Facun Jiao

Synchrotron-based XANES speciation of chromium in the oxy-fuel fly ash collected from lab-scale drop-tube furnace.

Speciation of chromium (Cr) in the fly ash collected from oxy-firing of Victorian brown coal has been reported for the first time to address the potential formation of toxic Cr(VI) and the variation of the quantities of Cr(III)-bearing species with flue gas composition. Synchrotron-based X-ray absorption near-edge structure (XANES) was employed for Cr speciation. Apart from a pure O(2)/CO(2) mixture (27/73, v/v) versus air, the O(2)/CO(2) mixtures doped with SO(2), HCl, and steam individually or together to simulate real flue gas have also been tested. Under all of the conditions tested here, the fractions of Cr(VI) in the fly ashes are insignificant, constituting no more than 5% of the total Cr. The test of Cr-doped brown coal in pyrolysis further confirmed that the Cr(VI) formation preferentially occurred through a local oxidation of Cr(III) at the oxygen-containing functions sites within coal matrix, rather than through an oxidation by external bulk O(2). This reaction is also highly temperature-dependent and slower than the interaction between Cr(III) and other metals such as iron oxide. Increasing temperature to 1000 °C inhibited the oxidation of Cr(IIII) to Cr(VI). Shifting the combustion gas from air to O(2)/CO(2) exerted little effect on the Cr(VI) formation. Instead, the formation of iron chromite (FeCr(2)O(4)) was facilitated in O(2)/CO(2), probably due to a strong reducing microenvironment formed by the CO(2) gasification reaction within the char matrix. The accumulation of HCl in flue gas favored the vaporization of chromium as gaseous chloride/oxychloride, as expected. The coexistence of SO(2) inhibited this phenomenon by promoting the formation of sulfate. The presence of steam was even beneficial for the inhibition of water-soluble Cr sulfate through stabilizing the majority of Cr into alumino-silicate which is in the slagging phase.

Use of Synchrotron XANES and Cr-Doped Coal to Further Confirm the Vaporization of Organically Bound Cr and the Formation of Chromium(VI) During Coal Oxy-Fuel Combustion

Through the use of synchrotron XANES and Cr-doped brown coal, extensive efforts have been made to clarify the volatility of organically bound Cr during oxy-fuel combustion and the mode of occurrence and leachability of Cr in resulting fly ashes. As the continuation of our previous study using raw coal, the Cr-doped coal has been tested in this study to improve the signal-to-noise ratio for Cr K-edge XANES spectra, and hence the accuracy for Cr(VI) quantification. As has been confirmed, the abundant CO(2) as a balance gas for oxy-firing has the potential to inhibit the decomposition of organically bound Cr, thereby favoring its retention in solid ash. It also has the potential to promote the oxidation of Cr(III) to Cr(VI) to a minor extent. Increasing the oxygen partial pressure, particularly in the coexistence of HCl in flue gas, favored the oxidation of Cr(III) into gaseous Cr(VI)-bearing species such as CrO(2)Cl(2). Regarding the solid impurities including Na(2)SO(4) and CaO, Na(2)SO(4) has proven to preferentially capture the Cr(III)-bearing species at a low furnace temperature such as 600 °C. Its promoting effect on the oxidation of Cr(III) to Cr(VI), although thermodynamically available at the temperatures examined here, is negligible in a lab-scale drop tube furnace (DTF), where the particle residence time is extremely short. In contrast, CaO has proven facilitating the capture of Cr(VI)-bearing species particularly oxychloride vapors at 1000 °C, forming Ca chromate with the formulas of CaCrO(4) and Ca(3)(CrO(4))(2) via a direction stabilization of Cr(VI) oxychloride vapor by CaO particle or an indirect oxidation of Cr(III) via the initial formation of Ca chromite. The fly ash collected from the combustion of Cr-doped coal alone has a lower water solubility (i.e., 58.7%) for its Cr(VI) species, due to the formation of Ba/Pb chromate and/or the incorporation of Cr(VI) vapor into a slagging phase which is water-insoluble. Adding CaO to coal increased the water-solubility of both Cr(VI) and Cr(III) by forming Ca chromite and chromate, respectively.

Elucidating the mechanism of Cr(VI) formation upon the interaction with metal oxides during coal oxy-fuel combustion

The thermodynamics underpinning the interaction of Cr-bearing species with basic metal oxides, i.e. K2O, Fe2O3, MgO and CaO, during the air and oxy-fuel combustion of coal have been examined. The synchrotron-based X-ray adsorption near-edge spectroscopy (XANES) was used for Cr speciation. For the oxides tested, Cr(VI) formation is dominated by the reduction potential of the metals. The oxides of Ca(2+) with high reduction potential favored the oxidation of Cr(III), same for K(+). The other two basic metals, Fe2O3 and MgO with lower reduction potentials reacted with Cr(III) to form the corresponding chromites at the temperatures above 600°C. Coal combustion experiments in drop-tube furnace have confirmed the rapid capture of Cr vapors, either trivalent or hexavalent, by CaO into solid ash. The existence of HCl in flue gas favored the vaporization of Cr as CrO2Cl2, which was in turn captured by CaO into chromate. Both Fe2O3 and MgO exhibited less capability on scavenging the Cr(VI) vapor. Particularly, MgO alone exhibited a low capability for capturing the vaporized Cr(III) vapors. However, its co-existence with CaO in the furnace inhibited the Cr(VI) formation. This is beneficial for minimizing the toxicity of Cr in the coal combustion-derived fly ash.

Effect of Coal Blending on the Leaching Characteristics of Arsenic and Selenium in Fly Ash from Fluidized Bed Coal Combustion

The capture ability of fly ash to arsenic (As) and selenium (Se) was investigated through the combustion of two single bituminous coals A and B and their mixture (blending ratio of 1:1, wt/wt) in a lab-scale fluidized bed reactor. The leaching characteristics of As and Se in corresponding fly ash were also conducted according to Japanese Industrial Standard (JIS). Speciation of As and Se during fly ash leaching test were predicted from the perspective of thermodynamic equilibrium. The results indicate that, combustion of coal B, containing abundant calcium, possesses a higher capture ability of As and Se than that of coal A through possible chemical reaction between As/Se with CaO. Leaching behavior of As and Se from fly ash is strongly dependent on the pH of the leachate. Free calcium in fly ash generates an alkaline leachate during leaching test and subsequently reduces As and Se leaching, which cause the leaching ratio of As and Se in fly ash derived from the combustion of coal B was much lower, relative to that in coal A. Combustion of blending coal promotes the overall capture ability of the fly ash to As/Se and reduces their leaching from fly ash through the synergy of free CaO between this two kind of fly ash.