Compositional and structural variations of bitumen and its interactions with mineral matters during Huadian oil shale pyrolysis

Thermal bitumen is an important intermediate derived from kerogen decomposition during oil shale pyrolysis. In this study, free bitumen (FB) and bound bitumen (BB) were obtained by extracting oil shale chars (300–550 °C) before and after demineralization, and then analyzed by liquid chromatography fractionation, Fourier transform infrared spectroscopy, and gas chromatography/mass spectrometry. The FB yield first increased and then decreased with increasing temperature, and the maximum value was 2.10% at 400 °C. The decarboxylation of acids and decomposition of esters at 350–450 °C decreased the content of these compounds. Meanwhile, the intense cracking reactions of aliphatic compounds and alkyl chains at 400–450 °C decreased the carbon chain lengths and molecular weights of these compounds. From the analytical results obtained for the BB fractions, we suggest that some carboxylic acids or carboxyl group-containing compounds may be trapped on carbonate particles by the formation of Ca₂₊COO_? bonds, whereas other oxygenated compounds (e.g., esters and phenols) can be adsorbed preferentially by clay minerals through Lewis acid-base interactions.     

Thermophysical characterization of oil sands. 1. Specific heats

Differential scanning calorimetry is used to measure the specific heats (C_p) of oil sands selected from four major deposits in the US and Canada. The C_p values are in the range 0.670–1.57 J g^?1 K^?1 for temperatures ranging from 100 to 350 °C. The temperature dependence of C_p for N.W. Asphalt Ridge (94.5 m burial depth) and P.R. Springs oil sands is larger than for Circle Cliffs and N.W. Asphalt Ridge (158.5 m burial depth) oil sands. Oil sands from the Athabasca deposit have slightly lower C_p values relative to other deposits. Specific heats of oil sand bitumen are always appreciably higher than those of the corresponding parent samples. Predictive equations, obtained from regression analyses of the experimental data, are presented, which allow computation of C_p values for an oil sand at a given temperature.     

Pyrolysis kinetics of Athabasca bitumen using a TGA under the influence of reservoir sand

Pyrolysis kinetics of thermal decomposition of bitumen was investigated by thermogravimetric analysis (TGA). TGA experiments were conducted at multiple heating rates of 5, 10, 20°C min^–1 up to 800°C to obtain the pyrolysis characteristics of bitumen. Weight loss curve from TGA shows that two different stages occurred during bitumen pyrolysis. Differential method has been used for determining the kinetic parameters and the best fit for the order of reaction was found based on the R² values. Kinetics results confirm the presence of two different stages in bitumen pyrolysis with varying kinetic parameters. The average activation energy for the first and second stage was 29 and 60 kJ mol^?1 and the average order of the reaction was 1.5 and 0.25, respectively. Experiments have been conducted with different reservoir sand. The effect of different source of sand reveals no effect on the pyrolysis behaviour of bitumen. A considerable difference was found with the pyrolysis of bitumen–sand mixtures and bitumen alone based on coke yield and activation energy. © 2011 Canadian Society for Chemical Engineering     

Measurements of specific heat,thermal conductivity and thermal diffusivity of Utah tar sands

A constant applied heat flux method has been used to measure the specific heat and thermal conductivity of large samples of Utah (North-west Asphalt Ridge) tar sands as a function of temperature. Independent measurements of density allowed for the calculation of thermal diffusivity. Constituent analysis of the tar sand samples also permitted the calculation of bitumen and sand specific heats. Specific heat of the bitumen was found to increase with temperature from 1.85 to 3.9 kJ kg^?1 K^?1 for temperatures between 300 and 480 K. Specific heat of the sand matrix increased only slightly, from 0.85 to 1.0 kJ kg^?1 K^? for the same range of temperature. Corresponding thermal diffusivities for tar sand were found to decrease with temperature, and had a range of 5 · 10^?7–9 · 10^?7 m² s^?1 over the measured temperatures. It was concluded that the latent heat of both bitumen and water have a strong influence on the apparent overall specific heat of tar sand.     

