The kinetics and pore structure of sorbents during the simultaneous calcination/sulfation of limestone in CFB

The interaction of calcination and sulfation in the simultaneous calcination/sulfation of limestone sorbent under circulating fluidized bed boiler conditions was studied. A specially designed constant-temperature reactor which can stop the reaction at a given time was employed. When limestone entered the furnace of mixed gases of CO2, O2, SO2, etc., its weight went down first, then up, so there was a minimum weight point. The whole reaction period could be divided into two stages by this minimum weight point, named the weight-loss stage and the weight-growth stage, which were dominated by the calcination reaction and by the sulfation reaction, respectively. In the weight-loss stage, the sulfation reaction took place and CaSO4 formed simultaneously together with limestone calcination as long as SO2 was present. In the weight-growth stage, the sulfation ratio at 60 min in simultaneous calcination/sulfation is 30.7% higher than that in the sequential calcination then sulfation process. The weight loss rate of limestone calcined in the presence of SO2 was lower than that without SO2 present but the final weight was higher. The calcination of limestone was slowed by the presence of SO2; a probable mechanism was proposed, namely that the CaSO4 formed may fill or plug the pores in the CaO layer, and impede the transfer of CO2 and, therefore, retard the calcination reaction. This mechanism was supported by the observation that the effective diffusion coefficient of CO2 in CaO produced in the presence of SO2 was reduced. The impeding effect increased with increasing SO2 concentration (0–3000 ppm), while, when the particle size decreased from 0.4–0.45 mm to 0.2–0.25 mm, the calcination rate of limestone was higher, no matter whether there was SO2 present or not. The impeding effect was less pronounced at 880 °C than at 850 °C. The reason for this appears to be the fact that there was less CaSO4 formed at 880 °C and, therefore, fewer pores of the particle were filled or plugged

The simultaneous calcination/sulfation reaction of limestone under oxy-fuel CFB conditions

Using a customized thermogravimetric analyzer, the characteristics of the simultaneous calcination/sulfation reaction of limestone (the simultaneous reaction) under oxy-fuel circulating fluidized bed (CFB) boiler conditions were investigated. The results were compared with the calcination-then-sulfation reaction (the sequential reaction) that has been widely adopted by previous investigators. The sample mass in the simultaneous reaction was higher than that in the sequential reaction. With the increase of SO2 concentration (0–0.9%), the mass difference between the two reaction scenarios increased; while with the increase of temperature (890–950 °C), the difference became smaller. Calcination in the presence of SO2 was slower than that without SO2. With the increase of SO2 concentration, the pore volume of the calcined CaO decreased, and the effectiveness factors of the calcination reaction also declined. This indicates when CaSO4 forms, the pores in CaO were filled or blocked, thus increasing the internal resistance to CO2. Because the simultaneous process is the real one in CFB boilers, and it shows different characteristics from the sequential reaction, all investigations of CaO sulfation in CFB should follow this approach. Also in this work, the effects of SO2 concentration, temperature and H2O on the simultaneous reaction were studied. The sulfation ratio in the simultaneous reaction increased with higher SO2 concentration. Compared with that in the absence of H2O, 8% H2O in flue gas significantly improved sulfation. In the tested range (890–950 °C), the optimum temperature for sulfation was around 890 °C. The sulfation rate in the mass-loss stage was higher than that in the fast sulfation stage, which is likely due to the continuous generation of nascent CaO in this stage

Modelling the simultaneous calcination/sulfation behavior of limestone under circulating fluidized bed combustion conditions

The simultaneous calcination/sulfation (SCS) reaction is the realistic reaction process for limestone use in CFB boilers. A SCS reaction model based on the randomly-overlapped pore concept, which takes into consideration the calcination of CaCO3, the sulfation of CaO and the sintering effect simultaneously, was developed. The results of this model fit well with the results from the thermogravimetric analyzer (TGA) tests and, thus this model was used to study the characteristics of the SCS reaction. The SCS reaction consists of a mass-loss stage and a mass-growth stage, and the two stages are seperated by a minimum mass point. The mass-loss stage is dominated by the calcination of CaCO3, while the mass-growth stage is dominated by the sulfation of CaO. The minimum mass point is a balance point of the mass change caused by the two reactions. The calcination reaction occurred in a layer of the particle. As the calcination reaction progresses, the reaction front moves inward and a CaO layer is formed. The SO2 in the calcination atmosphere can react with the CaO layer and produce CaSO4. The CaSO4 can fill the pores of the CaO layer and narrow the pore width, increase the CO2 diffusion resistance and consequently slow the calcination reaction. The sulfation reaction becomes slower as the reaction progresses. There was an upper limit to the sulfation conversion, which is much higher in the outer layer of the particle. For a typical particle with a radius of 200 μm, the sulfation reaction ceases in the inner part (0-150 μm) of the particle due to the exhaustion of SO2, while in the outer part of the particle (150-200 μm), the decrease of the sulfation rate is caused by the simultaneous decline of the reaction surface area, surface Ca2+ ion concentration and SO2 concentration

Effect of H2O on the volatilization characteristics of arsenic during isothermal O2/CO2 combustion

