Chemical Aspects of In-Situ Combustion - Heat of Combustion and Kinetics

1972 ◽  
Vol 12 (05) ◽  
pp. 410-422 ◽  
Author(s):  
J.G. Burger
Keyword(s):  
Porous Media ◽  
Combustion Front ◽  
Combustion Process ◽  
Heat Of Combustion ◽  
Oxidation Reactions ◽  
In Situ Combustion ◽  
Oxidation Of Hydrocarbons ◽  
Kinetics Of ◽  
Heat Released

Abstract General remarks on the oxidation reactions of hydrocarbons involved in in-situ combustion are followed by estimates of heat releases. A formula is derived for computing the heat of combustion in the high-temperature zone. Reaction kinetics in porous media applied to the in-situ combustion porous media applied to the in-situ combustion process is discussed. It is observed that there is process is discussed. It is observed that there is some similarity between the kinetics of reverse and partially quenched combustion processes. The influence of additives on crude oil oxidation in porous media is illustrated by effluent gas analysis experiments. Some information concerning the values of the kinetic parameters of the reaction controlling the velocity of a reverse combustion front is derived from the interpretation of laboratory experiments, using a numerical model. Introduction A great deal of laboratory and field work has been done on thermal recovery methods. The importance and limitations of these techniques have been extensively studied. However, some of the chemical and physical problems involved that needed to be elucidated were studied as part of a research program carried out by the Institut Francais du Petrole. Specific problems are created by in-situ combustion since both the possibility of combustion-front propagation and the air requirement are controlled by the extent of the exothermic oxidation reactions. Actually, the propagation velocity of a forward combustion front depends on the fuel formation and combustion, which are controlled by the kinetics of these processes; furthermore, the peak temperature is related to the heat released by oxidation and combustion reactions. Therefore, a quantitative estimation of the parameters related to the chemical aspects of the parameters related to the chemical aspects of the process is a necessary step in studying combustion process is a necessary step in studying combustion through a porous medium. General and theoretical considerations on heats of reaction and kinetics are presented and illustrated by experimental data and numerical interpretation of the results. HEAT RELEASED IN THE OXIDATION OF HYDROCARBONS DESCRIPTION OF OXIDATION REACTIONS A great number of reaction products are produced by the oxidation of hydrocarbons. By taking into account the formation of bonds between one carbon atom and oxygen, it is possible to derive the most important processes. Complete combustion, (1) 2 2 2 2H H3R C R  +  ---- O  → RR  +  CO + H O Incomplete combustion, (2) 2 2H H R C R  +  O  → RR  +  CO  +  H O Oxidation to carboxylic acid, (3) 2 2 2H OH H3 OR C H  +  --- O  → R - C  +  H O Oxidation to aldehyde, (4) H H R C Oxidation to ketone, (5) 2 2H O H R C R '  +  O  → R - C - R;  +  H O Oxidation to alcohol, (6) R' R; R C H SPEJ p. 410

Kinetics of Wet In-Situ Combustion: A Review of Kinetic Models

2014 ◽  
Author(s):  
E. A. Cavanzo ◽  
S. F. Muñoz ◽  
A.. Ordoñez ◽  
H.. Bottia
Keyword(s):  
Kinetic Model ◽  
Crude Oil ◽  
Kinetic Models ◽  
Combustion Front ◽  
Chemical Interaction ◽  
Combustion Process ◽  
Oxidation Reactions ◽  
In Situ Combustion ◽  
Temperature Oxidation

