Removal of oxyanions from synthetic wastewater via carbonation process of calcium hydroxide: Applied and fundamental aspects

Abstract

Removal of oxyanions (selenite, selenate, arsenate, phosphate and nitrate) during calcite formation was experimentally studied using aqueous carbonation of calcium hydroxide under moderate pressure (P CO2 ≅ 20 bar) and temperature (30 °C). The effects of Ca(OH) 2 dose (10 and 20 g), Ca(OH) 2 source (commercial pure material or alkaline paper mill waste) and oxyanion initial concentration (from 0 to 70 mg atom/L) were investigated for this anisobaric gas–liquid–solid system. The Ca(OH) 2 carbonation reaction allowed successfully the removal of selenite (>90%), arsenate (>78%) and phosphate (≅100%) from synthetic solutions. Conversely, nitrate and selenate had not any physicochemical affinity/effect during calcite formation. The rate of CO 2 transfer during calcite formation in presence of oxyanions was equal or slower than for an oxyanion-free system, allowing to define a retarding kinetic factor RF that can vary between 0 (no retarding effect) to 1 (total inhibition). For selenite and phosphate RF was quite high, close to 0.3. A small retarding effect was detected for arsenate ( RF ≈ 0.05) and no retarding effect was detected for selenate and nitrate ( RF ≈ 0). In general, RF depends on the oxyanion initial concentration, oxyanion nature and Ca(OH) 2 dose. The presence of oxyanions could also influence the crystal morphology and aggregation/agglomeration process. For example, a c-axis elongation of calcite crystals was clearly observed at the equilibrium, for calcite formation in presence of selenite and phosphate. The oxyanions removal process proposed herein was inspired on the common physicochemical treatment of wastewater using calcium hydroxide (Ca(OH) 2). The particularity, for this novel method is the simultaneous calcium hydroxide carbonation with compressed carbon dioxide in order to stabilise the solid matter. This economical and ecological method could allow the removal of various oxyanions as well as the ex situ mineral sequestration of CO 2; particularly, when the Ca(OH) 2 source comes from alkaline solid waste.