David Key

Treatment of Acid Mine Drainage with Fly Ash: Removal of Major Contaminants and Trace Elements

Acid mine drainage (AMD) has been reacted with two South African fly ashes in a batch setup in an attempt to evaluate their neutralization and major, trace elements removal capacity. Different fly ash: acid mine drainage ratios (FA: AMD) were stirred in a beaker for a set time and the process water analyzed for major, trace elements and sulphate content. The three factors that finally dictated the nature of the final solution in these neutralization reactions were the FA: AMD ratio, the contact time of the reaction and the chemistry of the AMD. Efficiency of the elements removal was directly linked to the amount of FA in the reaction mixture and to the final pH attained. Most elements attained ≈100% removal only when the pH of minimum solubility of their hydroxides was achieved (i.e., Mg = 10.49–11.0, Cu2+ = 6, Pb2+ = 6–7). Dissolution of CaO and subsequent precipitation of gypsum and formation of Al, Fe oxyhydroxysulphates, Fe oxyhydroxides with subsequent adsorption of sulphate contributed to the sulphate attenuation. Significant leaching of B, Sr, Ba and Mo was observed as the reaction progressed and was observed to increase with quantity of fly ash in the reaction mixture. However B was observed to decrease at high FA: AMD ratios probably as result of co-precipitation with CaCO3(s).

The use of X-ray fluorescence (XRF) analysis in predicting the alkaline hydrothermal conversion of fly ash precipitates into zeolites.

The use and application of synthetic zeolites for ion exchange, adsorption and catalysis has shown enormous potential in industry. In this study, X-ray fluorescence (XRF) analysis was used to determine Si and Al in fly ash (FA) precipitates. The Si and Al contents of the fly ash precipitates were used as indices for the alkaline hydrothermal conversion of the fly ash compounds into zeolites. Precipitates were collected by using a co-disposal reaction wherein fly ash is reacted with acid mine drainage (AMD). These co-disposal precipitates were then analysed by XRF spectrometry for quantitative determination of SiO(2) and Al(2)O(3). The [SiO(2)]/[Al(2)O(3)] ratio obtained in the precipitates range from 1.4 to 2.5. The [SiO(2)]/[Al(2)O(3)] ratio was used to predict whether the fly ash precipitates could successfully be converted to faujasite zeolitic material by the synthetic method of [J. Haz. Mat. B 77 (2000) 123]. If the [SiO(2)]/[Al(2)O(3)] ratio is higher than 1.5 in the fly ash precipitates, it favours the formation of faujasite. The zeolite synthesis included an alkaline hydrothermal conversion of the co-disposal precipitates, followed by aging for 8h and crystallization at 100 degrees C. Different factors were investigated during the synthesis of zeolite to ascertain their influence on the end product. The factors included the amount of water in the starting material, composition of fly ash related starting material and the FA:NaOH ratio used for fusing the starting material. The mineralogical and physical analysis of the zeolitic material produced was performed by X-ray diffraction (XRD) and nitrogen Brunauer-Emmett-Teller (N(2) BET) surface analysis. Scanning electron microscopy (SEM) was used to determine the morphology of the zeolites, while inductively coupled mass spectrometry (ICP-MS), Fourier transformed infrared spectrometry (FT-IR) and Cation exchange capacity (CEC) [Report to Water Research Commission, RSA (2003) 15] techniques were used for chemical characterisation. The heavy and trace metal concentrations of the zeolite products were compared to that of the post-synthesis filtrate and of the precipitate materials used as Si and Al feed stock for zeolite formation, in order to determine the trends (increase or decrease) and ultimate fate of any toxic metals incorporated in the co-disposed precipitated residues.

