Thermal characterisation of Australian oil shales

There has been a significant research effort on the development of an oil industry based on Australian oil shales. However, to date the research has been based mainly on the processing aspects of oil shale. The thermal analyses of oil shales, while having been the subject of many studies, have been limited to some extent by instrumentation and analytical techniques. This paper reports on thermal analysis studies utilising traditional thermogravimetry/differential thermal analysis (TG/DTA) and differential scanning calorimetry (DSC). The application of modern thermal analysis techniques such as high resolution TG (HRTG) and modulated differential scanning calorimetry (MDSC) is also examined and compared to the traditional methods.     

Thermal analysis of Australian coals—A short review

It is evident that thermal analysis studies of Australian coals are of primary significance in the rationalisation of the various physical and chemical processes inherent in energy generation from these fossil fuels. To data, considerable such data has been accumulated correlating combustion efficiency with the coal primary structure, surface phenomena, included metal ions, volatile matter release profiles, particle size and corresponding char properties. The kinetics of these complex processes are now also modelled.

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Zusammenfassung Für die Rationalisierung der physikalischen und chemischen Prozesse bei der Energiegewinnung aus australischer Kohle sind thermoanalytische Untersuchungen dieser fossilen Rohstoffe von erstrangiger Bedeutung. Es wurde eine bedeutende Menge von Angaben gesammelt, die eine Beziehung zwischen dem Verbrennungsgrad und der Primärstruktur der Kohle, Oberflächenerscheinungen, enthaltenen Metallionen, des Emissionsprofiles flüchtiger Verbindungen, der Partikelgröße und der entsprechenden Halbkokseigenschaften herstellen. Die Kinetik dieser komplexen Vorgänge wurde nun auch modelliert.

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Thermooxidative decomposition of oil shales

The thermooxidative decomposition of four oil shale samples from Estonia, Jordan, Israel and Morocco and one sample of Estonian oil shale derivative, semicoke, was studied with the aim to determine the characteristics of the process and the differences of it related to the origin of oil shale. The experiments with a Setaram Setsys 1750 thermoanalyzer coupled to a Nicolet 380 FTIR Spectrometer were carried out under non-isothermal conditions up to 1000 °C at the heating rates of 1, 2, 5, 10 and 20 °C min⁻¹ in an oxidizing atmosphere. A model-free kinetic analysis approach based on the differential isoconversional method of Friedman was used to calculate the kinetic parameters. The results of TG–DTA–FTIR analyses and the variation of activation energy E along the reaction progress α indicated the complex character of thermooxidative decomposition of oil shale and semicoke, being at that the most complicated for Estonian and Jordanian oil shale characterized by higher content of organic matter as compared to the other samples studied.     

Pyrolysis and combustion model of oil sands from non-isothermal thermogravimetric analysis data

Thermogravimetric (TG) data of oil sand obtained at Engineering Research Center of Oil Shale Comprehensive Utilization were studied to evaluate the kinetic parameters for Indonesian oil sand samples. Experiments were carried out at heating rates of 5, 15, and 25 °C min^?1 in nitrogen, 10, 20, and 50 °C min^?1 in oxygen atmosphere, respectively. The extent of char combustion was found out by relating TG data for pyrolysis and combustion with the ultimate analysis. Due to distinct behavior of oil shale during pyrolysis, TG curves were divided into three separate events: moisture release, devolatilization, and evolution of fixed carbon/char, where for each event, kinetic parameters, based on Arrhenius theory, were calculated. Coats–Redfern method, Flynn–Wall–Ozawa method, and distributed activation energy model method have been used to determine the activation energies of degradation. The methods are compared with regard to their characteristics and the ease of interpretation of the thermal kinetics. Activation energies of the samples were determined by three different methods and the results are discussed.     