Abstract In Situ Combustion is an enhanced oil recovery method which consists on injecting air to the reservoir, generating a series of oxidation reactions at different temperature ranges by chemical interaction between oil and oxygen, the high temperature oxidation reactions are highly exothermic; the oxygen reacts with a coke like material formed by thermal cracking, they are responsible of generating the heat necessary to sustain and propagate the combustion front, sweeping the heavy oil and upgrading it due to the high temperatures. Wet in situ combustion is variant of the process, in which water is injected simultaneously or alternated with air, taking advantage of its high heat capacity, so the steam can transport heat more efficiently forward the combustion front due to the latent heat of vaporization. A representative model of the in situ combustion process is constituted by a static model, a dynamic model and a kinetic model. The kinetic model represents the oxidative behavior and the compositional changes of the crude oil; it is integrated by the most representative reactions of the process and the corresponding kinetic parameters of each reaction. Frequently, the kinetic model for a dry combustion process has Low Temperature Oxidation reactions (LTO), thermal cracking reactions and the combustion reaction. For the case of wet combustion, additional aquathermolysis reactions take place. This article presents a full review of the kinetic models of the wet in situ combustion process taking into account aquathermolysis reactions. These are hydrogen addition reactions due to the chemical interaction between crude oil and steam. The mechanism begins with desulphurization reactions and subsequent decarboxylation reactions, which are responsible of carbon monoxide production, which reacts with steam producing carbon dioxide and hydrogen; this is the water and gas shift reaction. Finally, during hydrocracking and hydrodesulphurization reactions, hydrogen sulfide is generated and the crude oil is upgraded. An additional upgrading mechanism during the wet in situ combustion process can be explained by the aquathermolysis theory, also hydrogen sulphide and hydrogen production can be estimated by a suitable kinetic model that takes into account the most representative reactions involved during the combustion process.

scholarly journals Study of the Radical Chain Mechanism of Hydrocarbon Oxidation for In Situ Combustion Process

2017 ◽  
Vol 2017 ◽  
pp. 1-11 ◽  
Author(s):  
Alexandra Ushakova ◽  
Vladislav Zatsepin ◽  
Mikhail Varfolomeev ◽  
Dmitry Emelyanov
Keyword(s):  
Heat Release ◽  
Oil Recovery ◽  
Combustion Process ◽  
Chain Process ◽  
Oxidation Reactions ◽  
Scanning Calorimetry ◽  
Radical Chain ◽  
Initial Oxidation ◽  
In Situ Combustion

Despite the abundance of in situ combustion models of oil oxidation, many of the effects are still beyond consideration. For example, until now, initial stages of oxidation were not considered from a position of radical chain process. This is a serious difficulty for the simulation of oil recovery process that involves air injection. To investigate the initial stages of oxidation, the paper considers the sequence of chemical reactions, including intermediate short-living compounds and radicals. We have attempted to correlate the main stages of the reaction with areas of heat release observed in the experiments. The system of differential equations based on the equations of oxidation reactions was solved. Time dependence of peroxides formation and start of heat release is analytically derived for the initial stages. We have considered the inhibition of initial oxidation stages by aromatic oil compounds and have studied the induction time in dependence on temperature. Chain ignition criteria for paraffins and crude oil in presence of core samples were obtained. The calculation results are compared with the stages of oxidation that arise by high-pressure differential scanning calorimetry. According to experimental observations we have determined which reactions are important for the process and which can be omitted or combined into one as insignificant.

Contribution of thermal analysis and kinetics of Siberian and Tatarstan regions crude oils for in situ combustion process

2015 ◽  
Vol 122 (3) ◽  
pp. 1375-1384 ◽  
Author(s):  
Mikhail A. Varfolomeev ◽  
Ruslan N. Nagrimanov ◽  
Andrey V. Galukhin ◽  
Alexey V. Vakhin ◽  
Boris N. Solomonov ◽  
...  
Keyword(s):  
Thermal Analysis ◽  
Combustion Process ◽  
Crude Oils ◽  
In Situ Combustion ◽  
Kinetics Of

In Situ Combustion Away From Thin, Horizontal Gas channels

1968 ◽  
Vol 8 (01) ◽  
pp. 18-32 ◽  
Author(s):  
M. Prats ◽  
R.F. Jones ◽  
N.E. Truitt
Keyword(s):  
Combustion Front ◽  
Combustion Process ◽  
Field Tests ◽  
Combustion Surface ◽  
Gas Production ◽  
In Situ Combustion ◽  
Secondary Combustion ◽  
Field Evidence ◽  
Production Wells

