Pietro Altimari

Cobalt products from real waste fractions of end of life lithium ion batteries.

An innovative process was optimized to recover Co from portable Lithium Ion Batteries (LIB). Pilot scale physical pretreatment was performed to recover electrodic powder from LIB. Co was extracted from electrodic powder by a hydrometallurgical process including the following main stages: leaching (by acid reducing conditions), primary purification (by precipitation of metal impurities), solvent extraction with D2EPHA (for removal of metal impurities), solvent extraction with Cyanex 272 (for separation of cobalt from nickel), cobalt recovery (by precipitation of cobalt carbonate). Tests were separately performed to identify the optimal operating conditions for precipitation (pH 3.8 or 4.8), solvent extraction with D2EHPA (pH 3.8; Mn/D2EHPA=4; 10% TBP; two sequential extractive steps) and solvent extraction with Cyanex 272 (pH 3.8; Cyanex/Cobalt=4, 10% TBP, one extractive step). The sequence of optimized process stages was finally performed to obtain cobalt carbonate. Products with different degree of purity were obtained depending on the performed purification steps (precipitation with or without solvent extraction). 95% purity was achieved by implementation of the process including the solvent extraction stages with D2EHPA and Cyanex 272 and final washing for sodium removal.

Leaching of electrodic powders from lithium ion batteries: Optimization of operating conditions and effect of physical pretreatment for waste fraction retrieval

Experimental results of leaching tests using waste fractions obtained by mechanical pretreatment of lithium ion batteries (LIB) were reported. Two physical pretreatments were performed at pilot scale in order to recover electrodic powders: the first including crushing, milling, and sieving and the second granulation, and sieving. Recovery yield of electrodic powder was significantly influenced by the type of pretreatment. About 50% of initial LIB wastes was recovered by the first treatment (as electrodic powder with size <0.5mm, Sample 1), while only 37% of powder with size <1mm (Sample 2) can be recovered by the second treatment. Chemical digestion put in evidence the heterogeneity of recovered powders denoting different amounts of Co, Mn, and Ni. Leaching tests of both powders were performed in order to determine optimized conditions for metal extraction. Solid/liquid ratios and sulfuric acid concentrations were changed according to factorial designs at constant temperature (80°C). Optimized conditions for quantitative extraction (>99%) of Co and Li from Sample 1 are 1/10g/mL as solid/liquid ratio and +50% stoichiometric excess of acid (1.1M). Using the same solid/liquid ratio, +100% acid excess (1.2M) is necessary to extract 96% of Co and 86% of Li from Sample 2. Best conditions for leaching of Sample 2 using glucose are +200% acid excess (1.7M) and 0.05M glucose concentration. Optimized conditions found in this work are among the most effective reported in the literature in term of Co extraction and reagent consumption.

Effect of Ca2+ concentration on Scenedesmus sp. growth in heterotrophic and photoautotrophic cultivation

The influence of Ca2+ concentration on the growth of the microalga Scenedesmus sp. in heterotrophic and photoautotrophic cultivations was investigated. Heterotrophic growth was induced by the addition of olive mill wastewaters (9% v·v-1) to the culture. Variations in the calcium concentration affected differently biomass production depending on whether microalgae were cultivated under heterotrophic or photoautotrophic regime. In photoautotrophic regime, increasing the calcium concentration from 20 to 230mg⋅L-1 decreased maximum cell concentration and growth rate. In heterotrophic cultivation, cell concentration and growth rate decreased with Ca2+ concentration increasing from 20 to 80mg⋅L-1 but then increased with Ca2+ concentration increasing to 230mg⋅L-1. Increasing calcium concentration invariably promoted cell aggregation. The precipitation of calcium phosphates can explain the decreasing growth rate and cell concentration attained with increasing calcium concentration, while the influence of Ca2+ concentration on the adsorption of phenols on suspended solids can explain the enhanced growth attained at large Ca2+ concentration under heterotrophic regime. Implications of the illustrated results for industrial scale application of microalgae are thoroughly discussed.

