A. Erto

Equilibrium and dynamic study on hexavalent chromium adsorption onto activated carbon

In this work, the results of equilibrium and dynamic adsorption tests of hexavalent chromium, Cr (VI), on activated carbon are presented. Adsorption isotherms were determined at different levels of pH and temperature. Dynamic tests were carried out in terms of breakthrough curves of lab-scale fixed bed column at different pH, inlet concentration and flow rate. Both the adsorption isotherms and the breakthrough curves showed non-linear and unconventional trends. The experimental results revealed that chromium speciation played a key role in the adsorption process, also for the occurrence of Cr(VI)-to-Cr(III) reduction reactions. Equilibrium tests were interpreted in light of a multi-component Langmuir model supported by ion speciation analysis. For the interpretation of the adsorption dynamic tests, a mass transfer model was proposed. Dynamic tests at pH 11 were well described considering the external mass transfer as the rate controlling step. Differently, for dynamic tests at pH 6 the same model provided a satisfying description of the experimental breakthrough curves only until a sorbent coverage around 1.6mgg(-1). Above this level, a marked reduction of the breakthrough curve slope was observed in response to a transition to an inter-particle adsorption mechanism.

Experimental and modelling analysis of As(V) ions adsorption on granular activated carbon

In this work the adsorption of pentavalent arsenic on a granular activated carbon (GAC) has been experimentally studied. The effects of arsenic concentration, pH, temperature and salinity on equilibrium adsorption capacity have been investigated. Experimental results show that the adsorption capacity is the highest at neutral pH conditions, low salinity levels and high temperatures. A model for the description of the arsenic adsorption mechanism is reported. This is based on the multicomponent Langmuir adsorption theory applied to the ionic species in solution. The model points out that the adsorption capacity is proportional to the concentration of arsenic anions in solution and decreases by increasing the concentration of competitive ions such as hydroxides and chlorides, allowing a correct interpretation of the pH and salinity effects on the adsorption capacity. Finally, one of the main goals of the proposed model is to preserve the exothermicity of the adsorption phenomena despite the observed trend of experimental results: the increase of adsorption capacity with temperature appears to be related to a higher arsenic dissociation.

Mercury adsorption on granular activated carbon in aqueous solutions containing nitrates and chlorides

Adsorption is an effective process to remove mercury from polluted waters. In spite of the great number of experiments on this subject, the assessment of the optimal working conditions for industrial processes is suffering the lack of reliable models to describe the main adsorption mechanisms. This paper presents a critical analysis of mercury adsorption on an activated carbon, based on the use of chemical speciation analysis to find out correlations between mercury adsorption and concentration of dissolved species. To support this analysis, a comprehensive experimental study on mercury adsorption at different mercury concentrations, temperatures and pH was carried out in model aqueous solutions. This study pointed out that mercury capture occurs mainly through adsorption of cationic species, the adsorption of anions being significant only for basic pH. Furthermore, it was shown that HgOH(+) and Hg(2+) are captured to a higher extent than HgCl(+), but their adsorption is more sensitive to solution pH. Tests on the effect of temperature in a range from 10 to 55 °C showed a peculiar non-monotonic trend for mercury solution containing chlorides. The chemical speciation and the assumption of adsorption exothermicity allow describing this experimental finding without considering the occurrence of different adsorption mechanisms at different temperature.

A descriptive model for metallic ions adsorption from aqueous solutions onto activated carbons

The design of adsorber units is mainly dependent on the equilibrium adsorption capacity of the sorbent in the working conditions. At the moment, these data are available in a limited number of experimental conditions and, for the case of activated carbon, there are no predictive models to assess the adsorption capacity as a function of the process parameters. This makes the adsorber design a complex and approximated task. In this work, a model for the description of metallic ions adsorption onto activated carbon is presented. The model starts from an evaluation of ion speciation and it considers the approach of the multi-component Langmuir model to correlate the metal uptake to the ion concentration in solution. The model has been used to analyse available experimental data on the adsorption of As(V), Cd(II), Cr(III) and Cr(VI) ions on activated carbon. A good matching between experimental results and model predictions has been obtained for all the investigated conditions.

Cadmium adsorption by coal combustion ashes-based sorbents—Relationship between sorbent properties and adsorption capacity

A very interesting possibility of coal combustion ashes reutilization is their use as adsorbent materials, that can also take advantage from proper beneficiation techniques. In this work, adsorption of cadmium from aqueous solutions was taken into consideration, with the emphasis on the intertwining among waste properties, beneficiation treatments, properties of the beneficiated materials and adsorption capacity. The characterization of three solid materials used as cadmium sorbents (as-received ash, ash sieved through a 25 μm-size sieve and demineralized ash) was carried out by chemical analysis, infrared spectroscopy, laser granulometry and mercury porosimetry. Cadmium adsorption thermodynamic and kinetic tests were conducted at room temperature, and test solutions were analyzed by atomic absorption spectrophotometry. Maximum specific adsorption capacities resulted in the range 0.5-4.3 mg g(-1). Different existing models were critically considered to find out an interpretation of the controlling mechanism for adsorption kinetics. In particular, it was observed that for lower surface coverage the adsorption rate is governed by a linear driving force while, once surface coverage becomes significant, mechanisms such as the intraparticle micropore diffusion may come into play. Moreover, it was shown that both external fluid-to-particle mass transfer and macropore diffusion hardly affect the adsorption process, which was instead regulated by intraparticle micropore diffusion: characteristic times for this process ranged from 4.1 to 6.1d, and were fully consistent with the experimentally observed equilibrium times. Results were discussed in terms of the relationship among properties of beneficiated materials and cadmium adsorption capacity. Results shed light on interesting correlations among solid properties, cadmium capture rate and maximum cadmium uptake.

