Modeling of the chemical behavior of sodium fire aerosols during atmospheric dispersion

The use of liquid sodium as a coolant in sodium-cooled fast reactors (SFR) circuits requires studying the consequences of a sodium fire for safety analysis, and particularly the toxicological impact of sodium fire aerosols. More particularly, the carbonation of sodium fire aerosols from sodium hydroxide (NaOH) to sodium carbonate (Na₂CO₃) is investigated. A new kinetic model, based on the CO₂ reactive absorption and the two-film theory, is developed to describe the carbonation process of NaOH solutions, taking into account the NaOH aerosols' initial characteristics in equilibrium with the atmosphere. This model is applied for the case of NaOH aerosols considering the CO₂ absorption at the particle external surface. The estimation for the model parameters is detailed as function of NaOH degree of conversion, relative humidity (RH), and temperature. By comparisons with available experimental data, the absorption interfacial area is empirically estimated over the studied range of RH and initial particle diameter. The global sensitivity study of the model confirms its capabilities to describe NaOH aerosols' carbonation, waiting for new experimental data for validation.

© 2016 American Association for Aerosol Research     

Influence of relative humidity on the carbonation of calcium hydroxide nanoparticles and the formation of calcium carbonate polymorphs

A consolidating product based on nanoparticles of slaked lime (Ca(OH)₂) dispersed in isopropyl alcohol was exposed under different relative humidities (RH), 33%, 54%, 75% and 90% during 7, 14, 21 and 28 days. The characterization of the calcium hydroxide nanoparticles and the formed calcium carbonate polymorphs have been performed by Micro Raman spectroscopy, Transmission Electron Microscopy (TEM), Environmental Scanning Electron Microscopy (ESEM) with Energy Dispersive X-ray Spectroscopy (EDS) and X-ray Diffraction (XRD). Precipitation and transformation of calcium carbonate polymorphs strongly depend on the relative humidity (RH). Higher RH (75%–90% RH) gives rise to amorphous calcium carbonate and monohydrocalcite, calcite, aragonite and vaterite, faster carbonation and larger particles sizes with higher crystallinity compared to lower RH (33%–54% RH) that gives rise mainly to portlandite and vaterite, slower carbonation and smaller particle sizes with lower crystallinity.     

Rapid Carbonation for Calcite from a Solid-Liquid-Gas System with an Imidazolium-Based Ionic Liquid

Aqueous carbonation of Ca(OH)₂ is a complex process that produces calcite with scalenohedral calcite phases and characterized by inadequate carbonate species for effective carbonation due to the poor dissolution of CO₂ in water. Consequently, we report a solid-liquid-gas carbonation system with an ionic liquid (IL), 1-butyl-3-methylimidazolium bromide, in view of enhancing the reaction of CO₂ with Ca(OH)₂. The use of the IL increased the solubility of CO₂ in the aqueous environment and enhanced the transport of the reactive species (Ca²⁺ and CO₃²⁻) and products. The presence of the IL also avoided the formation of the CaCO₃ protective and passivation layer and ensured high carbonation yields, as well as the production of stoichiometric rhombohedral calcite phases in a short time.     

Carbonation of geothermal grouts — Part 2: CO2 attack at 250°C

Exposure of cement grouts containing a range of added silica contents to CO₂ dissolved in water at 250°C has shown that the preferred binding phases xonotolite and truscottite are reasonably resistant to CO₂ attack. However, their carbonation products are permeable so that some carbonation occurs through the center of samples, reducing alkalinity and the ability to protect well casings. Specimens which contain less than 10% added silica form hydrates, which when carbonated, form an impervious layer of calcite which slows CO₂ penetration.Ultimately, all portland cement based grouts will carbonate and allow penetration of ions such as chloride. Corrosion will occur in fluids that are under-saturated with respect to calcium carbonate.     

Numerical modeling of supercritical carbonation process in cement-based materials

In this paper, a mathematical model is developed to simulate the physical–chemical coupling process of supercritical carbonation in cement-based materials. This model takes into account the rate of chemical reaction, mass conservation for gas–liquid two phase flow, diffusion and dispersion of CO₂ in water, energy conservation for porous medium and the solubility of CO₂ in water. Numerical results are obtained and compared with experimental results. The degree of carbonation, temperature, gaseous pressure, moisture content and saturation of water within the material are predicted and presented. The influence of material saturation, temperature and pressure of supercritical CO₂ on carbonation depth is investigated through parametric studies. The comparisons with test results suggest that the coupled model can be used to predict carbonation process of cement-based materials under supercritical conditions.     

