A rate equation for Ca(OH)2 and CO2 reaction in a spouted bed reactor at low gas concentrations

In the present study, the carbonation reaction of hydrated lime in semi-dry condition is investigated experimentally in a laboratory-scale spouted bed reactor. Results show that for operating conditions where the concentration of CO₂ is low, the capture efficiency is raised by increasing the inlet CO₂ concentration. Additionally, because of the inconsistency between the experimental reaction rate and the calculated values based on the previous proposed equations, a new rate equation is introduced that considers the dependency of CO₂ concentration too. To validate the proposed equation, its predictions were compared with another set of experimental data.     

The experimental investigation of concrete carbonation depth

Phenolphthalein indicator has traditionally been used to determine the depth of carbonation in concrete. This investigation uses the thermalgravimetric analysis (TGA) method, which tests the concentration distribution of Ca(OH)₂ and CaCO₃, while the X-ray diffraction analysis (XRDA) tests the intensity distribution of Ca(OH)₂ and CaCO₃. The Fourier transformation infrared spectroscopy (FTIR) test method detects the presence of C-O in concrete samples as a basis for determining the presence of CaCO₃. Concrete specimens were prepared and subjected to accelerated carbonation under conditions of 23 °C temperature, 70% RH and 20% concentration of CO₂. The test results of TGA and XRDA indicate that there exist a sharp carbonation front. Three zones of carbonation were identified according to the degree of carbonation and pH in the pore solutions. The TGA, XRDA and FTIR results showed the depth of carbonation front is twice of that determined from phenolphthalein indicator.     

铵基循环碳酸化固定CO2

引言由煤等化石燃料燃烧产生的温室气体CO2的捕集与封存已引起国际社会的广泛关注[1-2];其中,模仿自然界钙镁硅酸盐矿物风化过程的碳酸化固定是实现大规模封存CO2的重要途径,与其他封存技术相比,碳酸化固定CO2环境风险性小,并可     

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 and simulation for the methane steam reforming enhanced by in situ CO2 removal utilizing the CaO carbonation for H2 production

The transient behavior of catalytic methane steam reforming (MSR) coupled with simultaneous carbon dioxide removal by carbonation of CaO pellets in a packed bed reactor for hydrogen production has been analyzed through a mathematical model with reaction experiments for model verification. A dynamic model has been developed to describe both the MSR reaction and the CaO carbonation-enhanced MSR reaction at non-isothermal, non-adiabatic, and non-isobaric operating conditions assuming that the rate of the CaO carbonation in a local zone of the packed bed is governed by kinetic limitation or by mass transfer limitation of the reactant CO₂. Apparent carbonation kinetics of the CaO pellet prepared has been determined using the TGA carbonation experiments at various temperatures, and incorporated into the model. The resulting model is shown to successfully depict the transient behavior of the in situ CaO carbonation-enhanced MSR reaction. The effects of major operating parameters on the transient behavior of the CaO carbonation-enhanced MSR have been investigated using the model. The bed temperature is the most important parameter for determining the amount of CO₂ removed by carbonation of CaO, and at temperatures of 600°C, 650°C, 700°C and 750°C, the CO₂ uptake is 1.43, 2.29, 3.5 and -CO₂/kg-CaO, respectively. Simultaneously with the increase in CO₂ uptake with increasing temperature, the corresponding amounts of hydrogen produced are 1.56, 2.54, 3.91 and -H₂/kg-CaO, at the same temperatures as above. Operation at high pressure, high steam to methane feed ratio, and the decreased feed rate at a given temperature are favorable for increasing the degree of the overall utilization of CaO pellets in the reactor bed, and for lowering the CO concentration in the product.     

