Analysis of carbonation behavior in concrete using neural network algorithm and carbonation modeling

Carbonation on concrete structures in underground sites or metropolitan cities is one of the major causes of steel corrosion in RC (Reinforced Concrete) structures. For quantitative evaluation of carbonation, physico-chemo modeling for reaction with dissolved CO₂ and hydrates is necessary. Amount of hydrates and CO₂ diffusion coefficient play an important role in evaluation of carbonation behavior, however, it is difficult to obtain a various CO₂ diffusion coefficient from experiments due to limited time and cost.In this paper, a numerical technique for carbonation behavior using neural network algorithm and carbonation modeling is developed. To obtain the comparable data set of CO₂ diffusion coefficient, experimental results which were performed previously are analyzed. Mix design components such as cement content, water to cement ratio, and volume of aggregate including exposure condition of relative humidity are selected as neurons. Training of learning for neural network is carried out using back propagation algorithm. The diffusion coefficient of CO₂ from neural network are in good agreement with experimental data considering various conditions such as water to cement ratios (w/c: 0.42, 0.50, and 0.58) and relative humidities (R.H.: 10%, 45%, 75%, and 90%). Furthermore, mercury intrusion porosimetry (MIP) test is also performed to evaluate the change in porosity under carbonation. Finally, the numerical technique which is based on behavior in early-aged concrete such as hydration and pore structure is developed considering CO₂ diffusion coefficient from neural network and changing effect on porosity under carbonation.     

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.     

Deterministic size effect in the strength of cracked concrete structures

This paper is concerned with identifying and quantifying the deterministic (as opposed to statistical) size effect in the strength of cracked concrete structures that is believed to be a result of stress discontinuities introduced by the cracks. For this, the strength of geometrically similar pre-cracked specimens of varying sizes made from three concrete mixes is measured in three-point bend and wedge splitting geometries. The true, size-independent specific fracture energy and the corresponding tension softening diagram of each of the three mixes are independently established in order to exclude their influence on the strength size effect. The test results show that the deterministic strength size effect weakens as the size of the crack reduces. This is confirmed by theoretical/computational studies based on the fictitious crack model in the range of sizes tested in the laboratory. The theoretical/computational model has been extended beyond this limited range to include cracked concrete structures in the size range 1 : 80. The computational results have been fitted by a simple strength size effect formula with appropriate asymptotic behaviour at both size extremes. The three unknown coefficients in this formula depend only on the size of the crack and they can be obtained by conducting tests on geometrically similar specimens of any shape but of varying sizes that can be conveniently handled in a laboratory. The three material properties of the concrete mix appearing in this formula, namely the Young modulus E, the direct tensile strength f_t and the size-independent specific fracture energy G_F must be independently measured.     

Carbonation of fly ash in oxy-fuel CFB combustion

Oxy-fuel combustion of fossil fuel is one of the most promising methods to produce a stream of concentrated CO₂ ready for sequestration. Oxy-fuel FBC (fluidized bed combustion) can use limestone as a sorbent for in situ capture of sulphur dioxide. Limestone will not calcine to CaO under typical oxy-fuel circulating FBC (CFBC) operating temperatures because of the high CO₂ partial pressures. However, for some fuels, such as anthracites and petroleum cokes, the typical combustion temperature is above 900 °C. At CO₂ concentrations of 80-85% (typical of oxy-fuel CFBC conditions with flue gas recycle) limestone still calcines, but when the ash cools to the calcination temperature, carbonation of fly ash deposited on cool surfaces may occur. This phenomenon has the potential to cause fouling of the heat transfer surfaces in the back end of the boiler, and to create serious operational difficulties. In this study, fly ash generated in a utility CFBC boiler was carbonated in a thermogravimetric analyzer (TGA) under conditions expected in an oxy-fuel CFBC. The temperature range investigated was from 250 to 800 °C with CO₂ concentration set at 80% and H₂O concentrations at 0%, 8% and 15%, and the rate and the extent of the carbonation reaction were determined. Both temperature and H₂O concentrations played important roles in determining the reaction rate and extent of carbonation. The results also showed that, in different temperature ranges, the carbonation of fly ash displayed different characteristics: in the range 400 °C < T ? 800 °C, the higher the temperature the higher the CaO-to-carbonate conversion ratio. The presence of H₂O in the gas phase always resulted in higher CaO conversion ratio than that obtainable without H₂O. For T ? 400 °C, no fly ash carbonation occurred without the presence of H₂O in the gas phase. However, on water vapour addition, carbonation was observed, even at 250 °C. For T ? 300 °C, small amounts of Ca(OH)₂ were found in the final product alongside CaCO₃. Here, the carbonation mechanism is discussed and the apparent activation energy for the overall reaction determined.     

