourier transform infrared spectroscopy. In the batch tests, the effect of pH, initial concentration, and contact time on the adsorption were studied. The data were fitted with Langmuir and Freundlich equations to describe the equilibrium isotherms. The maximum adsorption capacity of Pb(II) on the resultant activated carbon was 36.63 mg g⁻¹ with H₃PO₄ and 28.74 mg g⁻¹ with ZnCl₂. To regenerate the spent adsorbents, desorption experiments were performed using 0.25 mol L⁻¹ HCl. Here we propose that the activated carbon produced from Amygdalus Scoparia shell is an alternative low-cost adsorbent for Pb(II) adsorption.     

A new way for calculating the adsorption capacity from surface excess isotherms

 Adsorption of n-butanol and water from butanol–water mixtures is studied on adsorbents of different hydrophobicity (activated carbon and hydrophobized montmorillonites). The shape of the adsorption isotherms of the hydrophobized clay minerals does not indicate preferential adsorption of butanol. Therefore, the adsorption capacity cannot be determined on the basis of the Langmuir isotherm. A new equation for determining the adsorption capacity is derived by combining the free enthalpy of adsorption with the adsorption excess amount. Both collections of data are obtained from the surface excess isotherm. The reliability of the adsorption capacity is checked by X-ray diffraction measurements. Received: 1 November 1997 Accepted: 19 February 1998     

Water adsorption with hysteresis effect onto microporous activated carbon fabrics

Understanding the adsorption of water vapor onto activated carbons is important for designing processes to remove dilute contaminants from humid gas streams, such as providing protection against chemical warfare agents (CWAs), or against toxic industrial compounds (TICs) used in a terrorist chemical attack. Water vapor isotherms for Calgon BPL granular activated carbon (GAC), military ASZM-TEDA GAC, electrospun activated carbon nanofibers (ACnF), Calgon Zorflex^™ activated carbon cloth, and Novoloid-based activated carbon fiber cloth (ACFC) are presented. Of particular interest are the ACFC isotherms, which exhibit an unusually high degree of hydrophobicity. The ACFC isotherms also show a correlation between water vapor adsorption hysteresis and the level of activation. Water vapor isotherm models from the literature are compared.     

Description of the adsorption equilibrium of organic substances absorbed from a flow of moist air by a fixed bed of active carbon moistened to equilibrium

Isotherms of the adsorption of benzene vapor from moist air on active carbon (AC) moistened to equilibrium are obtained from dynamic experiments. The experimental data on the adsorption equilibrium of some organic substances from a flow of moist air by a fixed bed of AC moistened to equilibrium are obtained. The data on the equilibrium adsorption of benzene vapor is analyzed using the Dubinin-Radushkevich equation (the theory of volume filling of micropores). It is revealed that the characteristic adsorption energy of benzene vapor decreases as the filling of the microporous volume with water molecules increases. The characteristic adsorption energy depends on the following factors: polarizability of a substance in the adsorption field created by micropores, the number of carbon atoms in the adsorbate molecules, and parameters of the porous structure. The equation for the calculation of the parameters of equilibrium adsorption of organic substances from moist air on AC moistened to equilibrium are obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 434–438, March, 1995.     

Competitive adsorption of toxic metals on activated carbon

Competitive adsorption of zinc and copper on activated carbon is studied in this article. Main aim was to suggest an advanced model for competitive adsorption of both metals considering pH influence and precipitation. A surface-complexation approach was employed for the modeling. Two models were considered: simple adsorption and ion exchange. System “The Geochemists Workbench” was used for calculation of both static and dynamic adsorption tasks. From the batch experiments, concentration of four types of sorbing sites on the carbon surface and its protonation and sorption constants were deduced. Then, batch competitive adsorption experiments were compared with the models’ results. Finally, a column experiment (fixed bed adsorption) was carried out. It was observed that the model of ion exchange can satisfyingly predict both chromatographic effect and increase of zinc concentration in effluent over its initial value, although a quantitative agreement between the model and the experiment was not totally precise.     

Use of x-ray microtomography to visualise dynamic adsorption of organic vapour and water vapour on activated carbon

X-ray microtomography coupled with image analysis was used to quantify the adsorption of vapours on activated carbon beds. This technique was tested using three different challenges: CCl₄, water vapour and a mixture of water- and organic vapour. It is shown that the used technique allows determining the adsorption front progress in the case of organic vapour and mixture of water and organic vapour whereas the existence of this front was not so obvious in the case of water vapour. Experimental results obtained for organic vapours were interpreted on the basis of the Wheeler-Jonas equation: a good agreement was found between experimental and theoretical breakthrough times.     

