Extracting hydrocarbons from Huadian oil shale by sub-critical water

The possibility of extracting hydrocarbons from Huadian oil shale by sub-critical water was found in a stainless steel vessel. The effects of temperature and pressure on the extraction of hydrocarbons were studied. After extraction experiments, the residual solid, liquid and gas phase samples were collected and characterized, respectively. The extract yield could reach 7 wt.% (ad) when the extraction of oil shale was conducted at 260 °C for 2.5 h with the pressure of 15 MPa. The results of thermogravimetry (TG) showed that the weight loss of residual solid samples was much smaller than that of the original oil shale. It indicated that kerogen components had been decomposed partly by treatment with sub-critical water. Gas chromatography-mass spectrometry (GC-MS) analysis showed that there were more than 300 recognizable peaks in the extracting solution following processing at 330 °C and 18 MPa. Large amounts of high molecular weight hydrocarbons were gradually decompounded by the increase in types and levels of low molecular weight hydrocarbons, and polycyclic and heterocyclic compounds with the rising of pressure and temperature. These indicated that sub-critical water is capable of cracking kerogen into smaller hydrocarbon compounds at relatively low temperatures.     

Changes in char reactivity due to char-oxygen and char-steam reactions using Victorian brown coal in a fixed-bed reactor

This study was to examine the influence of reactions of char–O2 and char–steam on the char reactivity evolution. A newly-designed fixed-bed reactor was used to conduct gasification experiments using Victorian brown coal at 800 °C. The chars prepared from the gasification experiments were then collected and subjected to reactivity characterisation (ex-situ reactivity) using TGA (thermogravimetric analyser) in air. The results indicate that the char reactivity from TGA was generally high when the char experienced intensive gasification reactions in 0.3%O2 in the fixed-bed reactor. The addition of steam into the gasification not only enhanced the char conversion sig-nificantly but also reduced the char reactivity dramatical y. The curve shapes of the char reactivity with involve-ment of steam were very different from that with O2 gasification, implying the importance of gasifying agents to char properties.     

Low-temperature oxidation of Victorian brown coal

A study has been made of low-temperature oxidation of Victorian brown coal at 35 °C and oxygen pressure of 0.1 M Pa and regression analysis of the experimental results shows that the reaction can best be described by the continuous reaction model. The reaction is subject to reaction product inhibition, apparently caused by product adsorption. Progressive conversion is obtained through a series of cycles consisting of a reaction step followed by evacuation of the coal. The rate equation developed from the continuous reaction model describes satisfactorily the progress of the reaction in each of these cycles. A study of earlier findings on the nature of Victorian brown coal oxidation products indicates that the product water may be significant in this reaction inhibition.     

Release of alkali and alkaline earth metallic species during rapid pyrolysis of a Victorian brown coal at elevated pressures

Possible reaction mechanisms responsible for the release of Na and Mg during pyrolysis at elevated pressures are described in this paper. In order to evaluate these mechanisms a Victorian brown coal, Loy Yang coal, was pyrolysed in a wire-mesh reactor at pressures up to 6.1 MPa at a heating rate of 1000 °C s⁻¹. Release of Na and Mg were quantified as functions of temperature and pressure. The results demonstrated that increasing pressure suppresses or promotes release of Na and Mg depending on the combination of pressure and temperature. The results obtained have been explained qualitatively by the proposed reaction mechanisms. At temperatures of 600 °C and lower, the release of Na and Mg from the pyrolysing coal/char particles, as light carboxylates, other organic salts and/or metals, was controlled by their diffusion through the pore system of the particles and, therefore, was suppressed by increasing pressure. At higher temperatures, the release of Na and Mg seems to be affected by the changes in intra-particle mass transfer mechanism due to increasing pressure as well as by chemical reactions responsible for the formation of volatile Na and Mg species.     