Thermal analyses of Ohio bituminous coals

A suite of twenty-one bituminous coal samples from Ohio were analyzed by differential scanning calorimetry (DSC) and non-isothermal thermogravimetry (TG) techniques. Three regions of endothermic activity may be distinguished in the DSC scans in an inert atmosphere. The first peak (25–150°C) corresponds to loss of moisture from the coal, a second, very broad endotherm peaking in the range 400–500°C corresponds to devolatilization of the organic matter and a partially resolved endotherm at temperatures above 550°C probably corresponds to cracking and coking processes subsequent to the pyrolysis step. Evidence obtained from experiments with sealed pans suggest an autocatalytic effect exerted by the pyrolysis products. The use of the DSC technique to quantify the volatile matter content of coal seems less reliable than the proximate analyses obtained from non-isothermal TG in inert and O₂ atmospheres. Good agreement with ASTM values is observed by the latter method for a range of volatile matter and ash content.     

Oxidation kinetics of timahdit and tarfaya moroccan oil shales

Organic matter evolution and kinetics of combustion of Tarfaya and Timahdit oil shales have been examined by thermogravimetry (TG) and by differential thermal analysis (DTA). An agreement is observed between both techniques where it was found that combustion of organic matter occurs in two steps. Kissinger's method applied on experimental results gives an activation energy of the same magnitude for the first step of both oil shales (103 kJ mol^–1) whereas the second is 148 kJ mol^–1 for Timahdit and 118 kJ mol^–1 for Tarfaya.The changes in specific surface area during thermal combustion of Timahdit and Tarfaya oil shales have been studied by thermogravimetric gas sorption balance and correlated with experimental results obtained on TG/DTA in air. For Timahdit oil shale oxidation products, specific surface areas calculated from nitrogen adsorption data shows a slight increase during the temperature domain of 280 to 430°C and after this temperature, they increase sharply. However, data obtained with Tarfaya oil shales shows a significant increase at the temperature of maximum oxidation of the first stage of combustion of organic matter.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal analysis of soybean oil based polyols

Soybean oil based polyols (5-OH polyol, 10-OH polyol and 15-OH polyol) were synthetised from epoxidized soybean oil. The melting peak of polyols and the relationship between melting peak and the number-average functionality of hydroxyl in polyols were investigated by differential scanning calorimetry (DSC). The thermal decomposition of polyols and some of their thermal properties by thermogravimetry (TG) and derivative thermogravimetry (DTG) were also studied. The thermal stability of polyols in a nitrogen atmosphere was very close hence they had a same baseplate of triglyceride for polyols. The extrapolated onset temperature of polyols in their thermal mass loss, first step had a decreasing order: 5-OH polyol>10-OH polyol>15-OH polyol due to the difficulty in forming multiple elements ring of them had the same order. The thermal behavior of polyols under non-isothermal conditions using Friedman’s differential isoconversional method with different heating rates indicated that the 5-OH polyol had the lowest activation energy in thermal decomposition amongst these polyols according to the same fractional mass loss because of the weakest intramolecular oligomerization. The 15-OH polyol was prior to reach the mass loss region because the six-member ring is more stable than the three-member ring from 10-OH polyol and more easily formed.     

Thermal analysis study of the effect of coal-burning additives on the combustion of coals

Thermal analysis is widely used in combustion research for both fundamental and practical investigations. Efficient combustion of coals in cement industry is very important and necessary. In this research, the effects of three coal-burning additives on burning behaviour of bituminous coal and anthracite were studied with the help of thermogravimetry (TG) and differential scanning calorimetric (DSC) analysis. The kinetic study was carried out and the results were presented. The results showed that the coal-burning additives especially LSZ can reduce the ignition temperature, increase the ignition index D _i, combustion ending index D _f and affect the activation energy of the coal samples studied. The coal-burning additives especially LSZ can improve coal combustion effectiveness.     

Thermal analysis studies of oil shale residual carbon

Thermal analysis has been used to determine the impact of heating on the decomposition reaction of two Moroccan oil shales between ambient temperature and 500°C. During pyrolysis of raw oil shale, the residual organic matter (residual carbon) obtained for both shales depends on the heating rate (5 to 40°C min^-1). Three stages characterize the overall process: the concentration of carbonaceous residue decreases with increase of heating rate, become stable around 12°C min^-1 and continue to decrease at higher heating rates. Activation energies were determined using the Coats-Redfern method. Results show a change in the reaction mechanism at around 350°C. Below this temperature, the activation energy was 41.3 kJ mol^-1 for the decomposition of Timahdit, and 40.5 kJ mol^-1 for Tarfaya shale. Above this temperature the respective values are 64.3 and 61.3 kJ mol^-1. The reactivity of Timahdit and Tarfaya oil shale residual carbon prepared at 12°C min^-1 was subject to a dynamic air atmosphere to determine their thermal behaviour. Residual carbon obtained from Tarfaya oil shale is shown to be more reactive than that obtained from Timahdit oil shale. This revised version was published online in July 2006 with corrections to the Cover Date.     

