Precipitated CaCO(3) compounds recovered from pulped waste gypsum using some carbonate and hydroxide-based reagents were evaluated for their utilization in acid mine drainage (AMD) neutralization. The neutralization potentials, acid neutralization capacities and compositions of the CaCO(3) compounds were determined and compared with some commercial CaCO(3). It was observed that CaCO(3) recovered from waste gypsum using Na(2)CO(3) significantly neutralized AMD compared with commercial CaCO(3) and that recovered using both (NH(4))(2)CO(3) or NH(4)OH-CO(2) reagents. Moreover, a higher acid neutralization capacity of 1,370 kg H(2)SO(4)/t was determined for CaCO(3) recovered from waste gypsum using Na(2)CO(3) compared with an average of 721 and 1,081 kg H(2)SO(4)/t for ammonium-based CaCO(3) and commercial CaCO(3) respectively. The inorganic carbon content for the CaCO(3) recovered using Na(2)CO(3) and ammonium-based reagents of 49 and 34% respectively confirmed their observed neutralization potentials and acid neutralization capacities, while energy dispersive X-ray fluorescence suggested absence of major oxide impurities, with the exception of residual SO(4)(2-) and Na(2)O which still requires further reduction in the respective compounds.
The dissolution characteristics of CaS in the presence of CO2 has been investigated by monitoring sulfide speciation, solution conductivity and pH during dissolution. The sulfide speciation associated with CaS dissolution was utilized for metal precipitation from acidic wastewater effluents. The mechanism involved in the dissolution process was observed to be pH-dependent, characterized by increased solution conductivity as the HS(-) species becomes dominant in solution in the form of the Ca(HS)2 complex. The replacement of HS(-) by CO3(2-) in the Ca(HS)2 complex triggered CaCO3 precipitation and H2S stripping and this was characterized by decreased solution pH and conductivity. The sulfide to total metal molar ratio was observed to have an effect on the pH and therefore sulfide speciation as well as extent of metal removal. The utilization of CaS in the treatment of acidic wastewater effluents demonstrated complete metal removal, with the potential of a pH-controlled selective metal removal and recovery.
This study investigated the implications of using two grades of limestone from a paper and pulp industry for neutralization of acid mine drainage (AMD) in a pilot sequencing batch reactor (SBR). In this regard, two grades of calcium carbonate were used to neutralize AMD in a SBR with a hydraulic retention time (including settling) of 100 min and a sludge retention time of 360 min, by simultaneously monitoring the Fe(II) removal kinetics and overall assessment of the AMD after treatment. The Fe(II) kinetics removal and overall AMD treatment were observed to be highly dependent on the limestone grade used, with Fe(II) completely removed to levels lower than 50 mg/L in cycle 1 after 30 min using high quality or pure paper and pulp limestone. On the contrary, the other grade limestone, namely waste limestone, could only achieve a similar Fe(II) removal efficiency after four cycles. It was also noticed that suspended solids concentration plays a significant role in Fe(II) removal kinetics. In this regard, using pure limestone from the paper and pulp industry will have advantages compared with waste limestone for AMD neutralization. It has significant process impacts for the SBR configuration as it allows one cycle treatment resulting in a significant reduction of the feed stock, with subsequent generation of less sludge during AMD neutralization. However, the use of waste calcium carbonate from the paper and pulp industry as a feed stock during AMD neutralization can achieve significant cost savings as it is cheaper than the pure limestone and can achieve the same removal efficiency after four cycles.
This study investigated Fe(II) oxidation during acid mine drainage (AMD) neutralization using CaCO3 in a pilot-scale Sequencing Batch Reactor (SBR) of hydraulic retention time (HRT) of 90 min and sludge retention time (SRT) of 360 min in the presence of air. The removal kinetics of Fe(II), of initial concentration 1,033 ± 0 mg/L, from AMD through oxidation to Fe(III) was observed to depend on both pH and suspended solids, resulting in Fe(II) levels of 679 ± 32, 242 ± 64, 46 ± 16 and 28 ± 0 mg/L recorded after cycles 1, 2, 3 and 4 respectively, with complete Fe(II) oxidation only achieved after complete neutralization of AMD. Generally, it takes 30 min to completely oxidize Fe(II) during cycle 4, suggesting that further optimization of SBR operation based on both pH and suspended solids manipulation can result in significant reduction of the number of cycles required to achieve acceptable Fe(II) oxidation for removal as ferric hydroxide. Overall, complete removal of Fe(II) during AMD neutralization is attractive as it promotes recovery of better quality waste gypsum, key to downstream gypsum beneficiation for recovery of valuables, thereby enabling some treatment-cost recovery and prevention of environmental pollution from dumping of sludge into landfills.
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