Effects of volatile-char interactions on the evolution of char structure during the gasification of Victorian brown coal in steam

The purpose of this study is to investigate the effects of volatile-char interactions on the evolution of char structure during the gasification of Victorian brown coal in steam. A novel one-stage fluidised-bed/fixed-bed quartz reactor was employed to carry out the experiments in the presence and absence of volatile-char interactions. The effects of thermal annealing on char structure were also investigated under similar conditions. The structural features of char were evaluated using FT-Raman spectroscopy. The results indicate that the char structural features were considerably affected by volatile-char interactions, which was shown from the Raman band area or the ratios between the band areas. H radicals from the thermal cracking/reforming of volatiles are believed to play a vital role in the changes in char structure due to the volatile-char interactions. H radicals could penetrate into char matrix and favour the condensation of aromatic rings, which was the main reason for the decrease in the ratio of small (less than 6 fused rings) to large aromatic rings during the volatile-char interactions. The volatile-char interactions also greatly affected the concentrations of O-containing groups in char and thus significantly altered the observed Raman intensity of the char.     

Flameless incineration of pyrene under sub-critical and supercritical water conditions

Pyrene was used as a typical four-ring polycyclic aromatic hydrocarbon (PAH), to investigate the mechanisms and incineration behaviour of large organic molecules in a batch supercritical water oxidation reactor using hydrogen peroxide as oxidant. The distribution of carbon as gaseous species and organic species in relation to the temperature and pressure, and reaction time was monitored. The results showed that at 200 °C, pyrene was only slightly decomposed but as the temperature increased to 250 °C and then to 280 °C, carbonisation and thermal cracking became prevalent leading to char formation and decomposition of pyrene to phenanthrene, and later naphthalene. Rapid dissolution and oxidation of the char and organic species started occurring from 300 °C. Increasing reaction time resulted in increased formation of carbon dioxide and carbon monoxide. Initially high product formation of phenanthrene at short reaction times was followed by high decomposition of the organic products in solution as the reaction conditions became progressively more severe. Oxygenated organic species such as aldehydes, ketones, phenols, xanthone, and benzoic acid were identified as the temperature and reaction times were increased between 300 and 380 °C. From the analytical results obtained, carbon mass balances were calculated for each experiment. A proposed mechanism for the observed oxidative decomposition of pyrene is also reported.     

Evidence of poly-condensed aromatic rings in a Victorian brown coal

An attempt was made for obtaining UV/VIS absorption and fluorescence spectra of a whole Victorian brown coal and then examining the presence of aromatic ring systems (ARSs) with poly-condensed rings in the coal. Loy Yang brown coal was subjected to an alkali-promoted depolymerization in an aqueous solution of sodium hydroxide at 473 K and then dissolved nearly completely into the solution. The solution of the solubilized coal was analyzed by UV/VIS absorption and fluorescence spectroscopies. The spectra of the solubilized coal were compared with those of a tar that was produced from the rapid pyrolysis of the coal in a wire-mesh reactor. Absorbance of the solubilized coal per unit molar concentration of aromatic carbon and unit light path length was averaged over 50 nm wavelength intervals in a range from 250 to 600 nm. The averaged absorbance of the solubilized coal was much greater than those of mono-aromatic compounds and lignin at intervals from 400 to 600 nm while comparable to those of tetra- to hexa-aromatic compounds, suggesting that the coal is abundant of ARSs with poly-condensed rings. The fluorescence spectra of the solubilized coal also give indication of the presence of ARSs with three to six condensed rings. Furthermore, the presence of even larger ARSs is evidenced from appreciable difference in apparent quantum yield of the solubilized coal and that of the tar. By comparing the absorption and fluorescence spectra of the solubilized coal with those of the tar, it was revealed that the tar is richer in relatively small poly-ARSs than the solubilized coal while the larger poly-ARSs are abundant in the solubilized coal. Smaller poly-ARSs were thus released from the coal preferentially to larger poly-ARSs during the pyrolysis.     

