Constantino Fernández-Pereira

Coal fly ash-slag-based geopolymers: microstructure and metal leaching.

This study deals with the use of fly ash as a starting material for geopolymeric matrices. The leachable concentrations of geopolymers were compared with those of the starting fly ash to evaluate the retention of potentially harmful elements within the geopolymer matrix. Geopolymer matrices give rise to a leaching scenario characterised by a highly alkaline environment, which inhibits the leaching of heavy metals but may enhance the mobilization of certain oxyanionic species. Thus, fly ash-based geopolymers were found to immobilize a number of trace pollutants such as Be, Bi, Cd, Co, Cr, Cu, Nb, Ni, Pb, Sn, Th, U, Y, Zr and rare earth elements. However, the leachable levels of elements occurring in their oxyanionic form such as As, B, Mo, Se, V and W were increased after geopolymerization. This suggests that an optimal dosage, synthesis and curing conditions are essential in order to obtain a long-term stable final product that ensures an efficient physical encapsulation.

A study of the leachate toxicity of metal-containing solid wastes using Daphnia magna.

This paper examines the ecotoxicity of different actual inorganic wastes containing some potentially toxic metals commonly found in many industrial residues and the reduction in ecotoxicity obtained when the wastes are submitted to a solidification/stabilization process. The ecotoxicity was assessed as defined in the Spanish regulations on hazardous wastes, by means of the Daphnia magna Straus acute toxicity test applied to the toxicity characteristic leaching procedure (TCLP) waste leachate. On the basis of the EC50 values of the individual metals and the effect of the pH of the aqueous medium on D. magna, we have explored a method for estimating the toxicity of the TCLP waste leachate by calculating its EC50 value in the D. magna test. Although the method is only valid in cases in which a clear cause for the toxicity exists, the procedure described allows us to more completely explain the observed effects on the daphnids. The ecotoxicity of the residues after stabilization is less than that of the untreated waste, generally as a consequence of the reduction in metal leachability achieved by the immobilization treatment. The stabilization process was analyzed in terms of both the chemical and the ecotoxicological parameters, and the influence of leachate pH on the objectives of waste treatment is discussed.

Use of FGD gypsum in fire resistant panels

Gypsum from power plant flue gas desulphurization units (FGD gypsum) is a combustion by-product produced in high quantities. In this paper, gypsum panels composed of 100% FGD gypsum from two power plants have been subjected to different physico-chemical (density, pH, humidity), mechanical (flexural and compressive strength, surface hardness, impact resistance), fire resistance and environmental tests (leaching and radioactivity). The results obtained have been compared with the requirements established in some European standards for commercial gypsum and other standards for similar products. In addition, the panels manufactured have been compared with commercial gypsum panels in order to determine the recycling possibilities of this kind of material in this application.

Recycling potential of coal fly ash and titanium waste as new fireproof products

This paper studies the possibilities for joint recycling of fly ash (FA) from the combustion of coal in power plants and the waste of the first attack on ilmenite in the production of titanium dioxide (RTi). Studies have been made of the insulating properties of plates composed mainly of FA, together with RTi waste, subjecting them to thermal exposure using standardized fire-resistance tests, with a view to potential use as insulating and fireproof components of fire-resistant items such as fireproof doors and firewalls. Other physical and chemical properties of these products have also been determined in order to characterize their mechanical properties. In addition, given the nature of the raw materials used in the manufacture of the product, an environmental study has been carried out to assess their environmental impact and to compile an ecotoxicological report on the material prepared.

Germanium recovery from gasification fly ash: evaluation of end-products obtained by precipitation methods.

In this study the purity of the germanium end-products obtained by two different precipitation methods carried out on germanium-bearing solutions was evaluated as a last step of a hydrometallurgy process for the recovery of this valuable element from the Puertollano Integrated Gasification Combined Cycle (IGCC) fly ash. Since H(2)S is produced as a by-product in the gas cleaning system of the Puertollano IGCC plant, precipitation of germanium as GeS(2) was tested by sulfiding the Ge-bearing solutions. The technological and hazardous issues that surround H(2)S handling conducted to investigate a novel precipitation procedure: precipitation as an organic complex by adding 1,2-dihydroxy benzene pyrocatechol (CAT) and cetyltrimethylammonium bromide (CTAB) to the Ge-bearing solutions. Relatively high purity Ge end-products (90 and 93% hexagonal-GeO(2) purity, respectively) were obtained by precipitating Ge from enriched solutions, as GeS(2) sulfiding the solutions with H(2)S, or as organic complex with CAT/CTAB mixtures and subsequent roasting of the precipitates. Both methods showed high efficiency (>99%) to precipitate selectively Ge using a single precipitation stage from germanium-bearing solutions.