Carbonation of calcium-containing mineral and industrial by-products

The use of carbon dioxide (CO₂) and calcium-containing by-products from industrial activities is receiving increasing interest as a route to valuable carbonate materials while reducing CO₂ emissions and saving natural resources. In this work, wet-chemical experimental data was assessed, which involved the carbonation of three types of materials in aqueous solutions, namely, 1) wollastonite, a calcium silicate mineral, 2) steelmaking slag, a by-product of steel production, and 3) paper bottom ash (PBA) from waste paper incineration. Aims were to achieve either a high carbonation degree and/or a pure carbonate product with potential commercial value. Producing a pure precipitated calcium carbonate (PCC) material that may find use in paper industry products puts strong requirements on purity and brightness. The parameters investigated were particle size, CO₂ pressure, temperature, solid/liquid ratio, and the use of additives that affect the solubilities of CO₂ and/or calcium carbonate. Temperatures and pressures were varied up to 180°C and 4 MPa. Data obtained with the wollastinite mineral allowed for a comparison between natural resources and the industrial by-product materials, the latter typically being more reactive. With respect to temperature and pressure trends reported by others were largely confirmed, with temperatures above 150°C introducing thermodynamic limitations depending on CO₂ pressure. The influence of additives showed some promise, although costs may make recycling and reuse of additives a necessity for a large-scale process. When using steelmaking slag, magnetic separation may remove some iron-containing material from the process (although this is far from perfect), while the addition of bicarbonate supported the removal of phosphorous, aside from improving calcium extraction. The experiments with paper bottom ash (PBA) gave new data, showing that its reactivity resembles that of steelmaking slag, while its composition results in relatively pure carbonate product. Also, with PBA no additives were needed to achieve this.     

Synthesis of nanosized calcium carbonate (aragonite) via a polyacrylamide inducing process

A carbonation route for the synthesis of nanosized calcium carbonate (aragonite) was studied. In the process, polyacrylamide was used as an organic substrate to induce the nucleation and growth of calcium carbonate. The calcium carbonate particles were produced by means of carbonation of the mixture of calcium hydroxide and polyacrylamide by bubbling CO₂/N₂ gas mixture_. The operating parameters such as the concentration of organic substrate and temperature were varied to study their influences on the polymorph and crystal sizes of calcium carbonate particles. The morphology of the calcium carbonate particles was characterized with transmission electron micrograph (TEM). The synthesized calcium carbonate particles in the presence of organic substrate are the mixture of aragonite with needle shape and calcite with cubic shape. Fourier transform infrared spectroscopy (FTIR) analysis reveals the presence of aragonite and calcite. The polymorphs and their crystal sizes were characterized with X-ray diffraction (XRD). The calcium carbonate nucleated in the organic substrate exhibited different endothermic peak in differential thermal gravity (DTG) results compared to one coexisting with the organic substrate.     

Synthesis and characterization of hydrophobic calcium carbonate particles via a dodecanoic acid inducing process

A carbonation route for the synthesis of hydrophobic calcium carbonate was studied. In the process, dodecanoic acid was used as an organic substrate to induce the nucleation and growth of calcium carbonate. The calcium carbonate particles were produced by means of carbonation of the mixture of calcium hydroxide and dodecanoic acid by bubbling CO₂/N₂ gas mixture. The operating parameters such as temperature and the concentration of the organic substrate were varied to study their influences on the active ratio and contact angle of calcium carbonate particles. The morphology of the calcium carbonate particles was characterized with scanning electron microscopy (SEM). The synthesized calcium carbonate particles in the presence of the organic substrate are rod-like and ellipse-like particles. The polymorphs were characterized with X-ray diffraction (XRD).     

