J.M. Andrés

DIFFERENT APPROACHES TO PROXIMATE ANALYSIS BY THERMOGRAVIMETRY ANALYSIS

Abstract The experimental optimization by the simplex method of the proximate analysis of coal and biomass by thermogravimetry analysis (TGA) is reported. Heating rate, final temperature, holding time, Ar flow rate and sample size were the control variables. The response function used was chosen to minimize the difference in percentage of volatile matter with the ASTM characterization. The relative accuracy of the method was demonstrated by determination of the volatile matter contents of a number of coals in parallel with the ASTM certified method. The method is successfully used with biomass samples.Authors acknowledge the European Commission for the financial support by contract No. ECSC 7220-PR/048. M.C.M. and M.T.I. are thankful to the Ministry of Science and Technology.

Ion exchange uptake of ammonium in wastewater from a Sewage Treatment Plant by zeolitic materials from fly ash

The potential value of zeolitic materials (ZM) obtained from a hazardous waste, such as coal fly ash, for the retention of NH(4)(+) present in liquid effluents from a Sewage Treatment Plant (STP) is studied. A wastewater sample was taken from an STP in Zaragoza (Spain) after conventional treatment at the Plant. The water was treated with different amounts of three ZM: NaP1 zeolite, K-F zeolite and K-Chabazite/K-Phillipsite zeolites all of them in powdered and granulated state. The wastewater was treated by two kinds of processes: continuous stirring batch experiments with powdered ZM, and fixed packed bed of granulated ZM in a column. The powdered materials reduced about 80% of NH(4)(+) from wastewater, even in the presence of Ca(2+), which competes with NH(4)(+) for the cation exchange sites in zeolites. Around 70% of NH(4)(+) reduction was achieved with granulated materials. In both cases, moderate ZM/wastewater ratios had to be used to achieve those results, with K-zeolites slightly less effective in NH(4)(+) retention.

Microwave single walled carbon nanotubes purification

A new single walled carbon nanotubes (SWCNTs) purification procedure has been developed; it consists in a combination of air treatment and acid microwave digestion leading to a high purity SWCNTs material; the procedure reaches high metal removal percentages and the operation time is drastically reduced compared to conventional acid reflux treatments.

Aluminosilicates transformations in combustion followed by DSC

Abstract The behavior of quartz, kaolinite and calcite, as main components of coal mineral matter, has a direct impact on slags formations and development in pulverized coal combustion. The mineral transformations along temperature can be followed by differential scanning calorimetry (DSC), provided that the formation and crystallization of mullite (3Al2O3·2SiO2) are exothermic phenomena. Peak heights and areas allow to quantify the occurrence and extent of those mineral transformations for pure kaolinite and its mixture with calcite as fluxing agent. On the other hand, sinterization time at temperatures bellow mullite formation has a clear impact on the onset and the shape of the peaks. In this way, it is demonstrated that mineral transformations at solid state have a direct effect on the final structure of mineral species generated by slagging.

Coal analysis by diffuse reflectance near-infrared spectroscopy: Hierarchical cluster and linear discriminant analysis

An extensive study was carried out in coal samples coming from several origins trying to establish a relationship between nine coal properties (moisture (%), ash (%), volatile matter (%), fixed carbon (%), heating value (kcal/kg), carbon (%), hydrogen (%), nitrogen (%) and sulphur (%)) and the corresponding near-infrared spectral data. This research was developed by applying both quantitative (partial least squares regression, PLS) and qualitative multivariate analysis techniques (hierarchical cluster analysis, HCA; linear discriminant analysis, LDA), to determine a methodology able to estimate property values for a new coal sample. For that, it was necessary to define homogeneous clusters, whose calibration equations could be obtained with accuracy and precision levels comparable to those provided by commercial online analysers and, study the discrimination level between these groups of samples attending only to the instrumental variables. These two steps were performed in three different situations depending on the variables used for the pattern recognition: property values, spectral data (principal component analysis, PCA) or a combination of both. The results indicated that it was the last situation what offered the best results in both two steps previously described, with the added benefit of outlier detection and removal.

ASTM clustering for improving coal analysis by near-infrared spectroscopy.