Effect of iron on the gasification of Victorian brown coal with steam:enhancement of hydrogen production

This paper reports the significant enhancement of hydrogen production during the gasification of Victorian brown coal with steam using iron as a catalyst. Iron was loaded into the acid-washed Loy Yang brown coal using ferric chloride aqueous solution. Gasification experiments were carried out using a quartz reactor at a fast particle heating rate. The yield of char was determined by directly weighing the reactor before and after each experiment. Gases were analysed using a GC with dual columns. The overall gasification rate of a char increases greatly in the presence of iron. The transformation of iron species during pyrolysis and gasification was examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that both reduced-iron (α-Fe and γ-Fe) and magnetite (Fe₃O₄) highly dispersed in a char can catalyse the gasification of the char with steam. In particular, the char from iron-loaded coal samples gives much higher yields of H₂ than a char from the acid-washed coal under similar conditions. The mechanism for the enhancement of hydrogen production in the presence of iron is discussed.     

Kinetic studies on Victorian brown coal hydroliquefaction

Reaction kinetics of the liquefaction of Victorian brown coal in a process development unit (PDU) having three reactors in series have been studied at temperatures of 430–470°C, and pressures of 15–25 MPa. It is shown that the rate of hydrogen consumption can be expressed as a function of the concentrations of coal and catalyst, hydrogen partial pressure, reaction temperature and residence time, and is controlled by the rates of hydrogenation of polynuclear aromatic components, and the rates of formation and stabilization of radicals. The relative contribution of these reactions, at any temperature, determine the influence of the hydrogen partial pressure on the rate of the hydrogen consumption. The kinetics of the decomposition reactions of brown coal to preasphaltene, asphaltene and to oil also have been studied. The apparent activation energies determined are 25 kJ mol^?1 for the brown coal to preasphaltene, 50 kJ mol^?1 for preasphaltene to asphaltene, 76 kJ mol^?1 for asphaltene to oil, and 184 kJ mole^?1 for oil to gases.     

Variation in Victorian brown coal characteristics and hydrogenation potential

A detailed study of the variation of properties and characteristics of Victorian brown coal both within seams and between fields has been carried out. Within a seam, the organic coal properties are lithotype dependent whilst the exchangeable inorganic elements, Na, Mg, Ca and Fe, show no relation to lithotype and, hence, are believed to be of post-depositional origin. Considerable variation in coal properties between different brown coal fields has been demonstrated by analyses of 219 samples from 10 coal fields. The coal properties which correlate best with hydrogenation reactivity are primarily associated with the hydrogen content of the coal. The mineral matter also influences the hydrogenation reactivity, as demonstrated by the occurrence of the value for ash level in multiple linear regression equations.     

Measurement of volatile matter in Victorian brown coal

The effects of using one-stage and two-stage heating, using air-dried coal and coal oven-dried under nitrogen, and using final temperatures of 850°C and 900°C on the measured volatile matter for twelve Victorian brown coals have been examined by the use of a statistically controlled experiment. The repeatability of the two-stage method was found to be significantly better than that of the one-stage method (0.7% abs. compared to 0.9% abs.). The volatile matter of coals at the front of the furnace was found to be significantly different from that of coals at the back of the furnace for the one stage method but not for the two-stage method. A two-stage heating method (7 min at 400°C and then 7 min at 900°C) using oven-dried coal is recommended for the routine determination of volatile matter in brown coal.     

Attrition of Victorian brown coal during drying in a fluidized bed

Analyzing the attrition of Victorian brown coal during air and steam fluidized bed drying, the change in particle size distribution over a range of initial moisture contents (60% to 0%) and residence times (0 to 60 minutes) was determined. Dried at a temperature of 130°C with a fluidization velocity 0.55 m/s and an initial particle size of 0.5–1.2 mm, both fluidization mediums show a shift in the particle size distribution between three and four minutes of fluidization, with a decrease in mean particle size from 665 µm to around 560 µm. Using differential scanning calorimetry (DSC), the change in particle size has been attributed to the transition between bulk and non-freezable water (approximately 55% moisture loss) and can be linked to the removal of adhesion water, but not to fluidization effects. This is proved through the comparison of air fluidized bed drying, steam fluidized bed drying, and fixed bed drying—the fixed bed drying is being used to determine the particle size distribution as a function of drying. The results show the three drying methods produce similar particle size distributions, indicating that both fluidization and fluidization medium have no impact upon the particle size distribution at short residence times around ten minutes. The cumulative particle size distribution for air and steam fluidized bed dried coal has been modeled using the equation P_d = A₂ + (A₁ ? A₂)/(1 + (d/x₀)^p), with the resultant equations predicting the effects of moisture content on the particle size distribution. Analyzing the effect of longer residence times of 30 and 60 minutes, the particle size distribution for steam fluidized bed dried coal remains the same, while air fluidized bed dried coal has a greater proportion of smaller particles.     

