Pilar Coca

Differential behaviour of combustion and gasification fly ash from Puertollano Power Plants (Spain) for the synthesis of zeolites and silica extraction

Coal gasification (IGCC) and pulverised coal combustion (PCC) fly ashes (FAs), obtained from two power plants fed with the carboniferous bituminous coal from Puertollano (Spain), were characterised and used as raw materials for zeolite synthesis by direct conversion (DC) and by alkaline fusion (Fu), and SiO2 extraction (Si-Ex) at laboratory scale. The Puertollano FAs are characterised by a high SiO2 content (59%) with respect to EU coal FAs. High zeolite synthesis yields were obtained from both FAs by using conventional alkaline activation. However, the Si extraction yields were very different. The results of the zeolite synthesis from the Si-bearing extracts from both FAs demonstrated that high purity zeolites with high cation exchange capacity (CEC, between 4.3 and 5.3meq/g) can be produced. The solid residue arising from Si-Ex is also a relatively high NaP1 zeolite product (CEC 2.4-2.7 meq/g) equivalent to the DC products. The zeolitic materials synthesised from both FAs by Fu showed an intermediate (between the high purity zeolites and the DC products) zeolite content with CEC values from 3.4 to 3.7 meq/g. Low leachable metal contents were obtained from high purity A and X zeolites and zeolite material synthesised by Fu for PCC FA.

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.

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.