Characteristics and reactivities of Ca(OH)2/silica fume sorbents for low-temperature flue gas desulfurization

Ca(OH)₂/silica fume sorbents were prepared with various Ca(OH)₂/silica fume weight ratios and slurrying times at 65°C and a water/solid ratio of 10/1. Dry sorbents prepared were characterized, and their reactivities toward SO₂ were measured in a differential fixed-bed reactor at the conditions similar to those in the bag filters in the dry and semidry flue gas desulfurization (FGD) processes. The reaction between Ca(OH)₂ and silica fume in the slurry was very fast. The formation of calcium silicate hydrates, which were mainly C-S-H(I), resulted in sorbent particles with a highly porous structure that seemed compressible under high pressures. The sorbents were mesoporous, and their specific surface areas and pore volumes were much larger than those of Ca(OH)₂ alone. The utilization of Ca of sorbent increased with increasing silica fume content mainly due to the increase in the specific surface area of sorbent. The sorbent with Ca(OH)₂ had the maximum SO₂ capture. Sorbents with Ca(OH)₂ contents less than and greater than would have a SO₂ capture greater than that of Ca(OH)₂ alone. Both the utilization of Ca and SO₂ capture per unit specific surface area of sorbent decreased in general with increasing specific surface area. At the same Ca(OH)₂ content, the utilization of Ca or SO₂ capture of the Ca(OH)₂/silica fume sorbent was greater than that of the Ca(OH)₂/fly ash sorbent; however, the amount of SO₂ captured per unit surface area of the former sorbent was smaller than that of the latter sorbent. The results of this study are useful to the preparation of silica-enhanced sorbents for use in the dry and semidry FGD processes.     

Preparation of diatomite/Ca(OH)2 sorbents and modelling their sulphation reaction

Mixtures of Ca(OH)₂ and diatomite were hydrated at different conditions to produce reactive SO₂ sorbents. Two different hydration techniques were used; namely, atmospheric and pressure hydration. The effect of the hydration temperature, time and diatomite/Ca(OH)₂ weight ratio on the physical properties of the activated sorbents were investigated. In atmospheric hydration, it was found that increasing the temperature and hydration time caused an increase in the total surface area of the sorbents. However, surface area values of the sorbents prepared from mixtures which have different diatomite/Ca(OH)₂ weight ratio were generally not changed significantly. In pressure hydration, the surface area of the activated sorbents was positively affected from the hydration temperature and pressure. Finally, Ca(OH)₂ and two diatomite/Ca(OH)₂ sorbents were sulphated at constant temperature using a synthetic gaseous mixture consisting of 5% O₂, 10% CO₂, and the balance of nitrogen with a 55% relative humidity. The sulphation reaction of these sorbents were investigated and modelled. The unreacted shrinking core model was chosen to describe this non-catalytic solid/gas (hydrated sorbent/SO₂) reaction mechanism. The experimental results were found to be correlated successfully by this model.     

Removal of sulfur dioxide using absorbent synthesized from coal fly ash: Role of oxygen and nitrogen oxide in the desulfurization reaction

Removal of SO₂ from flue gas by the absorbent synthesized from coal fly ash and calcium oxide was studied under different reaction conditions to elucidate the effect of the coexistence of NO and O₂ in the flue gas. The presence of O₂ and NO in the flue gas was found to be necessary to produce sulfate salts instead of sulfite salts as the final product of the desulfurization reaction. The roles of O₂ and NO were postulated as an oxidizing agent to oxidize SO₂ to SO₃, which then reacts with the absorbent. NO itself is not an oxidizing agent, but with the presence of O₂, it can be oxidized to NO₂ which acts as an oxidizing agent. It was also found that NO₂ (from NO) is a better oxidizing agent compared to O₂ in oxidizing SO₂ to SO₃.     

Reduction and oxidation kinetics of Mn3O4/Mg-ZrO2 oxygen carrier particles for chemical-looping combustion

The kinetics of reduction with methane and oxidation with oxygen of Mn₃O₄ supported on Mg-ZrO₂ prepared by freeze granulation has been investigated. The reactivity experiments were performed in a thermogravimetric analyzer (TGA) using different reacting gas concentrations and temperatures in the range of 1073-1223 K. The oxygen carrier particles showed high reactivity during both reduction and oxidation at all investigated temperatures. An empirical reaction model, which assumes a linear relation between time and conversion, was used to determine the kinetic parameters for reduction and oxidation, with chemical reaction being the main resistance to the reaction. The order of reaction found was 1 with respect to CH₄ and 0.65 with respect to O₂. The activation energy for the reduction reaction was 119 and for the oxidation reaction. The reactivity data and kinetic parameters were used to estimate the solid inventory in the air and fuel reactor of a CLC system. The optimum solid inventory obtained was at a value of ΔX_s=0.4. At these conditions, the recirculation rate of oxygen carrier between air and fuel reactor was per MW of fuel, which could be accomplished in an industrial reactor. The high reactivity of the Mn₃O₄/Mg-ZrO₂ with both methane and oxygen showed that this is a very promising oxygen carrier for CLC.     

