Ash
Dynamic High-temperature X-ray Diffraction Analysis – A New Approach to Coal Mineral Matter High Temperature Transformation
D French, L Dale and C Matulis  CSIRO Energy Technology
X-ray diffraction has been an invaluable tool for the characterization of coal mineral matter and the capability to perform dynamic X-ray diffraction (XRD) analysis under controlled atmosphere conditions and variable heating rates to 2400oC (1600oC in oxidising atmospheres) provides a powerful new tool for the study of coal mineral matter reactions at high temperature. Used in conjunction with SIROQUANTä, a quantitative XRD package developed by CSIRO Energy Technology, quantitative abundance data can be obtained not only for the crystalline phases but also for any solid or liquid amorphous phase which may be formed.
An immediate application of high-temperature XRD is investigation of the mineral reactions that occur during coal combustion in power plant boilers which lead to the formation of slagging and fouling deposits. Examples of the application of high temperature XRD to mineral reactions relevant to pf combustion are presented with studies of a synthetic ash and ashes of a high-volatile bituminous and a medium-volatile bituminous coal

Rheology of Coal Ash in Fluidised Bed Combustion of Low Rank Coal
N Tonmukayakul and Q  Nguyen  CRC for Clean Power from Lignite University of Adelaide, Adelaide
Development of more effective technologies for utilizing low rank coals for power generation has been driven by a demand for higher efficiency, low capital costs and minimal environment impacts. Fluidised bed systems are regarded as one of the most promising alternative technologies for power generation to overcome the disadvantages of the existing pulverized coal burning power generation plants for low rank coals. However, ash deposition and bed agglomeration are potential problems in fluidised bed processing of high alkali coals. Thus, in order to gain a better understanding the mechanism of agglomeration in fluidised bed technologies, a good knowledge of the rheological behavior of coal ash deposits at high temperatures and under processing conditions is necessary. This paper presents a detailed investigation of rheological characterisation of high alkali low rank coal ashes under different operating temperatures. The rheological properties of the coal ashes were measured using the unique high temperature ash rheometer recently developed in our laboratory. The experimental results obtained will be presented the effect of the alkali content on the rheological characteristics discussed in terms of the implication of coal ash rheology on agglomeration.
 
Evaluation of the Slag Flow Characteristics of Australian Bituminous Coals in Slagging Gasifiers
J H Patterson, H J Hurst, A Quintanar CSIRO Energy Technology, Brisbane; R Boyd and H Tran Pacific Power International, Sydney
The slag viscosity and crystallisation characteristics of coal ash slags have been further examined, confirming the suitability of Australian bituminous coals for use in slagging gasifiers. Data has been obtained for the reference coals of the CRC for Black Coal Utilisation. For a slag tapping temperature of 1450oC, about half the coals examined are shown to require a limestone flux addition of <3% CaCO3 by weight of coal. However, high temperatures of critical viscosity proved more of a problem than expected, particularly for Queensland coals, increasing flux requirements at 1400oC. Limitations arising from slag crystallisation appear to be associated with SiO2/Al2O3 ratios of < 2 and iron contents > 10% FeO. Empirical viscosity models have been developed for Australian bituminous coals ash slags in the range 10-15% FeO. Relative coal value modelling has been used for economic optimisation of limestone flux addition and gasification temperature. The efficacy of coal blending has been demonstrated for reducing flux requirements and lowering the temperature of critical viscosity.

Fates and Roles of Alkali and Alkaline Earth Metal Species during Gasification of Victorian Lignite
D Mody, H Wu and C Z Li   CRC for Clean Power from Lignite, Melbourne
The transformation of alkali and alkaline earth metal (AAEM) species in a Victorian lignite during the pyrolysis and subsequent gasification in CO2 was studied in a novel quartz fluidised-bed reactor. Lignite samples prepared by physically adding NaCl and ion-exchanging Na+ and Ca++ into the lignite were used to investigate the effects of chemical forms and valency of the AAEM species in the substrate lignite on their transformation during pyrolysis and gasification.   Carboxyl-bound Na was found to be less volatile than Na present as NaCl, but more volatile than carboxyl-bound Ca, during pyrolysis at temperatures between 400°C and 900°C.  However, the carboxyl-bound Na was volatilised to a much greater extent than the carboxyl-bound Ca in the same lignite during pyrolysis.  It was seen that the loading of NaCl into the lignite did not significantly affect the char reactivity in the fluidised-bed reactor at 900°C.

Predicting Coal Ash Slag Flow Characteristics (Viscosity Model in Al2O3-CaO “FeO”-SiO2 System)
A Kondratiev and E Jak   University of Queensland, Brisbane
A model has been developed which enables the viscosities of coal ash slags to be predicted as a function of composition and temperature under reducing conditions. The model describes both completely liquid and heterogeneous, partly crystallised slags in the Al2O3-CaO-“FeO”-SiO2 system in equilibrium with metallic iron. The Urbain formalism has been modified to describe the viscosities of the liquid slag phase over the complete range of compositions and a wide range of temperatures. The computer package F*A*C*T was used to predict the proportion of solids and the composition of the remaining liquid phase. The Roscoe equation has been used to describe the effect of presence of solid suspension (slurry effect) on the viscosity. The model provides a good description of the experimental data in liquid phase, and liquid + solid mixtures, over the complete range of compositions and a wide range of temperatures. This model can now be used for viscosity predictions in industrial slag systems. Examples of the application of the new model to coal ash fluxing and blending are given in the paper.
 
