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.     

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 2 h–7 days 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.     

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.     

A preliminary investigation on the use of organic ionic liquids as green solvents for acylation and oxidation reactions

Different organic ionic liquids (OILs) have been used as green solvents in Friedel–Crafts acylation and alcohol oxidation reactions. Specifically, three OILs were employed, 1-ethyl-3-methylimidazolium chloride, tetraethylammonium bromide, and 1-butyl-3-methylimidazolium chloride, and four reactions studied, acylation of toluene by acetyl chloride, acylation of benzene by propionyl chloride, oxidation of benzyl alcohol by N-methylmorpholine N-oxide, and oxidation of salicylic alcohol by o-iodoxybenzoic acid. The reactions were carried out, at room temperature, in a well-stirred lab-scale glass batch reactor, under inert atmosphere and for reaction times ranging from 5 to 90 min. Gas chromatography was employed to characterize the reaction products. First of all, the desired products yield as a function of the reaction time was investigated. Moreover, simple kinetic models were built for the interpretation of the experimental results. Additional tests were carried out to assess the possibility of recycling the OILs employed. The results of this preliminary study were satisfactory as the OILs investigated proved to be good media in which to carry out the reactions studied in this work (desired products yield greater than 90% were achieved). Moreover, the reaction rate expressions of the kinetic models were able to satisfactorily predict the experimental results. Finally, the possibility of recycling the OIL (in one of the reactions) was proved to be feasible and this suggests the use of recycled OIL together with a fresh make-up, to match high yield values with economical/ecological advantages.     

Liquid–solid adsorption processes interpreted by fractal-like kinetic models

Environmental Chemistry Letters - The transport of an adsorbate molecule from the bulk of a fluid phase to the active centre of an adsorbent particle involves complex mechanisms. Mechanisms need to...     

Mechanochemistry of ibuprofen pharmaceutical

In this paper mechanochemistry has been studied in view of possible application to detoxification of expired pharmaceuticals. The experiments have been carried out with a commercial medication containing ibuprofen ((RS)-2-(4-(2-methylpropyl)phenyl)propanoic acid) which has been submitted to prolonged milling up to 40 h. When Al(OH)₃ is used as co-reagent, the first degradation step induced by the mechanochemical treatment is an acid-base reaction with the ibuprofen carboxylic acid group. The subsequent degradation follows a complex pathway leading to 1-(4-isobutylphenyl)ethanone, 1-isobutyl-4-vinylbenzene and 2-(4-(3-methylbutan-2-yl)phenyl)propan-1-ol after 10 h milling and, in addition, 1-(4-acetylphenyl)-2-methylpropan-1-one, 1-(4-(1-hydroxy-2-methylpropyl)phenyl)ethanone and 1-(4-(2-hydroxy-2-methylpropyl)phenyl)ethanone after 40 h milling. The degradation reaction path and products have been identified by means of FT-IR spectroscopy, thin layer chromatography, NMR spectroscopy, mass spectroscopy and elemental analysis. The observed ibuprofen decarboxylation makes the drug simultaneously lose both its pharmaceutical activity and toxicity.     

Coal fly ash as raw material for the manufacture of geopolymer-based products

In this work coal fly ash has been employed for the synthesis of geopolymers. Two different systems with silica/alumina ratios stoichiometric for the formation of polysialatesiloxo (PSS, SiO2/Al2O3=4) and polysialatedisiloxo (PSDS, SiO2/Al2O3=6) have been prepared. The alkali metal hydroxide (NaOH or KOH) necessary to start polycondensation has been added in the right amount as concentrated aqueous solution to each of the two systems. The concentration of each alkali metal solution has been adjusted in order to have the right liquid volume to ensure constant workability. The systems have been cured at four different temperatures (25, 40, 60, and 85 degrees C) for several different times depending on the temperature (16-672 h at 25 degrees C; 72-336 h at 40 degrees C; 16-120 h at 60 degrees C and 1-6h at 85 degrees C). The products obtained in the different experimental conditions have been submitted to the quantitative determination of the extent of polycondensation through mass increase and loss on ignition, as well as to qualitative characterization by means of FT-IR spectroscopy. Furthermore, physico-structural and mechanical characterization has been carried out through microscopic observations and the determination of unconfined compressive strength, elasticity modulus, apparent density, porosity and specific surface area. The results have indicated that the systems under investigation are suited for the manufacture of pre-formed building blocks at room temperature.     

TG, FT-IR and NMR characterization of n-C16H34 contaminated alumina and silica after mechanochemical treatment

This paper deals with the application of mechanochemistry to model systems composed of alumina or silica artificially contaminated with n-C16H34. The mechanochemical treatment was carried out by means of a ring mill for times ranging from 10 to 40h. Thermogravimetry and infrared and nuclear magnetic resonance spectroscopies were used for the characterization of the mechanochemical products. The results have indicated that, in the case of alumina, almost all the contaminant n-C16H34 undergoes a complex oxidative reaction path whose end products are strongly held on the surface. These end products are most likely made of crosslinked, partially oxidized hydrocarbon chains bond to the solid surface via COO(-) groups. In the case of silica, the hydrocarbon undergoes a different, equally complex reaction path, but to a lower extent. In this case the end products are most probably carbonylic compounds and graphitic carbon. Then, for both solid matrices, the mechanochemical treatment promotes significant modification of the chemical nature of the polluting hydrocarbon with end products much more difficult to remove from the surface. As the systems studied are models of sites contaminated by aliphatic hydrocarbon, the results are worthy of consideration in relation to the mobility of the contaminants in the environment.