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.     

Thermal activation of CaO-based sorbent and self-reactivation during CO2 capture looping cycles

In this study, the thermal activation of different types of CaO-based sorbents was examined. Pretreatments were performed at different temperatures (800--1300 degrees C) and different durations (6--48 h) using four Canadian limestones. Sieved fractions of the limestones, powders obtained by grinding, and hydroxides produced following multiple carbonation/calcination cycles achieved in a tube furnace were examined. Pretreated samples were evaluated using two types of thermogravimetric reactors/ analyzers. The most important result was that thermal pretreatment could improve sorbent performance. In comparison to the original, pretreated sorbents showed better conversions over a longer series of CO2 cycles. Moreover, in some cases, sorbent activity actually increased with cycle number, and this effectwas especially pronounced for powdered samples preheated at 1000 degrees C. In these experiments, the increase of conversion with cycle number (designated as self-reactivation) after 30 cycles produced samples that were approximately 50% carbonated for the four sorbents examined here, and there appeared to be the potential for additional increase. These results were explained with the newly proposed pore--skeleton model. This model suggests, in addition to changes in the porous structure of the sorbent, that changes in the pore--skeleton produced during pretreatment strongly influence subsequent carbonation/ calcination cycles.     

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.     

Modeling the temperature in coal char particle during fluidized bed combustion

The temperatures of a coal char particle in hot bubbling fluidized bed (FB) were analyzed by a model of combustion. The unsteady model includes phenomena of heat and mass transfer through a porous char particle, as well as heterogeneous reaction at the interior char surface and homogeneous reaction in the pores. The parametric analysis of the model has shown that above 550 °C combustion occurs under the regime limited by diffusion. The experimental results of temperature measurements by thermocouple in the particle center during FB combustion at temperatures in the range 590-710 °C were compared with the model predictions. Two coals of different rank were used: lignite and brown coal, with particle size in the range 5-10 mm. The comparisons have shown that the model can adequately predict the histories of temperatures in char particles during combustion in FB. In the first order, the model predicts the influence of the particle size, coal rank (via porosity), and oxygen concentration in its surroundings.     

Investigation on thermal radiation spectra of coal ash deposits

This paper deals with thermal radiation properties of ash deposits on a pulverized coal boiler of an electric power plant. Normal emittance spectra in the 2.5–25 μm interval, and total normal emittance, were measured on 4 kinds of ash layers of a mm magnitude order thickness, at 560 → 1460 → 560 K in heating and cooling. It was found that ash powder layers are opaque for infrared radiation. The emittance increases with ash radiation wavelength and temperature. Ash powder is sintered and fused above 1200 K. The emittance of the sintered layer is above that of the unsintered layer. The authors propose, and explain by an example, correlating the experimentally obtained emittance spectra of ash deposits with a continuous curve, the formula of which defines the dependence of emittance on wavelength and temperature, i.e. ε = ε(λ,Т). Use of this formula, with parameter values determined by the proposed methodology, may greatly simplify the practical application of the experimentally determined emittances in the thermal design of existing and new steam boiler furnaces.     

Steam reactivation of spent CaO-based sorbent for multiple CO2 capture cycles

This study examines steam reactivation of sorbent to improve the reversibility of multiple CaO-CO2 capture cycles. Experiments to obtain spent sorbent were performed in a tube furnace, and reactivation was achieved using steam in a pressurized reactor. Sorbent activity for CO2 capture was then tested in a thermogravimetric analyzer (TGA), in multi-cycle carbonation tests. After reactivation the sorbent had even better characteristics for CO2 capture than that of the natural sorbent. The average carbonation degree over 10 cycles for the reactivated sorbent approached 70%, significantly higher than for the original sorbent (35-40%). This means that the same sorbent may achieve effective CO2 capture over a large number of cycles, in the absence of other phenomena such as attrition. Partially sulfated sorbents may also be reactivated, but hydration itself is also hindered by sulfation.     

