Karen M. Steel

The production of ultra clean coal by chemical demineralisation

A high-volatile UK coal, with a particle size of < 500 mum, an ash content of approximately 7.9% by weight and a sulphur content of 2.6% by weight, was treated with aqueous HF followed by aqueous HNO3. The reaction residence time and temperature for both treatments were 3 h and 65 degreesC, respectively. HF reduces the ash content to approximately 2.6% by weight. The remaining ash largely consists of fluoride compounds such as AlF3, NaAlF4, CaF2 and MgF2, Which form during leaching, and pyrite (FeS2), which does not react with HF. HNO3 then further reduces the ash content to approximately 0.6% by weight, by dissolving fluoride compounds and the Fe present as FeS2. The remaining ash consists largely of unreacted FeS2, which is encapsulated in the coal structure. This investigation also showed that HNO3 only reacts with FeS2 above a particular HNO3 Concentration, which suggests that it is consumed preferentially, and to a certain extent, with the organic coal structure. The final sulphur content following treatment with HF and HNO3 was 1.4% by weight.

Production of Ultra Clean Coal, Part I – Dissolution behaviour of mineral matter in black coal toward hydrochloric and hydrofluoric acids

The mineral matter in an Australian black coal has been isolated using a low-temperature ashing (LTA) procedure. This LTA procedure is a modification of the Australian Standard for LTA at 370 degrees C, and alleviates adverse effects to thr: minerals caused by the heat of combustion. The leaching behaviour of the mineral matter towards aqueous HCl and hydrofluoric acid (HF) is presented. HCl can dissolve simple compounds such as phosphates and carbonates, yet it cannot completely dissolve the clays. HF resets with almost every mineral in the mineral matter, except pyrite, and most of the reaction products are water soluble. However, at HF concentrations greater than that required to dissolve the aluminosilicate compounds in the mineral matter, insoluble compounds form. These compounds include CaF2, MgF2 and a compound containing Na, which is believed to be NaAlF4. It is proposed that HF reacts preferentially with the aluminosilicates in the mineral matter to form largely AlF2+, AlF3 and SiF4, and that the concentrations of free fluoride (F-) and AlF4- are not high enough to complex cations such as Ca2+, Mg2+ and Na+. When the mineral matter is treated with HF concentrations greater than that required to dissolve all of the aluminosilicates, AlF3, AlF4- and SiF62- form, the concentration of F- is high enough to complex Ca2+ and Mg2+ and form insoluble CaF2 and MgF2, and the concentration of AlF4- is high enough to complex Na+ and form insoluble NaAlF4. This work has application toward the development of a process for producing Ultra Clean Coal with less than 0.1% by weight mineral matter

Coal structure and reactivity changes induced by chemical demineralisation

The aim of this work was to determine the influence that an advanced demineralisation procedure has on the combustion characteristics of coal. A high-volatile bituminous coal with 6.2% ash content was treated in a mixture of hydrofluoric and fluorosilicic acids (HF/H2SiF6). Nitric acid was used either as a pretreatment, or as a washing stage after HF/H2SiF6 demineralisation, with an ash content as low as 0.3% being attained in the latter case. The structural changes produced by the chemical treatment were evaluated by comparison of the FTIR spectra of the raw and treated coal samples. The devolatilisation and combustibility behaviour of the samples was studied by using a thermobalance coupled to a mass spectrometer (TGA-MS) for evolved gas analysis. The combustibility characteristics of the cleaned samples were clearly improved, there being a decrease in SO2 emissions.

The production of ultra clean coal by sequential leaching with HF followed by HNO3

A UK bituminous coal with particle size < 62 mum and containing 5.0 wt% ash and 2.4 wt% S was treated with a two-stage leaching sequence of aqueous HF followed by aqueous HNO3. The ash and S contents reduced to 0.2 wt% and 1.3 wt%, respectively. In addition, the calorific value (CV) dropped from 31.5 to 29.5 MJ/kg, and the N content increased from 2.0 to 2.8 wt%, due to attack on the carbonaceous matrix during the HNO3 leach. Interestingly, this attack only occurs when HNO3 reacts with and dissolves pyrite, suggesting that it is the products of reaction between HNO3 and pyrite which react with the coal. It is proposed here that localised concentrations of sulphuric and nitric acids at the pyrite site may react to form the powerful nitrating agent NO2+ which then reacts with the carbonaceous coal matrix. The fluoride content of the coal increases from 80 to 3240 ppm after the HF leach, yet drops to 130 ppm following the HNO3 leach. The mineral matter remaining in the coal after the leaching sequence consists largely of Fe, which is most likely present as finely disseminated unreacted pyrite.

Production of Ultra Clean Coal: Part II—Ionic equilibria in solution when mineral matter from black coal is treated with aqueous hydrofluoric acid

A model fur determination of the concentration of fluoride complexed aluminium and silicon species, free fluoride (F-), II+ ions and molecular HF in solution when aluminosilicate compounds are treated with aqueous HF is presented. The model elucidates chemical mechanisms governing both the dissolution behaviour of the mineral matter in coal towards aqueous HF, and the unwanted precipitation of various fluoride compounds, such as CaF2, MgF2 and NaAIF(4). The controlling parameter for the precipitation of fluoride compounds is the free F- concentration in solution. The model has application toward the development of chemical strategies for dissolving virtually all of the mineral matter from coal and avoiding the unwanted precipitation of fluoride compounds. The model also has application toward the development of a strategy for recovering fluoride from spent leaching solutions. Ultimately, this work will assist in the development of a process for the production of Ultra Clean Coal (UCC) containing less than 0.1% by weight mineral matter.