Multivariate analysis techniques have been applied to near-infrared (NIR) spectra coals to investigate the relationship between nine coal properties (moisture (%), ash (%), volatile matter (%), fixed carbon (%), heating value (kcal/kg), carbon (%), hydrogen (%), nitrogen (%) and sulphur (%)) and the corresponding predictor variables. In this work, a whole set of coal samples was grouped into six more homogeneous clusters following the ASTM reference method for classification prior to the application of calibration methods to each coal set. The results obtained showed a considerable improvement of the error determination compared with the calibration for the whole sample set. For some groups, the established calibrations approached the quality required by the ASTM/ISO norms for laboratory analysis. To predict property values for a new coal sample it is necessary the assignation of that sample to its respective group. Thus, the discrimination and classification ability of coal samples by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) in the NIR range was also studied by applying Soft Independent Modelling of Class Analogy (SIMCA) and Linear Discriminant Analysis (LDA) techniques. Modelling of the groups by SIMCA led to overlapping models that cannot discriminate for unique classification. On the other hand, the application of Linear Discriminant Analysis improved the classification of the samples but not enough to be satisfactory for every group considered.

Mechanism of interaction of pyrite with hematite as simulation of slagging and fireside tube wastage in coal combustion

Abstract Iron-bearing minerals have been recognised as a mayor source of fire-side wall slagging in pulverised fuel boilers, which not only reduces the thermal efficiency of heat transfer of the exchangers surface, but also affects its integrity as a result of corrosion and erosion. Nevertheless, the root cause of adhesion and growing of deposits has not been clearly addressed. Our approach suggests that differential scanning calorimetry (DSC) combined with simultaneous thermogravimetry can follow the chemical reaction between pyrite and the outer layer of iron oxide on tubewalls. The changes in composition are followed by X-ray diffraction (XRD). The results indicated that the mechanism of wetting and adherence of molten pyrite over iron oxides is chemically induced: both di and mono iron sulphides interact with the oxide layer, changing the oxidation state of iron in oxide scale, from hematite to magnetite. This would imply a change in the protective ability of the scale as well as a great increment in corrosion tendency.

Reflection and transmission mid-infrared spectroscopy for rapid determination of coal properties by multivariate analysis.

In the present paper, the influence of different acquisition techniques (transmission, diffuse reflectance infrared Fourier transform and attenuated total reflectance) in the determination of nine coal properties related to combustion power plants has been studied. Raw coal samples of different origins were pooled for developing a correlation between the resultant spectra and the corresponding coal properties by multivariate analysis techniques. Thus, the existent collinearity in mid-infrared coal spectra led to the application of partial least squares regression (PLS), studying simultaneously the influence of different spectroscopic units as well as several spectral data mathematical pre-treatments. On the other hand, a principal component analysis (PCA) revealed a relationship between principal components and coal composition in both transmission and reflection techniques. Although the best accuracy and precision results were obtained for coal properties related to organic matter, the system was also able to differentiate coal samples attending to the presence of a specific mineral matter, kaolinite.

Radial changes in the microstructure of LFZ-textured Bi-2212 thin rods induced by stoichiometry modifications

Three different Bi-2212 powders, with stoichiometric deviations both in the Bi and Sr content as well as in the Bi/Sr ratio, have been used as precursors in the processing of laser floating zone-textured thin rods. The developed microstructure in the as-grown and annealed rods has been studied by ICP analysis, scanning electron microscopy and energy dispersive spectroscopy microanalysis. The marked differences in phase distribution, composition and concentration found among the rods have been correlated with the initial stoichiometry. Finally, the effect of these microstructural inhomogeneities on the critical temperature, critical current density at 77 K and pinning behaviour of the rods is discussed.

Correlation of radial inhomogeneties and critical current at 77 K in LFZ Bi-2212 textured thin rods

Abstract The fabrication of thin Bi-2212 rods by laser floating zone techniques gives high critical currents, Ic, but strong radial inhomogeneities in microstructure and physical properties. By changing the precursor stoichiometry or the processing parameters, we have succeeded in improving the homogeneity and the Ic values. Towards the centre of the rods, the superconducting material tends to have lower Tc values associated to higher Bi content in the Bi-2212 superconducting grains. At 77 K, this gradient of Bi originates strong variations of critical current density across the rod.