Cyclic calcination/carbonation looping of dolomite modified with acetic acid for CO2 capture

The dolomite modified with acetic acid solution was proposed as a CO₂ sorbent for calcination/carbonation cycles. The carbonation conversions for modified and original dolomites in a twin fixed-bed reactor system with increasing the numbers of cycles were investigated. The carbonation temperature in the range of 630 °C–700 °C is beneficial to the carbonation reaction of modified dolomite. The carbonation conversion for modified dolomite is significantly higher than that for original sorbent at the same reaction conditions with increasing numbers of reaction cycles. The modified dolomite exhibits a carbonation conversion of 0.6 after 20 cycles, while the unmodified sorbent shows a conversion of 0.26 at the same reaction conditions, which is calcined at 920 °C and carbonated at 650 °C. At the high calcination temperature over 920 °C modified dolomite can maintain much higher conversion than unmodified sorbent. The mean grain size of CaO derived from modified dolomite is smaller than that from original sorbent with increasing numbers of reaction cycles. The calcined modified dolomite possesses greater surface area and pore volume than calcined original sorbent during the multiple cycles. The pore volume and pore area distributions for calcined modified dolomite are also superior to those for calcined unmodified sorbent during the looping cycle. The modified dolomite is proved as a new and promising type of regenerable CO₂ sorbent for industrial applications.     

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.     

Low Temperature Liquid State Synthesis of Lithium Zirconate and its Characteristics as a CO2 Sorbent

Abstract

In this study, a new preparation method providing greatly improved CO₂ sorption is introduced. Li₂ZrO₃ sorbent was prepared by low temperature co‐precipitation and compared in CO₂ sorption performance with a sorbent prepared by the conventional high temperature solid‐state reaction method. The two sorbents were characterized using scanning electron microscopy, X‐ray diffraction and thermo‐gravimetric analysis. The Li₂ZrO₃ powder prepared by the relatively simple co‐precipitation method showed significantly better performance than the one prepared by solid‐state reaction with respect to both kinetics and CO₂ sorption capacity. Extensive study of the powder prepared by co‐precipitation has been performed at various conditions.     

Calcium-based sorbents behaviour during sulphation at oxy-fuel fluidised bed combustion conditions

Sulphur capture by calcium-based sorbents is a process highly dependent on the temperature and CO₂ concentration. In oxy-fuel combustion in fluidised beds (FB), CO₂ concentration in the flue gas may be enriched up to 95%. Under so high CO₂ concentration, different from that in conventional coal combustion with air, the calcination and sulphation behaviour of the sorbent must be defined to determine the optimum operating temperature in the FB combustors.In this work, the SO₂ retention capacity of two different limestones was tested by thermogravimetric analysis at typical oxy-fuel conditions in FB combustors. The effect of the main operating variables affecting calcination and sulphation reactions, like CO₂ and SO₂ concentrations, temperature, and sorbent particle size, was analysed.It was observed a clear difference in the sulphation conversion reached by the sorbent whether the sulphation takes place under indirect or direct sulphation, being much higher under indirect sulphation. But, in spite of this difference, for a given condition and temperature, the CO₂ concentration did not affect to the sulphation conversion, being its major effect to delay the CaCO₃ decomposition to a higher temperature.For the typical operating conditions and sorbent particle sizes used in oxy-fuel FB combustors, the maximum sorbent sulphation conversions were reached at temperatures of about 900 °C. At these conditions, limestone sulphation took place in two steps. The first one was controlled by diffusion through porous system of the particles until pore plugging, and the second controlled by the diffusion through product layer. As a consequence, the maximum sulphation conversion increased with decreasing the particle size and increasing the SO₂ concentration.     

Effect of water pretreatment on CO<Subscript>2</Subscript> capture using a potassium-based solid sorbent in a bubbling fluidized bed reactor

A bubbling fluidized bed reactor was used to study CO₂ capture from flue gas by using a potassium-based solid sorbent, sorbKX35 which was manufactured by the Korea Electric Power Research Institute. A dry sorbent, sorbKX35, consists of K₂CO₃ for absorption and supporters for mechanical strength. To increase initial CO₂ removal, some amount of H₂O was absorbed in the sorbent before injecting simulated flue gas. It was possible to achieve 100% CO₂ removal for more than 10 minutes at 60°C and a residence time of 2 s with H₂O pretreatment. When H₂O pretreatment time was long enough to convert K₂CO₃ of sorbKX35 into K₂CO₃ · 1.5H₂O, CO₂ removal was excellent. The results obtained in this study can be used as basic data for designing and operating a large scale CO₂ capture process with two fluidized bed reactors. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

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.     