Oxidation of FGD-CaSO3 and effect on soil chemical properties when applied to the soil surface

Use of high-sulfur coal for power generation in the United States requires the removal of sulfur dioxide (SO₂) produced during burning in order to meet clean air regulations. If SO₂ is removed from the flue gas using a wet scrubber without forced air oxidation, much of the S product created will be sulfite (). Plants take up S in the form of sulfate (). Sulfite may cause damage to plant roots, especially in acid soils. For agricultural uses, it is thought that in flue gas desulfurization (FGD) products must first oxidize to in soils before crops are planted. However, there is little information about the oxidation of in FGD product to under field conditions. An FGD-CaSO₃ was applied at rates of 0, 1.12, and 3.36 Mg ha⁻¹ to the surface of an agricultural soil (Wooster silt loam, Oxyaquic Fragiudalf). The in the surface soil (0-10 cm) was analyzed on days 3, 7, 17, 45, and 61. The distribution of and Ca in the 0-90 cm soil layer was also determined on day 61. Results indicated that in the FGD-CaSO₃ rapidly oxidized to on the field surface during the first week and much of the and Ca moved downward into the 0-50 cm soil layer during the experimental period of two months. It is safe to grow plants in soil treated with FGD-CaSO₃ if the application is made at least three days to several weeks before planting.     

Preparation and electrochemical studies of metal–carbon composite catalysts for small-scale electrosynthesis of H2O2

Numerous transition metal–carbon composite catalysts (M = V, Zn, Ni, Sn, Ce, Ba, Fe, Cu) have been synthesized and tested for electroreduction of O₂ to H₂O₂, The activity and selectivity of all synthesized catalysts for electrosynthesis of H₂O₂ were determined by the rotating ring-disk electrode method in acidic and neutral electrolytes. The Co-based catalysts in general showed the highest activity towards H₂O₂ formation. Experiments with different loading contents of Co showed that the activation overpotential losses of oxygen reduction to H₂O₂ reduces as loading increases to about 4 wt% Co. Addition of Co beyond this level did not seem to impact the overpotential losses. The cobalt-based catalysts, were spray-coated onto 120 μm thick Toray^® graphite substrates, and were studied in bulk electrolysis cells for up to 100 h at potentiostatic conditions (0.25 V vs. RHE) in pH 0, 3, and 7 electrolytes. At (25 °C and 1 bar) with a catalysts loading of about and using dissolved O₂ in 0.5 M H₂SO₄, typical H₂O₂ electrosynthesis rates of about were reached with current efficiencies of about 85 ± 5% at 0.25 V (vs. RHE).     

Investigations on the synthesis of KVO3 and Cl2 from KCl and V2O5 in the presence of oxygen

Investigation was carried out on the optimal conditions of the synthesis of KVO₃ and Cl₂ from KCl and V₂O₅ in the presence of atmospheric oxygen. The research was performed for the temperature range 673- for 1-. The influence of the air flux rate on the reaction yield was investigated.     

CFD simulation of dilute phase gas-solid riser reactors: part II—simultaneous adsorption of SO2-NOx from flue gases

Simultaneous adsorption of SO₂-NO_x in a riser configuration is a novel route for flue gas cleaning. The riser operates at a low flux of small diameter Na-γ-Al₂O₃ sorbent particles. The reaction scheme is adopted from previous work (Ind. Eng. Chem. Res. 40 (2001) 119), without adjusting any of the kinetic parameters. The significant concentration gradient between the gas and solid phase mainly arises from the low solid fraction (typically 5×10⁻⁴) in the riser. Enhancing the fluctuating kinetic motion of gas and solid phase increases the SO₂ adsorption, whereas the NO adsorption is decreased marginally. The solid recirculation in the top section of the riser, induced by the abrupt T outlets, significantly decreases the NO and NO₂ removal, while the SO₂ removal remains mostly unaffected. Therefore, it is desirable to avoid recirculation for a maximum NO_x removal. A comparison of the 3D and a 1D model shows that higher SO₂ and NO removal efficiencies are predicted by the 3D model in the major part of the riser. However, these positive effects are largely neutralized by the negative effects of the outlet-induced recirculation, resulting in similar overall removal efficiencies calculated by the two models. Unlike the 1D model, the 3D simulation shows a considerable axial variation in the solid fraction and slip velocity. The 3D simulation also allows to calculate the effects of outlet geometry on the flow and reaction fields. The reactor efficiency can be improved by modifying the outlet configuration to minimize the recirculation.     

