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.     

An experimental study on the primary fragmentation and attrition of limestones in a fluidized bed

In this paper, an experimental study on the primary fragmentation and attrition of 5 limestones in a fluidized bed was conducted. The intensity of fragmentation and attrition were measured in the same apparatus but at different fluidizing velocities. It was found that the averaged size of the particles decreased by about 10-20% during the fragmentation process. The important factors for particle comminution include limestone types, heating rate, calcination condition and ambient CO₂ concentration. Fragmentation mainly occurred in the first a few minutes in the fluidized bed and it was more intense than that in the muffle furnace at the same temperature. The original size effect was ambiguous, depending on the limestone type. The comminution caused by attrition mainly occurred during calcination process rather than sulphation process. The sulphation process was fragmentation and attrition resisted. The attrition rate of sulphate was similar to that of lime in trend, decaying exponentially with time, but was one-magnitude-order smaller than that of lime. Present experimental results indicate that fragmentation mechanism of the limestone is dominated by CO₂ release instead of thermal stress.     

Modified CaO-based sorbent looping cycle for CO2 mitigation

CaO-based sorbent looping cycle, i.e. cyclic calcination/carbonation, is one of the most interesting technologies for CO₂ capture during coal combustion and gasification processes. In order to improve the durability of limestone during the multiple calcination/carbonation cycles, modified limestone with acetic acid solution was proposed as an CO₂ sorbent. The cyclic carbonation conversions of modified limestone and original one were investigated in a twin fixed bed reactor system. The modified limestone shows the optimum carbonation conversion at the carbonation temperature of 650 °C and achieves a conversion of 0.5 after 20 cycles. The original limestone exhibits the maximum carbonation conversion of 0.15 after 20 cycles. Conversion of the modified limestone decreases slightly as the calcination temperature increases from 920 °C to 1100 °C with the number of cycles, while conversion of the original one displays a sharp decay at the same reaction conditions. The durability of the modified limestone is significantly better than the original one during the multiple cycles because mean grain size of CaO derived from the modified limestone is lower than that from the original one at the same reaction conditions. The calcined modified limestone shows higher surface area and pore volume than the calcined original one with the number of cycles, and pore size distribution of the modified limestone is superior to the original one after the same number of calcinations.     

CO2 capture from flue gases using a fluidized bed reactor with limestone

The CO₂ capture from flue gases by a small fluidized bed reactor was experimentally investigated with limestone. The results showed that CO₂ in flue gases could be captured by limestone with high efficiency, but the CO₂ capture capacity of limestone decayed with the increasing of carbonation/calcination cycles. From a practical point of view, coal may be required to provide the heat for CaCO₃ calcination, resulting in some potential effect on the sorbent capacity of CO₂ capture. Experiment results indicated that the variation in the capacity of CO₂ capture by using a limestone/coal ash mixture with a cyclic number was qualitatively similar to the variation of the capacity of CO₂ capture using limestone only. Cyclic stability of limestone only undergoing the kinetically controlled stage in the carbonation process had negligible difference with that of the limestone undergoing both the kinetically controlled stage and the product layer diffusion controlled stage. Based on the experimental data, a model for the high-velocity fluidized bed carbonator that consists of a dense bed zone and a riser zone was developed. The model predicted that high CO₂ capture efficiencies (>80%) were achievable for a range of reasonable operating conditions by the high-velocity fluidized bed carbonator in a continuous carbonation and calcination system.     

Enhancement of Ca‐Based Sorbent Multicyclic Behavior in Ca Looping Process for CO2 Separation

The Ca‐based sorbent looping cycle represents an innovative way of CO₂ capture for power plants. However, the CO₂ capture capacity of the Ca‐based sorbent decays sharply with calcination/carbonation cycle number increasing. In order to improve the CO₂ capture capacity of the sorbent in the Ca looping cycle, limestone was modified with acetic acid solution. The cyclic carbonation behaviors of the modified and original limestones were investigated in a twin fixed‐bed reactor system. The modified limestone possesses better cyclic carbonation kinetics than the original limestone at each cycle. The modified limestone carbonated at 640–660 °C achieves the optimum carbonation conversion. The acetic acid modification improves the long‐term performance of limestone, resulting in directly measured conversion as high as 0.4 after 100 cycles, while the original limestone remains at a conversion of less than 0.1 at the same reaction conditions. Both the pore volume and pore area distributions of the calcines derived from the modified limestone are better than those derived from the original limestone. The CO₂ partial pressure for carbonation has greater effect on conversion of the original limestone than on that of the modified sorbent because of the difference in their pore structure characteristics. The carbonation conversion of the original limestone decreases with the increase in particle size, while the change in particle size of the modified sorbent has no clear effect on cyclic carbonation behavior.     