The CO2 uptake of concrete in a 100 year perspective

More than 50% of the CO₂ emitted during cement production originates from the calcination of limestone. This CO₂ is reabsorbed during the life cycle of cement based product such as concrete and mortars in a process called carbonation.The impact that concrete carbonation has in the assessment of CO₂ emissions from cement production has not been fully documented. Specifically, there is a lack of knowledge about the carbonation of demolished and crushed concrete. The existing models for calculating carbonation do not take into account what takes place after the concrete has been demolished. Consequently, the contribution of the cement and concrete industry to net CO₂ emissions may be significantly overestimated.This paper encompasses theoretical work, laboratory studies, surveys and calculations based on the concrete production in the Nordic countries of Denmark, Iceland, Norway and Sweden. The estimated CO₂-uptake through carbonation of the concrete produced in the year 2003 seems during a 100 year period to amount to a significant proportion of the CO₂ emitted by calcination of the raw mix used to produce the Portland cement used in the concrete.     

Liquid CO2 extraction of flowers and fractionation of floral concrete of Michelia champaca Linn

Extraction of the fresh flowers of Michelia champaca L. with liquid CO₂ provided a floral extract in 1.0 ± 0.04 wt% yields. The extract so obtained contains far less waxes and is organoleptically very superior. Similarly extraction with pentane gave the so-called ‘Concrete’ in 1.58 ± 0.06 wt%. While the concrete contains co-extracted floral waxes that make it unsuitable for blending with other perfumes, direct extraction with CO₂ is an expensive process mainly due to low bulk density of flowers and their availability during short flowering season. On the other hand, fractionation of the concrete with liquid CO₂ to separate the waxy components has provided solvent and almost wax free fractions. The duration of extractive fractionation has been optimized for selective extraction with liquid CO₂ at 62 bar. These liquid CO₂ fractions of concrete and liquid CO₂ extract of flowers were analyzed by GC and GC/MS and their composition compared with that of concrete and partially de-waxed absolute obtained in the conventional way. The major fragrance compounds enriched in the direct liquid CO₂ extract were methyl benzoate (11.5 ± 0.8%), phenyl ethyl alcohol (5.0 ± 0.6%), phenyl acetonitrile (10.4 ± 1.1%), indole (1.2 ± 0.3%), methyl anthranilate (1.3 ± 0.5%), E-β-ionone (1.5 ± 0.4%), and Z-methyl jasmonoate (1.0 ± 0.3%). The liquid CO₂ fractionation of concrete is a practical process and the first fraction is comparable with direct liquid CO₂ flower extract in terms of composition of the major compounds.     

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.     

Dependency of C–S–H carbonation rate on CO2 pressure to explain transition from accelerated tests to natural carbonation

The use of normalized accelerated carbonation tests is currently limited to the classification of concretes in terms of carbonation resistance and the results are not easily transposable to forecasting concrete carbonation in natural conditions. Common models assume that the kinetics of the carbonation front ingress in concrete is a square root function of the CO₂ pressure but observations in the field generally invalidate this assumption. Based on an experimental program including carbonation tests at several CO₂ pressures, this paper shows that the amount of carbonated product depends largely on the CO₂ pressure. Several experimental analyses of carbonated concrete under different pressures are confronted, to finally propose a new analytical model able to predict carbonation ingress in natural conditions using the results of accelerated tests. The model takes both the cement chemical composition and its amount in concrete into account. The carbonation kinetics dependence on CO₂ pressure is considered through two underlying functions including, for the first, the dependence of the CSH carbonation rate on the pressure and, for the second, the effect of this additional carbonation on the reduction of the CO₂ diffusion coefficient.     