Investigation of formic acid oxidation on Ti/IrO2 electrodes

A model has been proposed according to which the voltammetric charge involved in the Ti/IrO₂ electrodes is due to two contributions: a faradaic contribution due to surface redox activities at the IrO₂ coating and a non-faradaic contribution due to the charging of electrical double layer (). The later has been proposed as a tool for the estimation of the relative surface area of the Ti/IrO₂ electrodes.Differential electrochemical mass spectrometry (DEMS) measurements using H₂¹⁸O has demonstrated that we are dealing with an active electrode in which the surface redox couple IrO₃/IrO₂ acts as mediator in the oxidation of formic acid (FA).From the voltammetric measurements using different IrO₂ loading and FA concentrations, the kinetic parameters of FA oxidation via the surface redox couple IrO₃/IrO₂ have been determined.Finally a model has been proposed considering that FA oxidation at Ti/IrO₂ anodes is controlled by mass transfer. The good agreement between the experimental results and the model indicates that the surface reaction between FA and the electrogenerated IrO₃ is a fast reaction.     

Experimental investigation of a pilot-scale jet bubbling reactor for wet flue gas desulphurisation

In the present work, an experimental parameter study was conducted in a pilot-scale jet bubbling reactor for wet flue gas desulphurisation (FGD). The pilot plant is downscaled from a limestone-based, gypsum producing full-scale wet FGD plant. Important process parameters, such as slurry pH, inlet flue gas concentration of SO₂, reactor temperature, and slurry concentration of Cl⁻ have been varied. The degree of desulphurisation, residual limestone content of the gypsum, liquid phase concentrations, and solids content of the slurry were measured during the experimental series.The SO₂ removal efficiency increased from 66.1% to 71.5% when the reactor slurry pH was changed from 3.5 to 5.5. Addition of Cl⁻ (in the form of CaCl₂·2H₂O) to the slurry increased the degree of desulphurisation to above 99%, due to the onset of extensive foaming, which substantially increased the gas-liquid contact area. An increase in the inlet flue gas SO₂ concentration from 502 to led to a decrease in the SO₂ removal efficiency from 80.1% to 69.4%. A temperature increase from 296 to caused a reduction in the degree of desulphurisation from 69.4% to 68.1%, but this result is almost within the experimental uncertainty. The residual limestone level in the gypsum formed increased with increasing values of reactor slurry pH, inlet flue gas SO₂ concentration, and slurry concentration of Cl⁻.     

A study on sulphidation and regeneration of Z-Sorb III sorbent for H2S removal from simulated ELCOGAS IGCC syngas

The sulphidation and regeneration of the sorbent Z-Sorb III has been investigated at bench scale in a high-temperature, high-pressure fixed-bed unit, over a range of conditions relevant to the Puertollano IGCC plant (Spain). The effect of gas hourly space velocity (1000-), temperature (673-773 K) and pressure (1-2 MPa) on sulphidation is studied. As predicted by thermodynamics, the sorbent is capable of reducing the H₂S concentration from 10,000 ppmv to near 0 ppmv. The analysis of the experimental results shows that gas residence time has a strong effect on sorbent utilization. Below , the sorbent seems to promote the Boudouard reaction. As a result of this, CO content in the gas stream increases with simultaneous carbon formation in the solid phase. At higher gas velocities , CO disproportionation does not occur and the sulphidation reaction proceeds isothermally to complete conversion of ZnO. Further increase in space velocity to leads to lower sorbent utilization, which is typical of diffusion-limited gas-solid heterogeneous reactions. On the other hand, sulphidation temperature has very little effect on sulphur loading uptake which is slightly higher at 773 K than at 673 K. Regarding the effect of pressure, the sorbent is most effective at 2 MPa, almost reaching the theoretical saturation capacity. The study of the durability of the sorbent is investigated through multiple sulphidation-regeneration cycles. Oxidative dry mild regeneration using an oxygen concentration of 2% v/v results in complete regeneration of the sulphided sorbent without severe structural property changes or activity loss. The primary reaction during regeneration of the sulphided sorbent is direct oxidation of the metal sulphide with SO₂ release.     

Selective oxidation of methanol to dimethoxymethane over acid-modified V2O5/TiO2 catalysts

Selective oxidation of methanol to dimethoxymethane (DMM) was conducted in a fixed-bed reactor over an acid-modified V₂O₅/TiO₂ catalyst. The influence of the acid modification on its structure, redox and acidic properties, and catalytic performance for methanol oxidation were investigated. The results indicated that the content of vanadia in the catalyst exhibits a vital influence on the dispersion of vanadium species, while the acid modification can enhance its surface acidity. Proper amounts of the acid (W() = 15%) and V₂O₅ (W(V₂O₅) = 15%) components loaded in the acid-modified V₂O₅/TiO₂ catalyst are able to build a bi-functional circumstance that is favorable for the formation of DMM with high activity and selectivity. As a result, for the selective oxidation of methanol, the H₂SO₄-modified V₂O₅/TiO₂ catalyst gives a much higher DMM yield at 150 °C than the unmodified one.