CaO-Ca9Al6O18吸收剂的碳酸化反应动力学

以柠檬酸钙和硝酸铝为前体,采用湿法混合法制备了CaO质量分数为80%的CaO-Ca₉Al₆O₁₈吸收剂,并对其CO₂吸收性能进行了研究。结果表明,CaO-Ca₉Al₆O₁₈具有优异的CO₂吸收容量和长周期循环使用稳定性,经过50次循环使用后,其转化率仍保持在78%以上,远优于传统的CaO吸收剂。在500～700℃和CO₂分压为0.005～0.015 MPa条件下,研究了CaO-Ca₉Al₆O₁₈吸收剂的碳酸化反应动力学,分别采用离子反应模型和表观模型描述化学反应动力学控制阶段(快反应段)和产物层扩散阶段(慢反应段)。实验测得的吸收剂转化率与模型预测值吻合较好,快慢反应段的活化能分别为25.6、57.7 kJ·mol^-1。该动力学模型可准确模拟CaO-Ca₉Al₆O₁₈吸收剂在长周期循环使用条件下的碳酸化反应。     

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.     

Feasibility of Na-based thermochemical cycles for the capture of CO2 from air—Thermodynamic and thermogravimetric analyses

Three Na-based thermochemical cycles for capturing CO₂ from air are considered: (1) a NaOH/NaHCO₃/Na₂CO₃/Na₂O cycle with 4 reaction steps, (2) a NaOH/NaHCO₃/Na₂CO₃ cycle with 3 reactions steps, and (3) a Na₂CO₃/NaHCO₃ cycle with 2 reaction steps. Depending on the choice of CO₂ sorbent – NaOH or Na₂CO₃ – the cycles are closed by either NaHCO₃ or Na₂CO₃ decomposition, followed by hydrolysis of Na₂CO₃ or Na₂O, respectively. The temperature requirements, energy inputs, and expected products of the reaction steps were determined by thermodynamic equilibrium and energy balance computations. The total thermal energy requirement for Cycles 1, 2, and 3 are 481, 213, and 390 kJ/mol of CO₂ captured, respectively, when heat exchangers are employed to recover the sensible heat of hot streams. Isothermal and dynamic thermogravimetric runs were carried out on the pertinent carbonation, decomposition, and hydrolysis reactions. The extent of the NaOH carbonation with 500 ppm CO₂ in air at 25 °C – applied in Cycles 1 and 2 – reached 9% after 4 h, while that for the Na₂CO₃ carbonation with water-saturated air – applied in Cycle 3 – was 3.5% after 2 h. Thermal decomposition of NaHCO₃ – applied in all three cycles – reached completion after 3 min in the 90–200 °C range, while that of Na₂CO₃ – applied in Cycle 1 – reached completion after 15 min in the 1000–1400 °C range. The significantly slow reaction rates for the carbonation steps and, consequently, the relatively large mass flow rates required, introduce process complications in the scale-up of the reactor technology and impede the application of Na-based sorbents for capturing CO₂ from air.     

Investigation of the carbonation front shape on cementitious materials: Effects of the chemical kinetics

Carbonation depth-profiles have been determined by thermogravimetric analysis and by gammadensitometry after accelerated carbonation tests on ordinary Portland cement (OPC) pastes and concretes. These methods support the idea that carbonation does not exhibit a sharp reaction front. From analytical modelling, this feature is explained by the fact that the kinetics of the chemical reactions become the rate-controlling processes, rather than the diffusion of CO₂. Furthermore, conclusions are drawn as to the mechanism by which carbonation of Ca(OH)₂ and C-S-H takes place. Carbonation gives rise to almost complete disappearance of C-S-H gel, while Ca(OH)₂ remains in appreciable amount. This may be associated with the CaCO₃ precipitation, forming a dense coating around partially reacted Ca(OH)₂ crystals. The way in which CO₂ is fixed in carbonated samples is studied. The results indicate that CO₂ is chemically bound as CaCO₃, which precipitates in various forms, namely: stable, metastable, and amorphous. It seems that the thermal stability of the produced CaCO₃ is lower when the carbonation level is high. It is also shown that the poorly crystallized and thermally unstable forms of CaCO₃ are preferentially associated with C-S-H carbonation.     

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.     