Steady-state behaviour of PFR-separation-recycle systems with simultaneous exothermic and endothermic, first-order reactions

A systematic investigation of plug-flow reactor (PFR)-separation-recycle systems where first-order exothermic and endothermic reactions are simultaneously performed is presented. The nonlinear behaviour is analyzed for two flowsheet alternatives and four plantwide control structures. It is shown that the system can exhibit a complex nonlinear behaviour. For the parameter values used, regions of unfeasibility, two or three multiple steady states and branches of isolated solutions were found. The undesired nonlinear phenomena can be avoided by fixing the reactor-inlet flow rates of each reactant or, when this is impossible due to the flowsheet structure, by providing sufficient cooling capacity.

Physical and chemical treatment of end of life panels: An integrated automatic approach viable for different photovoltaic technologies

Different kinds of panels (Si-based panels and CdTe panels) were treated according to a common process route made up of two main steps: a physical treatment (triple crushing and thermal treatment) and a chemical treatment. After triple crushing three fractions were obtained: an intermediate fraction (0.4-1mm) of directly recoverable glass (17%w/w); a coarse fraction (>1mm) requiring further thermal treatment in order to separate EVA-glued layers in glass fragments; a fine fraction (<0.4mm) requiring chemical treatment to dissolve metals and obtain another recoverable glass fraction. Coarse fractions (62%w/w) were treated thermally giving another recoverable glass fraction (52%w/w). Fine fractions can be further sieved into two sub-fractions: <0.08mm (3%w/w) and 0.08-0.4mm (22%w/w). Chemical characterization showed that 0.08-0.4mm fractions mainly contained Fe, Al and Zn, while precious and dangerous metals (Ag, Ti, Te, Cu and Cd) are mainly present in fractions <0.08mm. Acid leaching of 0.08-0.4mm fractions allowed to obtain a third recoverable glass fraction (22%w/w). The process route allowed to treat by the same scheme of operation both Si based panels and Cd-Te panels with an overall recycling rate of 91%.

Two stage process of microalgae cultivation for starch and carotenoid production

Biotechnological processes based on microalgae cultivation are promising for several industrial applications. Microalgae are photoautotrophic microorganisms and can thus grow by using renewable and inexpensive resources as sunlight, inorganic salts, water and CO2. They can store high amounts of neutral lipids (bioil), carbohydrates (mainly starch), carotenoids (such as lutein, astaxanthin, β-carotene), proteins and other molecules. Productions of lipids and carbohydrates have recently received an increasing interest for biofuel production, while proteins, carotenoids and other minor products are usable as feed additives and nutraceutical compounds. Biofuel production from microalgae is not yet economically sustainable, while there are different industrial plants in the world for the production of high values chemicals as carotenoids. Starch production from microalgae has been investigated mainly for the production of biofuels (e.g. bioethanol) by successive fermentation. However, purified starch can be used for other aims such as the production of bioplastics. Superior plants as corn, potato and wheat are currently used for this purpose. However, there are different environmental and economic issues related to the use of fertile lands and edible plants for these kinds of productions. Microalgae can solve these social and ethical issues because they can grow on nonfertile lands and also reach starch productivity per hectare higher than plants. In this work, the production of starch and carotenoids from Scenedesmus sp. microalgal strain is reported. A two-stage process has been developed in order to reduce operative and investment costs. In the first stage, microalgae are cultivated in photoautotrophic conditions and then, when biomass concentration rises and light becomes a limiting factor for growth, microalgae are transferred to a heterotrophic reactor. In this reactor, microalgae are cultivated by using wastewaters as source of nutrients (mainly organic carbon). Microalgae use organic carbon to synthesize starch and simultaneously reduce the content of pollutants in the wastewater (codepuration). Biomass separated by the culture medium is treated for the extraction of lipids containing different antioxidant carotenoids (such as astaxanthin and lutein) and starch granules as raw material for biopolymers.

Recovery of critical metals from LCDs and Li-ion batteries

In 2014, the European Union defined a list of 20 raw materials critical for economic importance and high supply risk. The aim of this work is to present the main results achieved within the EU-FP7 Project HydroWEEE-Demo dealing with the recovery of indium and cobalt, metals included in such European list, from LCD scraps and end of life Li-ion batteries, respectively. A complete indium recovery was achieved carrying out an acidic leaching, followed by a zinc cementation. Cobalt was extracted from the electrodic powder according to the following main operations: leaching (by acid reducing conditions), primary purification (by precipitation of metal impurities), solvent extraction with D2EPHA (for the removal of metal impurities), solvent extraction with Cyanex 272 (for the separation of cobalt from nickel), cobalt recovery (by precipitation as cobalt hydroxide). Co products with 95% purity were obtained by implementation of the solvent extraction with D2EHPA and Cyanex 272.

