The Effect of Metallic Additives on the Kinetics of Oil Oxidation Reactions in In-Situ Combustion
Abstract/Contents
- Abstract
- In-situ combustion is a process whose applicability is partly determined by the combustion characteristics of the specific crude oil in question. These characteristics are directly influenced by the rate of oxidation reactions occurring in the rock matrix ahead of the combustion front. A method is therefore sought by which these characteristics may be altered within a reservoir, thus making the process feasible for a wider variety of crude oils. The presence of catalysts may have a significant influence on the reactions. The effects of catalyzing agents on the kinetics of these reactions were therefore studied to gain a more thorough understanding of the mechanisms involved in the catalysis of crude oil oxidation.Experiments were conducted wherein samples of a Huntington Beach oil/sand mixture were subjected to a continuous flow of air and a linear heating schedule. The effects of differing operating pressure and ten different metallic additives were examined in an experimental program of sixteen runs.Oxygen consumption data from the kinetic experiments were analyzed by decoupling the total oxygen consumption curve into three parts representing the three competing oxidation reactions. A curve fitting algorithm was devised in order to standardize the procedure by which the temperature ranges were chosen that characterize each reaction. This algorithm resulted in data matches that were quite good near the reaction peaks, but that were poor in the temperature range between the medium and high temperature peaks. As a consequence, the kinetic parameters determined through this procedure failed to show trends consistent enough to quantitatively assess the effects of the metallic additives. These effects were therefore evaluated through visual comparisons of the effluent gas composition data in combination with comparisons of the reaction rates, as illustrated in Arrhenius graphs. Comparisons such as these showed that increased pressure resulted in greater oxygen reactivity over the entire temperature range of the experiments. This behavior was due to larger pre-exponential constants (ArP^^ I a) in all three reactions. Pressure generally had no effect on the activation energies (EIR) of the reactions. Ferrous chloride, stannous chloride, and aluminum chloride additives each caused increases in the rates of oxidation of the crude, but the effects of the iron and tin were much more pronounced. These effects were generally due to lower activation energies in the low temperature reactions (resulting in increased fuel deposition) and larger pre-exponential constants in the medium and high temperature reactions. Zinc, magnesium, chromium, and manganese exerted similar influences on the rates of oxidation of the crude. The relative effects of these four metals varied on low and medium temperature oxidation, but in general, higher reaction rates were apparent, resulting in additional fuel deposition. These effects were less pronounced in the case of manganese. Each of these metals, however, caused a lower activation energy in the high temperature reaction. The result was that the increased amount of fuel deposited at lower temperatures was allowed to burn over wider temperature ranges at high temperatures.The addition of compounds containing copper, nickel, and cadmium produced only small changes in the effluent gas composition curves.
Description
| Type of resource | text |
|---|---|
| Date created | October 1987 |
Creators/Contributors
| Author | De los Rios, Carlos Fernando |
|---|---|
| Primary advisor | Brigham, William E. |
| Advisor | Castanier, Louis |
| Degree granting institution | Stanford University, Department of Petroleum Engineering |
Subjects
| Subject | School of Earth Energy & Environmental Sciences |
|---|---|
| Genre | Thesis |
Bibliographic information
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Preferred citation
- Preferred Citation
- De los Rios, Carlos Fernando. (1987). The Effect of Metallic Additives on the Kinetics of Oil Oxidation Reactions in In-Situ Combustion. Stanford Digital Repository. Available at: https://purl.stanford.edu/mj124jm1210
Collection
Master's Theses, Doerr School of Sustainability
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