Synthetic Ca‐based solid sorbents suitable for capturing CO2 in a fluidized bed

Coprecipitation and hydrolysis of CaO have been employed to produce Ca‐based synthetic sorbents suitable for capturing CO₂ in a fluidized bed. Their composition, CO₂ uptake, volume in small pores (2–200 nm) and resistance to attrition were measured and compared to those of limestone and dolomite. Sorbents produced by hydrolysis showed the highest uptake and resistance to attrition. After 20 cycles of carbonation and calcination, two sorbents exceeded the uptake of both limestone and dolomite, when subjected to the same regimes of reaction. A sorbent's uptake of CO₂ was shown to be determined by the volume in pores narrower than ～200 nm.     

Multiphase CFD-based models for chemical looping combustion process: Fuel reactor modeling

Chemical looping combustion (CLC) is a flameless two-step fuel combustion that produces a pure CO₂ stream, ready for compression and sequestration. The process is composed of two interconnected fluidized bed reactors. The air reactor which is a conventional circulating fluidized bed and the fuel reactor which is a bubbling fluidized bed. The basic principle is to avoid the direct contact of air and fuel during the combustion by introducing a highly-reactive metal particle, referred to as oxygen carrier, to transport oxygen from the air to the fuel. In the process, the products from combustion are kept separated from the rest of the flue gases namely nitrogen and excess oxygen. This process eliminates the energy intensive step to separate the CO₂ from nitrogen-rich flue gas that reduce the thermal efficiency.Fundamental knowledge of multiphase reactive fluid dynamic behavior of the gas-solid flow is essential for the optimization and operation of a chemical looping combustor.Our recent thorough literature review shows that multiphase CFD-based models have not been adapted to chemical looping combustion processes in the open literature. In this study, we have developed the reaction kinetics model of the fuel reactor and implemented the kinetic model into a multiphase hydrodynamic model, MFIX, developed earlier at the National Energy Technology Laboratory. Simulated fuel reactor flows revealed high weight fraction of unburned methane fuel in the flue gas along with CO₂ and H₂O. This behavior implies high fuel loss at the exit of the reactor and indicates the necessity to increase the residence time, say by decreasing the fuel flow rate, or to recirculate the unburned methane after condensing and removing CO₂.     

Influence of calcination conditions on carrying capacity of CaO-based sorbent in CO2 looping cycles

This study examines the loss of sorbent activity caused by sintering under realistic CO₂ capture cycle conditions. The samples tested here included two limestones: Havelock limestone from Canada (New Brunswick) and a Polish (Upper Silesia) limestone (Katowice). Samples were prepared both in a thermogravimetric analyzer (TGA) and a tube furnace (TF). Two calcination conditions were employed: in N₂ at lower temperature; and in CO₂ at high temperature. The samples obtained were observed with a scanning electron microscope (SEM) and surface compositions of the resulting materials were analyzed by the energy dispersive X-ray (EDX) method. The quantitative influence of calcination conditions was examined by nitrogen adsorption/desorption tests, gas displacement pycnometry and powder displacement pycnometry; BET surface areas, BJH pore volume distributions, skeletal densities and envelope densities were determined. The SEM images showed noticeably larger CaO sub-grains were produced by calcination in CO₂ during numerous cycles than those seen with calcination in nitrogen. The EDX elemental analyses showed a strong influence of impurities on local melting at the sorbent particle surface, which became more pronounced at higher temperature. Results of BET/BJH testing clearly support these findings on the effect of calcination/cycling conditions on sorbent morphology. Envelope density measurements showed that particles displayed densification upon cycling and that particles calcined under CO₂ showed greater densification than those calcined under N₂. Interestingly, the Katowice limestone calcined/cycled at higher temperature in CO₂ showed an increase of activity for cycles involving calcination under N₂ in the TGA. These results clearly demonstrate that, in future development of CaO-based CO₂ looping cycle technology, more attention should be paid to loss of sorbent activity caused by realistic calcination conditions and the presence of impurities originating from fuel ash and/or limestone.     