Enhancing the carbonation of MgO cement porous blocks through improved curing conditions

The use of reactive magnesia (MgO) as the binder in porous blocks demonstrated significant advantages due to its low production temperatures and ability to carbonate, leading to significant strengths. This paper investigates the enhancement of the carbonation process through different curing conditions: water to cement ratio (0.6–0.9), CO₂ concentration (5–20%), curing duration (1–7 days), relative humidity (55–98%), and wet/dry cycling frequency (every 0–3 days), improving the carbonation potential through increased amounts of CO₂ absorbed and enhanced mechanical performance. UCS results were supported with SEM, XRD, and HCl acid digestion analyses. The results show that CO₂ concentrations as low as 5% can produce the required strengths after only 1 day. Drier mixes perform better in shorter curing durations, whereas larger w/c ratios are needed for continuous carbonation. Mixes subjected to 78% RH outperformed all the others, also highlighting the benefits of incorporating wet/dry cycling to induce carbonation.     

Chemical, microstructural and strength development of calcium and magnesium carbonate binders

The influence of magnesium on the chemistry of calcium carbonate formation has been studied. It was found that the type of carbonate formed by subjecting compacts of Ca(OH)₂ and Mg(OH)₂ to carbon dioxide (up to 20 atm CO₂ pressure) for variable periods of time is largely controlled by the molar proportion of calcium to magnesium in the initial mixture. Increasing magnesium content in the initial mixture favours the formation of nesquehonite and other carbonates containing both calcium and magnesium. The compressive strength of the carbonate is improved with the presence of nesquehonite and/or other magnesium-containing phases. Curing time and CO₂ exposure influence the strength differently, depending on the initial Ca/Mg ratio of the initial mixture. The formation of magnesium-containing carbonate phases is particularly favoured at higher CO₂ pressures combined with prolonged exposure times.     

Control of corrosive water in advanced water treatment plant by manipulating calcium carbonate precipitation potential

The corrosion of metal pipes in water distribution networks is a complex electrochemical and physicochemical phenomenon between a metal surface and corrosive water. The level of corrosion in water distribution systems was controlled by manipulating the calcium carbonate precipitation potential (CCPP) concentration, and the corrosive water quality was controlled in two steps within the advanced water treatment plant (AWTP) constructed at the Institute of Water Quality Research (IWQR), Busan Metropolitan City, Korea. The 1 ^st control step was located before a coagulation process included on a rapid mixer, and the 2 ^nd control step was located after a biological activated carbon (BAC) process. The capacity of the AWTP in IWQR was 80 m³/day. The CCPP concentration was controlled from the calcium hardness, alkalinity, and pH by adding calcium hydroxide (Ca(OH)₂), sodium carbonate (Na₂CO₃), and carbon dioxide (CO₂) in the above two steps. A CCPP control system was installed and operated according to the developed algorithm to maintain a CCPP range of 0–4 mg/L. The CCPP range was reasonably controlled to induce the formation of a CaCO₃ film on the surface of the simulated water distribution system (SWDS). From the result of the corrosive water control, the CCPP formed greater than 0.0 mg/L. The crystalloid structure of the scale produced by CCPP control in the inner surface of pipe was zinc carbonate hydroxide hydrate (Zn₄CO₃(OH)₆·H₂O).     

Permeability characteristics of carbonated concrete considering capillary pore structure

During carbonation process, the calcium phases present in cement are attacked by CO₂ and converted into CaCO₃ and the permeability of concrete is changing due to the change in porosity. The rate of carbonation depends upon porosity and moisture content of the concrete. Especially in underground reinforced concrete structures, the interior portion of concrete surface may be exposed to carbonation and the exterior portion of concrete surface exposed to wet soil or underground water. As carbonation proceeds from outer surface into internal portion of concrete, microstructure is also changed continuously from outer surface into internal portion of concrete. Even the deteriorations in the structures due to the carbonation have been reported more, research on permeability characteristics of concrete considering carbonation and micro-structural information is very scarce.In this study, the permeability coefficient in carbonated concrete is derived by applying a capillary pore structure formation model in carbonated cement mortar and assuming that aggregates do not affect carbonation process in early-aged concrete as a function of porosity. The permeability obtained from the micro-level modeling for carbonated concrete is verified with the results of accelerated carbonation test and water penetration test in cement mortar.     

