Sulfation rates of cycled CaO particles in the carbonator of a Ca‐looping cycle for postcombustion CO2 capture

Calcium looping is an energy‐efficient CO₂ capture technology that uses CaO as a regenerable sorbent. One of the advantages of Ca‐looping compared with other postcombustion technologies is the possibility of operating with flue gases that have a high SO₂ content. However, experimental information on sulfation reaction rates of cycled particles in the conditions typical of a carbonator reactor is scarce. This work aims to define a semiempirical sulfation reaction model at particle level suitable for such reaction conditions. The pore blocking mechanism typically observed during the sulfation reaction of fresh calcined limestones is not observed in the case of highly cycled sorbents (N > 20) and the low values of sulfation conversion characteristic of the sorbent in the Ca‐looping system. The random pore model is able to predict reasonably well, the CaO conversion to CaSO₄ taking into account the evolution of the pore structure during the calcination/carbonation cycles. The intrinsic reaction parameters derived for chemical and diffusion controlled regimes are in agreement with those found in the literature for sulfation in other systems. © 2011 American Institute of Chemical EngineersAIChE J, 2012     

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.     

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.     

Stabilized Performance of Al‐Decorated and Al/Mg Co‐Decorated Spray‐Dried CaO‐Based CO2 Sorbents

The sharp loss‐in‐capacity in CO₂ capture as a result of sintering is a major drawback for CaO‐based sorbents used in the calcium looping process. The decoration of inert supports effectively stabilizes the cyclic CO₂ capture performance of CaO‐based sorbents via sintering mitigation. A range of Al‐decorated and Al/Mg co‐decorated CaO‐based sorbents were synthesized via an easily scaled‐up spray‐drying route. The decoration of Al‐based and Al/Mg‐based supports efficiently enhanced the cyclic CO₂ capture capability of CaO‐based sorbents under severe testing conditions. The CO₂ capture capacity losses of Al‐decorated and Al/Mg co‐decorated CaO‐based sorbents were alleviated, representing more stable CO₂ capture performance. The stabilized CO₂ capture performance is mainly attributed to the formation of Ca₁₂Al₁₄O₃₃, MgAl₂O₄, and MgO that act as the skeleton structures to mitigate the sintering of CaCO₃ during carbonation/calcination cycles.     

Experimental investigation of a circulating fluidized‐bed reactor to capture CO2 with CaO

Calcium looping processes for capturing CO₂ from large emissions sources are based on the use of CaO particles as sorbent in circulating fluidized‐bed (CFB) reactors. A continuous flow of CaO from an oxyfired calciner is fed into the carbonator and a certain inventory of active CaO is expected to capture the CO₂ in the flue gas. The circulation rate and the inventory of CaO determine the CO₂ capture efficiency. Other parameters such as the average carrying capacity of the CaO circulating particles, the temperature, and the gas velocity must be taken into account. To investigate the effect of these variables on CO₂ capture efficiency, we used a 6.5 m height CFB carbonator connected to a twin CFB calciner. Many stationary operating states were achieved using different operating conditions. The trends of CO₂ capture efficiency measured are compared with those from a simple reactor model. This information may contribute to the future scaling up of the technology. © 2010 American Institute of Chemical Engineers AIChE J, 57: 000–000, 2011     

Thermodynamic Simulation of CO2 Capture for an IGCC Power Plant using the Calcium Looping Cycle

A CO₂ capture process for an integrated gasification combined cycle (IGCC) power plant using the calcium looping cycle was proposed. The CO₂ capture process using natural and modified limestone was simulated and investigated with the software package Aspen Plus. It incorporated a fresh feed of sorbent to compensate for the decay in CO₂ capture activity during long‐term cycles. The sorbent flow ratios have significant effect on the CO₂ capture efficiency and net efficiency of the CO₂ capture system. The IGCC power plant, using the modified limestone, exhibits higher CO₂ capture efficiency than that using the natural limetone at the same sorbent flow ratios. The system net efficiency using the natural and modified limestones achieves 41.7 % and 43.1 %, respectively, at the CO₂ capture efficiency of 90 % without the effect of sulfation.     

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     

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.     

Comprehensive sulfation model verified for T-T sorbent clusters during flue gas desulfurization at moderate temperatures

An empirical sulfation model for T-T sorbent clusters was developed based on amassed experimental results under moderate temperatures (300-800 °C). In the model, the reaction rate is a function of clusters mass, SO₂ concentration, CO₂ concentration, calcium conversion and temperature. The smaller pore volume partly results in a lower reaction rate at lower temperatures. The exponent on SO₂ concentration is 0.88 in the rapid reaction stage and then decreases gradually as reaction progresses. The exponent on the fraction of the unreacted calcium is 1/3 in the first stage and then increases significantly in the second stage. The CO₂ concentration has a negative influence on SO₂ removal, especially for the temperature range of 400-650 °C, which should be avoided to achieve a high effective calcium conversion. The sulfation model has been verified for the T-T sorbent clusters and has also been applied to CaO particles. Over extensive reaction conditions, the predictions agree well with experimental data.     