Pyrolysis and oxidation of heavy fuel oils and their fractions in a thermogravimetric apparatus

Using the derivative thermogravimetric technique, an investigation was made of the pyrolysis and oxidation of some heavy fuel oils and their separate paraffinic, aromatic, polar and asphaltene fractions. The thermal behaviour of fuel oil can be interpreted in terms of a low-temperature (< 400 °C) phase involving the volatilization of paraffinic and aromatic fractions, and a high-temperature phase in which the polar and asphaltene fractions pyrolyse and leave a particulate carbon residue. In an oxidizing atmosphere, the first phase (< 400 °C) consists of the simultaneous evaporation and oxidation of paraffinic and aromatic fractions. The second phase (400–550 °C) consists mainly of pyrolysis of oxidized polar materials, the asphaltenes, with a final phase involving the burning of the carbonaceous residue formed in the second stage.     

Electrical conductivity of Colorado oil shale to 900 °C

Electrical conductivity of oil shale from the Anvil Points Mine, Colorado was measured to temperatures > 900 °C with conductance bridges operating at frequencies from 100 to 100 000 Hz. The conductivity of low, intermediate and high grade oil shales (15,124,233 ml kg^?1, respectively) is dependent on water content up to ≈ 100 °C. At ≈ 120 °C, values of conductivity at ≈ 10^?7 S m^?1 are observed for all grades. A strong, time-dependent, increase in conductivity, beginning at ≈400 °C, marks the loss of light hydrocarbons and the formation of a conductive char. The frequency dependence of conductivity-slightly less than a decade increase in conductivity per decade increase in frequency over the temperature range 100–400 °C-vanishes at temperatures near 500 °C. At 600–800 °C, the conductivity of these oil shales reaches a maximum value which is as much as 10⁸ times larger than the conductivity near 250 °C.     

Thermophysical characterization of oil sands. 2. Acoustic properties

Propagation characteristics of shear (S) and compressional (P) waves are investigated for oil sands from the Athabasca, P.R. Spring, N.W. Asphalt Ridge and Circle Cliffs deposits. These studies are oriented towards applications of acoustic techniques in characterization, diagnostics and control of in-situ extraction methods currently envisaged for oil sand bitumen. The magnitude of the temperature dependence of S and P wave velocities is directly related to the bitumen content of the oil sand. The origin of the pronounced changes in Sand P wave velocities (or travel times) in the temperature regions 24–200 °C and 425–500 °C is traced to the thermal decomposition of oil and sand bitumen. The S and P wave velocities generally decrease with increasing bitumen content. Other variables that are studied, such as moisture content and bulk density, have relatively minor effects on the magnitude of the measured S and P wave velocities.     

Kinetics of the thermo-oxidative and thermal cracking reactions of Athabasca bitumen

The thermo-oxidative and thermal cracking reactions of Athabasca bitumen were examined qualitatively and quantitatively using differential thermal analysis (DTA). Reaction kinetics of low temperature oxidation (LTO) and high temperature cracking (HTC) were determined. The rate of the LTO reaction was found to be first order with respect to oxygen concentration. The activation energy and the Arrhenius pre-exponential factor were 64 MJ kg^?1 mol^?1 and 10^5.4 s^?1, respectively. The effects of atmosphere, pressure, heating rate and support material on the thermal reactions of bitumen were studied. In general, it was found that partial pressures of oxygen > 10% O₂ favoured exothermic oxidation reactions. High pressure increased the rates of LTO and HTC as well as the exothermicity of these reactions. A major contribution of this study to thermal in-situ processes is that heating rate can be used effectively to control the extent of low temperature oxidation and hence fuel availability during in-situ combustion. Low linear heating rates (2.8 °C min^?1) favoured low temperature oxidative addition and fission reactions. The reaction products readily formed coke and combusted upon heating. High linear heating rates (24.5 °C min ^?1) led to rapid oxidation reactions in the high temperature zone; the high temperature and the energy released during oxidation appeared to promote combustion. Finally, when sand was used as the support material there appeared to be a catalytic effect in both LTO and HTC reactions.     