Ca-based sorbent looping combustion for CO2 capture in pilot-scale dual fluidized beds

To demonstrate process feasibility of in situ CO₂ capture from combustion of fossil fuels using Ca-based sorbent looping technology, a flexible atmospheric dual fluidized bed combustion system has been constructed. Both reactors have an ID of 100 mm and can be operated at up to 1000 °C at atmospheric pressure. This paper presents preliminary results for a variety of operating conditions, including sorbent looping rate, flue gas stream volume, CaO/CO₂ ratio and combustion mode for supplying heat to the sorbent regenerator, including oxy-fuel combustion of biomass and coal with flue gas recirculation to achieve high-concentration CO₂ in the off-gas. It is the authors' belief that this study is the first demonstration of this technology using a pilot-scale dual fluidized bed system, with continuous sorbent looping for in situ CO₂ capture, albeit at atmospheric pressure. A multi-cycle test was conducted and a high CO₂ capture efficiency (> 90%) was achieved for the first several cycles, which decreased to a still acceptable level (> 75%) even after more than 25 cycles. The cyclic sorbent was sampled on-line and showed general agreement with the features observed using a lab-scale thermogravimetric analysis (TGA) apparatus. CO₂ capture efficiency decreased with increasing number of sorbent looping cycles as expected, and sorbent attrition was found to be another significant factor to be limiting sorbent performance.     

Sequential SO2/CO2 capture enhanced by steam reactivation of a CaO-based sorbent

The steam hydration reactivation characteristics of three limestone samples after multiple CO₂ looping cycles are presented here. The CO₂ cycles were performed in a tube furnace (TF) and the resulting samples were hydrated by steam in a pressure reactor (PR). The reactivation was performed with spent samples after carbonation and calcination stages. The reactivation tests were done with a saturated steam pressure at 200 °C and also at atmospheric pressure and 100 °C. The characteristics of the reactivation samples were examined using BET and BJH pore characterization (for the original and spent samples, and samples reactivated under different conditions) and also by means of a thermogravimetric analyzer (TGA). The levels of hydration achieved by the reactivated samples were determined as well as the conversions during sulphation and multiple carbonation cycles. It was found that the presence of a CaCO₃ layer strongly hinders sorbent hydration and adversely affects the properties of the reactivated sorbent with regard to its behavior in sulphation and multiple carbonation cycles. Here, hydration of calcined samples under pressure is the most effective method to produce superior sulphur sorbents. However, reactivation of calcined samples under atmospheric conditions also produces sorbents with significantly better properties in comparison to those of the original sorbents. These results show that separate CO₂ capture and SO₂ retention in fluidized bed systems enhanced by steam reactivation is promising even for atmospheric conditions if the material for hydration is taken from the calciner.     

Effect of bed height on the carbon dioxide capture by carbonation/regeneration cyclic operations using dry potassium-based sorbents

The effect of bed height on CO₂ capture was investigated by carbonation/regeneration cyclic operations using a bubbling fluidized bed reactor. We used a potassium-based solid sorbent, SorbKX35T5 which was manufactured by the Korea Electric Power Research Institute. The sorbent consists of 35% K₂CO₃ for absorption and 65% supporters for mechanical strength. We used a fluidized bed reactor with an inner diameter of 0.05 m and a height of 0.8 m which was made of quartz and placed inside of a furnace. The operating temperatures were fixed at 70 °C and 150 °C for carbonation and regeneration, respectively. The carbonation/regeneration cyclic operations were performed three times at four different L/D (length vs diameter) ratios such as one, two, three, and four. The amount of CO₂ captured was the most when L/D ratio was one, while the period of maintaining 100% CO₂ removal was the longest as 6 minutes when L/D ratio was three. At each cycle, CO₂ sorption capacity (g CO₂/g sorbent) was decreased as L/D ratio was increased. The results obtained in this study can be applied to design and operate a large scale CO₂ capture process composed of two fluidized bed reactors. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, Shanxi, China, June 26–28, 2008.     

Experiments on the Dynamic Behavior of the Chemical Looping Combustion Process

The dynamic operation of thermal power plants becomes more and more important due to more diverse and volatile power sources. Load changes of biomass, bituminous coal and methane were conducted during six experimental runs in a chemical looping combustion pilot plant which combines power generation and CO₂ capture. The resulting step responses of the hydrodynamics and gas concentrations were compared to each other to understand the transient behavior of the interconnected fluidized bed system. The influence of the fuel rate and solid circulation on the response time and intensity was assessed.     