扎赉特旗油砂在氮气气氛下的热解制油研究

油砂是一种含有沥青或其他重质石油的沉积岩,主要用于提取油砂沥青,以生产合成原油。中国拥有相当数量的油砂资源,目前还未开采,仅处于初步研究阶段。加拿大在20世纪初期就展开了油砂的开采及制油研究工作,并于20世纪70年代由加拿大合成油公司实现了工业化生产。油砂生产的沥青和合成油已占其石油总产量的1／4以上。     

Trace elements in Nigerian oil sands and extracted bitumens

The Nigerian oil sands are very extensive with an estimated in place reserves of bitumen/heavy oil of over 30 billion barrels. Instrumental Neutron Activation Analysis (INAA) has been used to determine the trace and minor elements in the raw oil sands and bitumens. About 43 trace elements in the raw oil sands and 30 in bitumen extracts were determined. The results are compared with values of Canadian bitumens and some Nigerian conventional light crude oils. In general, the Nigerian bitumens has higher hydrocarbon concentration than the Athabasca bitumen but slightly lower than in the Nigerian crude oils. The sulphur, vanadium and nickel contents of the Nigerian bitumens and crude oils are appreciably lower than those of Athabasca bitumen, thus indicating that the extraction and refining of Nigerian tar sand oil would pose less technological and environmental problems than the Athabasca syncrude.     

New adsorbents from oil shales: Preparation, characterization and U, Th isotope adsorption tests

New activated adsorbents for radionuclides have been produced from Moroccan oil shales by pyrolysis of the natural material at 550 °C flowed by a KMnO₄ activation. The texture and composition of the native rock and the adsorbents were studied before their use in tests for adsorption of radionuclides from standard solutions prepared from uranylnitrate and thorium nitrate in equilibrium with their daughters. The distribution coefficients between solutions containing U, Th and Ra and the adsorbents were evaluated by means of specific activities, measured by g-ray spectrometry. The adsorbents were observed to eliminate U, Th, Ra, Ac and Tl from aqueous solutions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Comparative TG-DTG oxidative profiles of selected American and Australian oil shales

The oxidative profiles for oil shale specimens of the U.S. Green River as well as the Australian Rundle, Glen Davis, and Alpha deposits obtained from microcomputer-controlled thermogravimetry in dynamic air atmospheres are reported. The oxidative behavior of these specimens is discussed relative to the organic maceral components and, in some cases, mineral matter content.     

Interaction forces in bitumen extraction from oil sands

Water-based extraction process (WBEP) has been successfully applied to bitumen recovery from Athabasca oil sand ore deposits in Alberta. In this process, two essential steps are involved. The bitumen first needs to be "liberated" from sand grains, followed by "aeration" with air bubbles. Bitumen "liberation" from the sand grains is controlled by the interaction between the bitumen and sand grains. Bitumen "aeration" is dependent, among other mechanical and hydrodynamic variables, on the hydrophobicity of the bitumen surface, which is controlled by water chemistry and interactions between bitumen and fine solids. In this paper, the interaction force measured with an atomic force microscope (AFM) between bitumen-bitumen, bitumen-silica, bitumen-clays and bitumen-fines is summarized. The measured interaction force barrier coupled with the contacted adhesion force allows us to predict the coagulative state of colloidal systems. Zeta potential distribution measurements, in terms of heterocoagulation, confirmed the prediction of the measured force profiles using AFM. The results show that solution pH and calcium addition can significantly affect the colloidal interactions of various components in oil sand extraction systems. The strong attachment of fines from a poor processing ore on bitumen is responsible for the corresponding low bitumen flotation recovery. The identification of the dominant non-contact forces by fitting with the classical DLVO or extended DLVO theory provides guidance for controlling the interaction behavior of the oil sand components through monitoring the factors that could affect the non-contact forces. The findings provide insights into megascale industrial operations of oil sand extraction.     

