No abstract

The release and transformation of inorganic elements during grate-firing of bran was studied via experiments in a laboratory-scale reactor, analysis of fly ash from a grate-fired plant, and equilibrium modeling. It was found that K, P, S, and to a lesser extent Cl and Na were released to the gas phase during bran combustion. Laboratory-scale experiments showed that S was almost fully vaporized during pyrolysis below 700°C. Sixty to seventy percent of the K and P in bran was released during combustion, in the temperature range 900À1100°C. The release of K and P was presumably attributed to the vaporization of KPO 3 generated from thermal decomposition of inositol phosphates, which were considered to be a major source of P and K in bran. The influence of additives such as CaCO 3 , Ca(OH) 2 , and kaolinite on the release was also investigated. Ca-based additives generally increased the molar ratio of the released K/P, whereas kaolinite showed an opposite effect. Thermodynamic modeling indicated that the fly ash chemistry was sensitive to the molar ratio of the released K/P. When the molar ratio of the released K/P was below 1, KPO 3 and P 4 O 10 (g) were the main stable K and P species at temperatures higher than 500°C. Below 500°C, the KPO 3 and P 4 O 10 (g) may be converted to H 3 PO 4 (l), which may cause severe deposit build-up in the economizers of a grate-fired boiler. By increasing the molar ratio of the released K/P to above 2, the equilibrium distribution of the K and P species was significantly changed and the formation of H 3 PO 4 (l) was not predicted by thermodynamic modeling.

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The KOH-capture reaction by coal fly ash at suspension-fired conditions was studied through entrained flow reactor (EFR) experiments and chemical equilibrium calculations. The influence of KOH-concentration (50-1000 ppmv), reaction temperature (800-1450 °C), and coal fly ash particle size (D 50 = 6.03-33.70 μm) on the reaction was investigated. The results revealed that, at 50 ppmv KOH (molar ratio of K/(Al+Si) = 0.048 of feed), the measured K-capture level (C K ) of coal fly ash was comparable to the equilibrium prediction, while at 250 ppmv KOH and above, the measured data were lower than chemical equilibrium. Similar to the KOH-kaolin reaction reported in our previous study, leucite (KAlSi 2 O 6 ) and kaliophilite (KAlSiO 4 ) were formed from the KOH-coal fly ash reaction. However, coal fly ash captured KOH less effectively compared to kaolin at 250 ppmv KOH and above. Studies at different temperatures showed that, at 800 °C, the KOH-coal fly ash reaction was probably kinetically controlled. At 900-1300 °C it was diffusion limited, while at 1450 °C, it was equilibrium limited to some extent. At 500 ppmv KOH (molar ratio of K/(Al+Si) = 0.481), and a gas residence time of 1.2 s, 0.063 g K/(g additive) and 0.087 g K/(g additive) was captured by coal fly ash (D 50 = 10.20 μm) at 900 and 1450 °C, respectively. Experiments with coal fly ash of different particle sizes showed that a higher K-capture level were obtained using finer particle sizes, indicating some internal diffusion control of the process.

The objective of this paper is to systematically investigate the influences of different preparation methods on the properties of NiFe2O4 nanoparticles as oxygen carrier in chemical looping hydrogen production (CLH). The solid state (SS), coprecipitation (CP), hydrothermal (HT), and sol–gel (SG) methods were used to prepare NiFe2O4 oxygen carriers. Samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) surface area measurement, as well as Barrett–Joyner–Halenda (BJH) porosity test. The performance of the prepared materials was first evaluated in a TGA reactor through a CO reduction and subsequent steam oxidation process. Then a complete redox process was conducted in a fixed-bed reactor, where the NiFe2O4 oxygen carrier was first reduced by simulated biomass pyrolysis gas (24% H2 + 24% CO + 12% CO2 + N2 balance), then reacted with steam to produce H2, and finally fully oxidized by air. The NiFe2O4 oxygen carrier prepared by the sol–gel method showed the best capacity for hydrogen production and the highest recovery degree of lattice oxygen, in agreement with the characterization results. Furthermore, compared to individual nickel ferrite particles, the mixture of NiFe2O4 and SiO2 presented remarkably higher stability during 20 cycles in the fixed-bed reactor. The structural and morphological stability of samples after reactions was also examined by XRD, XPS, and SEM analyses.