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Municipal solid waste incineration (MSWI) fly ashes are hazardous waste since they contain organic pollutants, heavy metals and an important amount of various soluble salts. However their chemical composition is interesting for their valorization in cement production. The objective of this paper is to assess the possibility of MSWI fly ashes reuse as cement raw meal, after pre-treatment, at a laboratory scale. The environmental impact has also been studied (analyses of the metals, of dioxins and furans and leaching tests on clinker produced). Experimental results show that the replacement of MSWI fly ash could be taken up to 30% in the raw mixes, according to the chemical composition of the MSWI fly ashes. This substitution is also to be refined according to the content of hazardous elements contents. This study also shows that the pre-treatment must be well carried out in order to limit the alkaline contents which may affect the quality of the cementitious phases.

Petroleum industries continuously consume catalysts on very large scales. The recycling of spent catalysts is thus of major economic and environmental importance and its first step consists of the characterization of the valuable metal content. Wavelength dispersive X-ray fluorescence (WDXRF) analysis is compared with inductively coupled plasma atomic emission spectrometry (ICP-AES) for the analysis of five samples of spent hydrodesulphurization (HDS) and hydrodemetallization (HDM) catalysts. The elements are considered for their economic interest (Co, Ni, Mo, and V) or for the problems that can arise when they are present in the sample in significant quantities (Al, As, P, Fe). First, the systematic comparison of the analysis of known synthetic samples was performed. The originality here is that the samples were first beaded with lithium tetraborate (Li 2 B 4 O 7 ) for WDXRF analysis and then dissolved in hot HCl 6M for ICP-AES measurements. With this processing, we were able to clearly identify the origin of analytical problems when they arose. Second, the semi-quantitative protocol of WDXRF is compared with the quantitative procedure. Finally, the analysis of the spent catalysts is presented and the information gained by the systematic comparison of ICP-AES and WDXRF is shared. The interest of the simultaneous determination by the two techniques when such complicated heterogeneous matrices are involved is clearly demonstrated.

The platinum nanoparticles used as the catalyst in proton exchange membrane fuel cells (PEMFCs) represent approximately 46 % of the total price of the cells for a large-scale production, and this is one of the barriers to their commercialization. Therefore, the recycling of the platinum catalyst could be the best alternative to limit the production costs of PEMFCs. The usual recovery routes for spent catalysts containing platinum are pyro-hydrometallurgical processes in which a calcination step is followed by aqua regia treatment, and these processes generate fumes and NO x emissions, respectively. The electrochemical recovery route proposed here is more environmentally friendly, performed under "soft" temperature conditions, and does not result in any gas emissions. It consists of the coupling of the electrochemical leaching of platinum in chloride-based ionic liquids (ILs), followed by its electrodeposition. The leaching of platinum was studied in pure ILs and in ionic-liquid melts at different temperatures and with different chloride contents. Through the modulation of the composition of the ionic-liquid melts, it is possible to leach and electrodeposit the platinum from fuel-cell electrodes in a single-cell process under an inert or ambient atmosphere., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Major uses of thermoelectricity concern refrigeration purposes, using Peltier devices, mainly composed of antimony, bismuth and tellurium. Antimony was identified as a critical raw material by EU and resources of bismuth and tellurium are not inexhaustible, so it is necessary to imagine the recycling of thermoelectric devices. That for, a complete characterization is needed, which is the aim of this work. Peltier devices were manually dismantled in three parts: the thermoelectric legs, the alumina plates on which remain the electrical contacts and the silicone paste used to connect the plates. The characterization was performed using five Peltier devices. It includes mass balances of the components, X-ray diffraction analysis of the thermoelectric legs and elemental analysis of each part of the device. It appears that alumina represents 45% of a Peltier device in weight. The electrical contacts are mainly composed of copper and tin, and the thermoelectric legs of bismuth, tellurium and antimony. Thermoelectric legs appear to be Se-doped Bi 2 Te 3 and (Bi 0,5 Sb 1,5 )Te 3 for n type and p type semiconductors, respectively. This work shows that Peltier devices can be considered as a copper ore and that thermoelectric legs contain high amounts of bismuth, tellurium and antimony compared to their traditional resources.

The aim of this paper is the characterization of spent NiCd batteries and the characterization of an industrial Black Mass obtained after crushing spent NiCd batteries and physical separation in a treatment plant. The characterization was first performed with five cylindrical NiCd batteries which were manually dismantled. Their characterization includes mass balance of the components, active powders elemental analysis and phase identification by X-ray powder diffraction. Chemical speciation of the two metals was also investigated. For cadmium, speciation was previously developed on solid synthetic samples. In a spent battery, the active powders correspond to about 43% of the battery weight. The other components are the separator and polymeric pieces (5%), the support plates (25%) and the carbon steel external case (27%). The sequential procedure shows that the nickel in the positive powders from the dismantled Ni-Cd batteries is distributed between Ni0 (39.7%), Ni(OH)2 (58.5%) and NiOOH (1.8%). Cadmium in the negative powder is about 99.9% as the Cd(OH)2 form with 0.1% of metal cadmium. In the industrial Black Mass, the distribution of cadmium is the same, whereas the distribution of nickel is Ni0 (46.9%), Ni(OH)2 (43.2%) and NiOOH (9.9%). This material contains also 1.8% cobalt and approx. 1% iron.