Heating rate effect on the DSC kinetics of oil shales

This research was aimed to investigate the combustion and kinetics of oil shale samples (Mengen and Himmetoğlu) by differential scanning calorimetry (DSC). Experiments were performed in air atmosphere up to 600°C at five different heating rates. The DSC curves clearly demonstrate distinct reaction regions in the oil shale samples studied. Reaction intervals, peak and burn-out temperatures of the oil shale samples are also determined. Arrhenius kinetic method was used to analyze the DSC data and it was observed that the activation energies of the samples are varied in the range of 22.4–127.3 kJ mol⁻¹ depending on the oil shale type and heating rate.     

Microwve inducdd catalytic decomposition of some alberta oil sands and bitumens

The processing of oil sands materials and upgrading of bitumens present a variety of problems for conventional technologies. This article describes a preliminary study of the concept of using microwave induced catalytic techniques to decompose the complex and viscous hydrocarbon compounds contained in these materials to allow efficient extraction of volatile and economically useful organic products such as C₂ and C₃ hydrocarbons. Addition of water to the tar sand material prior to reaction facilitated separation from the sand component as well as promoting the formation of economically very useful, liquid, oxygenated hydrocarbon products.     

PIGE-PIXE analysis of Nigerian tar sands

As a rapidly growing vast country, there is need in Nigeria to develop alternative energy sources to meet its ever increasing energy demands. Tar sands apart from its popular use as a source of asphaltic material for road surfacing is a new energy raw material in Nigeria. The immense industrial applications and utilization of the by-products of tar sands provide great incentives for its development. PIGE and PIXE techniques were employed for the determination of the major, minor and trace elemental concentrations in Nigerian tar sands including sulfur which occurs as pyrites, organic sulfur and sulfates. Proton beams produced by the 7 MV CN and 2.5 MV AN 200 Van de Graaff accelerators at I.N.F.N. Laboratori Nazionali di Legnaro (LNL) at Padova, Italy, were used for the PIGE and PIXE analysis, respectively. Results of this novel study are presented, discussed, and compared with some data from previous worker and values from Athabasca (Canada).     

Neutron activation analysis of Turkish coals

Neutron activation analysis of lignites taken from five different zones were carried out. It was observed that the elements which are selectively consumed by plants show relatively larger depositions in coals.     

Differential thermal analysis of low-rank coals

Differential thermal analysis (DTA) of low-rank coals of high lignite to subbituminous rank from coal mines of Pakistan is reported. The studies carried out in dynamic oxygen atmosphere indicate that the exothermic reactions occur between 300 and 650°C and that the samples undergo stepwise oxidation of the organic matter rather than a continuous process as indicated by the pattern of shoulders from 250 to 350°C accompanying the main peak around 450°C. The effect of heating rate, particle size and volatile content was also studied in relation to oxidation. The results show that the increase in heating rate from 10 to 80 deg min⁻¹ results in a marked shift in all the events in the DTA curve towards higher temperatures. As for the effect of particle size, the DTA records of 100–75, 150–100, 250–150 μm and greater than 250 μm fractions show that the magnitude and position of shoulder peaks are more sensitive to changes in particle sizes compared to the main peak. The curves recorded to study the effect of changing volatile content of samples between 30–40% indicate a complex pattern of shoulders accompanying the main peak. In general, the number of shoulder peaks increases with increasing volatile content of samples but their positions do not follow any trend. The DTA curves recorded in nitrogen contain ill-de-fined oxothermic effects over the 300–750°C temperature range. These curves consist of an endothermic peak around 150°C, two exothermic shoulders in the temperature region 300–400°C and a large broad exothermic whip between 500 and 700°C. The heating rates have similar effects as in oxygen while the particle size do not influence the results. It has been concluded that the organic matter in the coals studied here is extremely heterogeneous with different burning characteristics; as a result it is very difficult to quantify energy changes associated with poorly resolved exothermic events along the DTA curve. The effects also dominate in N₂ atmosphere thus making identification of mineral matter difficult. The overall pattern of DTA events in oxygen can be correlated with the heating rate, particle size and volatile content of samples.