The calcium looping cycle for CO2 capture from power generation, cement manufacture and hydrogen production

Calcium looping is a CO₂ capture scheme using solid CaO-based sorbents to remove CO₂ from flue gases, e.g., from a power plant, producing a concentrated stream of CO₂ (∼95%) suitable for storage. The scheme exploits the reversible gas-solid reaction between CO₂ and CaO(s) to form CaCO₃(s). Calcium looping has a number of advantages compared to closer-to-market capture schemes, including: the use of circulating fluidised bed reactors—a mature technology at large scale; sorbent derived from cheap, abundant and environmentally benign limestone and dolomite precursors; and the relatively small efficiency penalty that it imposes on the power/industrial process (i.e., estimated at 6-8 percentage points, compared to 9.5-12.5 from amine-based post-combustion capture). A further advantage is the synergy with cement manufacture, which potentially allows for decarbonisation of both cement manufacture and power production. In addition, a number of advanced applications offer the potential for significant cost reductions in the production of hydrogen from fossil fuels coupled with CO₂ capture. The range of applications of calcium looping are discussed here, including the progress made towards demonstrating this technology as a viable post-combustion capture technology using small-pilot scale rigs, and the early progress towards a 2 MW scale demonstrator.     

Integration of a Ca looping system for CO2 capture in existing power plants

This work analyses a Ca looping system that uses CaO as regenerable sorbent to capture CO₂ from the flue gases generated in power plants. The CO₂ is captured by CaO in a CFB carbonator while coal oxycombustion provides the energy required to regenerate the sorbent. Part of the energy introduced into the calciner can be transferred to a new supercritical steam cycle to generate additional power. Several case studies have been integrated with this steam cycle. Efficiency penalties, mainly associated with the energy consumption of the ASU, CO₂ compressor and auxiliaries, can be as low as 7.5% p. of net efficiency when working with low‐CaCO₃ make‐up flows and integrating the Ca looping with a cement plant that makes use of the spent sorbent. The penalties increase to 8.3% p. when this possibility is not available. Operation conditions aiming at minimum calciner size result in slightly higher‐efficiency penalties. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

NO removal performance of CO in carbonation stage of calcium looping for CO2 capture

Calcium looping realizes CO2 capture via the cyclic calcination/carbonation of CaO.The combustion of fuel supplies energy for the calciner.It is unavoidable that some unburned char in the calciner flows into the carbonator,generating CO due to the hypoxic atmosphere in the carbonator.CO can reduce NO in the flue gases from coal-fired power plants.In this work,NO removal performance of CO in the carbonation stage of calcium looping for CO2 capture was investigated in a bubbling fluidized bed reactor.The effects of carbonation temperature,CO concentration,CO2 capture,type of CaO,number of CO2 capture cycles and presence of char on NO removal by CO in carbonation stage of calcium looping were discussed.CaO possesses an efficient catalytic effect on NO removal by CO.High temperature and high CO concen-tration lead to high NO removal efficiency of CO in the presence of CaO.Taking account of better NO removal and CO2 capture,the optimal carbonation temperature is 650 ℃.The carbonation of CaO reduces the catalytic activity of CaO for NO removal by CO due to the formation of CaCO3.Besides,the catalytic performance of CaO on NO removal by CO gradually decreases with the number of CO2 capture cycles.This is because the sintering of CaO leads to the fusion of CaO grains and blockage of pores in CaO,hin-dering the diffusion of NO and CO.The high CaO content and porous structure of calcium-based sorbents are beneficial for NO removal by CO.The presence of char promotes NO removal by CO in the carbonator.CO2/NO removal efficiencies can reach above 90％.The efficient simultaneous NO and CO2 removal by CO and CaO in the carbonation step of the calcium looping seems promising.     

The combined effect of H2O and SO2 on the simultaneous calcination/sulfation reaction in CFBs

The combined effect of H₂O and SO₂ on the reaction kinetics and pore structure of limestone during simultaneous calcination/sulfation reactions under circulating fluidized bed (CFB) conditions was first studied in a constant-temperature reactor. H₂O can accelerate the sulfation reaction rate in the slow-sulfation stage significantly but has a smaller effect in the fast-sulfation stage. H₂O can also accelerate the calcination of CaCO₃, and should be considered as a catalyst, as the activation energy for the calcination reaction was lower in the presence of H₂O. When the limestone particles are calcining, SO₂ in the flue gas can react with CaO on the outer particle layer and the resulting CaSO₄ blocks the CaO pores, increases the diffusion resistance of CO₂, and, in consequence, decreases the calcination rate of CaCO₃. Here, gases containing 15% H₂O and 0.3% SO₂ are shown to increase the calcination rate. This means that the accelerating effect of 15% H₂O on CaCO₃ decomposition is stronger than the impeding effect caused by 0.3% SO₂. The calcination rate of limestone particles was controlled by both the intrinsic reaction and the CO₂ diffusion rate in the pores, but the intrinsic reaction rate played a major role as indicated by the effectiveness factors determined in this work. This may explain the synergic effect of H₂O and SO₂ on CaCO₃ decomposition observed here. Finally, the effect of H₂O and SO₂ on sulfur capture in a 600 MWe CFB boiler burning petroleum coke is also analyzed. The sulfation performance of limestone evaluated by simultaneous calcination/sulfation is shown to be much higher than that by sulfation of CaO. Based on our calculations, a novel use of the wet flue gas recycle method was put forward to improve the sulfur capture performance for high-sulfur low-moisture fuels such as petroleum coke. © 2019 American Institute of Chemical Engineers AIChE J, 65: 1256–1268, 2019     

