Fabio Montagnaro

Manufacture of artificial aggregate using MSWI bottom ash.

This paper reports the results of an investigation on material recovery by stabilization/solidification of bottom ash coming from a municipal solid waste incineration plant. Stabilization/solidification was carried out to produce artificial aggregate in a rotary plate granulator by adding hydraulic binders based on cement, lime and coal fly ash. Different mixes were tested in which the bottom ash content ranged between 60% and 90%. To avoid undesirable swelling in hardened products, the ash was previously milled and then granulated at room temperature. The granules were tested to assess their suitability to be used as artificial aggregate through the measurement of the following properties: density, water absorption capacity, compressive strength and heavy metals release upon leaching. It was demonstrated that the granules can be classified as lightweight aggregate with mechanical strength strongly dependent on the type of binder. Concrete mixes were prepared with the granulated artificial aggregate and tested for in-service performance, proving to be suitable for the manufacture of standard concrete blocks in all the cases investigated.

Soluble salt removal from MSWI fly ash and its stabilization for safer disposal and recovery as road basement material

Fly ash from municipal solid waste incinerators (MSWI) is classified as hazardous in the European Waste Catalogue. Proper stabilization processes should be required before any management option is put into practice. Due to the inorganic nature of MSWI fly ash, cementitious stabilization processes are worthy of consideration. However, the effectiveness of such processes can be severely compromised by the high content of soluble chlorides and sulphates. In this paper, a preliminary washing treatment has been optimized to remove as much as possible soluble salts by employing as little as possible water. Two different operating conditions (single-step and two-step) have been developed to this scope. Furthermore, it has been demonstrated that stabilized systems containing 20% of binder are suitable for safer disposal as well as for material recovery in the field of road basement (cement bound granular material layer). Three commercially available cements (pozzolanic, limestone and slag) have been employed as binders.

Adsorption of chlorophenol, chloroaniline and methylene blue on fuel oil fly ash

Fuel oil fly ash has been tested as low-cost carbon-based adsorbent of 2-chlorophenol (CP), 2-chloroaniline (CA) and methylene blue (MB) from aqueous solutions. In all the cases the adsorption was found to be of cooperative type. Different adsorption capacities were found for the three organics. Specifically, it was highest for 2-chlorophenol, reaching about 70 mg g(-1), and quite lower in the other two cases, that is about 47 and 36 mg g(-1) for methylene blue and 2-chloroaniline, respectively. Varying the initial pH and adding KCl were found to have different effects on the adsorption of the three organics. In particular, the presence of other ions had no effect on the adsorption of methylene blue, adverse effect in the case of 2-chlorophenol and enhancing effect in the case of 2-chloroaniline.

Use of reservoir clay sediments as raw materials for geopolymer binders

Abstract Abstract Among low cost or readily available raw materials, reservoir clay sediments are of interest as potential precursors in geopolymer binder manufacture. These materials come from dredging of reservoirs because periodical sediment removal is necessary in order to keep a satisfactory level of functionality. In this paper, two sediments, coming from reservoirs located in Southern Italy, have undergone preliminary characterisation by X-ray diffraction, differential thermogravimetry and Fourier transformed infrared (FTIR) spectroscopy. Then, the sediments were submitted to 1 and 2 h calcination treatments at 650 and 750°C. The effects of calcination were evaluated by means of 27Al magic angle spinning nuclear magnetic resonance and FTIR. The calcined samples were mixed with 5M NaOH solution, and the obtained mixtures were studied for reactivity by means of differential scanning calorimetry. Finally, cylindrical samples were prepared with the same mixtures and cured for 3 days at 60°C plus 4 and 25 days at room temperature. The obtained samples were subjected to unconfined compressive strength determinations in order to verify the actual occurrence of geopolymerisation. The results show that the calcined clay sediments can be suitable precursors in polycondensation reactions.

Flue gas desulfurization gypsum and coal fly ash as basic components of prefabricated building materials.