Thermogravimetry and differential scanning calorimetry of Kentucky bituminous coals

A detailed investigation has been made of the thermal characteristics of six Kentucky bituminous coals undergoing pyrolysis in an inert atmosphere at three different heating rates. The specific heats of the coals and the enthalpy changes characterizing their thermal degradation were measured by differential scanning calorimetry. Thermogravimetry was employed to measure the attendant weight changes, which were used to normalize the heat flow data to unit sample weight, enabling a quantitative comparison of the thermal behaviour of the several coals. The specific heats of the dry coals lie in the range 1.21–1.47 J gK^?1, 100–300 °C. The exothermic heat flow from 300 to 550 °C, where the major weight loss occurs, has been associated with the primary carbonization process, the development of the plastic state, and the onset of secondary gasification, which is responsible for coke formation. In the high pyritic sulphur coals, the endothermic pyrite/pyrrhotite transformation at ≈580 °C is clearly defined. A preliminary global kinetic analysis of the thermogravimetric data has been made, using a modified Kissinger equation at the maximum rate of weight loss. Activation energy and pre-exponential factor values of the order 198–220 kJ mol ^?1 and 2–85×10¹²s^?1 have been obtained. These compare well with the limited published values for similar coals.     

Ultra-high creep resistant SiC ceramics prepared by rapid hot pressing

The high-temperature compression creep of additive-free β/α silicon carbide ceramics fabricated by rapid hot pressing (RHP) was investigated. The creep tests were accomplished in vacuum at temperature range 1500 °C–1750 °C and compressive loads of 200 MPa to 400 MPa. Under investigated condition the RHP ceramics possessed the lowest creep rate reported in the literature. The observed strain rates changed from 2.5 × 10^?9 s^?1 at 1500 °C and a lowest load of 275 MPa to 1.05 × 10^?7 s^?1 at 1750 °C and a highest load of 400 MPa. The average creep activation energy and the stress exponent remain essentially constant along the whole range of investigated parameters and were 315 ± 20 kJ?mol^?1, and 2.22 ± 0.17, respectively. The suggested creep mechanism involves GB sliding accommodated by GB diffusion and β?α SiC phase transformation.     

Thermophysical properties of Devonian shales

A detailed study of the thermophysical properties of Devonian shales from the central and eastern United States has been carried out. Thermal conductivity, thermal diffusivity, specific heat and dielectric constant data are presented. A Michigan shale sample with an oil yield of 28 litres per metric ton (1 t^?1) and a Kentucky shale (oil yield: 52 l t^?1) were selected. The specific heats of these shales are in the range 0.20–0.30 cal gm^?1 °C^?1, and increase with increasing temperature. The thermal conductivity (κ) of the two shale samples are comparable (ca. 1 W m^?1 °C^?1). The κ values show only a weak temperature dependance. The thermal diffusivity (α) of these shales range from 0.3–0.5 × 10^?2 cm² s^?1 and tend to decrease with increasing temperature. The dielectric constants show anomalously high values at temperatures above 200 °C. This effect is indicative of interfacial polarization mechanisms presumably arising from loss of water and onset of pyrolysis of the shale organic matter. Comparison of the trends in thermophysical behaviour of Devonian shales with data obtained previously on Green River oil shales is presented. The importance of thermophysical measurements in on-field applications in oil shale technology is highlighted.     

Effect of temperature on bitumen conversion in a supercritical water flow

This article deals with a study of bitumen conversion (the gross-formula CH_1.47N_0.01S_0.007) in a supercritical water (SCW) flow continuously supplied at the bottom of the vertically located tubular reactor. At the first stage, bitumen was continuously supplied from the top of the reactor into a counter-current SCW flow (400 °C, 30 MPa) for 60 min. At the second stage (after ceasing the supply of bitumen into the reactor), SCW was pumped through the layer of bitumen residue at uniform (2.5 °C/min) temperature increase from 400 to 700 °C at 30 MPa. The amount and composition of the liquid and volatile conversion products were measured. It is revealed that during bitumen supply into the reactor and subsequent pumping of SCW through the layer of bitumen residue in the temperature increasing mode from 400 to 500 °C, the yields of liquid conversion products are equal to 26.9 and 45.4%, respectively, relative to the weight of bitumen supplied into the reactor. Oils are the major components of these liquid products. Participation of H₂O molecules in redox reactions became evident due to the formation of CO and CO₂ even at 400 °C. A significant increase in the yields of H₂, CH₄, and CO₂ are detected at T > 600 °C. Based on the sulfur balance, it can be stated that the degree of bitumen desulfurization at 400–700 °C due to sulphur removal in form of H₂S accounts for 21.6 wt.% A solid carbonaceous bitumen residue, obtained after SCW conversion, is characterized by high specific surface (224 m²/g).     