Partitioning of major and trace inorganic contaminants in fly ash acid mine drainage derived solid residues

Acid mine drainage was reacted with coal fly ash over a 24 h reaction time and species removal trends evaluated. The evolving process water chemistry was modeled by the geochemical code PHREEQC using WATEQ4 database. Mineralogical analysis of the resulting solid residues was done by X-ray diffraction analysis. Selective sequential extraction was used to evaluate the transfer of species from both acid mine drainage and fly ash to less labile mineral phases that precipitated out. The quantity of fly ash, volume of acid mine drainage in the reaction mixture and reaction time dictated whether the final solution at a given contact time will have a dominant acidic or basic character. Inorganic species removal was dependent on the pH regime generated at a specific reaction time. Sulphate concentration was controlled by precipitation of gypsum, barite, celestite and adsorption on iron-oxy-hydroxides at pH > 5.5. Increase of pH in solution with contact time caused the removal of the metal ions mainly by precipitation, co-precipitation and adsorption. PHREEQC predicted precipitation of iron, aluminium, manganese-bearing phases at pH 5.53–9.12. An amorphous fraction was observed to be the most important in retention of the major and minor species at pH > 6.32. The carbonate fraction was observed to be an important retention pathway at pH 4–5 mainly due to initial local pockets of high alkalinity on surfaces of fly ash particles. Boron was observed to have a strong retention in the carbonate fraction.

Inorganic contaminants attenuation in acid mine drainage by fly ash and its derivatives: column experiments

Treatment of AMD with fly ash (FA) is a promising technology but solid residues (SR) generated in the process pose a disposal challenge. This study evaluates the suitability of the SR and SR, FA/ordinary Portland cement (OPC) blends for backfill in mine voids and in-situ treatment of AMD flows. The mitigation of AMD in a mine void was simulated by addition of simulated acid mine drainage (SAMD) to FA, SR, SR + 25 % FA and SR + 6 % OPC packed columns. Acidity neutralisation in AMD was achieved over the study period. PHREEQC modelling indicated that precipitation of contaminants bearing mineral phases contributed to low levels of contaminants. Leaching of toxic trace elements and attenuation of contaminants strongly depended on the pH regime. Results revealed that backfill of coal mine voids with SR is a promising approach for large scale disposal of SR and treatment of AMD flows insitu.

Interaction of acid mine drainage with Ordinary Portland Cement blended solid residues generated from active treatment of acid mine drainage with coal fly ash

Fly ash (FA) has been investigated as a possible treatment agent for Acid mine drainage (AMD) and established to be an alternative, cheap and economically viable agent compared to the conventional alkaline agents. However, this treatment option also leads to generation of solid residues (SR) that require disposal and one of the proposed disposal method is a backfill in coal mine voids. In this study, the interaction of the SR with AMD that is likely to be present in such backfill scenario was simulated by draining columns packed with SR and SR + 6% Ordinary Portland Cement (OPC) unsaturated with simulated AMD over a 6 month period. The evolving geochemistry of the liquid/solid (L/S) system was evaluated in-terms of the mineral phases likely or controlling contaminants attenuation at the different pH regimes generated. Stepwise acidification of the percolates was observed as the drainage progressed. Two pH buffer zones were observed (7.5–9 and 3–4) for SR and (11.2–11.3 and 3.5–4) for SR + 6% OPC. The solid residue cores (SR) appeared to have a significant buffering capacity, maintaining a neutral to slightly alkaline pH in the leachates for an extended period of time (97 days: L/S 4.3) while SR + 6% OPC reduced this neutralization capacity to 22 days (L/S 1.9). Interaction of AMD with SR or SR + 6% OPC generated alkaline conditions that favored precipitation of Fe, Al, Mn-(oxy) hydroxides, Fe and Ca-Al hydroxysulphates that greatly contributed to the contaminants removal. However, precipitation of these phases was restricted to the pH of the leachates remaining at neutral to circum-neutral levels. Backfill of mine voids with SR promises to be a feasible technology for the disposal of the SR but its success will greatly depend on the disposal scenario, AMD generated and the alkalinity generating potential of the SR. A disadvantage would be the possible re-dissolution of the precipitated phases at pH < 4 that would release the contaminants back to the water column. However extrapolation of this concept to a field scenario can greatly enhance beneficial application of fly ash (FA) and solid residues (SR) generated from treatment of AMD.