Abstract In most published discussions and theories of in situ combustion, the combustion fronts are assumed to be vertical. However, evidence from field tests leaves no doubt that combustion fronts often advance more rapidly along the top than near the bottom of a formation as a result of difference in density between injected air and formation liquids. The approximation proposed in this paper to determine the movement of the resultant tilted combustion surfaces states that the vertical rate of movement of combustion surfaces is proportional to the horizontal oxygen flux. Where self-ignition is possible, the proposed method demands that a secondary combustion surface exist around production wells which produce some oxygen. These secondary combustion surfaces may be formed long before the primary combustion surface can advance from injection to production wells. Heat liberated near production wells at these secondary combustion surfaces can contribute to an early increase in production rate. Results indicate that significant oil recoveries cannot be obtained from the usual flood patterns (five-spots, seven-spots, etc.) without producing large volumes of unused oxygen. Ideally, to increase oxygen-consumption efficiency, well patterns should allow oil production from a first line of production wells and gas production from more distant lines of producers. However, it may be desirable to produce some gas at all wells to support (and benefit from) active secondary combustion surfaces. Results indicate that the well spacing through which combustion can be advanced is larger than that predicted by other methods. A large number of production wells may still be desirable to take quick advantage of gravity drainage. From a comparison with results at South Belridge field, California, it appears that this method adequately describes oxygen concentration and temperature histories and combustion-front shapes. However, this method does not accurately locate the most advanced point of the combustion surface. There is some field evidence to substantiate the actual presence of secondary combustion surfaces at South Belridge. Use of the proposed method appears warranted at this time when lay-over of the combustion surface can be anticipated. Introduction The assumption of vertical combustion fronts has been embodied in all previous publications which use the movement of combustion fronts away from injection wells to determine the temperature and fluid distributions in the reservoir. The only paper concerned with a mathematical model of the combustion process in which a nonvertical combustion front is used was written by Gottfried. Actually, nonvertical combustion fronts have been observed in most in situ combustion field tests for which adequate data are available. In practice, the typical vertical extent of the burned zone decreases with distance from the injection well, and this burned zone is at or near the top of the sand body. In some cases, such as at South Belridge field near Taft, Calif., the combustion surface is almost horizontal over a very large area. Thus, for some years an obvious and serious gap has existed between theory (vertical fronts) and practice (tilted fronts). This is indicated in Fig. 1. Tilted combustion fronts such as observed at South Belridge sometimes result from the natural tendency of injected gases to rise to the top of an oil sand. SPEJ P. 18ˆ

Low-Temperature-Oxidation Reaction Kinetics and Effects on the In-Situ Combustion Process

1974 ◽  
Vol 14 (03) ◽  
pp. 253-262 ◽  
Author(s):  
Mahmoud K. Dabbous ◽  
Paul F. Fulton
Keyword(s):  
Porous Medium ◽  
Low Temperature ◽  
Crude Oil ◽  
Partial Oxidation ◽  
Combustion Process ◽  
Oxidation Reactions ◽  
In Situ Combustion ◽  
Temperature Oxidation ◽  
Partial Oxidation Reactions

Abstract The kinetics of low-temperature oxidation (LTO) of crude oils in porous media was studied. Isothermal integral reactor data were analyzed to obtain rate equations for the over-all rate of the partial oxidation reactions at temperatures below partial oxidation reactions at temperatures below 500 deg. F. The reaction order with respect to oxygen was found to be between 0.5 and 1.0. The order of the reaction was dependent upon the crude but independent of the properties of the porous medium. The activation energy of the reaction was insensitive to the type of crude or porous medium and is in the neighborhood of 31,000 Btu/lb mol. LTO reactions were found to be in the kinitics-influenced region. The measured reaction rates for a 19.9 deg. API and a 27.1 deg. API crude indicated higher oxidation rates under similar reaction conditions for the higher API gravity crude. Light crudes appear to be m ore susceptible to partial oxidation at low temperatures because of the react ed oxidation reactions rather than by carbon oxidation. Other information includes the fraction of reacted oxygen utilized in carbon atom oxidation by the LTO reaction and the molar ratio of CO2 and CO produced in the low-temperature region. Effect of partial oxidation of the crude on the in-situ combustion process was studied by experimentally simulating the zones preceding the combustion front where temperatures and injection rates of linear reservoir model were programmed with time according to a predesigned schedule. Oxidation of the crude at temperatures below 400 deg.F had significant effects on the behavior of the crude-oil/water system in the porous medium at elevated temperatures and on the fuel available for combustion. A substantial decline in the recoverable oil from the evaporation and cracking zones, an increase in fuel deposition, and drastic changes in fuel characteristics and coked sand properties were obtained when the crude was subjected to LTO during the simulation process. Introduction The application of thermal energy to petroleum reservoirs as a means of increasing crude oil recovery has been given a great deal of attention. In underground combustion, thermal energy is induced by the partial burning of the crude oil in situ. The production of heat by the exothermic oxidation reactions of the hydrocarbons constitutes a unique feature of the in-situ combustion process. The chemical reactions and the accompanying heat released create a new temperature profile and cause drastic redistribution in the reservoir fluid saturations. With oxygen available in the transient zones of variable temperature and hydrocarbon saturations, several oxidation reactions of differing nature can take place during an underground combustion process. Because of the complex composition of process. Because of the complex composition of crudes and the great number of reaction products that can be produced, it is convenient to classify the hydrocarbon oxidation reactions ascombustion reactions that take place in the high-temperature combustion zone (above 600 deg. F) with CO2, CO, and H2O as the principal reaction products andpartial oxidation or low-temperature products andpartial oxidation or low-temperature (LTO) reactions that occur in zones where the temperature is lower than 600 deg. F. Several partial oxidation reactions are known to take place, producing primarily water and oxygenated producing primarily water and oxygenated hydrocarbons such as carboxylic acid aldehydes, ketones, alcohols, and hydroperoxides. High-temperature combustion reactions are desirable because they generate most of the heat required for the in-situ combustion process. Partial oxidation reactions, on the other hand, are in most cases undesirable because of their adverse effect on the viscosity and distillation characteristics of the crude. SPEJ P. 253