Ammonium Ion Adsorption and Settleability Improvement Achieved in a Synthetic Zeolite-Amended Activated Sludge

Abstract Municipal wastewater treatment plants typically exhibit two classic problems: high ammonium concentration in water after conventional biological treatment and, in some cases, poor activated sludge sediment ability. Potential solutions to these problems were investigated by adding a synthetic zeolite obtained from coal fly ash to different steps of activated sludge treatment. The experimental results for ammonium removal fit well with the theoretical adsorption isotherms of the Freundlich model with a maximum adsorption capacity of 13.72 mg·g −1 . Utilization of this kind of zeolite to improve activated sludge sediment ability is studied for the first time in this work. It is found that the addition of the zeolite (1 g·L −1 ) to an activated sludge with settling problems significantly enhances its sediment ability and compact ability. This is confirmed by the sludge volume index (SVI), which was reduced from 163 ml·g −1 to 70 ml·g −1 , the V 60 value, which was reduced from 894 ml·L −1 to 427 ml·L −1 , and the zeta potential (ζ), which was reduced from −19.81 mV to −14.29 mV. The results indicate that the addition of this synthetic zeolite to activated sludge, as an additional waste management practice, has a positive impact on both ammonium removal and sludge settleability.

Solar photocatalytic treatment of landfill leachate using a solid mineral by-product as a catalyst

The treatment of municipal solid waste landfill leachate in a pilot plant made up of solar compound parabolic collectors, using a solid industrial titanium by-product (WTiO(2)) containing TiO(2) and Fe(III) as a photocatalyst, was investigated. In the study evidence was found showing that the degradation performed with WTiO(2) was mainly due to the Fe provided by this by-product, instead of TiO(2). However, although TiO(2) had very little effect by itself, a synergistic effect was observed between Fe and TiO(2). The application of WTiO(2), which produced coupled photo-Fenton and heterogeneous catalysis reactions, achieved a surprisingly high depuration level (86% of COD removal), higher than that reached by photo-Fenton using commercial FeSO(4) (43%) in the same conditions. After the oxidation process the biodegradability and toxicity of the landfill leachate were studied. The results showed that the leachate biodegradability was substantially increased, at least in the first stages of the process, and again that WTiO(2) was more efficient than FeSO(4) in terms of increasing biodegradability.

Precipitation of Germanium from Coal Fly Ash Leachates

The valorization of a coal gasification fly ash was studied by leaching the fly ash using different aqueous solutions followed by the subsequent precipitation of the germanium solubilized from the ash. Experimental investigations were focused on the precipitation of a germanium-catechol (CAT) complex with cetyl trimethyl ammonium bromide (CTAB). The influences of pH and amounts of CTAB and CAT on the precipitation yield were investigated. To this aim, a central composite rotatable design and ANOVA Design Expert 7.0.3 Wiley software were employed for experimental design and analysis of the results. Thus, the independent and combined effects of pH, CAT/Ge and CTAB/Ge molar ratios were investigated and optimized using a quadratic mathematical model. The optimum values of these factors were found to be 10, 12, and 4, respectively (in this case, the germanium precipitation yield was 98.8% for water leachates). The precipitation of germanium as a complex compound with CAT and CTAB was found to be selective towards germanium and this element can be effectively separated from As, Mo, Sb, V, or Zn. Total organic carbon in solution was measured to estimate the amounts of CAT and CTAB precipitated with germanium and with the interferences present in aqueous leachates. In addition, thermogravimetric analyses have been performed on the germanium-complex solids as a result of which 600°C was determined as the minimum temperature to completely remove the organic content of the precipitate.

Valorisation of a by-product from the TiO2 pigment industry for its application in advanced oxidation processes

AbstractThe aim of this study was to find a recycling use for waste material (WTiO2) that results from the extraction process of TiO2 from ilmenite in the pigment industry. In view of its high TiO2 content, the photocatalytic activity of this material was tested in the degradation of humic and fulvic acid substances (HFAs) and showed low levels of photoactivity, as was the case for the commercial photocatalyst Aeroxide TiO2 P25 (P25). However, due to its high Fe3+ content, an important application was observed for WTiO2 as an HFA coagulant and catalyst in Fenton and photo-Fenton processes. A two-stage process of coagulation and photo-Fenton treatment was subsequently designed and conducted at laboratory and small pilot scale. High percentages (above 95%) were obtained in total organic carbon (TOC) removal.