CO2 uptake of modified calcium-based sorbents in a pressurized carbonation-calcination looping

This study focuses on enhancing CO₂ uptake by modifying limestone with acetate solutions under pressurized carbonation condition. The multicycle tests were carried out in an atmospheric calcination/pressurized carbonation reactor system at different temperatures and pressures. The pore structure characteristics (BET and BJH) were measured as a supplement to the reaction studies. Compared with the raw limestone, the modified sorbent showed a great improvement in CO₂ uptake at the same reaction condition. The highest CO₂ uptake was obtained at 700 °C and 0.5 MPa, by 88.5% increase over the limestone at 0.1 MPa after 10 cycles. The structure characteristics of the sorbents on N₂ absorption and SEM confirm that compared with the modified sorbent, the effective pores of limestone are greatly driven off by sintering, which hinders the easy access of CO₂ molecules to the unreacted-active sites of CaO. The morphological and structural properties of the modified sorbent did not reveal significant differences after multiple cycles. This would explain its superior performance of CO₂ uptake under pressurized carbonation. Even after 10 cycles, the modified sorbent still achieved a CO₂ uptake of 0.88.     

Modeling of chloride diffusivity coupled with non-linear binding capacity in sound and cracked concrete

The objective of this research is to establish a model that can predict chloride transport phenomena in sound and cracked concrete. The chloride diffusivity is formulated based on computed micro-pore structure, which considers tortuosity and constrictivity of porous network as reduction factors in terms of complex micro-pore structure and electric interaction of chloride ions and pore wall. In the real environment, concrete structures are not always crack-free, therefore chloride transport in cracked concrete is also simulated by section large void spaces in a control volume to represent the crack and by proposing a model of chloride diffusivity through the cracked region The proposed models are implemented into a finite-element computational program DuCOM, which simulates the early-age development process of cementitious materials. The calculated concentration profiles of total chloride ions are verified through a comparison with experiments results.     

Solubility and diffusivity of CO2 in poly(l-lactide)-hydroxyapatite and poly(d,l-lactide-co-glycolide)-hydroxyapatite composite biomaterials

Solubility and diffusivity of supercritical CO₂ in poly(l-lactide)-hydroxyapatite (PLLA-HA) and poly(d,l-lactide-co-glycolide)-hydroxyapatite (PLGA-HA) composite materials were measured using a magnetic suspension balance at a temperature of 313 K and a pressures range of 10-30 MPa. The effect of the HA concentration on the solubility and diffusivity was investigated by varying filler content in the range of 0-50 wt%. For the PLLA-HA composites the solubility decreases with the increase of filler concentration. Diffusivity of the gas in the substrate is also lower as the HA content increases. In the case of PLGA-HA composites, small filler content favors the solubility and diffusivity of CO₂ due to incomplete wetting of the solid particles by the polymer. As the amount of HA increases solubility decreases. The results suggest that dense CO₂ could be used as a ‘green’ processing agent for composite biomaterials when organic solvents or high temperatures should be avoided.     

Dissolution rates of alkaline rocks by carbonic acid: Influence of solid/liquid ratio,temperature, and CO2 pressure

Dissolution rates of alkaline rocks, including wollastonite (CaSiO₃), olivine (Mg₂SiO₄), and phlogopite (KMg₃AlSi₃O₁₀(OH)₂), with high pressure aqueous CO₂ solution were measured to examine the feasibility of CO₂ fixation via carbonation. Influence of solid/liquid ratio (1.0–10 g/250 mL), temperature (303–353 K), and CO₂ pressure (1.0–3.0 MPa) on the extraction rates of calcium or magnesium ions was investigated. Under the experimental conditions studied, the calcium ion extraction rate from wollastonite was the highest among the three rock samples studied. The calcium concentration reached about 120 mg/L, and about 12% of the calcium in wollastonite sample was extracted after 60 min at 353 K with 1.0 MPa CO₂. The calcium and magnesium extraction ratios from the alkaline rocks were much lower than those from waste concrete powder. Increasing the extraction time and temperature would be an effective way to promote calcium extraction from wollastonite.     