Characterization of calcium oxide derived from waste eggshell and its application as CO2 sorbent

The carbonation-calcination looping cycle of calcium-based sorbents is considered as an attractive method for CO₂ capture from combustion gases because it can reduce the cost during the capture steps compared to conventional technologies, e.g., solvent scrubbing. In this study, waste eggshell was used as raw material for calcium oxide-based sorbent production. The commercially available calcium carbonate was employed for comparison purpose. Calcination behavior, crystal type and crystallinity, surface chemistry, qualitative and quantitative elemental information, specific surface area and pore size, morphology of the waste eggshell and the calcined waste eggshell were characterized by thermal gravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray fluorescence (XRF), N₂ sorption analysis and scanning electron microscopy (SEM), respectively. The carbonation-calcination cycles were carried out using a TGA unit with high purity CO₂ (99.999%). It was found that the carbonation conversion of the calcined eggshell was higher than that of the calcined commercially available calcium carbonate after several cycles at the same reaction conditions. This could be due to the fact that the calcined eggshell exhibited smaller particle size and appeared more macropore volume than the calcined commercially available calcium carbonate. As results, the calcined eggshell provided a higher exposed surface for the surface reaction of CO₂.     

A breakthrough technique for the preparation of high-yield precipitated calcium carbonate

Precipitated calcium carbonate (PCC) is conventionally produced through the gas-solid-liquid carbonation route, which consists on bubbling gaseous CO₂ through a concentrated calcium hydroxide (Ca(OH)₂) slurry. However, atmospheric carbonation processes are slow and have low carbonation efficiency. A novel technology based on the combination of supercritical carbon dioxide (scCO₂) and ultrasonic agitation is described here for the preparation of high-yield PCC. The combination of both techniques has demonstrated to produce outstanding improvement for the conversion of Ca(OH)₂ to the stable calcite polymorph of calcium carbonate (CaCO₃). These experiments were carried out at 313 K and 13 MPa using a high-pressure reactor immersed in an ultrasounds cleaner bath. The process kinetics and the characteristics of the precipitated particles using ultrasonic agitation were compared with those obtained under similar experimental conditions using mechanical stirring and non-agitated systems. The crystal characteristics of the samples obtained using the three different agitation techniques were characterized by X-ray diffraction and scanning electron microscopy.     

CO2 Capture Using CaO Modified with Ethanol/Water Solution during Cyclic Calcination/Carbonation

The calcium‐based sorbent cyclic calcination/carbonation reaction is an effective technique for capturing CO₂ from combustion processes. The CO₂ capture capacity for CaO modified with ethanol/water solution was investigated over long‐term calcination/carbonation cycles. In addition, the SEM micrographs and pore structure for the calcined sorbents were analyzed. The carbonation conversion for CaO modified with ethanol/water solution is greater than that for CaO hydrated with distilled water and is much higher than that for calcined limestone. Modified CaO achieves the highest conversion for carbonation at the range of 650–700 °C. Higher values of ethanol concentration in solution result in higher carbonation conversion for modified CaO, and lead to better anti‐sintering performance. After calcination, the specific surface area and pore volume for modified CaO are higher than those for hydrated CaO, and are much greater than those for calcined limestone. The ethanol molecule enhances H₂O molecule affinity and penetrability to CaO in the hydration reaction so that the pores in CaO modified are obviously expanded after calcination. CaO modified with ethanol/water solution can act as a new and promising type of calcium‐based regenerable CO₂ sorbent for industrial applications.     

Mechanisms of aqueous wollastonite carbonation as a possible CO2 sequestration process

The mechanisms of aqueous wollastonite carbonation as a possible carbon dioxide sequestration process were investigated experimentally by systematic variation of the reaction temperature, CO₂ pressure, particle size, reaction time, liquid to solid ratio and agitation power. The carbonation reaction was observed to occur via the aqueous phase in two steps: (1) Ca leaching from the CaSiO₃ matrix and (2) CaCO₃ nucleation and growth. Leaching is hindered by a Ca-depleted silicate rim resulting from incongruent Ca-dissolution. Two temperature regimes were identified in the overall carbonation process. At temperatures below an optimum reaction temperature, the overall reaction rate is probably limited by the leaching rate of Ca. At higher temperatures, nucleation and growth of calcium carbonate are probably limiting the conversion, due to a reduced (bi)carbonate activity. The mechanisms for the aqueous carbonation of wollastonite were shown to be similar to those reported previously for an industrial residue and a Mg-silicate. The carbonation of wollastonite proceeds rapidly relative to Mg-silicates, with a maximum conversion in 15 min of 70% at , 20 bar CO₂ partial pressure and particle size of . The obtained insight in the reaction mechanisms enables the energetic and economic assessment of CO₂ sequestration by wollastonite carbonation, which forms an essential next step in its further development.     