The effects of temperature and shear rate on the apparent viscosity of Nigerian oil sand bitumen

The apparent viscosities of Nigerian oil sand bitumen were measured over a temperature range of 50–110°C and a shear rate range of 60–320 s⁻¹. Apart from temperature which is the most important variable influencing the viscosity of a liquid, the viscosities of the bitumen are affected by shearing effects. The apparent viscosity of the bitumen depended on the rate of shear at which it is measured, that is, it has an unlimited number of apparent viscosity values as the shear rate was varied. The shearing effects decreased as the temperature increased; that is, the bitumen became more Newtonian in the higher temperature region.     

Hydrodenitrogenation and Hydrodesulphurization of Heavy Gas Oil Using NiMo/Al2O3 Catalyst Containing Phosphorus: Experimental and Kinetic Studies

In this work, a systematic study has been conducted to optimize the process conditions and to evaluate kinetic parameters for hydrodenitrogenation (HDN) and hydrodesulphurization (HDS) of heavy gas oil derived from Athabasca bitumen using NiMo/Al₂O₃ catalysts containing phosphorus (P). In the catalyst, the concentration of phosphorus was maintained at 2.7 wt%. Experiments were performed in a tickle‐bed reactor at the temperature, pressure and liquid hourly space velocity (LHSV) of 340‐420°C, 6.1‐10.2 MPa and 0.5‐2 h^?1, respectively. H₂ flow rate and catalyst weight were maintained constant at 50 mL/min and 4 g, respectively in all cases. Statistical analysis of all experimental data was carried out using ANOVA to optimize the process conditions for HDN and HDS reactions. Kinetic studies for HDN and HDS reactions were studied within the temperature range of 340‐400°C using the power law model as well as the Langmuir‐Hinshelhood model. The power law model showed that HDN and HDS of heavy gas oil follow first order kinetics. The activation energies for HDN and HDS reactions from the power law and Langmuir‐Hinshelwood models were 94 and 96 kJ/mol and 113 and 137 kJ/mol, respectively.     

Heterogeneous and homogeneous reactions of pyrolysis vapors from pine wood

To maximize oil yields in the fast pyrolysis of biomass it is generally accepted that vapors need to be rapidly quenched. The influence of the heterogeneous and homogeneous vapor‐phase reactions on yields and oil composition were studied using a fluidized‐bed reactor. Even high concentrations of mineral low char (till 55 vol %) appeared not to be catalytically active. However, the presence of minerals, either in biomass or added, does influence the yields, especially by the occurrence of vapor‐phase charring/polymerization reactions. Contradictory, in the absence of minerals, homogeneous vapor‐phase cracking reactions were dominant over polymerization/charring reactions (400–550°C, 1–15 s). With increasing vapor residence time, the oil yield reached an asymptotic value, which decreased with temperature. At a vapor temperature of 400°C no decrease in oil yield was observed, but dedicated analysis showed that homogeneous vapor to vapor reactions had occurred. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Composition of oils produced during an echoing, in-situ combustion of a Utah tar sand

The Laramie Energy Technology Center (DOE) has completed its second in-situ combustion experiment (TS-2C), which was carried out in the Northwest Asphalt Ridge tar sand deposit near Vernal, Utah. During the experiment (183 days) 92 m³ (580 barrels) of oil was produced, 25% of the original oil in place. The in-situ process utilized is best described as a series of reverse- and forward-combustion phases or echoes traversing the 405 m² (0.1 acre) pattern. Several of the chemical and physical properties of the oil produced are significantly altered with respect to the original bitumen. These include pour point, specific gravity, average molecular weight, wax and nickel content, and the percentage of residue boiling at >538 °C (1000 °F). These and other changes effected on the bitumen during this experiment result in a product oil that closely resembles a heavy fuel oil.     

Reactivity of Australian coal-derived chars to carbon dioxide

The reactivities to CO₂ of four chars derived from Australian coals at 610 °C, were measured thermogravimetrically. Reaction rates in 100% CO₂ (total pressure, 101 kPa) varied from 0.026 mg h^?1 mg^?1 at 803 °C for char derived from a Lithgow coal to 6.3 mg h^?1 mg^?1 at 968 °C for a Millmerran coal char. Activation energies for the four chars were in the range 219–233 kJ mol^?1. The results show that for Lithgow (Hartley Vale) coal char, reactivity increases with CO₂ concentration and decreasing particle size. The apparent reaction order for this char with respect to CO₂ concentration was found to be 0.7. For different chars, reactivity is inversely proportional to the rank of the parent coal. No general correlation has been established between total mineral content (ash) and char reactivity.     