MTE water remediation using Loy Yang brown coal as a filter bed adsorbent

The future development of a non-evaporative brown coal dewatering technique called Mechanical Thermal Expression (MTE) will produce large volumes of acidic, salty and organic rich product water. The overall viability of the MTE process will, in turn rely on the availability of a simple and energy-efficient water remediation strategy. Water treatment using the feed coal itself as an adsorbent may provide such an option. In this study a fixed-bed configuration of raw Loy Yang coal was employed.When the adsorbent was first exposed to MTE water, most of the dissolved organic carbon (DOC) and most of the multivalent cations in solution were adsorbed. However, breakthrough of monovalent cations occurred after a volume of MTE water equivalent to just two times the volume of the adsorbent bed itself (2 bed volumes (BVs)) had passed, with only small proportions of Na and K being retained.About 60% (30 mg/g, db) of the dissolved organic carbon (DOC) and about 25% (0.16 mmol/g, db) of the total cations were removed after passing 20 BV of MTE water through the adsorbent bed. This corresponds to an adsorbent requirement that is 1.4% of the amount of coal to be dewatered. Thus, the use of brown coal adsorbent beds may be an effective primary water treatment option. However specific organic and inorganic components are likely to require further reduction prior to discharge to the environment.     

Generation of ultra-clean coal from Victorian brown coal — Sequential and single leaching at room temperature to elucidate the elution of individual inorganic elements

This paper addressed the probability of the generation of ultra-clean coal from chemical leaching of low-rank Victorian brown coal. Sequential leaching was employed to determine the modes of occurrence of the major elements in the two coals studied, including Na, K, Mg, Ca, Fe, Al, Ti, and Si. The results indicate that, the modes of occurrence of individual metals vary greatly with brown coal sample and elemental type. For one brown coal tested, it is dominated by water-soluble and ammonium acetate-soluble ion-exchangeable cations. Therefore, a single washing through the use of woody biomass-derived pyroligneous acid or citric acid easily reduced the concentrations of its overall ash and even sulphur and chlorine to meet the requirements for gas turbine fuel. The leaching of the organically bound cations in this coal was also very rapid and completed in 5 min. In contrast, another brown coal tested is mainly composed of quartz and/or clay compounds which remained intact even after being leached with 5 M nitric acid. These mineral grains possess two peak size ranges in the coal, 1.0-2.2 μm and 4.6-10 μm. The former size bin was embedded deeply in coal matrix, and hence, its leaching upon acids was very slow when compared with coarse particles which are mostly discrete grains residing separately from coal matrix. The Na-EDTA was found to be able to mobilise the small grains substantially through its Na ion to penetrate coal matrix to react with Al, forming acid-soluble Na aluminates. The ammonium acetate-insoluble Ti and Fe polyhedra were also mobilised by the EDTA. Accordingly, the overall ash content in coal residue accounts for ~ 1.5 wt.%, relative to 2.6 wt.% in the corresponding raw coal and 2.0 wt.% in the ammonium acetate-insoluble residue.     

Pyrolysis of brown coal under different process conditions

Pyrolysis tests were performed under laboratory conditions, simulating possible processes in the burning of brown coal mines. These tests focused on gaseous products of thermal decomposition of coal and how their concentrations changed depending on pyrolysis temperature. Results obtained can help to quantify the contributions of particular gases to overall explosiveness of a gaseous mixture and can explain the process of explosive gas release during conflagration.     