Enhancement of reactivity in surfactant-modified sorbent for CO2 capture in pressurized carbonation

The calcination/carbonation loop of calcium-based (Ca-based) sorbents is considered as a viable technique for CO₂ capture from combustion gases. Recent attempts to improve the CO₂ uptake of Ca-based sorbents by adding calcium lignosulfonate (CLS) with hydration have succeeded in enhancing its effectiveness. The optimum mass ratio of CLS/CaO is 0.5 wt.%. The reduction in particle size and grain size of CaO appeared to be parts of the reasons for increase in CO₂ capture. The primary cause of increase in reactivity of the modified sorbents was the ability of the CLS to retard the sintering rate and thus to remain surface area and pore volume for reaction. The CO₂ uptake of the modified sorbents was also enhanced by elevating the carbonation pressure. Experimental results indicate that the optimal reaction condition of the modified sorbents is at 0.5 MPa and 700 °C and a high conversion of 0.7 is achieved after 10 cycles, by 30% higher than that of original limestone, at the same condition.     

Cyclic CO2 capture behavior of KMnO4-doped CaO-based sorbent

This study examines the CO₂ capture behavior of KMnO₄-doped CaO-based sorbent during the multiple calcination/carbonation cycles. The cyclic carbonation behavior of CaCO₃ doped with KMnO₄ and the untreated CaCO₃ was investigated. The addition of KMnO₄ improves the cyclic carbonation rate of the sorbent above carbonation time of 257 s at each carbonation cycle. When the mass ratio of KMnO₄/CaCO₃ is about 0.5-0.8 wt.%, the sorbent can achieve an optimum carbonation conversion during the long-term cycles. The carbonation temperature of 660-710 °C is beneficial to cyclic carbonation of KMnO₄-doped CaCO₃. The addition of KMnO₄ improves the long-term performance of CaCO₃, resulting in directly measured conversion as high as 0.35 after 100 cycles, while the untreated CaCO₃ retains conversion less than 0.16 at the same reaction conditions. The addition of KMnO₄ decreases the surface area and pore volume of CaCO₃ after 1 cycle, but it maintains the surface area and pores between 26 nm and 175 nm of the sorbent during the multiple cycles. Calculation reveals that the addition of KMnO₄ improves the CO₂ capture efficiency significantly using a CaCO₃ calcination/carbonation cycle and decreases the amount of the fresh sorbent.     

Kinetics of absorption of carbon dioxide into aqueous solutions of 2-amino-2-hydroxymethyl-1,3-propanediol

In this work the kinetics of the reaction between CO₂ and a sterically hindered alkanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD) were determined at temperatures of 303.15, 313.15 and 323.15 K in a wetted wall column contactor. The AHPD concentration in the aqueous solutions was varied in the range 0.5-2.4 kmol m⁻³. The ratio of the diffusivity and Henry's law constant for CO₂ in solutions was estimated by applying the N₂O analogy and the Higbie penetration theory, using the physical absorption data of CO₂ and N₂O in water and of N₂O in amine solutions. Based on the pseudo-first-order for the absorption of CO₂, the overall pseudo-first-order rate constants were determined from the kinetics measurements. By considering the zwitterion mechanism for the reaction of CO₂ with AHPD, the zwitterion deprotonation and second-order rate constants were calculated. The second-order rate constant, k₂, was found to be 285, 524, and 1067 m³ kmol⁻¹ s⁻¹ at 303.15, 313.15, and 323.15 K, respectively.     

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.     

