Effect of Uncertainty of the Pre-Exponential Factor on Kinetic Parameters of Hydrocarbon Generation from Organic Matter and its Geological Applications

The source rock sample of the Shahejie Formation （upper Es4） in Jiyang Sag was pyrolyzed under open system with the Rock-Eval-lI apparatus, and then kinetic model parameters were calibrated for investigating the effect of uncertainty of pre-exponential factors on kinetic parameters and geological applications, where the parallel first-order reaction rate model with an average pre- exponential factor and discrete distribution activity energies was used. The results indicate that when the pre-exponential factor changes from low to high, an extreme value for residual errors occurs. And with the increasing pre-exponential factor, the distribution shape of activation energies are nearly the same, but the values of activation energies move higher integrally, and the average activation energy increases about 12 kJ/mol for every 10-fold of the pre-exponential factors. Extrapolating the geological heating rate of 3.3 ~C/Ma, the results show that with the increases in pre-exponential factor, the geological temperature corresponding to TRo.5 （transforming ratio of hydrocarbon generation is 50%） increases gradually, and the additional temperature gradually decreases. Combined with geochemical data of source rock, the kinetic parameters with different pre-exponentia[ factors are used to calculate the transformation ratio of hydrocarbon generation, and the result indicates that kinetic parameters corresponding to the better optimized pre-exponential factor are more suitable. It is suggested that the risk assessment of hydrocarbon generation kinetic parameters should be enhanced when using the kinetic method to appraise the oil-gas resources. Meantime, the application result of different kinetic parameters should be verified with geological and geochemical data of source rock in the target area; therefore, the most suitable kinetic parameters for target can be obtained.

Non-isothermal thermal decomposition kinetics of high iron gibbsite ore based on Popescu method

The thermal decomposition kinetics of high iron gibbsite ore was investigated under non-isothermal conditions.Popescu method was applied to analyzing the thermal decomposition mechanism.The results show that the most probable thermal decomposition mechanism is the three-dimensional diffusion model of Jander equation,and the mechanism code is D3.The activation energy and pre-exponential factor for thermal decomposition of high iron gibbsite ore calculated by the Popescu method are 75.36 kJ/mol and 1.51×10-5 s-（-1）,respectively.The correctness of the obtained mechanism function is validated by the activation energy acquired by the iso-conversional method.Popescu method is a rational and reliable method for the analysis of the thermal decomposition mechanism of high iron gibbsite ore.

Kinetic Implication from Temperature Effect on Hydrogen Evolution Reaction at Ag Electrode

Hydrogen evolution reaction （HER） at polycrystalline silver electrode in 0.1 mol/L HClO4 solution is investigated by cyclic voltammetry in the temperature range of 278-333 K. We found that at electrode potential φa,app decreases with φ, while pre-exponential factor A remains nearly unchanged,which conforms well the prediction from Butler-Volmer equation. In contrast, with φ nega-tive shifts from the onset potential for HER to the potential of zero charge （PZC≈-0.4 V）, both Ea,app and A for HER increase （e.g., Ea,app increases from 24 kJ/mol to 32 kJ/mol）. The increase in Ea,app and A with negative shift in φ from -0.25 V to PZC is explained by the increases of both internal energy change and entropy change from reactants to the transition states, which is correlated with the change in the hydrogen bond network during HER. The positive entropy effects overcompensate the adverse effect from the increase in the activation energy, which leads to a net increase in HER current with the activation energy negative shift from the onset potential of HER to PZC. It is pointed out that entropy change may contribute greatly to the kinetics for electrode reaction which involves the transfer of electron and proton, such as HER.

Restraining effect of nitrogen on coal oxidation in different stages:Non-isothermal TG-DSC and EPR research

Nitrogen is widely used to prevent the spontaneous combustion of coal in underground coal mines. A spontaneous combustion-prone coal seam was studied to investigate the restraining effect of nitrogen on coal oxidation in different oxidation stages, based on non-isothermal thermogravimetry-differential scanning calorimetry(TG-DSC) and electron paramagnetic resonance(EPR) experiments. We found that the key feature temperatures grow steadily with increasing nitrogen in the oxidation environment,resulting in longer oxidation stages. The most significant finding is that there is a stagnation of the inhibitory effect of nitrogen on coal oxidation in the range of 85.0–95.0% nitrogen in the slow and the rapid oxidation stages, owing to the competitive adsorption of coal by nitrogen and oxygen. However, the restraining effect cannot be reflected by the kinetic parameters of the coal before it reaches the thermal decomposition and combustion stage. Nitrogen can also affect free radical types and free radical concentrations during coal oxidation: the higher the concentration of nitrogen in the oxidation environment, the greater the number of free radical types and the lower the free radical concentration. This experimental study improves the understanding of the restraining effect of nitrogen on coal oxidation in different oxidation stages and provides an important reference for coal fire prevention in spontaneous combustionprone coal seams.

Numerical study on the propagation characteristics of forward smoldering in a cellulosic packed bed

Based on a three-step kinetic mechanism, a one-dimensional, time dependent, numerical model is presented for the smoldering propagation in a horizontally packed bed of cellulosic material. The kinetic processes include pyrolysis and oxidation degradation of fuel and oxidation of char. Heat transfer between solid and gas is taken into account, and the diffusion coefficient varies with the temperature. Radiative heat transfer is included by using the diffusion approximation. The effects of airflow velocity and oxygen concentration are simulated on the smoldering velocity and the averaged maximum temperature of smoldering fuel. The results indicate that the spread rate varies linearly with increasing airflow velocity, and the inlet air velocity has little effect on the maximum temperature. The evolutions of gas species and solid compositions are predicted. The effects of frequency factors （A1, A2 and A3） are analyzed. Simulations show that the smoldering spread rate increases with increasing A2 （fuel oxidation）, but decreases with A1 （fuel pyrolysis） and A3 （char oxidation）.

A Model-based Phenomenological Investigation of Char Combustion Kinetics through Thermogravimetry

Five coal char samples were burnt in thermobalance with ramp heating rate of 30 K/min. The pore structure of these char samples was studied through mercury intrusion method. Combined with the kinetic theory of gases, the data of surface area was used in fitting the results. As a result, the kinetic triplet was given. The analysis showed that five char samples share almost the same intrinsic activation energy of the overall reaction. The phenomenological implication of the derived combustion rate equation was given.

Reaction kinetics of CaC2 formation from powder and compressed feeds

The production of CaC2 from coke/lime powders and compressed powder pellets are low cost and fast processes. A number of studies have reported the reaction kinetics of these reactions but they are still not well understood and the proposed kinetic models are not comparable due to differences in the reaction conditions. Therefore the reaction behavior of CaO/C powders （0.074 mm） and cubes （5 mm × 5 mm × （4.6-5.1） mm） compressed from a mixture of powders have been studied using thermal gravimetric analysis （TGA） at 1700- 1850 ℃. Kinetic models were obtained from the TGA data using isoconversional and model-fitting methods. The reaction rates for the compressed feeds were lower than those for the powder feeds. This is due to the reduced surface area of the compressed samples which inhibits heat transfer from the surrounding environment （or the heating source） to the sample. The compression pressure had little influence on the reaction rate. The reaction kinetics of both the powder and the compressed feeds can be described by the contracting volume modelf（α） = 3（1 -α）^2/3, where a is the conversion rate of reactant. The apparent activation energy and pre-exponential factor of the powder feed were estimated to 346-354 kJ·mol^-1 and 5.9 x 10^7 min^-1, respectively, whereas those of the compressed feed were 305-327 kJ·mol^-1 and 3.6 ×10^6 min^-1, respectively.