• Journal of the Mineralogical Society of Korea
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• v.27 no.1
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• pp.17-30
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• 2014

Waste cement generated from recycling processes of waste concrete is a potential raw material for mineral carbonation. For the $CO_2$ sequestration utilizing waste cement, this study was conducted to obtain basic information on the aqueous carbonation methods and the characteristics of carbonate mineral formation. Cement paste was made with W:C= 6:4 and stored for 28 days in water bath. Leaching tests using two additives (NaCl and $MgCl_2$) and two aqueous carbonation experiments (direct and indirect aqueous carbonation) were conducted. The maximum leaching of $Ca^{2+}$ ion was occurred at 1.0 M NaCl and 0.5 M $MgCl_2$ solution rather than higher tested concentration. The concentration of extracted $Ca^{2+}$ ion in $MgCl_2$ solution was more than 10 times greater than in NaCl solution. Portlandite ($Ca(OH)_2$) was completely changed to carbonate minerals in the fine cement paste (< 0.15 mm) within one hour and the carbonation of CSH (calcium silicate hydrate) was also progressed by direct aqueous carbonation method. The both additives, however, were not highly effective in direct aqueous carbonation method. 100% pure calcite minerals were formed by indirect carbonation method with NaCl and $MgCl_2$ additives. pH control using alkaline solution was important for the carbonation in the leaching solution produced from $MgCl_2$ additive and carbonation rate was slow due to the effect of $Mg^{2+}$ ions in solution. The type and crystallinity of calcium carbonate mineral were affected by aqueous carbonation method and additive type.

• Clean Technology
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• v.30 no.2
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• pp.113-122
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• 2024

In order to better understand carbon dioxide recycling, the carbon dioxide capture characteristics of six different alkaline industrial by-products, including incineration ash, desulfurized gypsum, low-grade quicklime, and steelmaking slag were investigated using a laboratory-scale direct aqueous carbonation reactor. In addition to the dissolution characteristics of each sample, the main reaction structure was confirmed through thermogravimetric analysis before and after the reaction, and the reactive CaO content was also defined through thermogravimetric analysis. The carbon dioxide capture capacity and efficiency of quicklime were determined to be 473 g/kg and 86.9%, respectively, and desulfurized gypsum and incineration ash were also evaluated to be relatively high at 51.1 to 131.7 g/kg and 51.2 to 87.7%, respectively. On the other hand, the capture efficiency of steelmaking slag was found to be less than 10% due to the influence of the production and post-cooling conditions. Therefore, in order to apply the carbonation process to steelmaking slag, it is necessary to optimize the slag production conditions. Through this study, it was confirmed that the carbon dioxide capture characteristics of incineration ash, quicklime, and desulfurized gypsum are at levels suitable for carbonation processes. Furthermore, this study was able to secure basic data for resource development technology that utilize carbon dioxide conversion to produce calcium carbonate for construction materials.

• Economic and Environmental Geology
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• v.50 no.1
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• pp.27-34
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• 2017

Mineral carbonation for the storage of carbon dioxide is a CCS option that provides an alternative for the more widely advocated method of geological storage in underground formation. Carbonation of magnesium- or calcium-based minerals, especially the carbonation of waste materials and industrial by-products is expanding, even though total amounts of the industrial waste are too small to substantially reduce the $CO_2$ emissions. The mineral carbonation was performed with steelmaking reduction slag as starting material. The steelmaking reduction slag dissolution experiments were conducted in the $H_2SO_4$ and $NH_4NO_3$ solution with concentration range of 0.3 to 1 M at $100^{\circ}C$ and $150^{\circ}C$. The hydrothermal treatment was performed to the starting material via a modified direct aqueous carbonation process at the same leaching temperature. The initial pH of the solution was adjusted to 12 and $CO_2$ partial pressure was 1MPa for the carbonation. The carbonation rate after extracting $Ca^^{2+}$ under $NH_4NO_3$ was higher than that under $H_2SO_4$ and the carbonation rates in 1M $NH_4NO_3$ solution at $150^{\circ}C$ was dramatically enhanced about 93%. In this condition well-faceted rhombohedral calcite, and rod or flower-shaped aragonite were appeared together in products. As the concentration of $H_2SO_4$ increased, the formation of gypsum was predominant and the carbonation rate decreased sharply. Therefore it is considered that the selection of the leaching solution which does not affect the starting material is important in the carbonation reaction.