Nanostructured Ca-based sorbents with high CO2 uptake efficiency

Calcium-based carbon dioxide sorbents were made in the gas phase by scalable flame spray pyrolysis (FSP) and compared to the ones made by calcination (CAL) of selected calcium precursors. Such flame-made sorbents consisted of nanostructured CaO and CaCO₃ with twice as much specific surface area (40-60 m²/g) as the CAL-made sorbents. All FSP-made sorbents exhibited faster and higher CO₂ uptake capacity than all CAL-made sorbents at intermediate temperatures. CAL of calcium acetate monohydrate resulted in sorbents with the best CO₂ uptake among all CAL-made ones. At higher temperatures both FSP- and CAL-made sorbents (esp. from CaAc₂·H₂O) exhibited very high initial molar conversions (95%) but sintering contributed to grain growth that reduced the molar conversion down to 50%. In multiple carbonation/decarbonation cycles, the nanostructured FSP-made sorbents demonstrated stable, reversible and high CO₂ uptake capacity sustaining maximum molar conversion at about 50% even after 60 such cycles, indicating high potential for CO₂ uptake. The top performance of flame-made sorbents is best attributed to their nanostructure (30-50 nm grain size) that allows operation in the reaction-controlled carbonation regime rather than in the diffusion-controlled one when sorbents made with larger particles are employed.     

Regenerable MgO-based sorbents for high-temperature CO2 removal from syngas: 1. Sorbent development, evaluation, and reaction modeling

Highly reactive and mechanically strong low-cost regenerable MgO-based sorbents were prepared by modification of dolomite which involved partial calcinations followed by impregnation with a potassium-based salt. The sorbents are capable of removing CO₂ from gasification-based processes such as Integrated Gasification Combined Cycle (IGCC). The sorbents have high reactivity and good capacity toward CO₂ absorption in the temperature range of 300-450 °C at 20 atm. and can be easily regenerated at 500 °C. The reaction appears to be first order with respect to CO₂ concentration with an activation energy of 44 kJ/mol. The reactivity and the absorption capacity of the sorbents increase with increasing temperature, as long as the partial pressure of CO₂ is above the equilibrium value for sorbent carbonation. The reactivity of the sorbents appears to improve in the presence of steam, which is likely due to the increase in the BET surface area and the porosity of the sorbent. A two-zone expanding grain model, consisting of a high-reactivity outer shell and a low-reactivity inner core is shown to provide an excellent fit to the TGA experimental data on sorbent carbonation at various operating conditions.     

The decrease of carbonation efficiency of CaO along calcination-carbonation cycles: Experiments and modelling

Successive calcination-carbonation cycles, using CaO as sorbent, have been performed either in a classical fixed bed reactor or using a thermogravimetric analyser. Significant differences in carbonation efficiencies were obtained, possibly due to different conditions prevailing for CaO sintering during the calcination stage. The effect of the presence of CO₂ on sintering was confirmed.A simple model of the decay of the carbonation capacity along cycles based on the specific surface area of non-sintered micrograins of CaO is able to predict the decrease of the extent of conversion obtained after 40 carbonations along calcination-carbonation cycles. The asymptotic extent of conversion is obtained when all the micrograins present within a grain are sintered. A detailed model of the carbonation shows that the voids present between the micrograins are filled up by carbonate when a critical thickness of the carbonate layer around each micrograin reaches 43 nm. Then, carbonation becomes controlled by diffusion at the scale of the whole grain, with the CO₂ diffusion coefficient decreasing (at ) from 2×10^-12 to as carbonation proceeds from 50% conversion to 76% (first cycle). This scale change for diffusion is responsible for the drastic decrease of the carbonation rate after the voids between micrograins are filled up.     

Experimental study on CO2 capture conditions of a fluidized bed limestone decomposition reactor

In this study, the decomposition conditions of limestone particles (0.25-0.50 mm) for CO₂ capture in a steam dilution atmosphere (20-100% steam in CO₂) were investigated by using a continuously operating fluidized bed reactor. The results show that the decomposition conversion of limestone increased with the steam dilution percentage in the CO₂ supply gas. At a bed temperature of 920 °C, the conversions were 72% without steam dilution and 98% with 60% steam dilution. The conversion was 99% with 100% steam dilution at 850 °C of the bed temperature. Steam dilution can decrease not only the decomposition temperature of limestone, but also the residence time required for nearly complete decomposition of CaCO₃. The hydration and carbonation reactivities of the CaO produced were also tested and the results show that both the reactivities increased with the steam dilution percentage for decomposing limestone.