scholarly journals Use of two vertical injectors in place of a horizontal injector to improve the efficiency and stability of THAI in situ combustion process for producing heavy oils

2021 ◽  
Author(s):  
Muhammad Rabiu Ado
Keyword(s):  
Oil Recovery ◽  
Combustion Front ◽  
Combustion Process ◽  
Oil Production ◽  
Steam Injection ◽  
Electrical Heating ◽  
Heavy Oils ◽  
In Situ Combustion ◽  
Start Up

AbstractThe current commercial technologies used to produce heavy oils and bitumen are carbon-, energy-, and wastewater-intensive. These make them to be out of line with the global efforts of decarbonisation. Alternative processes such as the toe-to-heel air injection (THAI) that works as an in situ combustion process that uses horizontal producer well to recover partially upgraded oil from heavy oils and bitumen reservoirs are needed. However, THAI is yet to be technically and economically well proven despite pilot and semi-commercial operations. Some studies concluded using field data that THAI is a low-oil-production-rate process. However, no study has thoroughly investigated the simultaneous effects of start-up methods and wells configuration on both the short and long terms stability, sustainability, and profitability of the process. Using THAI validated model, three models having a horizontal producer well arranged in staggered line drive with the injector wells are simulated using CMG STARS. Model A has two vertical injectors via which steam was used for pre-ignition heating, and models B and C each has a horizontal injector via which electrical heater and steam were respectively used for pre-ignition heating. It is found that during start-up, ultimately, steam injection instead of electrical heating should be used for the pre-ignition heating. Clearly, it is shown that model A has higher oil production rates after the increase in air flux and also has a higher cumulative oil recovery of 2350 cm3 which is greater than those of models B and C by 9.6% and 4.3% respectively. Thus, it can be concluded that for long-term projects, model A settings and wells configuration should be used. Although it is now discovered that the peak temperature cannot in all settings tell how healthy a combustion front is, it has revealed that model A does indeed have far more stable, safer, and efficient combustion front burning quality and propagation due to the maintenance of very high peak temperatures of mostly greater than 600 °C and very low concentrations of produced oxygen of lower than 0.4 mol% compared to up to 2.75 mol% in model C and 1 mol% in model B. Conclusively, since drilling of, and achieving uniform air distribution in horizontal injector (HI) well in actual field reservoir are costly and impracticable at the moment, and that electrical heating will require unphysically long time before mobilised fluids reach the HP well as heat transfer is mainly by conduction, these findings have shown decisively that the easy-and-cheaper-to-drill two vertical injector wells configured in a staggered line drive pattern with the horizontal producer should be used, and steam is thus to be used for pre-ignition heating.