Application of new FACT Database for the Prediction of melting Behavior of Coal Mineral Matter
E Jak and P Hayes   University of Queensland, Brisbane
A range of technological coal utilisation issues, including prediction of the Ash Fusion Temperatures (AFT), fluxing in IGCC, coal blending, slagging and fouling in PF combustion, are related to the melting behaviour of the coal mineral matter.  A new thermodynamic database for the system Al-Ca-Fe-O-Si has recently been developed.  This new database, in conjunction with the F*A*C*T computer package, can now be used to calculate the proportions and compositions of liquid and solid phases, liquidus temperatures and other phase equilibrium information over a wide range of compositions, temperatures and atmospheric conditions.  These predictions, examples of which are given in the paper, are important for the characterisation of melting behaviour of the coal ash slags and are applied to assist in solving a range of the related coal utilisation technological issues.
AFTs are widely used as a measure of coal ash fusibility and melting behaviour, and hence is a widely used parameter in coal marketing and utilisation. The research described in the present paper examines the relationship between measured AFTs and F*A*C*T liquidus calculations for a selected set of coals. The formation of the solid phases in these coal ashes is also examined and compared with the F*A*C*T equilibrium predictions.  A model for the AFTs predictions based on the F*A*C*T calculations is developed and applied to coal blending.

Slagging in a Pulverised-Coal-Fired Boiler
G Devir, J Pohl University of Queensland, Brisbane Australia; and R Creelman RA Creelman and Associates, Sydney
This paper describes a technique to evaluate the severity of slagging of a coal in a pulverised-coal-fired boiler. From an operator’s perspective, the performance of a coal can be gauged by the time lapsed between sootblowing cycles that allows control of furnace deposits. This translates to the time taken for the superheater metal tube surface temperature to exceed a nominal value. However, to ultimately describe the slagging performance of pulverised coals in a boiler, several descriptors of deposit behaviour need to be nominated and quantified. There is precious little data in the literature on the nature of in-situ boiler slags, their rate of growth and/or their strength properties relevant to sootblowing. The latter is thought to be of more concern to boiler operators and gives rise to the significance of selecting suitable strength tests. As well as standardised methods for characterising pulverised coal performance in a boiler, several novel and less popular techniques will be discussed in detail. A suite of three sub-bituminous coals from the Callide Coalfields, Biloela (600 kilometres north of Brisbane), has been selected for slagging tests in the 350 MWe units of Callide ‘B’ Power Station. Disposable air-cooled mild steel slagging probes have been constructed to simulate the conditions for deposit formation in the boiler region. To date, tests for one of these coals has been completed and preliminary results are presented below. Once testing for the remaining coals has been completed, it is anticipated that the differences exhibited in deposit growth and strength may be correlated with typical variations in physical and chemical properties of the pulverised coal.

The Heterogeneous Nature of Mineral Matter, Fly-Ash and Deposits
R Creelman RA Creelman  and Associates; J Pohl, G Devir and S Shi University of Queensland, Brisbane
Deposits that cannot be easily removed cost the Utility Industry several billion dollars per year in reduced capacity and maintenance. These deposits are cause by complex mineral matter transformations to fly ash and the interaction of fly ash during combustion and in the deposits. This paper reports on a series of studies looking at the heterogeneous nature of mineral matter, fly ash, and deposits and how this heterogeneity affects deposition. The data comes from Low Temperature Ashing (LTA) of coal, fly ash from boilers, and deposits from pilot scale furnaces and boilers. The paper presents optical and Scanning Electron (SEM) micrographs, Electron Micro Probe Analysis (EMPA) and Energy Dispersive X-Rays Analysis (EDXA) analysis of mineral matter, individual fly ash particles, and isolated regions of the deposits. During combustion, included mineral matter is transformed into fly ash, melts and partially adheres to the char surface, and may form agglomerated masses. Excluded mineral matter has little chance of encountering another ash particle and agglomerating in the gas phase, but can react with other particles in the wall deposits. Certain fly ash particles adhere to the wall where they can combine with other fly ash particles. Analyses of molten regions of deposits have shown, so far, three types of minerals, made of mixed minerals, to be responsible for forming difficult deposits with melting points below deposit temperatures which range from 1200-1350. These compounds are iron cordierite (2FeO-2Al2O3-5SiO2) with melting points around 1100-1300 C, Juniper, et al (1993); albite (Na2O-Al2O3-6SiO2) and its silica undersaturated equivalent nepheline (Na2O-Al2O3-2SiO2) with melting points around 850 - 1100 C Su (1999), anorthite (CaO-Al2O3-2SiO2) with melting points around 1300-1400 C Pollman (1967), and compounds with ratios of CaO/P2O5 of 2.3-2.5 and melting points around 1300 C, Su (1999).
 
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