CO2 Capture Behavior of Shell during Calcination/Carbonation Cycles

The cyclic carbonation performances of shells as CO₂ sorbents were investigated during multiple calcination/carbonation cycles. The carbonation kinetics of the shell and limestone are similar since they both exhibit a fast kinetically controlled reaction regime and a diffusion controlled reaction regime, but their carbonation rates differ between these two regions. Shell achieves the maximum carbonation conversion for carbonation at 680–700 °C. The mactra veneriformis shell and mussel shell exhibit higher carbonation conversions than limestone after several cycles at the same reaction conditions. The carbonation conversion of scallop shell is slightly higher than that of limestone after a series of cycles. The calcined shell appears more porous than calcined limestone, and possesses more pores > 230 nm, which allow large CO₂ diffusion‐carbonation reaction rates and higher conversion due to the increased surface area of the shell. The pores of the shell that are greater than 230 nm do not sinter significantly. The shell has more sodium ions than limestone, which probably leads to an improvement in the cyclic carbonation performance during the multiple calcination/carbonation cycles.     

A novel dual circulating fluidized bed system for chemical looping processes

A fluidized bed system combining two circulating fluidized bed reactors is proposed and investigated for chemical looping combustion. Direct hydraulic communication of the two circulating fluidized bed reactors via a fluidized loop seal allows for high rates of global solids circulation and results in a stable solids distribution in the system. A 120 kW fuel power bench scale unit was designed, built, and operated. Experimental results are presented for natural gas as fuel using a nickel‐based oxygen carrier. No carbon was lost to the air reactor under any conditions operated. It is shown from fuel power variations that a turbulent/fast fluidized bed regime in the fuel reactor is advantageous. Despite the relatively low riser heights (air reactor: 4.1 m, fuel reactor: 3.0 m), high CH₄ conversion and CO₂ yield of up to 98% and 94%, respectively, can be reported for the material tested. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

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.     

Performance of limestone-based sorbent for sorption-enhanced gasification in dual interconnected fluidized bed reactors

A possibility to carry out sorption-enhanced gasification (SEG) is represented by its integration with the calcium looping concept in dual interconnected fluidized beds (DIFB). This article is focused on the sorbent CO₂ uptake performance and attrition/fragmentation tendency when operating conditions simulating those of a DIFB-SEG process are adopted. Experiments were carried out on a commercial Italian limestone in a laboratory-scale DIFB reactor. Carbonation was carried out in a range of test conditions, including variable temperature (600–700°C) and absence/presence of steam (10% by volume); CO₂ concentration was set at 10% by volume. The characterization is extended by investigating the behavior of preprocessed DIFB-SEG samples on impact fragmentation tests, conducted in an ex situ apparatus. Tests were carried out for impact velocities in the range 17–45 m/s. Results were discussed considering both the impact velocity value and the operating conditions under which the sample was preprocessed in the fluidized bed.     

Primary fragmentation of limestone under oxy-firing conditions in a bubbling fluidized bed

Primary fragmentation of two limestones was studied in a lab-scale bubbling fluidized bed under simulated oxy-firing conditions and, for comparison, under traditional air-firing conditions. The influence of bed temperature, particle size and simultaneous occurrence of sulphation reaction was tested. Additional experiments in a heated strip apparatus were performed to determine if primary fragmentation occurred under high heating rate conditions, but in the absence of particle collisions.Results of the experiments show that only limited fragmentation occurred to both limestones tested under all operating conditions. Under oxy-firing conditions primary fragmentation was significantly reduced with respect to air-fired operation, most likely because of the absence of limestone calcination under high CO₂ atmospheres. Thermal shock upon limestone injection in the hot bed appears not to be able to induce significant particle fragmentation by its own.Particle size, bed temperature and simultaneous occurrence of sulphation reaction were found not to influence significantly the limestone primary fragmentation extent under both oxy-firing and air-firing conditions. On the contrary, the limestone type was found to be a more important variable with respect to the fragmentation tendency.     

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.     

Natural Calcium‐Based Sorbents Doped with Sea Salt for Cyclic CO2 Capture

The calcium‐looping process for post‐combustion carbon dioxide capture, an economically and technically feasible method suitable for large‐scale use, has recently gained much attention. However, the capture capacity of calcium‐based sorbents rapidly decreases after only a few cycles. Herein, calcium‐based sorbents with enhanced cyclic CO₂‐capture capacity have been derived from cheap, natural raw materials by using a simple impregnation method. Limestone and shells were used as the calcium‐based raw materials, with sea salt as dopant. Modified limestone had the highest CO₂‐capture capacity after multiple carbonation‐calcination cycles. Sea‐salt‐doped sorbent showed a relatively stable porous surface during cycles, which resulted in a higher CO₂‐capture capacity.