• Journal of the Mineralogical Society of Korea
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• v.28 no.1
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• pp.39-49
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• 2015

Recently, carbon capture and storage (CCS) techniques have been globally studied. This study was conducted to use waste cement powder as an efficient raw material of mineral carbonation for $CO_2$ sequestration. Direct aqueous carbonation experiment was conducted with injecting pure $CO_2$ gas (99.9%) to a reactor containing $200m{\ell}$ reacting solution and the pulverized cement paste (W:C = 6:4) having particle size less than 0.15 mm. The effects of two additives (NaCl, $MgCl_2$) in carbonation were analyzed. The characteristics of carbonate minerals and carbonation process according to the type of additives and pH change were carefully evaluated. pH of reacting solution was gradually decreased with injecting $CO_2$ gas. $Ca^{2+}$ ion concentration in $MgCl_2$ containing solution was continuously decreased. In none $MgCl_2$ solution, however, $Ca^{2+}$ ion concentration was increased again as pH decreased. This is probably due to the dissolution of newly formed carbonate mineral in low pH solution. XRD analysis indicates that calcite is dominant carbonate mineral in none $MgCl_2$ solution whereas aragonite is dominant in $MgCl_2$ containing solution. Unstable vaterite formed in early stage of experiment was transformed to well crystallized calcite with decreasing pH in the absence of $MgCl_2$ additives. In the presence of $MgCl_2$ additives, the content of aragonite was increased with decreasing pH whereas the content of calite was decreased.

• Economic and Environmental Geology
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• v.53 no.1
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• pp.1-9
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• 2020

Magnesium silicate minerals such as serpentine [Mg₃Si₂O₅(OH)₄] have a high potential for the sequestration of CO₂; thus, their reactivity toward dissolution under CO₂-free and CO₂-containing conditions in acidic solvents is a critical process with respect to their carbonation reactions. To examine the carbonation efficiency and dissolution mechanism of serpentine, hydrothermal treatment was performed to the starting material via a modified direct aqueous carbonation process at 100 and 150℃. The serpentine dissolution experiments were conducted in H₂SO₄ solution with concentration range of 0.3-1 M and at a CO₂ partial pressure of 3 MPa. The initial pH of the solution was adjusted to 13 for the carbonation process. Under CO₂-free and CO₂-containing conditions, the carbonation efficiency increased in proportion to the concentration of H₂SO₄ and the reaction temperature. The leaching rate under CO₂-containing conditions was higher than that under CO₂-free conditions. This suggests that shows the presence of CO₂ affects the carbonation reaction. The leaching and carbonation efficiencies at 150℃ in 1 M H₂SO₄ solution under CO₂-containing conditions were 85 and 84%, respectively. The dissolution rate of Mg was higher than that of Si, such that the Mg : Si ratio of the reacted serpentine decreased from the inner part (approximately 1.5) to the outer part (less than 0.1). The resultant silica-rich layer of the reaction product ultimately changed through the Mg-depleted skeletal phase and the pseudo-serpentine phase to the amorphous silica phase. A passivating silica layer was not observed on the outer surface of the reacted serpentine.

• Economic and Environmental Geology
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• v.55 no.4
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• pp.377-388
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• 2022

Laboratory-scale experiments were performed to identify the As removal mechanism of the residual slag generated after the mineral carbonation process. The residual slags were manufactured from the steelmaking slag (blast oxygen furnace slag: BOF) through direct and indirect carbonation process. RDBOF (residual BOF after the direct carbonation) and RIBOF (residual BOF after the indirect carbonation) showed different physicochemical-structural characteristics compared with raw BOF such as chemical-mineralogical properties, the pH level of leachate and forming micropores on the surface of the slag. In batch experiment, 0.1 g of residual slag was added to 10 mL of As-solution (initial concentration: 203.6 mg/L) titrated at various pH levels. The RDBOF showed 99.3% of As removal efficiency at initial pH 1, while it sharply decreased with the increase of initial pH. As the initial pH of solution decreased, the dissolution of carbonate minerals covering the surface was accelerated, increasing the exposed area of Fe-oxide and promoting the adsorption of As-oxyanions on the RDBOF surface. Whereas, the As removal efficiency of RIBOF increased with the increase of initial pH levels, and it reached up to 70% at initial pH 10. Considering the PZC (point of zero charge) of the RIBOF (pH 4.5), it was hardly expected that the electrical adsorption of As-oxyanion on surface of the RIBOF at initial pH of 4-10. Nevertheless it was observed that As-oxyanion was linked to the Fe-oxide on the RIBOF surface by the cation bridge effect of divalent cations such as Ca²⁺, Mn²⁺, and Fe²⁺. The surface of RIBOF became stronger negatively charged, the cation bridge effect was more strictly enforced, and more As can be fixed on the RIBOF surface. However, the Ca-products start to precipitate on the surface at pH 10-11 or higher and they even prevent the surface adsorption of As-oxyanion by Fe-oxide. The TCLP test was performed to evaluate the stability of As fixed on the surface of the residual slag after the batch experiment. Results supported that RDBOF and RIBOF firmly fixed As over the wide pH levels, by considering their As desorption rate of less than 2%. From the results of this study, it was proved that both residual slags can be used as an eco-friendly and low-cost As remover with high As removal efficiency and high stability and they also overcome the pH increase in solution, which is the disadvantage of existing steelmaking slag as an As remover.