Effect of Regeneration Temperature on the Composition and Carbon Dioxide Sorption Ability of a K2CO3/Al2O3 Solid Sorbent in a Bubbling Fluidized Bed Reactor

The effect of the regeneration temperature (150°, 250°, and 350°C) during multiple CO₂ cyclic sorption-regeneration cycles of a K₂CO₃/Al₂O₃ solid sorbent in a bubbling fluidized bed reactor was evaluated in terms of the CO₂ capture capacity and chemical composition of the solid sorbent. The CO₂ capture capacity after regeneration at 150° and 250°C decreased with increasing cycle numbers, reaching approximately 57 and 78%, respectively, and 19.0 and 39.3%, respectively, of the original capacity after one and five regeneration cycles. This decline in the CO₂ capture capacity was due to the accumulation of KHCO₃ (at 150°C) and KAl(CO₃)₂(OH)₂ (150° and 250°C) from their incomplete degradation back to the K₂CO₃/Al₂O₃ solid sorbent. When regenerated at 350°C, the CO₂ capture capacity remained essentially constant in each cycle number because of complete desorption (no residual KHCO₃ and KAl(CO₃)₂(OH)₂). The formation mechanism of complex structure occurred similar to the one in a fixed bed reactor/thermogravimetric analyzer with lower regeneration temperature. The general operation conditions for K₂CO₃/Al₂O₃ solid sorbents are summarized.     

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.     

Enhanced hydrogen production from biomass with in situ carbon dioxide capture using calcium oxide sorbents

The steam gasification of biomass, in the presence of a calcium oxide (CaO) sorbent for carbon dioxide (CO₂) capture, is a promising pathway for the renewable and sustainable production of hydrogen (H₂). In this work, we demonstrate the potential of using a CaO sorbent to enhance hydrogen output from biomass gasifiers. In addition, we show that CaO materials are the most suitable sorbents reported in the literature for in situ CO₂ capture. A further advantage of the coupled gasification-CO₂ capture process is the production of a concentrated stream of CO₂ as a byproduct. The integration of CO₂ sequestration technology with H₂ production from biomass could potentially result in the net removal of CO₂ from the atmosphere.Maximum experimental H₂ concentrations reported for the steam gasification of biomass, without CO₂ capture, range between 40%-vol and 50%-vol. When CaO is used to remove CO₂ from the product gas, as soon as it is formed, we predict an increase in the H₂ concentrations from 40%-vol to 80%-vol (dry basis), based on thermodynamic modelling and previously published data.We examine the effect of key variables, with a specific focus on obtaining fundamental data relevant to the design and scale-up of novel biomass reactors. These include: (i) reaction temperature, (ii) pressure, (iii) steam-to-biomass ratio, (iv) residence time, and (v) CO₂ sorbent loading. We report on operational challenges related to in situ CO₂ capture using CaO-based sorbents. These include: (i) sorbent durability, (ii) limits to the maximum achievable conversion and (iii) decay in reactivity through multiple capture and release cycles. Strategies for enhancing the multicycle reactivity of CaO are reviewed, including: (i) optimized calcination conditions, and (ii) sorbent hydration procedures for reactivation of spent CaO. However, no CaO-based CO₂ sorbent, with demonstrated high reactivity, maintained through multiple CO₂ capture and release cycles, has been identified in the literature. Thus, we argue that the development of a CO₂ sorbent, which is resistant to physical deterioration and maintains high chemical reactivity through multiple CO₂ capture and release cycles, is the limiting step in the scale-up and commercial operation of the coupled gasification-CO₂ capture process.     

Development of new alumina-modified sorbents for CO2 sorption and regeneration at temperatures below 200 °C

A new regenerable alumina-modified sorbent was developed for CO₂ capture at temperatures below 200 °C. The CO₂ capture capacity of a potassium-based sorbent containing Al₂O₃ (KAlI) decreased during multiple CO₂ sorption (60 °C) and regeneration (200 °C) tests due to the formation of the KAl(CO₃)(OH)₂ phase, which could be converted into the original K₂CO₃ phase above 300 °C. However, the new regenerable potassium-based sorbent (Re-KAl(I)) maintained its CO₂ capture capacity during multiple tests even at a regeneration temperature of 130 °C. In particular, the CO₂ capture capacity of the Re-KAl(I)60 sorbent which was prepared by the impregnation of Al₂O₃ with 60 wt.% K₂CO₃ was about 128 mg CO₂/g sorbent. This excellent CO₂ capture capacity and regeneration property were due to the characteristics of the Re-KAl(I) sorbent producing only a KHCO₃ phase during CO₂ sorption, unlike the KAlI30 sorbent which formed the KHCO₃ and KAl(CO₃)(OH)₂ phases even at 60 °C. This result was explained through the structural effect of the support containing the KAl(CO₃)(OH)₂ phase which was prepared by impregnation of Al₂O₃ with K₂CO₃ in the presence of CO₂.     