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.     

Multiphase CFD Modeling for a Chemical Looping Combustion Process (Fuel Reactor)

There are growing concerns about increasing emissions of greenhouse gases and a looming global warming crisis. CO₂ is a greenhouse gas that affects the climate of the earth. Fossil fuel consumption is the major source of anthropogenic CO₂ emissions. Chemical looping combustion (CLC) has been suggested as an energy‐efficient method for the capture of carbon dioxide from combustion. A chemical‐looping combustion system consists of a fuel reactor and an air reactor. The air reactor consists of a conventional circulating fluidized bed and the fuel reactor is a bubbling fluidized bed. The basic principle involves avoiding direct contact of air and fuel during the combustion. The oxygen is transferred by the oxygen carrier from the air to the fuel. The water in combustion products can be easily removed by condensation and pure carbon dioxide is obtained without any loss of energy for separation. With the improvement of numerical methods and more advanced hardware technology, the time required to run CFD (computational fluid dynamic) codes is decreasing. Hence, multiphase CFD‐based models for dealing with complex gas‐solid hydrodynamics and chemical reactions are becoming more accessible. To date, there are no reports in the literature concerning mathematical modeling of chemical‐looping combustion using FLUENT. In this work, the reaction kinetics models of the (CaSO₄ + H₂) fuel reactor is developed by means of the commercial code FLUENT. The effects of particle diameter, gas flow rate and bed temperature on chemical looping combustion performance are also studied. The results show that the high bed temperature, low gas flow rate and small particle size could enhance the CLC performance.     

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.     

Development of a Scalable Method for Manufacturing High‐Temperature CO2 Capture Sorbents

An engineered process for scalable manufacture of a calcium aluminum carbonate CO₂ sorbent with production amounts of about 1000 g per hour has been developed. The process includes mixing and heating, solid‐liquid separation, drying and extrusion, crushing and conveying, and calcined molding steps. The sorbent preparation involves the coprecipitation of Ca²⁺, Al³⁺, and CO₃^2– under alkaline conditions. By adjusting the Ca:Al molar ratio, a series of Ca‐rich materials could be synthesized for use as CO₂ sorbents at 750 °C. A calcium acetate‐derived sorbent exhibited better cyclic stability than sorbents originating from CaCl₂ and Ca(NO₃)₂. The initial sorption capacity increased with CaO concentration. High stability of more than 90 % was maintained by the Ca:Al sorbents after 40 looping tests.     

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.     

Simultaneous Carbonation and Sulfation of CaO in Oxy‐Fuel CFB Combustion

For anthracites and petroleum cokes, the typical combustion temperature in a circulating fluidized bed (CFB) is > 900 °C. At CO₂ concentrations of 80–85 % (typical of oxy‐fuel CFBC conditions), limestone still calcines. When the ash which includes unreacted CaO cools to the calcination temperature, carbonation of fly ash deposited on cool surfaces may occur. At the same time, indirect and direct sulfation of limestone also will occur, possibly leading to more deposition. In this study, CaO was carbonated and sulfated simultaneously in a thermogravimetric analyzer (TGA) under conditions expected in an oxy‐fuel CFBC. It was found that temperature, and concentrations of CO₂, SO₂, and especially H₂O are important factors in determining the carbonation/sulfation reactions of CaO.     

Increasing Porosity of Molded Calcium‐Based Sorbents by Glucose Templating for Cyclic CO2 Capture

With the aim to enhance the CO₂ capture capacity and anti‐attrition property of CaO‐based sorbents simultaneously, a novel CaO‐based sphere was prepared by extrusion‐spheronization using Ca(OH)₂ powder with glucose templating. The CO₂ capture characteristics and attrition resistance property of the sorbent were examined and the microstructure of the sorbents was analyzed. The results demonstrate that the obtained spherical sorbents exhibit an outstanding anti‐attrition performance compared to limestone sorbent. After 100 cycles, all of the templated sorbents hold a CO₂ capture capacity of more than one time higher than that of limestone. The optimum templating rate of glucose in the sorbent was 1–5 wt %.