CO2 Capture Performance of Calcium‐Based Sorbents in the Presence of SO2 under Pressurized Carbonation

In order to understand the effect of SO₂ on the CO₂ capture performance under pressurized carbonation conditions, tests by orthogonal design were carried out in a calcination/pressurized carbonation reactor system. The effects of variables such as carbonation temperature, carbonation pressure, SO₂ concentration, CO₂ concentration, and the number of cycles on carbonation and sulfation were investigated. A range method was employed for analysis. Phase structure and scanning electron microscopy images were measured as supplement for a reaction study. Temperature increase enhanced the SO₂ capture, leading to a rapid decay in CO₂ uptake. The carbonation pressure had a stronger effect on the CO₂ uptake than the temperature. SO₂ uptake increased rapidly with increasing pressure while CO₂ uptake decreased.     

Production of Monoacylglycerols from Fully Hydrogenated Palm Oil Catalyzed by Hydrotalcite Loaded with K2CO3

This study reports a new method of producing high-purity monoacylglycerols (MAGs) by glycerolysis of fully hydrogenated palm oil (FHPO) catalyzed by hydrotalcite loaded with K₂CO₃ (K₂CO₃/HT). The effects of reaction temperature, reaction time, catalyst (K₂CO₃/HT) loading, and mass ratio of FHPO to glycerol on glycerolysis were investigated. The selected conditions included a reaction temperature of 200°C, K₂CO₃/HT loading at 0.8 wt.% (FHPO mass), a 5:2 mass ratio of FHPO to glycerol, and a reaction time of 2 h. Under these selected conditions, the yield of MAGs in the acylglycerol phase reached 46.8 wt.%. A two-stage molecular distillation was introduced to purify MAGs, and the final MAG product was obtained with a purity of 96.6 wt.% and a recovery of 96.8%. Furthermore, the recycled K₂CO₃/HT was reactivated with restored catalytic efficiency through impregnation, carbonation, and recalcination.     

Particle flow, mixing, and chemical reaction in circulating fluidized bed absorbers

A mixing model has been developed to simulate the particle residence time distribution (RTD) in a circulating fluidized bed absorber (CFBA). Also, a gas/solid reaction model for sulfur dioxide (SO₂) removal by lime has been developed. For the reaction model that considers RTD distribution inside the core and annulus regions of a CFBA, a macrochemical reaction can be simulated based on microchemical reaction dynamics. The presented model can predict SO₂ and lime concentration distributions inside the CFBA, and give the amount of lime needed to remove a given percentage of SO₂. It is found that SO₂ concentration decreases with the increase of CFBA distance from the bottom in the core region. However, lime concentration exhibits a very slight variation in the core region. This means that lime is efficiently utilized to remove SO₂. The model also predicts that SO₂ partial pressure at the exit of the CFBA decreases with the increase in the percentage of fresh lime injected in the CFBA.     

The rate and extent of uptake of CO2 by a synthetic, CaO-containing sorbent

A synthetic, Ca-based solid sorbent, showed a marked increase in its ultimate uptake for CO₂ at temperatures in excess of 750 °C when the concentration of CO₂ was increased during carbonation in a fluidised bed. In contrast, the uptakes by natural sorbents, e.g. dolomite, were relatively insensitive to the concentration of CO₂. It is apparent that the rate of reaction of the synthetic sorbent falls to zero once the small pores within the grains, of which the particle is composed, have largely filled and a thin layer of product has been deposited around each grain. To quantify this effect, theory has been developed in which the mechanical work required to disrupt the layer of product is taken into account. The resulting model for the overall uptake correlates experimental measurements well, except in circumstances where carbonation times are so long that sintering introduces gross changes in the morphology of the layer of product. The explanation for why the overall conversion of the synthetic sorbent is dependent on the concentration of CO₂, whilst the conversion of dolomite is insensitive to [CO₂], is attributed to differences in the yield stress, σ_Y, needed to disrupt the layer of product formed in the two materials. It was found that the value of σ_Y for dolomite is about an order of magnitude larger than that for the synthetic sorbent. The behaviour of the synthetic sorbent in response to increasing concentrations of CO₂ makes it an attractive solid for the separation of CO₂ from, e.g. the flue gases arising from combustion. By subsequently calcining the resulting solid, a pure stream of CO₂ can be produced whilst the sorbent is regenerated for further use.     