Application of engineered natural ores to intermediate- and high-temperature CO2 capture and conversion

Integrated CO₂ capture and conversion (ICCC) is a promising technology aiming at converting waste CO₂ to fuels and high value-added chemicals. Herein, we described a proof-of-concept study of applying engineered natural ores (dolomite, magnesite, and limestone) to two different ICCC processes—intermediate-temperature ICCC for CH₄ production (350–400°C) and high-temperature ICCC for syngas production (650–700°C). In the former process, a MgO-based CO₂ sorbent prepared from dolomite and magnesite was combined with a methanation catalyst in a dual-bed configuration, whereby a CH₄ yield of 7.1–7.3 mmol/g can be stably achieved per cycle over 20 consecutive ICCC cycles. In the latter process, a CaO-based sorbent derived from dolomite and limestone was coupled with a reforming catalyst also in a dual-bed mode, whereby syngas with a H₂/CO ratio of 0.9–1.0 can be produced over 20 cycles. This study will expand the application of natural ores in CO₂ emission reduction.     

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     

Sorbent-enhanced/membrane-assisted steam-methane reforming

Thermodynamic equilibrium and kinetic reactor models are used to simulate a fluidized bed membrane reactor with in situ or ex situ hydrogen and/or CO₂ removal for production of pure hydrogen by steam methane reforming. In the equilibrium model, the membranes and CO₂ removal are located in separate vessels downstream of the reformer. As the recycle ratio increases, the overall performance approaches that where membranes are located inside the reactor. Whether located in situ or ex situ, hydrogen removal by membranes and CO₂ capture by sorbents both enhance hydrogen production. In the kinetic reactor model, a circulating fluidized bed membrane reformer is coupled with a catalyst/sorbent regenerator. Sorbent enhancement combined with membranes could provide very high hydrogen yields. In addition, since carbonation is exothermic, with its heat of reaction similar in magnitude to the endothermic heat of reaction of the net reforming reactions, sorbent enhancement can provide much of the heat needed in the reformer. The overall heat needed for the process would then be provided in a separate calciner, acting as a sorbent regenerator. While the technology is promising, several practical issues need to be examined.     

Corrosion behavior of SM 80SS tube steel in stimulant solution containing H2S and CO2

Scanning electron microscopy, X-ray diffraction and electrochemical measurement technique were applied to investigate the corrosion of SM 80SS tube steel in stimulant solution with carbon dioxide (CO₂) and hydrogen sulfide (H₂S) at variable conditions of PCO₂/PH₂S and temperature. The results suggest that there exists a synergism of sweet corrosion and sour corrosion on the steel surface, corrosion attack increases in the initial stage and then decrease with the increase of PCO₂ or PH₂S; serious corrosion occurs in the PCO₂/PH₂S ranged from 31 to 520. In addition, the fitted parabola function equation Y = 0.47873 + 0.04014X - (3.23788E−5)X² is established, and the most serious corrosion is 600 for PCO₂/PH₂S. Under the moderate contents of PCO₂ and PH₂S, the corrosion scale consists of FeS_0.9 and FeCO₃; for relatively high PH₂S, additive product FeS comes into being at high temperature such as T = 150 °C, product FeO(OH) is found in the corrosion scale. The H₂S corrosion has a significant effect on the whole reaction process and iron sulfide is superior to precipitating on the steel surface compared with iron carbonate. In addition, the surface scales of iron sulfide almost act as a diffusion barrier and inhibit the corrosion by a coverage effect strongly depending on H₂S concentration by EIS measurement.     

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.     

The AEROPILs Generation: Novel Poly(Ionic Liquid)-Based Aerogels for CO2 Capture

CO₂ levels in the atmosphere are increasing exponentially. The current climate change effects motivate an urgent need for new and sustainable materials to capture CO₂. Porous materials are particularly interesting for processes that take place near atmospheric pressure. However, materials design should not only consider the morphology, but also the chemical identity of the CO₂ sorbent to enhance the affinity towards CO₂. Poly(ionic liquid)s (PILs) can enhance CO₂ sorption capacity, but tailoring the porosity is still a challenge. Aerogel’s properties grant production strategies that ensure a porosity control. In this work, we joined both worlds, PILs and aerogels, to produce a sustainable CO₂ sorbent. PIL-chitosan aerogels (AEROPILs) in the form of beads were successfully obtained with high porosity (94.6–97.0%) and surface areas (270–744 m²/g). AEROPILs were applied for the first time as CO₂ sorbents. The combination of PILs with chitosan aerogels generally increased the CO₂ sorption capability of these materials, being the maximum CO₂ capture capacity obtained (0.70 mmol g⁻¹, at 25 °C and 1 bar) for the CHT:P[DADMA]Cl_30% AEROPIL.     