Steam hydration of sorbents from a dual fluidized bed CO2 looping cycle reactor

Results are presented on steam hydration of spent residues obtained from a 75 kW_th dual fluidized bed combustion (FBC) pilot plant unit operating in a CO₂ looping cycle mode. The samples were collected from the unit under various conditions, which included electrical heating of the reactor, as well as firing with coal, and biomass under oxy-fuel combustion conditions. In addition, different operating times, i.e., number of cycles (25 min–455 min/1–25 cycles) were examined, with the carbonator operating at temperatures of 600–700 °C and the calciner at 850–900 °C. The samples collected came from the calciner, carbonator and cyclone. Steam hydration itself was done under atmospheric pressure in saturated steam at 100 °C for periods of 15, 30 and 60 min. The original limestone sample, as well as the spent samples from the pilot plant and the hydrated samples were examined to determine their hydration and carbonation levels, as well as their unreacted CaO content using TGA and XRD analysis. In addition, samples were characterized for pore distribution (nitrogen adsorption/desorption: BET and BJH), skeleton characterization, with density by He pycnometry and particle surface area morphology (SEM/EDX), as well as changes in sample volume during hydration (sample swelling). The results obtained showed successful hydration (typically only ～10% unreacted CaO) even for hydration periods as short as 15 min, and very favorable sample properties. Their pore surface area, pore volume distribution and swelling during hydration are promising with regard to their use in additional CO₂ capture cycles or SO₂ retention. However, their predisposition to fracture is the main disadvantage observed with these samples. This may result in difficulties in terms of their handling in FBC systems, due to intensified attrition and consequent elutriation from the reactor.     

The morphology of limestone-based pellets prepared with kaolin-based binders

Modifications and pelletization of limestone were investigated in order to improve the utilization of CaO-based materials for different catalytic reactions and environmental applications. Attempts to purify the limestone by ion-exchange with CaCl₂ solution did not result in significant removal of impurities. On the other hand, acetification with 10 vol.% acetic acid enhanced pore surface area and pore volume of the sorbent by 42% and 3-fold, respectively. The acetification was found to widen small pores, and thus create a beneficial pore size distribution with more pores in the range of 25–100 nm. In order to utilize such powdered materials in fluidized beds, pelletization is the next step. Unfortunately, pelletization results suggested that natural kaolin is an unsuitable binder for preparing CaO-based pellets due to its negative impact on pellet morphology. By contrast, Al(OH)₃ binder obtained from kaolin leaching had a strong positive effect on the porous texture of the pellets, demonstrated by pore surface area and volume of 22.48 m² g⁻¹ and 0.051 cm³ g⁻¹ for 1 mm pellets with CaO/binder ratio of 5.5, compared to 10.92 m² g⁻¹ and 0.039 cm³ g⁻¹ for natural materials. The enhancement in pellet morphology is mainly attributed to transformation of Al(OH)₃ to the highly porous Al₂O₃ at high temperatures. Pellets synthesized from limestone modified with 10 vol.% acetic acid with Al(OH)₃ binder (ratio of 5.5) exhibited high pore surface area and volume, represented by 1.3-fold and 44% increase over those for natural limestone. It was concluded that the combination of acetified limestone with Al(OH)₃ binder is a promising approach for synthesis of CaO-based pellets with enhanced morphology.     

Simulative optimization of catalyst configuration for biogas dry reforming

Biogas dry reforming is a promising technology for converting biomass into high-value products and reducing greenhouse gas emissions. Recent improvements to biogas reforming have mainly focused on the preparation of functional catalysts; however, little attention has been paid to the effects of catalyst configuration in plug flow reactors. In this study, a Ni/MgO catalyst for biogas reforming was synthesized via the wet impregnation method. Parameters were optimized using an experimental rig and then simulations were performed using an Aspen HYSYS reaction simulator. We simulated loading the same amount of catalyst into 1, 2, 3, or 10 zones inside the reactor and compared performance parameters, including H₂ yield, CO yield, CH₄ conversion, and CO₂ conversion. The results of simulations showed that a 2-zone configuration with a catalyst ratio of 1:4 was optimal, with 88.2% H₂ yield, 83.5% CO yield, 96.4% CH₄ conversion, and 91.7% CO₂ conversion. Catalyst zone number, catalyst distribution, and catalyst zone position all had significant effects on catalytic behavior. The findings of this study provide new insights into the processes of biogas reforming and other heterogeneous catalysis reactions.