Synthesis and characterization of copper ferrite magnetic nanoparticles by hydrothermal route

Secondary treatment of heavy metal bearing solutions requires highly expensive procedures including the application of ionic exchange resins or activated carbon packed in fixed bed reactors. The use of nanoparticles with magnetic properties as adsorbents can improve metal removal performances allowing for the achievement of high specific surface area. In addition, the simplification of the final solid-liquid separation by magnetic field can avoid the application of packed bed columns. In this study a simple synthetic pathway was optimized to produce copper nanoferrites (CuFe2O4), stable in water, magnetically active and with high specific area, to be further used as sorbent material for heavy metal removal in water solution. The hydrothermal route included surfactant-assisted coprecipitation (performed at different pH), hydrothermal treatment (1h at 120°C), washing with water and hexane, drying, and sintering (performed at 100 and 200°C for 1h). Structure and sizes of CuFe2O4 crystallites were studied as function of coprecipitation pH (8, 10, and 12.5) and sintering temperature (100-200°C). CuFe2O4 powders were characterized by field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), Brunauer-EmmettTeller (BET) analysis of porosimetric data. Releasing tests of Fe and Cu at different pH were performed to define the pH range of stability in water. Potentiometric titrations were performed to determine the net charge depending on bulk solution pH. Best samples in terms of magnetic characteristics were obtained at pH 12.5 not depending on the sintering temperature. Mean size of nanoparticles obtained in such conditions was estimated by SEM images as 35-45 nm. BET analysis gave specific surface area of 147.8 ± 0.2 m2/g. CFNs have shown chemical stability in water solutions from pH 6 to 10. Zero charge point was estimated as pH 5.5. Then in the stability range of pH, CFNs present negative surface charge being able to coordinate positively charged heavy metal species.

Effect of lipids and carbohydrates extraction on astaxanthin stability in Scenedesmus sp.

Elevated costs of biomass downstream processing represent a severe limit to the industrial development of microalgal production systems. Biorefinery solutions allowing simultaneously deriving biofuels and extracting high value compounds must be explored to enhance economic feasibility. In this work, the possibility to extract carbohydrates, lipids and astaxanthin from a strain of Scenedesmus sp. is investigated. The analysis is mainly focused on analyzing the effect of consolidated procedures of extraction of carbohydrates and lipids on the degradation and recovery of astaxanthin. Microalgae were cultivated till achieving stationary phase and maintained in this phase to enhance lipids and astaxanthin accumulation. The fractions of total lipids, carbohydrates and astaxanthin of the produced biomass were 17 %, 33 % and 0.02 % respectively. No statistically significant difference in the astaxanthin content determined following Soxhlet extraction and a more gentle extraction method (Yuan et al. 2002) was found. The effect of transesterification conditions was also evaluated revealing a scarce degradation of astaxanthin in response to the achievement of elevated temperature, NaOH and dissolved oxygen concentrations. Reductions in astaxanthin content were in contrast obtained in response to the addition of H2SO4. These reductions were proportional to acid sample concentration. However a regeneration of astaxanthin was obtained by NaOH addition indicating reversibility of the degradation process. In accordance with these results, the possibility to perform biomass saccharification for carbohydrate extraction at progressively lower acid concentrations was investigated.

Lanthanum biosorption by different saccharomyces cerevisiae strains

Lanthanum Biosorption by Different Saccharomyces cerevisiae Strains Fabrizio Di Caprio*, Pietro Altimari, Elena Zanni, Daniela Uccelletti, Luigi Toro, Francesca Pagnanelli Dipartimento di Chimica, Università “Sapienza” di Roma, Piazzale Aldo Moro 5, 00185, Roma, Italia. Dipartimento di Biologia e Biotecnologie “C.Darwin”, Università “Sapienza” di Roma, Piazzale Aldo Moro 5, 00185, Roma, Italia. fabrizio.dicaprio@uniroma1.it