Fuel Formation and Conversion During In-Situ Combustion of Crude Oil

SPE Journal ◽  
2013 ◽  
Vol 18 (06) ◽  
pp. 1217-1228 ◽  
Author(s):  
Hascakir Berna ◽  
Cynthia M. Ross ◽  
Louis M. Castanier ◽  
Anthony R. Kovscek
Keyword(s):  
Oil Recovery ◽  
Photoelectron Spectroscopy ◽  
Combustion Front ◽  
Combustion Products ◽  
Combustion Tube ◽  
Cross Sectional ◽  
In Situ Combustion ◽  
X Ray ◽  
Study Results

Summary In-situ combustion (ISC) is a successful method with great potential for thermal enhanced oil recovery. Field applications of ISC are limited, however, because the process is complex and not well-understood. A significant open question for ISC is the formation of coke or "fuel" in correct quantities that is sufficiently reactive to sustain combustion. We study ISC from a laboratory perspective in 1 m long combustion tubes that allow the monitoring of the progress of the combustion front by use of X-ray computed tomography (CT) and temperature profiles. Two crude oils—12°API (986 kg/m3) and 9°API (1007 kg/m3)—are studied. Cross-sectional images of oil movement and banking in situ are obtained through the appropriate analysis of the spatially and temporally varying CT numbers. Combustion-tube runs are quenched before front breakthrough at the production end, thereby permitting a post-mortem analysis of combustion products and, in particular, the fuel (coke and coke-like residues) just downstream of the combustion front. Fuel is analyzed with both scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). XPS and SEM results are used to identify the shape, texture, and elemental composition of fuel in the X-ray CT images. The SEM and XPS results aid efforts to differentiate among combustion-tube results with significant and negligible amounts of clay minerals. Initial results indicate that clays increase the surface area of fuel deposits formed, and this aids combustion. In addition, comparisons are made of coke-like residues formed during experiments under an inert nitrogen atmosphere and from in-situ combustion. Study results contribute to an improved mechanistic understanding of ISC, fuel formation, and the role of mineral substrates in either aiding or impeding combustion. CT imaging permits inference of the width and movement of the fuel zone in situ.

An Experimental Investigation of In Situ Combustion in High Permeability Contrast Systems

2021 ◽  
pp. 1-13
Author(s):  
Melek Deniz Paker ◽  
Murat Cinar
Keyword(s):  
Oil Recovery ◽  
Heavy Oil ◽  
Combustion Front ◽  
Fractured Reservoirs ◽  
Front Propagation ◽  
High Permeability ◽  
Vertical Orientation ◽  
In Situ Combustion ◽  
Horizontal Orientation

Abstract A significant portion of world oil reserves reside in naturally fractured reservoirs and a considerable amount of these resources includes heavy oil and bitumen. Thermal enhanced oil recovery methods (EOR) are mostly applied in heavy oil reservoirs to improve oil recovery. In situ combustion (/SC) is one of the thermal EOR methods that could be applicable in a variety of reservoirs. Unlike steam, heat is generated in situ due to the injection of air or oxygen enriched air into a reservoir. Energy is provided by multi-step reactions between oxygen and the fuel at particular temperatures underground. This method upgrades the oil in situ while the heaviest fraction of the oil is burned during the process. The application of /SC in fractured reservoirs is challenging since the injected air would flow through the fracture and a small portion of oil in the/near fracture would react with the injected air. Only a few researchers have studied /SC in fractured or high permeability contrast systems experimentally. For in situ combustion to be applied in fractured systems in an efficient way, the underlying mechanism needs to be understood. In this study, the major focus is permeability variation that is the most prominent feature of fractured systems. The effect of orientation and width of the region with higher permeability on the sustainability of front propagation are studied. The contrast in permeability was experimentally simulated with sand of different particle size. These higher permeability regions are analogous to fractures within a naturally fractured rock. Several /SC tests with sand-pack were carried out to obtain a better understanding of the effect of horizontal vertical, and combined (both vertical and horizontal) orientation of the high permeability region with respect to airflow to investigate the conditions that are required for a self-sustained front propagation and to understand the fundamental behavior. Within the experimental conditions of the study, the test results showed that combustion front propagated faster in the higher permeability region. In addition, horizontal orientation almost had no effect on the sustainability of the front; however, it affected oxygen consumption, temperature, and velocity of the front. On the contrary, the vertical orientation of the higher permeability region had a profound effect on the sustainability of the combustion front. The combustion behavior was poorer for the tests with vertical orientation, yet the produced oil AP/ gravity was higher. Based on the experimental results a mechanism has been proposed to explain the behavior of combustion front in systems with high permeability contrast.

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