The manufacture of prefabricated building materials containing binding products such as ettringite (6CaO·Al2O3·3SO3·32H2O) and calcium silicate hydrate (CSH) can give, in addition to other well-defined industrial activities, the opportunity of using wastes and by-products as raw materials, thus contributing to further saving of natural resources and protection of the environment. Two ternary mixtures, composed by 40% flue gas desulfurization (FGD) gypsum or natural gypsum (as a reference material), 35% calcium hydroxide and 25% coal fly ash, were submitted to laboratory hydrothermal treatments carried out within time and temperature ranges of 2h-7days and 55-85°C, respectively. The formation of (i) ettringite, by hydration of calcium sulfate given by FGD or natural gypsum, alumina of fly ash and part of calcium hydroxide, and (ii) CSH, by hydration of silica contained in fly ash and residual lime, was observed within both the reacting systems. For the FGD gypsum-based mixture, the conversion toward ettringite and CSH was highest at 70°C and increased with curing time. Some discrepancies in the hydration behavior between the mixtures were ascribed to differences in mineralogical composition between natural and FGD gypsum.

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.

Attrition of Limestone During Fluidized Bed Calcium Looping Cycles for CO2 Capture

Attrition of a limestone during calcium looping cycles for CO2 capture was studied in a lab-scale fluidized bed apparatus. Batch experiments under alternating calcination–carbonation conditions were carried out to investigate the effect of chemical reactions and temperature changes on the attrition propensity of the sorbent particles. Attrition processes were characterized by following the modifications of bed sorbent particle size distribution and the elutriation rates of fines throughout conversion over repeated cycles. Different bed temperatures and CO2 inlet concentrations during the calcination stage were tested in the experiments. Results show that relatively large attrition rates were experienced by the sorbent particles only during the first cycle. From the second cycle on the attrition rate progressively declines, also during the calcination stage where the softer CaO is produced. It is inferred that the combined chemical-thermal treatment affects the particle structure making it increasingly hard. At the same time, the CO2 capture capacity decays toward an asymptotic level, possibly related to the very same structural modifications. The bed temperature and CO2 concentration both appear to influence the sorbent behavior in the tests.

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.

Utilization of Coal Combustion Ashes for the Synthesis of Ordinary and Special Cements

Raw mixes containing pulverized coal fly ash (with limestone and silica sand) or fluidized bed coal combustion ash (fly and bottom, with added limestone, anodization mud, and, when necessary, flue gas desulfurization gypsum), aimed at generating ordinary Portland or calcium sulfoaluminate clinkers, respectively, were heated in a laboratory electric oven at temperatures ranging from 1150° to 1500°C and submitted to X-ray diffraction analysis. The former had the same qualitative phase composition as that of a reference mixture, composed by limestone and clay; furthermore, they exhibited an excellent burnability on the basis of their residual free lime contents, measured after heating at 1350°, 1400°, 1450°, and 1500°C. The latter showed very good results in terms of conversion of reactants and selectivity degree toward the main mineralogical constituent, calcium sulfoaluminate (4CaO·3Al2O3·SO3), even if the behavior of a reference mixture consisting of limestone, bauxite, and natural gypsum was slightly better. The introduction of a fluidized bed coal combustion ash in the raw mix generating calcium sulfoaluminate clinker implies a saving of bauxite and natural gypsum, which can be fully replaced through the addition of anodization mud and flue gas desulfurization gypsum, respectively.

Assessment of ettringite from hydrated FBC residues as a sorbent for fluidized bed desulphurization

Abstract The performance of synthetic ettringite as a sorbent in fluidized bed desulphurization has been assessed and compared with that of a commercial limestone. Experiments have been carried out in a bench scale fluidized bed reactor under simulated desulphurizing (steadily oxidizing) combustion conditions. Sorbent performance has been characterized in terms of desulphurization rate, maximum sulphur uptake and attrition propensity. Fluidized bed sulphation experiments have been complemented by microstructural characterization of solid samples, accomplished via X-ray diffraction analysis, scanning electron microscopy and sulphur mapping of cross-sections of particles embedded in epoxy resin. Experimental results show that both the rate and the maximum extent of sulphur uptake by ettringite significantly exceed those of the limestone. Maximum degree of free calcium utilization is 0.58 for ettringite compared with 0.27 for the limestone. Sulphation tests also indicate that attrition propensity of ettringite is larger than that correspondingly observed for the limestone. Microstructural characterization indicates that sulphation of ettringite takes place evenly throughout the particle cross-section, whereas sulphation of limestone mostly conforms to a core-shell pattern. Along a parallel pathway, the rate and yield of ettringite formation by hydration of fly ash from a utility fluidized bed boiler have been assessed. Formation of ettringite in these experiments appears to be quantitative upon curing of ash at 70 °C for times up to 4 days.