Mehdi Arjmand

Sulfur Tolerance of CaxMn1–yMyO3−δ (M = Mg, Ti) Perovskite-Type Oxygen Carriers in Chemical-Looping with Oxygen Uncoupling (CLOU)

Perovskite-structured oxygen carriers of the type CaxMn1–yMyO3−δ (M = Mg, Ti) have been investigated for the CLOU process. The oxygen carrier particles were produced by spray-drying and were calcined at 1300 °C for 4 h. A batch fluidized-bed reactor was used to investigate the chemical-looping characteristics of the materials. The effect of calcium content, dopants (Mg and Ti), and operating temperature (900, 950, 1000, and 1050 °C) on the oxygen uncoupling property and the reactivity with CH4 in the presence and absence of SO2 was evaluated. In addition, the attrition resistance and mechanical integrity of the oxygen carriers were examined in a jet-cup attrition rig. All of the investigated perovskite-type materials were able to release gas phase oxygen in inert atmosphere. Their reactivity with methane was high and increased with temperature and calcium content, approaching complete gas yield at 1000 °C. The reactivity decreased in the presence of SO2 for all of the investigated oxygen carriers. Decreasing the calcium content resulted in a less severe decrease in reactivity in the presence of SO2, with the exception of materials doped with both Mg and Ti, for which a higher resistance to sulfur deactivation could be maintained even at higher calcium contents. The drop in reactivity in the presence of SO2 also decreased at higher temperatures, and at 1050 °C, the decrease in the reactivity of the Mg- and Ti-doped material was minimal. Sulfur balance over the reactor system indicated that the fraction of the introduced SO2 that passed through the reactor increased with temperature. It was shown that it is possible to regenerate the oxygen carriers during reduction in the absence of SO2. Most of the materials also showed relatively low attrition rates. The results indicate that it is possible to modify the operating conditions and properties of perovskite-type oxygen carriers to decrease or avoid their deactivation by sulfur.

Standard Enthalpy of Formation of CuAl2O4 Revisited

Due to discrepancy in the standard enthalpy of formation, , of copper(II) aluminate (CuAl2O4) reported in thermodynamic databases, the calculated reaction enthalpy, ΔHr, of CuAl2O4 with reducing gases varies considerably. In this work, the standard enthalpy of formation, , of CuAl2O4 is reassessed using the reaction enthalpy, ΔHr, of CuAl2O4 with CO measured by differential scanning calorimetry. A value of −1824.4 ± 4.1 kJ/mol was found for the standard enthalpy of formation, , of CuAl2O4.

Use of natural ores and waste materials as oxygen carriers for chemical-looping combustion

The increasing CO2 levels in the atmosphere require an immediate action in order to avoid irreversible climate changes. Chemical-looping combustion (CLC) is an innovative technology that provides an energy and cost-effective separation of CO2 for further capture and storage and thereby helps to mitigate the anthropogenic CO2 emissions from thermochemical fuel conversion. The solid oxygen carrier is a core component of every CLC system and the choice of the oxygen carrier depends on the fuel and operation conditions. Low-cost oxygen carriers tend to be more suitable for the process as the lifetime of the oxygen carrier material is often limited by side reactions with fuel ash, or by carryover losses in the ash separation. A series of natural ores and waste products have been investigated as potential oxygen cares, such as Mn-ore, Fe-ore, ilmenite. The materials are chosen based on their content of oxides that have proven to have promising oxygen transporting capabilities. The results lead to summary of criterion for further screening of the existing materials for more reactive and better suited candidates for the process.