Long-term oxidation behaviors and strength retention properties of self-healing SiCf/SiC-SiBCN composites

The self-healing SiC_f/SiC-SiBCN composites with various boron contents in SiBCN were prepared, and their long-term oxidation behaviors and strength retention properties were investigated. The 100 h oxidation at 1200–1350 °C leads to parabolic mass gain of the obtained composites. With the oxidation temperature increased from 1200 °C to 1350 °C, the oxidation rate constants increase from 5.91 × 10^?8 mg²/(mm⁴ h) to 9.31 × 10^?7 mg²/(mm⁴ h) for the boron-lean (3.14%) composites, and from 2.57 × 10^?7 mg²/(mm⁴ h) to 6.04 × 10^?7 mg²/(mm⁴ h) for the boron-rich (7.18 wt%) composites. Correspondingly, the oxidation activation energy decreases from 363 kJ/mol to 112 kJ/mol due to the low initial oxidation temperature of boron-rich SiBCN. All the composites exhibit the higher strength retention rates after 1350 °C oxidation due to the enhanced self-healing performance. The boron-rich composites show a high strength retention rate of up to 104% due to the good self-healing capacity of the boron-rich SiBCN as well as the high CVI-SiC content.     

Flammability of polyacrylonitrile and its copolymers II. Thermal behaviour and mechanism of degradation

Homopolymeric polyacrylonitrile and fibre-forming copolymers containing either vinyl acetate or methyl acrylate comonomer have been studied by thermal analysis (DSC, TGA and DTG) at various heating rates (10–100 K min^?1) and under air and nitrogen. Three well-defined pyrolysis stages have been observed which occur over the temperature ranges 250–350°C, 350–550°C and above 550°C. Each stage involves a competition between volatilisation and cyclisation or char-forming reactions which depends on heating rate and the presence or absence of oxygen. The well-established dominance of cyclisation in the 250–350°C temperature range obtained during carbon fibre production from acrylic precursors occurs only at low heating rates. At high heating rates, volatilisation dominates and this explains why acrylic polymers have high flammabilities when heating rapidly. The full pyrolysis mechanism has been semi-quantitatively analysed and the role that comonomers play discussed. This has enabled a fuller understanding of the potential burning behaviour of these polymers to be developed.     

Comparison of Effects of Calcium and Magnesium Doping on the Structure and Biological Properties of NaTaO3 Film on Tantalum

Tantalum is widely used in hip joint replacement and knee joint repair, but its clinical application is limited due to its poor biological activity and weak ability to promote new bone formation. Ca and Mg ions are thought to be involved in bone metabolism and play an important physiological role in the angiogenesis, growth, and mineralization of bone tissue. In this work, NaTaO₃ films doped with Ca²⁺ and Mg²⁺ were prepared by hydrothermal synthesis and molten salt method. The doping amounts of Ca²⁺ doped at 450, 550, 650 and 750 °C were 0.59, 3.44, 32.75 and 29.88 at%, and that of Mg²⁺ doped at 300, 350, 400, 450, 500, 550 and 650 °C were 0.62, 1.03, 1.54, 20.12, 21.38, 14.37 and 0.74 at%, respectively. Ca²⁺ and Mg²⁺ are evenly incorporated into NaTaO₃ and cause the change of crystal plane spacing without any significant changes of morphologies below 550 and 400 °C respectively. XPS shows that the cations are the A-site substitution of perovskite structure (ABO₃). According to the morphology and composition analysis of Ca-incorporated samples and Mg-incorporated samples, the optimal preparation temperature of them is 550?°C and 400?°C, respectively. The results show that for “550?°C-Ca” and “400?°C-Mg” the hydrophilicity is 13.9° and 96.1°, the roughness is 114.3 and 54.3?nm, the doping ion concentration of Ca and Mg is 3.44 and 1.54 at%, and the 7-day ICP results is 69.8 and 1.4?ppm, respectively. In addition, cell proliferation experiments and cell morphology related to biological activity and osteogenic properties are discussed, and it is found that the performance of “550?°C-Ca” is better than “400?°C-Mg”. Ca²⁺–NaTaO₃ is a promising implantable material that will be extensive used in bone implants, joint replacements and dental implants.