A model of the two-stage condensation mechanism of water adsorption on nonporous carbon adsorbents

The mechanism of adsorption of water molecules on nonporous carbon adsorbents has been suggested in terms of two different states of adsorbed water; stretched liquid water and water that occupies an intermediate state between the liquid and vapor. Two stages of adsorption were distinguished: condensation and pre-condensation that assumes the formation of molecular associates. The BET model was used to describe the pre-condensation stage. The equations of the adsorption isotherm for water vapor in the region of condensation process and the expression for the determination of the specific hydrophilic surface of adsorbents were found. Examination of the experimental data on adsorption of water vapor on nongraphitized samples of carbon adsorbents shows that in the region of polymolecular adsorption, all isotherms fall into a common curve determined by the equation of the stretched liquid film and can be calculated regardless of the properties of individual liquid water. The equation for adsorption of water vapor on the hydrophobic surface was obtained. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1933–1939, October, 1998.     

Activated Carbon Adsorption of Some Phenolic Compounds Present in Agroindustrial Wastewater

Single solute and simultaneous experimental adsorption isotherms of three phenolic compounds: gallic acid, p-hydroxybenzoic acid and syringic acid, have been investigated at 20, 30 and 40°C, using a bituminous coal based activated carbon. Regardless of temperature, the capacity of the activated carbon used to adsorb these compounds presented the following order: syringic acid > p-hydroxybenzoic acid > gallic acid. The increase of temperature slightly favored the adsorption capacity of the phenolic compounds. In binary and ternary component adsorption, experimental data suggest that interactions between adsorbates improve the adsorption capacity of some of the phenolic acid compounds. On the contrary, at high organic concentrations, adsorbed gallic acid was partially removed from the activated carbon surface because of the presence of the other components.     

The heat of adsorption of water on nonporous hydrophilic carbon adsorbents in the model of two-stage adsorption

The behavior of integral and differential heats of adsorption of water in the region of transition from the first stage of adsorption (formation of clusters) to the second stage (formation of a stretched liquid film) was considered. The curve of integral heat of adsorption has an inflection at the transition point, and the differential heat of adsorption changes jumpwise. The values of these effects were estimated by the simplest model of formation of one and two hydrogen bonds between a water molecule and an adsorption center on the surface of the carbon adsorbent. Curves of differential heat of adsorption with transition points for real systems are presented. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1479–1483, August, 1999.     

Adsorption of Dyes from Aqueous Textile By-Products on Activated Carbon from Scenedesmus obliquus

The adsorption of activated carbon prepared from Scenedesmus obliquus (algae) was evaluated through adsorption of Astrazon red. The adsorption efficiency of activated carbon was determined based on the specific surface area and pore size distribution. These results were compared with the results obtained with untreated algae. Approximately a 3-fold increase in the percentage of dye removal was observed for activated carbon compared to the untreated material. The primary reason for this observation may be the increase in specific surface area and total pore volume by chemical activation from 0.0136 to 423.7001?m²?g^?1 and from 0.0012 to 0.1643?cm³?g^?1, respectively. A pseudo-second-order model was fit with the kinetic data and the results indicate chemical adsorption. The maximum adsorption capacity of activated carbon was 181.82?mg?g^?1 at 25°C according to Langmuir isotherm model.     

Hydrophobic organic micropollutants in samples of coastal waters: efficiencies of solid-phase extraction in the presence of humic substances

Solid-phase extraction (SPE) has been used to enrich organic micropollutants (hydrophobic chlorinated and polycyclic aromatic hydrocarbons, CHC and PAH) from coastal water samples and to systematically study the influence of humic substances (HS) on SPE. A reversed phase (RP) system with high flow rates (rapid chromatography, RC) was used to show the basic adsorption principles and interaction processes which influence the enrichment of organic compounds. A model humic substance was found to hinder the enrichment of individual hydrophobic micropollutants (MP), depending on their octanol-water distribution coefficient P _OW. This effect was found to be lower with natural humic substances. For longer contact time between water sample and adsorption material, the pollutant/humic substance bonding proved to be reversible. Received: 8 December 1997 / Revised: 2 March 1998 / Accepted: 4 March 1998     

Experimental and Theoretical Study of MTBE Adsorption from Polluted Water on GAC and PAC in Continuous Process

Methyl tertiary butyl ether (MTBE) is an organic compound thatis used to increase the gasoline octane number. At the beginning of 1980s, by discovering the undesirable effects of tetra ethyl lead usage in fuel, MTBE began to be used worldwide. But gradually the undesirable effects of MTBE on environment had been revealed. Adsorption is the most conventional and economical technology for MTBE removal from polluted water. In this research, some experiments have been done for studying the adsorption of MTBE on different solid adsorbent in continuous processes. In continuous experiments, the water polluted with known initial MTBE concentration passes through an adsorption column containing two kinds of adsorbent including granular activated carbon (GAC), powdered activated carbon (PAC). By measuring MTBE concentration in exit flow at different times the effect of different operating parameters such as temperature, pH, and flow rate have been studied and the optimum condition have been determined. The batch experimental results have been used to calculate the constant parameters of Langmuir adsorption isotherm equations. A dynamic simulation of MTBE adsorption on activated carbon in an adsorption column has been proposed. The comparison of the experimental data with the values given by the proposed model for similar operating conditions, verifies the accuracy of the proposed mathematical model.