Effective Separation and Recovery of Manganese and Potassium from Biomass Ash by Solvent Extraction.

Manganese (Mn) is considered an important, energy-critical metal due to its leading role in the production of electrochemical energy storage devices. One valuable source of Mn is hyperaccumulator plants used for the phytoremediation of contaminated soil. In this study, stems and leaves of ginger (Zingiber officinale), which accumulate Mn at moderate levels (∼0.2 wt %) and potassium (K) at high levels (>5 wt %), were analyzed to assess the potential of recovering metals from this plant. The extraction behaviors of Mn and K were studied using raw and ash samples (100-600 °C). It was crucial to set an appropriate incineration temperature (300 °C) to selectively extract K (∼96%) and Mn (∼90%) using water and nitric acid over two consecutive steps. Additionally, citric acid, a cost-effective and environmentally friendly solvent, was just as effective (∼85%) as nitric acid in extracting Mn. X-ray absorbance near-edge spectroscopy and X-ray diffraction analysis of the ash before and after extractions were applied to elucidate the extraction mechanism. The results revealed that selective extraction of both compounds was possible due to the change in the oxidative state of Mn(II) (soluble in water) into Mn(III) and Mn(IV) (insoluble in water) during sample incineration. Simultaneously, there were complex reactions associated with the changes within potassium carbonate compounds; however, these did not affect the K extraction efficiency.

Removal of Perfluorooctanoic Acid from Water Using a Hydrophobic Ionic Liquid Selected Using the Conductor-like Screening Model for Realistic Solvents.

The conductor-like screening model for realistic solvents was used to identify ionic liquids (ILs) to efficiently extract perfluorooctanoic acid (PFOA). The infinite dilution chemical potentials of PFOA in 14 000 ILs were calculated and used as descriptors of the chemical affinities between the ILs and PFOA. Trihexyltetradecylphosphonium pivalate ([P6,6,6,14][Piv]) was found to be a good IL for extracting PFOA because it gave a well-balanced combination of a strong chemical attraction for PFOA and useful physicochemical properties. The results of experiments indicated that [P6,6,6,14][Piv] could remove >99.9% of the PFOA in an aqueous solution. However, problematic emulsification of IL in the aqueous phase occurred at PFOA/IL molar ratios <1.9-2.1, and this limited the PFOA removal rate to 80-91%. The ability of the used IL to extract PFOA was found to be partially regenerated by washing the IL with 1% NaOH, and the IL could be reused to extract PFOA with a removal rate decreased by ∼10% in each cycle.

Mitigation of bromine-containing products during pyrolysis of polycarbonate-based tetrabromobisphenol A in the presence of copper(I) oxide.

Polycarbonate (PC) is an engineering thermoplastic that is widely used in electrical and electronic equipment. This plastic often contains tetrabromobisphenol A (TBBA), the most common brominated flame retardant. Thermal degradation of the PC-TBBA leads to generation of numerous bromo-organic products in the pyrolytic oil, hindering its appropriate utilization, as well as corrosive hydrogen bromide gas. The purpose of this study was to experimentally investigate and compare the pyrolysis products of PC-TBBA and PC-TBBA + Cu2O at various temperatures, with an emphasis on the yield and distribution of brominated compounds. In pyrolysis of PC-TBBA + Cu2O, at the maximum degradation temperature (600 °C), as much as 86% of total Br was trapped in the residue, while 3% and 11% were distributed in the condensate and gas fractions, respectively. In contrast, the distribution of Br from non-catalytic pyrolysis of PC-TBBA (600 °C) was 0.5% residue, 40% condensate, and 60% gas. The results of this study revealed that in the presence of Cu2O, organo-bromine products were most likely involved in Ullman-type coupling reactions, leading to early cross-linking of the polymer network that efficiently hinders their vaporization. HBr in the gas fraction was suppressed due to effective fixation of bromine in residue in the form of CuBr.

Comparison of sewage sludge mono-incinerators: Mass balance and distribution of heavy metals in step grate and fluidized bed incinerators.

We investigated the distribution of 18 elements including non-volatiles (Al, P, Ca, Fe, Mg, K, Mn, Cu, Na, Cr, and Ni), semi-volatiles (Zn, Pb, Ag, As, and Cd), and volatiles (Hg and S) and compared their behaviors in two types of full-scale sewage sludge mono-incinerators, namely, a step-grate stoker (GS) and two fluidized bed incinerators (F-types), with the same feed sludge. Most of the non-volatile elements were enriched five-fold in all incinerated sewage sludge ash (ISSA), while the volatile S and Hg were barely enriched in ash due to the combustion components generated in the gas phase. While the semi-volatile elements were also enriched five-fold in the F-types, a different enrichment behavior was observed in the GS. Boiler and multi-cyclone dust in the GS showed higher enrichments of Pb and Cd compared to ash due to the combined effects of lower temperature and smaller particle size. Compared to the F-types, the GS generated ashes with lower toxicity as the major component (99.7%) and hazardous dust as the minor component. In the future, more attention should be paid to grate stokers in terms of recycling ISSA.

Study on simultaneous recycling of EAF dust and plastic waste containing TBBPA.

In the present work we investigated the fates of zinc, lead, and iron present in electric arc furnace dust during thermal treatment of the dust with tetrabromobisphenol A (TBBPA) and tetrabromobisphenol A diglycidyl ether (TBBPADGE). Mixtures of these materials were compressed into pellets and heated in a laboratory-scale furnace at 550 °C for 80 min, under oxidizing and inert conditions. The solid, condensed, and gaseous-phase products were characterized using an array of analytical methods: scanning electron microscopy, X-ray diffraction, electron probe microscopy, inductively coupled plasma, ion chromatography, and gas chromatography. The results indicated that heating the mixtures under specific conditions enabled high separation of zinc and lead from iron-rich residues, by a bromination-evaporation process. In the case of TBBPADGE, a maximum of 85% of zinc and 81% of lead were effectively separated under the above conditions. The process is based on the reaction between the highly reactive HBr gas evolved during thermal degradation of the flame-retarded materials with zinc (ZnO and ZnFe2O4) and lead in the dust, followed by complete evaporation of the formed metallic bromides from the solid residue.

Fate of lead oxide during thermal treatment with tetrabromobisphenol A.

In this paper, the bromination reaction between lead oxide and hydrogen bromide originating from the thermal decomposition of tetrabromobisphenol A (TBBPA), under inert and oxidizing atmospheres, was investigated, using a laboratory-scale furnace. The results obtained under inert conditions indicated that bromination of PbO proceeded simultaneously with debromination of TBBPA, with an average effectiveness of 69% (max. 80%). Volatilization of the formed PbBr2 began at 315°C, intensified at 750°C, and reached 98% at 850°C. The formed organic char served as a source of carbon for reduction of the unreacted lead oxide to metallic lead in the range 315-750°C. Additional experiments conducted at selected temperatures under slightly oxidizing (5 vol% O2) and quasi-atmospheric (20 vol% O2) conditions showed no significant effects on bromination-evaporation of lead in the studied mixture. However, in isothermal treatment under quasi-atmospheric oxygen levels, complete vaporization of the formed lead bromide was obtained at a temperature of only 650°C.

Distribution of copper, silver and gold during thermal treatment with brominated flame retardants.

The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition. In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000°C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.