Changes in char reactivity and structure during the gasification of a Victorian brown coal: Comparison between gasification in O2 and CO2

Char reactivity is an important factor influencing the efficiency of a gasification process. As a low-rank fuel, Victorian brown coal with high gasification reactivity is especially suitable for use with gasification-based technologies. In this study, a Victorian brown coal was gasified at 800 °C in a fluidised-bed/fixed-bed reactor. Two different gasifying agents were used, which were 4000 ppm O₂ balanced with argon and pure CO₂. The chars produced at different gasification conversion levels were further analysed with a thermogravimetric analyser (TGA) at 400 °C in air for their reactivities. The structural features of these chars were also characterised with FT-Raman/IR spectroscopy. The contents of alkali and alkaline earth metallic species in these chars were quantified. The reactivities of the chars prepared from the gasification in pure CO₂ at 800 °C were of a much higher magnitude than those obtained for the chars prepared from the gasification in 4000 ppm O₂ also at 800 °C. Even though both atmospheres (i.e. 4000 ppm O₂ and pure CO₂) are oxidising conditions, the results indicate that the reaction mechanisms for the gasification of brown coal char at 800 °C in these two gasifying atmospheres are different. FT-Raman/IR results showed that the char structure has been changed drastically during the gasification process.     

Free radical involvement in the oxidation of Victorian brown coal

Electron spin resonance spectroscopy has been used to investigate free radical involvement in the oxidation of Victorian brown coal. Fresh, wet Yallourn brown coal exhibits two superimposed e.s.r. signals due to organic free radicals. The free radicals responsible for the narrow signal interact reversibly with atmospheric oxygen while the broad signal changes intensity dramatically during prolonged exposure to air. Coal:oxygen complex formation may explain these observations. Results also suggest that the free radical content of brown coal increases as a consequence of vacuum drying.     

Fractionation of brown coal by sequential high temperature solvent extraction

Separation of brown coal into fractions having rather uniform structure is believed to be one of the promising pretreatment methods for effective utilization of brown coal. The authors have recently presented a new coal fractionation method that can separate a bituminous coal into several fractions having different molecular weight compounds without decomposing the coal. The method extracts coal using a flowing stream of non-polar solvent such as tetralin or 1-methylnaphthalene by increasing the extraction temperature stepwise up to 350 °C. In this study the fractionation method was applied to fractionate a brown coal. Water was used as an extracting solvent in addition to tetralin and 1-methylnaphthalene by intending to utilize inherent water of brown coal as the extraction solvent. An Australian brown coal was successfully fractionated into six fractions by any solvents, but the properties of the fractions were significantly different depending on the extraction solvent. This is because tetralin, 1-methylnaphthalene, and water interacted significantly with the brown coal in different ways even at less than 350 °C. The difference in chemical structure and thermal properties of the fractions were examined in detail through ultimate analysis, ¹³C NMR, molecular weight distribution, and thermogravimetric and thermomechanical analyses.     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part IV. Catalytic effects of NaCl and ion-exchangeable Na in coal on char reactivity

The purpose of this study is to investigate the catalytic effects of Na as NaCl or as sodium carboxylates (-COONa) in Victorian brown coal on the char reactivity. A Na-exchanged coal and a set of NaCl-loaded coal samples prepared from a Loy Yang brown coal were pyrolysed in a fluidised-bed/fixed-bed reactor and in a thermogravimetric analyser (TGA). The reactivities of the chars were measured in air at 400 °C using the TGA. The experimental data indicate that the Na in coal as NaCl and as sodium carboxylates (-COONa) had very different catalytic effects on the char reactivity. It is the chemical form and dispersion of Na in char, not in coal, that govern the catalytic effects of Na. For the Na-form (Na-exchanged) coal, the char reactivity increased with increasing pyrolysis temperature from 500 to 700 °C and then decreased with pyrolysis temperature from 700 to 900 °C. The increase in reactivity with pyrolysis temperature (500-700 °C) is mainly due to the changes in the relative distribution of Na in the char matrix and on the pore surface. For the NaCl-loaded coals, when Cl was released during pyrolysis or gasification, the Na originally present in coal as NaCl showed good catalytic effects for the char gasification. Otherwise, Cl would combine with Na in the char to form NaCl during gasification, preventing Na from becoming an active catalyst. Controlling the pyrolysis conditions to favour the release of Cl can be a promising way to transform NaCl in coal into an active catalyst for char gasification.