Kinetic Aspect of Thermal Decomposition of Natural Phosphate and its Kerogen. Influence of heating rate and mineral matter

The natural phosphate and its demineralization products from Moroccan deposit were pyrolysed in a thermogravimetric analyser (TG) to examine the influence of the heating rate and mineral matter on their thermal decomposition. The heating rates investigated in the TG were 5–100°C min⁻¹ to final temperature of 1200°C. The integral method was used in the analysis of the TG to determine the kinetic parameters. It has been found that for the natural phosphate and corresponding kerogen analysed in the TG, the increase of the heating rate shifts the maximum rate loss to higher temperature. A first order reaction was found to be adequate for pyrolysis in the range 150–600°C which was attributed to kerogen decomposition. In addition, the results indicate that the removal of mineral matter affected the kinetic parameters found for kerogen in the natural phosphate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Supercritical fluid extraction of Moroccan (Timahdit) oil shale with water

Timahdit oil shale was subjected to supercritical water extraction. The results reveal significant difference in oil yields and composition when compared with those obtained from conventional pyrolysis. In addition, the effect of temperature and residence time on the supercritical water extraction of oil was investigated in a set of three experiments. The results revealed that the yield and the fraction of paraffins and aromatics increase while the percentage of asphaltenes decreases as the temperature is increased from 380 to 400°C. The residence time was found to affect the yield and the fraction of asphaltenes and polar compounds.     

Pyrolysis kinetics of polypropylene

The pyrolysis of oil shale and plastic wastes is being presently considered as an alternative means of partial substitution of fossil fuels to generate the necessary energy to supply the increasing energy demand and as well as new technology to reduce the negative environment of plastic wastes. However, Knowledge of pyrolysis kinetics is of great imponrtance for the design and simulation of the reactor and in order to establish the optimum process conditions. In this study, the thermal decomposition of polypropylene, oil shale and their mixture was studied by TG under a nitrogen atmosphere. Experiments were carried out for various heating rates (2, 10, 20, 50 K min⁻¹) in the temperature range 300–1273 K. The values of the obtained activation energies are 207 kJ mol⁻¹ for polyethylene, 57 kJ mol⁻¹ for the organic matter contained in the oil shale and 174 kJ mol⁻¹ for the mixture. The results indicate that the decomposition of these materials depends on the heating rate, and that polypropylene acts as catalyst in the degradation of the oil shale in the mixture.     

Study of thermal behaviour of organic matter from natural phosphates (Youssoufia - Morocco)

Thermogravimetry (TG), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were used to study the thermal behaviour of the organic matter in the natural phosphate and its concentrate kerogen from the Moroccan deposit. The TG analysis showed that both the investigated samples exhibited a one-step thermal oxidation in the main mass loss area, between 160 and 540°C, attributed to the hydrocarbon material. When DSC analyses of oxidation as well as pyrolysis yielded two evolutionary stages of the hydrocarbon in this temperature range : the first one at 160-360°C and the second one above 360°C. Pyrolytic kerogen decomposition was monitored by measuring changes in the principal FTIR organic bands. The results showed, in the first stage, the progressive decrease of signals due to CH₂ and CH₃ vibrations as well as the carbonyl and carboxylic bands, and their subsequent disappearance at 300°C. In the second stage above 400°C, the signal due to the aromatic components (1600 cm^-1) appeared but decreased with increasing temperature up to 540°C. This revised version was published online in August 2006 with corrections to the Cover Date.     

Raman scattering and X-ray diffraction study of structural phase transitions in the perovskite-type layer compound (C3H7NH3)2CdCl4

The structural phase transitions of (C₃H₇NH₃)₂CdCl₄ (PACC) have been studied by means of Raman scattering. X-ray diffraction and DSC measurements It is shown that the order-disorder phase transition Abma ? Pbca occurs at 156 K and not at 183 K as previously proposed by Chapuis (Acta CrystB34, 1506 (1978)) Apparently, the transition at 183 K does not change the Abma space group; it is suggested that it could be related to the occurrence of an incommensurate phase Another structural transformation of PACC is detected at 114 K, but no conclusion can be given as far as the structure of the low-temperature phase is not determined.     

Adsorption et desorption de l''eau vapeur sur un polymere polyacrylique superabsorbant IV. Effect de la masse sur les cinétiques d''adsorption et de désorption

The effect of steam adsorption-desorption on hydrophilic polymer processes is studied under controlled pressure and temperature. Experiments were performed using a relatively high mass of polymer (2 to 20 g), to examine the influence of different parameters on the adsorption-desorption mechanisms, such as the polymeric adsorbant mass, the steam pressure, the temperature and the number of adsorption-desorption cycles.

The limiting step of these processes varies from a pseudo-first-order step type for the low adsorbant mass (< 1 g), to a diffusive step for the mass range 2 to 20 g. In this last range, the process does not depend upon the adsorbant mass; only the adsorption and desorption rates change due to the modification of the space scale of the solid. The adsorption kinetics was not modified by the number of cycles, even for the first cycle; this is the opposite result as compared to when the experiment was performed with a low mass of polymer.     

Thermal analysis of Moroccan phosphates 'Youssoufia' in an oxidative atmosphere by TG and DSC

A non-isothermal experimental study using thermogravimetry (TG) and differential scanning calorimetry (DSC) was conducted for investigation the oxidation reactivity of natural phosphate and its demineralised products. The analyses were carried out in oxygen atmosphere and at different heating rate (5, 10, 20, 30, 50, 60°C min-1) up to 1000°C. The results indicated that the material washed with HCl from the original phosphate, mainly apatite and carbonates of calcium and magnesium, as well as with HCl/HF, silicates minreals, had an inhibition effect during oxidation reactions of organic material. The increase of the heating rate shifted the reactions to higher temperatures. In addition, kinetic parameters were determined by assuming a single first-order kinetic model, using the Coats-Redfern method. The influences of demineralization process of natural phosphate and the heating rate were examined and discussed. This revised version was published online in August 2006 with corrections to the Cover Date.