Combustion behaviour of ultra clean coal obtained by chemical demineralisation

The increasing environmental concern caused by the use of fossil fuels and the concomitant need for improved combustion efficiency is leading to the development of new coal cleaning and utilisation processes. However, the benefits achieved by the removal of most mineral matter from coal either by physical or chemical methods can be annulled if poor coal combustibility characteristics are attained. In this work a high volatile bituminous coal with 6% ash content was subjected to chemical demineralisation via hydrofluoric and nitric acid leaching, the ash content of the clean coal was reduced to 0.3%. The original and treated coals were devolatilised in a drop tube furnace and the structure and morphology of the resultant chars was analysed by optical and scanning electron microscopies. The reactivity characteristics of the chars were studied by isothermal combustion tests in air at different temperatures in a thermogravimetric system. Comparison of the combustion behaviour and pollutant emissions of both coals was conducted in a drop tube furnace operating at 1000 °C. The results of this work indicate that the char obtained from the chemically treated coal presents very different structure, morphology and reactivity behaviour than the char from the original coal. The changes induced by the chemical treatment increased the combustion efficiency determined in the drop tube furnace, in fact higher burnout levels were obtained for the demineralised coal.

Production of ultra clean coal: Part III. Effect of coal's carbonaceous matrix on the dissolution of mineral matter using hydrofluoric acid

An Australian bituminous coal was treated with increasing concentrations of hydrofluoric acid (HF), and the extraction levels of Al, Si, Fe, Ti, K, Na, Ca and Mg were determined. These extraction levels were compared to those obtained when the mineral matter alone, produced by ashing the coal at a low temperature, was treated with HF, in order to quantify the extent that the carbonaceous matrix inhibits extraction. The carbonaceous matrix inhibits the dissolution of Ti to a large extent. Si and Fe are the next most inhibited elements. It is proposed that the Ti is present as extremely small particles, of possibly less than 1 mum in length, which are finely disseminated throughout the coal.

Use of high-temperature, high-torque rheometry to study the viscoelastic properties of coal during carbonization

When coal is heated in the absence of oxygen it softens at approximately 400°C, becomes viscoelastic, and volatiles are driven off. With further heating, the viscous mass reaches a minimum viscosity in the range of 103–105Pas and then begins to resolidify. A high-torque, high-temperature, controlled-strain rheometer with parallel plates has been used to study the rheology during this process. Under shear, the viscosity of the softening mass decreases with increasing shear rate. During resolidification, the viscosity increases as C‐C bond formation and physical interactions gives rise to an aromatic network, but, under shear, the network breaks apart and flows. This is viewed as a yielding of the structure. The higher the shear rate, the earlier the yielding occurs, such that if the shear rate is low enough, the structure is able to build. Also, further into resolidification lower shear rates are able to break the structure. It is proposed that resolidification occurs through the formation of aromatic clus...

The effect of rank and lithotype on coal wettability and its application to coal relative permeability models

We report the effect of rank and lithotype on the wettability of artificial cleat channels in five coals from the Bowen Basin with ranks in the Rmax% range 0.98-1.91%. Wettability was assessed by measuring contact angles of air and water in the artificial cleats using a microfluidic Cleat Flow Cell (CFC) instrument. The artificial cleats were produced by reactive ion etching and had widths in the range 20-40 m that replicate the width and shape of some natural coal cleats under sub-surface reservoir conditions. These model cleats were developed to allow systematic laboratory investigations of water and gas relative permeability behaviour. Imbibition and drainage experiments were performed in the artificial channels using air and 0.1 %wt. fluorescein in fresh tap water to observe contact angles, the entry pressure of the air-water and water-air interface to the channel, and the pressure at which the channel was filled by the displacing fluid. Relative contact angles on the coal surface of 110 -140° were determined from images collected in the imbibition experiments. A trend of increasing contact angle with coal rank was observed. The low rank coal exhibited smaller contact angles and lower breakthrough pressures than the higher rank coal samples. In the drainage experiments the injection air displaced the water but left a residual liquid film on cleat walls across dull, inertinite rich bands. This residual film was not observed in the bright, vitrinite rich bands. The results of this study may provide the basis to consider an improved relative permeability model that explicitly accounts for wettability and the effect of coal rank.

The influence of cleat demineralisation on the compressibility of coal

The natural fracture system of coal is the primary conduit for gas flow. Low permeability is in many cases attributed to low fracture porosity and/or connectivity. Mineral occluded coal cleats are known to considerably reduce coal permeability. Whilst cleat demineralisation has been found to increase coal permeability, its influence on compressibility is poorly understood. In this study, we investigated the influence of mineral dissolution and secondary mineralisation on the compressibility of coal (Cf) following acidification with hydrochloric and hydrofluoric acid (HCl-HF). In-situ HCl core flooding and core immersion in 3% and 15% HF yielded a less compressible core (Cf 0.006 from 0.020 bar-1) with sustained, enhanced permeability to brine (k 0.40 from 0.10 mD). We attribute improved stress resilience and better fluid flow characteristics to the dissolution and subsequent secondary mineralisation of the cores circumferential periphery. Predictive geochemical speciation using OLI Analyzer 9.1, for surveying mineral solubilities and precipitation tendencies, identified the formation of radio-dense neofluoride salts K2SiF6 and CaF2 Structural modifications and mineralogical changes detected from scanning electron microscopy-electron diffraction spectroscopy (SEM-EDS), confirmed the presence of these salts. Results suggest that mineral alteration and subsequent secondary mineralisation of the core periphery following HCl-HF acidisation yielded well-formed crystalline salts, apparently serving as in-situ generated proppants buttressing newly created void spaces for enhanced fluid flow and improved resistance to increasing confining stress.