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.     

Application of the random pore model to the carbonation cyclic reaction

Calcium oxide has been proved to be a suitable sorbent for high temperature CO₂ capture processes based on the cyclic carbonation‐calcination reaction. It is important to have reaction rate models that are able to describe the behavior of CaO particles with respect to the carbonation reaction. Fresh calcined lime is known to be a reactive solid toward carbonation, but the average sorbent particle in a CaO‐based CO₂ capture system experiences many carbonation‐calcination cycles and the reactivity changes with the number of cycles. This study applies the random pore model (RPM) to estimate the intrinsic rate parameters for the carbonation reaction and develops a simple model to calculate particle conversion with time as a function of the number of cycles, partial pressure of CO₂, and temperature. This version of the RPM model integrates knowledge obtained in earlier works on intrinsic carbonation rates, critical product layer thickness, and pore structure evolution in highly cycled particles. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Preparation of ultrafine calcium carbonate particles with micropore dispersion method

Ultrafine particles of CaCO₃ were synthesized by dispersing the mixture of CO₂ and N₂ into the Ca(OH)₂/H₂O slurry with a micropore-plate. Because the micropore is micrometers scale, process of momentum transfer, mass transfer and reaction was significantly enhanced. The carbonation process of Ca(OH)₂/H₂O system was monitored with pH and conductivity. Operation conditions were investigated on the specific surface area of particles, such as initial slurry concentration and volume, gas flowrate and concentration, and temperature. The crystal structure of particles was characterized with BET, IR, TEM, SEM, etc. Results showed ultrafine particles were calcite with general shape of cube, whose size was about 40 nm and specific surface area was more than 25 m²/g. This preparation method is easy to operate.     

Economical assessment of competitive enhanced limestones for CO2 capture cycles in power plants

CO₂ capture systems based on the carbonation/calcination loop have gained rapid interest due to promising carbonator CO₂ capture efficiency, low sorbent cost and no flue gases treatment is required before entering the system. These features together result in a competitively low cost CO₂ capture system. Among the key variables that influence the performance of these systems and their integration with power plants, the carbonation conversion of the sorbent and the heat requirement at calciner are the most relevant. Both variables are mainly influenced by CaO/CO₂ ratio and make-up flow of solids. New sorbents are under development to reduce the decay of their carbonation conversion with cycles. The aim of this study is to assess the competitiveness of new limestones with enhanced sorption behaviour applied to carbonation/calcination cycle integrated with a power plant, compared to raw limestone. The existence of an upper limit for the maximum average capture capacity of CaO has been considered. Above this limit, improving sorbent capture capacity does not lead to the corresponding increase in capture efficiency and, thus, reduction of CO₂ avoided cost is not observed. Simulations calculate the maximum price for enhanced sorbents to achieve a reduction in CO₂ removal cost under different process conditions (solid circulation and make-up flow). The present study may be used as an assessment tool of new sorbents to understand what prices would be competitive compare with raw limestone in the CO₂ looping capture systems.     

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.     

Form coke reaction processes in carbon dioxide

Uncertainty in metallurgical coke supplies has prompted development of form coke from low quality coals and fines. Reaction rates have been measured and mechanisms identified that control carbonaceous briquette reaction rate in CO₂. Three briquette formulations were prepared, characterized and coked in an inert atmosphere at high temperature. A given weight of each formulation was then reacted in a packed bed with CO₂ at 1373 K for 0.5–2 h. Partially reacted briquettes contained a solid core with some internal reaction surrounded by a loosely adhering layer of carbon-containing ash. The reaction rate of briquettes with CO₂ was affected by diffusion of CO₂ through the bulk gas and the ash-carbon layer to the core surface, as well as CO₂–carbon reaction. Key variables governing briquette reaction rate included CO₂ mole fraction and briquette void fraction.