Lime enhanced gasification of solid fuels: Examination of a process for simultaneous hydrogen production and CO2 capture

The lime enhanced gasification (LEGS) process uses CaO as a CO₂ carrier and consists of two coupled reactors: a gasifier in which CO₂ absorption by CaO produces a hydrogen-rich product gas, and a regenerator in which the sorbent is calcined producing a high purity CO₂ gas stream suitable for storage. The LEGS process operates at a pressure of 2.0 MPa and temperatures less than 800 °C and therefore requires a reactive fuel such as brown coal. The brown coal ash and sulfur are purged from the regenerator together with CaO which is replaced by fresh limestone in order to maintain a steady-state CaO carbonation activity (a_ave). Equilibrium calculations show the influence of process conditions and coal sulfur content on the gasifier carbon capture (>95% is possible). Material balance calculations of the core process show that the required solid purge of the sorbent cycle is mainly attributed to the necessary removal of ash and CaSO₄ if the solid purge is used as a pre-calcined feedstock for cement production. The decay in the CaO capture capacity over many calcination–carbonation cycles demands a high sorbent circulation ratio but does not dictate the purge fraction. A thermodynamic analysis of a LEGS-based combined power and cement production process, where the LEGS purge is directly used in the cement industry, results in an electric efficiency of 42% using a state of the art combined cycle.     

KINETIC AND STRUCTURAL STUDIES OF REGENERATION OF SULFIDED DOLOMITE IN CARBON DIOXIDE II THE CYCLIC REGENERATION

(Communicated by H.L. Toor)

Regeneration of sulfided dolomite in CO₂, an alternative to regeneration in CO₂/H₂O, has been conducted in a TGA system up to 20 cycles under the optimal regeneration condition. The solid sorbent has shown a much slower deterioration in sulfidation capacity upon cycling by regeneration in CO₂ than in CO₂/H₂O. The utilization of Ca reached 50% in the 20th cycle, compared with the 20% by the CO₂/H₂O regeneration. The XES sulfur profile of partially reacted samples indicated a switch in reaction pattern, both in sulfidation and regeneration, from topochemical to nonlopochemical at the 3th/4th cycle. Incorporaling the concept of solid deactivation, a cyclic regeneration model was developed and successfully predicts the progress of regeneration in a specific cycle and the trend of change in reaction pattern.     

Palladium based sorbents for high temperature arsine removal from fuel gas

The use of Pd-based sorbents for high temperature removal of AsH₃ from gasified coal was investigated using a simulated gas feed. A sorbent consisting of 5 wt% Pd on alumina beads has been tested for AsH₃ removal from synthetic fuel gas (CO, CO₂, H₂) at 204 and 288 °C. Arsenic uptake was found to be essentially linear with exposure time and considerably higher than that for unpromoted alumina beads. Arsenic loadings in excess of 7 wt% were achieved, though the sorbent is unlikely to be saturated at this loading. As the arsenic loading on the sorbent increased a PdAs₂ phase was identified in the XRD pattern. The adsorption of arsine on palladium has potential implications for catalysts, electrodes, and membranes for the separation of hydrogen from fuel gas.     

Removal of hydrogen sulfide from a steam-hydrogasifier product gas by zinc oxide sorbent: Effect of non-steam gas components

Removal of H₂S from a steam-hydrogasifier product gas was studied at 636 K and 1 atm using a commercially available zinc oxide sorbent in a packed-bed reactor. A mixture gas containing 22% CH₄, 18.7% H₂, 8.8% CO and 5.5% CO₂ (non-steam components subtotaling to 55%) balanced with steam was used to simulate the steam-hydrogasifier product gas. Sorbent particles of 150–250 μm size were used to eliminate the effect of intraparticle mass transfer limitation. Experiments were conducted to monitor H₂S breakthrough of reactor effluent stream for operation parameters such as space velocity and inlet H₂S concentration. With space velocity varied from 6000 to 8000 to 12,000 h^?1 for inlet H₂S concentration in the range of 100–800 ppmv, sulfur capture capacity of the sorbent (S_cap) for 2 ppmv H₂S breakthrough did not change notably, indicating that, for each inlet H₂S concentration tested, sorbent utilization for sulfur removal was not affected by the space velocity. Meanwhile, for each space velocity tested, S_cap increased monotonically as the inlet H₂S concentration increased from 100 to 500 to 800 ppmv, which is opposite to the result observed for the mixture gas devoid of CH₄, H₂, CO and CO₂. As the overall content of these non-steam components of the simulation gas was halved for each inlet H₂S concentration tested at 8000 h^?1 space velocity, S_cap for non-steam gas components of 27.5% content corresponded approximately to the median value of those for the non-steam gas components of 55% and 0% content, suggestive of linear dependency of S_cap upon the content of the non-steam components for the inlet H₂S concentration tested.