Carboxylic acids and diacids were synthesized from monoenic fatty acids by using RuO4 catalysis, under ultrasonic irradiation, in various mixtures of solvents. Ultrasound associated with Aliquat 336 have promoted in water, the quantitative oxidative cleavage of the CH=CH bond of oleic acid. A design of experiment (DOE) shows that the optimal mixture of solvents (H2O/MeCN, ratio 1/1, 2.2% RuCl3/4.1 eq. NaIO4) gives 81% azelaic acid and 97% pelargonic acid. With the binary heterogeneous mixture H2O/AcOEt, the oxidation of the oleic acid leads to a third product, the alpha-dione 9,10-dioxostearic acid.

The detoxification mechanisms of the aquatic moss, Fontinalis antipyretica Hedw., exposed to Cr was analyzed. In addition, the influence of Cr salts (as Cr nitrate, chloride and potassium bichromate) on these mechanisms has also been studied. The activity of antioxidant enzymes superoxide dismutase (SOD, EC 1.15.1.1.), catalase (EC 1.11.1.6.), ascorbate peroxidase (APX, EC 1.11.1.11.), guaiacol peroxidase (GPX, EC 1.11.1.7.) and glutathione reductase (GR, EC 1.6.4.2.) increased in plants treated with Cr concentrations ranging from 6.25x10(-5) to 6.25mM when given as Cr(NO3)3. Antioxidant enzymes responded to the other two salts CrCl3 and K2Cr2O7 only with Cr concentrations higher than 6.25x10(-2)mM. Glutathione level and GSSG/GSH ratio also responded to Cr exposure but no dose-effect relationship could be observed. Moreover, two unknown thiol compounds were observed in mosses exposed to the highest Cr concentrations. Effects on chlorophyll contents and chlorophyll a/b ratios were also shown even at low Cr concentrations. Our results indicated that environmentally realistic concentrations of Cr could lead to impairment of the cellular activity towards F. antipyretica and that Cr(III), when present as a nitrate salt, was as harmful as Cr(VI).

Conventional methods for heavy metal removal from industrial wastewater involve a chemical precipitation. This process leads to sludges without any commercial value which are stored in specialized landfills. This paper describes a study on the possibility to perform selective precipitation of binary mixtures of metal cations using sodium decanoate. First, the solubility product of six metal decanoates is determined. These six compounds were prepared and controlled before determining their solubility in pure water at 20 degrees C. The solubility product K(sp) obtained for Cd, Cu, Mn, Ni, Pb and Zn decanoates are respectively 10(-11.69), 10(-14.65), 10(-10.16), 10(-9.17), 10(-16.05) and 10(-13.05). Additionally, the selective precipitation of binary mixtures was studied. Using pK(sp) values above, the solubility domain of each decanoate was established. The six superimposed curves allow prediction of the feasibility of separation. According to these curves, nine separations seem to be possible. In each case, precipitation was experimentally performed. The obtained results verify the reliability of this prediction tool. The feasibility of the selective precipitation of metal cations using sodium decanoate is clearly shown.

The purpose of this work was to study the feasibility at laboratory-scale of a new hydrometallurgical process for treating electric arc furnace dusts (EAFD). The proposed process is intended to extract zinc and lead from EAFD without destroying the iron oxides matrix. So, this material can be recycled by the steel industry. Independently of the origin of the samples, major mineralogical forms present in these wastes are Fe3O4, ZnO, ZnFe2O4 and PbOHCl. The proposed process consists of a hydrometallurgical treatment of wastes based on selective leaching of zinc and lead. Initially, a leaching is carried out utilizing a chelating agent, nitrilotriacetate anion (NTA3-), as the protonated form HNTA2-. Treatment of five EAFD samples for an hour at room temperature with a molar solution of reagent results in total leaching of the ZnO. In all cases the solubilized iron does not exceed 3 wt.%. The recovery of zinc and lead is performed by precipitation of metallic sulfides with a solution of Na2S4 sodium tetrasulfide 2M. These metallic sulfides can be used as metallurgical raw materials and the chelating reagent can be reused in the process after pH adjustment. The results of the normalized leaching test AFNOR X31-210 conducted on the leaching residues, shows that all the samples meet acceptance thresholds for hazardous wastes landfill. However, the residues contain a considerable amount of zinc as ZnFe2O4. The extraction of the zinc element requires the destruction of the ferrite structure. In this process, ZnFe2O4 is treated by FeCl3.6H2O. The reaction consists in a particle O2-/Cl- exchange allowing the recovery of zinc as ZnCl2 and iron as hematite Fe2O3. The separation of these products is accomplished by simple aqueous leaching. All of the zinc is extracted in a 8h treatment at 150 degrees C with a molar ratio FeCl3.6H2O/ZnFe2O4 equal to 10. Ultimate solid residues, which have been concentrated in iron, can be oriented towards the steel industry.