CO2 capture capacity of CaO in long series of pressure swing sorption cycles

One promising method for the capture of CO₂ from point sources is through the usage of a lime-based sorbent. Lime (CaO) acts as a CO₂ carrier, absorbing CO₂ from the flue gas (carbonation) and releasing it in a separate reactor (calcination) to create a pure stream of CO₂ suitable for sequestration. One of the challenges with this process is the decay in calcium utilization (CO₂ capture capacity) during carbonation/calcination cycling. The reduction in calcium utilization of natural limestone over large numbers of cycles (>250) was studied. Cycling was accomplished using pressure swing CO₂ adsorption in a pressurized thermogravimetric reactor (PTGA). The effect of carbonation pressure on calcium utilization was studied in CO₂ with the reactor operated at 1000 °C. The pressure was cycled between atmospheric pressure for calcination, and 6, 11 or 21 bar for carbonation. Over the first 250 cycles, the calcium utilization reached a near-asymptotic value of 12.5-27.7%, depending on the cycling conditions. Pressure cycling resulted in improved long-term calcium utilization compared to temperature swing or CO₂ partial pressure swing adsorption under similar conditions. An increased rate of de-pressurization caused an increase in calcium utilization, attributed to fracturing of the sorbent particle during the rapid calcination, as observed via SEM analysis.     

Crystallization of Nano‐Calcium Carbonate: The Influence of Process Parameters

Precipitated calcium carbonate was synthesized by carbonation of calcium hydroxide in the presence and absence of ultrasound (conventional stirring) at atmospheric as well as at elevated pressures and different initial concentrations of Ca(OH)₂. Spherical morphology of the formed calcite was favored at high Ca(OH)₂ concentrations and low CO₂ pressures. The presence of ultrasound did not show any influence on the reaction rate in case of efficient mixing. A small increase of the reaction rate was observed at lower CO₂ pressures. Elevated pressures in combination with ultrasound did not lead to notable changes of reaction rate or particle morphology.     

Experimental studies and thermodynamic modeling of the carbonation of Portland cement,metakaolin and limestone mortars

The carbonation of Portland cement, metakaolin and limestone mortars has been investigated after hydration for 91 days and exposure to 1% (v/v) CO₂ at 20 °C/57% RH for 280 days. The carbonation depths have been measured by phenolphthalein whereas mercury intrusion porosimetry (MIP), TGA and thermodynamic modeling have been used to study pore structure, CO₂ binding capacity and phase assemblages. The Portland cement has the highest resistance to carbonation due to its highest CO₂ binding capacity. The limestone blend has higher CO₂ binding capacity than the metakaolin blends, whereas the better carbonation resistance of the metakaolin blends is related to their finer pore structure and lower total porosity, since the finer pores favor capillary condensation. MIP shows a coarsening of the pore threshold upon carbonation for all mortars. Overall, the CO₂ binding capacity, porosity and capillary condensation are found to be the decisive parameters governing the carbonation rate.     

Mechanical performance and microstructure of the calcium carbonate binders produced by carbonating steel slag paste under CO2 curing

Calcium carbonate binders were prepared via carbonating the paste specimens cast with steel slag alone or the steel slag blends incorporating 20% of Portland cement (PC) under CO₂ curing (0.1 MPa gas pressure) for up to 14 d. The carbonate products, mechanical strengths, and microstructures were quantitatively investigated. Results showed that, after accelerated carbonation, the compressive strengths of both steel slag pastes and slag-PC pastes were increased remarkably, being 44.1 and 72.0 MPa respectively after 14 d of CO₂ curing. The longer carbonation duration, the greater quantity of calcium carbonates formed and hence the higher compressive strength gained. The mechanical strength augments were mainly attributed to the formation of calcium carbonate, which caused microstructure densification associated with reducing pore size and pore volume in the carbonated pastes. In addition, the aggregated calcium carbonates exhibited good micromechanical properties with a mean nanoindentation modulus of 38.9 GPa and a mean hardness of 1.79 GPa.