Remediation of an aquifer polluted with dissolved tetrachloroethylene by an array of wells filled with activated carbon.

In this work, an array of deep passive wells filled with activated carbon, namely a Discontinuous Permeable Adsorptive Barrier (PAB-D), has been proposed for the remediation of an aquifer contaminated by tetrachloroethylene (PCE). The dynamics of the aquifer in the particular PAB-D configuration chosen, including the contaminant transport in the aquifer and the adsorption onto the barrier material, has been accurately performed by means of a computer code which allows describing all the phenomena occurring in the aquifer, simultaneously. A PAB-D design procedure is presented and the main dimensions of the barrier (number and position of passive wells) have been evaluated. Numerical simulations have been carried out over a long time span to follow the contaminant plume and to assess the effectiveness of the remediation method proposed. The model results show that this PAB-D design allows for a complete remediation of the aquifer under a natural hydraulic gradient, the PCE concentrations flowing out of the barrier being always lower than the corresponding Italian regulation limit. Finally, the results have been compared with those obtained for the design of a more traditional continuous barrier (PAB-C) for the same remediation process.

A procedure to design a Permeable Adsorptive Barrier (PAB) for contaminated groundwater remediation.

A procedure to optimize the design of a Permeable Adsorptive Barrier (PAB) for the remediation of a contaminated aquifer is presented in this paper. A computer code, including different routines that describe the groundwater contaminant transport and the pollutant capture by adsorption in unsteady conditions over the barrier solid surface, has been developed. The complete characterization of the chemical-physical interactions between adsorbing solids and the contaminated water, required by the computer code, has been obtained by experimental measurements. A case study in which the procedure developed has been applied to a tetrachloroethylene (PCE)-contaminated aquifer near a solid waste landfill, in the district of Napoli (Italy), is also presented and the main dimensions of the barrier (length and width) have been evaluated. Model results show that PAB is effective for the remediation of a PCE-contaminated aquifer, since the concentration of PCE flowing out of the barrier is everywhere always lower than the concentration limit provided for in the Italian regulations on groundwater quality.

Carbon-supported ionic liquids as innovative adsorbents for CO2 separation from synthetic flue-gas

Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization.

Permeable Adsorptive Barrier (PAB) for the remediation of groundwater simultaneously contaminated by some chlorinated organic compounds

In this paper, a Permeable Reactive Barrier (PRB) made with activated carbon, namely a Permeable Adsorptive Barrier (PAB), is put forward as an effective technique for the remediation of aquifers simultaneously contaminated by some chlorinated organic compounds. A design procedure, based on a computer code and including different routines, is presented as a tool to accurately describe mass transport within the aquifer and adsorption/desorption phenomena occurring inside the barrier. The remediation of a contaminated aquifer near a solid waste landfill in the district of Napoli (Italy), where Tetrachloroethylene (PCE) and Trichloroethylene (TCE) are simultaneously present, is considered as a case study. A complete hydrological and geotechnical site characterization, as well as a number of dedicated adsorption laboratory tests for the determination of activated carbon PCE/TCE adsorption capacity in binary systems, are carried out to support the barrier design. By means of a series of numerical simulations it is possible to determine the optimal barrier location, orientation and dimensions. PABs appear to be an effective remediation tool for the in-situ treatment of an aquifer contaminated by PCE and TCE simultaneously, as the concentration of both compounds flowing out of the barrier is everywhere lower than the regulatory limits on groundwater quality.

Desorption of arsenic from exhaust activated carbons used for water purification

This work aims to the analysis of arsenic desorption from an exhaust activated carbon used for the purification of a natural water. This last was used to mimic the properties of common groundwater or drinking water. Different low-cost and harmless eluting solutions were considered, including distilled water, natural water, saline (NaCl, CaCl₂ and NaNO₃) and basic (NaOH) solutions. Experimental results showed that, for 1g of activated carbon with arsenic loading close to the maximum value available for the model natural water (ω ≈ 0.1 mg/g), it is possible to recover more than 80% of the arsenic using 20 ml of 0.1 M sodium chloride solution. A temperature variation within 20 and 40 °C has scarce effect on desorption efficiency. A comparison between desorption data and adsorption isotherms data suggests that arsenic adsorption is actually a reversible process. Therefore, it is virtually possible to increase arsenic recovery efficiency close to 100% by increasing the NaCl concentration or the volume of the desorption solution, but a preliminary cost benefit analysis lead to consider a NaCl 0.1M solution as an optimal solution for practical applications.