The effect of H2O on the volatilization behavior of arsenic in coal was studied under O2/CO2 combustion conditions at 800–1300 ºC, which covers the effective range of coal combustion temperatures appropriate for conventional coal combustion technologies. By controlling the combustion time of the coal, the volatilization percentage and rate of As emissions versus time were obtained. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses were used to study the evolution of minerals with and without H2O under O2/CO2 combustion conditions. The effect of CO2 on As volatilization was first investigated and it was found that increasing CO2 concentrations inhibits the volatilization of As, with this effect decreasing with increasing temperature. When a fraction of the CO2 was replaced with H2O, the volatilization of As increased, but the positive effect of H2O also decreased with increasing temperature. The volatilization percentage of As with 30% H2O was 6.1% higher than that without H2O at 800 ºC, while it was only 2.7% higher at 1300 ºC. When the concentration of H2O increased from 0 to 30%, the peak value of the As volatilization rate increased and the time needed to reach the peak value decreased. The volatilization characteristics of As for three coals were very similar, which demonstrates that the effect of H2O was not limited to only one specific coal

The effect of H2O on formation mechanism of arsenic oxide during arsenopyrite oxidation: Experimental and theoretical analysis

The effect of H2O on arsenic release behavior was investigated via experiment and first-principles density functional theory (DFT). The experimental results show that sulfide-bound arsenic is the main form present in coal, and that H2O has a positive influence on the release of arsenic during coal combustion. Furthermore, DFT calculations were performed to investigate the mechanism for H2O influence on arsenic oxidation. Thermodynamic and kinetic analyses were also conducted to study the influence of temperature on the reaction process. From thermodynamic analysis, arsenic oxide formation on the FeS2 (1 0 0) surface with and without H2O weakens with increasing temperature. In addition, the equilibrium constant for the reaction with H2O addition is slightly higher than that for the reaction without H2O, which suggests that the degree of the chemical reaction in the presence of H2O should increase. From kinetic analysis, the reaction rate constants increase with temperature, and the activation energy of the arsenic oxide formation reaction with and without H2O is 100.72 kJ/mol and 124.08 kJ/mol, respectively. This indicates that H2O adsorption on the surface can decrease the energy barrier and accelerate the reaction forming arsenic oxide. Based on the thermodynamic and kinetic analyses, it can be concluded that temperature has an inhibitory influence on reaction equilibrium and positive influence on the reaction rate. The experiment and calculation results explain the influence of H2O on the formation mechanism of arsenic oxide and provide a theoretical foundation for the emission and control of arsenic

Stabilization of Ni-containing Keggin-type polyoxometalates with variable oxidation states as novel catalysts for electrochemical water oxidation †

The development of new recyclable and inexpensive electrochemically active species for water oxidation catalysis is the most crucial step for future utilization of renewables. Particularly, transition metal complexes containing internal multiple, cooperative metal centers to couple with redox catalysts in the inorganic Keggin-type polyoxometalate (POM) framework at high potential or under extreme pH conditions would be promising candidates. However, most reported Ni-containing POMs have been highly unstable towards hydrolytic decomposition, which precludes them from application as water oxidation catalysts (WOCs). Here, we have prepared new tri-Ni-containing POMs with variable oxidation states by charge tailored synthetic strategies for the first time and developed them as recyclable POMs for water oxidation catalysts. In addition, by implanting corresponding POM anions into the positively charged MIL-101(Cr) metal–organic framework (MOF), the entrapped Ni2+/Ni3+ species can show complete recyclability for water oxidation catalysis without encountering uncontrolled hydrolysis of the POM framework. As a result, a low onset potential of approximately 1.46 V vs. NHE for water oxidation with stable WOC performance is recorded. Based on this study, rational design and stabilization of other POM-electrocatalysts containing different multiple transition metal centres could be made possible

Effect of Flammulina velutipes polysaccharides on the physicochemical properties of catfish surimi and myofibrillar protein oxidation during frozen storage

This study investigated the effect of Flammulina velutipes polysaccharides (FVPs) on the myofibrillar protein (MP) oxidation protein and physicochemical properties of catfish surimi during 75 days of frozen storage at −18°C. FVP was added to surimi at 1%, 1.5%, and 2%, respectively; the degree of MP oxidation and the physicochemical properties of the surimi were investigated, and the microstructure of the surimi was observed by scanning electron microscopy (SEM). The results showed that the carbonyl content and the thiobarbituric acid reactive substances (TBARS) in the FVP groups were lower than those in the CK group (the blank surimi). In comparison, the total sulfhydryl content, solubility, and Ca2+-ATPase activity were higher than those in the CK group after 75 days of storage. The addition of FVP significantly increased the water-holding capacity (WHC), gel strength, elastic modulus (G'), and loss modulus (G“) of surimi, and made the gel of surimi have stronger continuity and a denser structure. Therefore, FVP has a better cryoprotective effect on surimi. It improves the quality of surimi, decreases MP oxidation, and reduces lipid and water loss during frozen storage. The anti-freezing effect of FVP added at 2% was similar to that of commercial protectants (4% sucrose and 4% sorbitol)

Taking the pulse of COVID-19: A spatiotemporal perspective

The sudden outbreak of the Coronavirus disease (COVID-19) swept across the world in early 2020, triggering the lockdowns of several billion people across many countries, including China, Spain, India, the U.K., Italy, France, Germany, and most states of the U.S. The transmission of the virus accelerated rapidly with the most confirmed cases in the U.S., and New York City became an epicenter of the pandemic by the end of March. In response to this national and global emergency, the NSF Spatiotemporal Innovation Center brought together a taskforce of international researchers and assembled implemented strategies to rapidly respond to this crisis, for supporting research, saving lives, and protecting the health of global citizens. This perspective paper presents our collective view on the global health emergency and our effort in collecting, analyzing, and sharing relevant data on global policy and government responses, geospatial indicators of the outbreak and evolving forecasts; in developing research capabilities and mitigation measures with global scientists, promoting collaborative research on outbreak dynamics, and reflecting on the dynamic responses from human societies.Comment: 27 pages, 18 figures. International Journal of Digital Earth (2020