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US3127935A - In situ combustion for oil recovery in tar sands, oil shales and conventional petroleum reservoirs - Google Patents

In situ combustion for oil recovery in tar sands, oil shales and conventional petroleum reservoirs Download PDF

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US3127935A
US3127935A US2104360A US3127935A US 3127935 A US3127935 A US 3127935A US 2104360 A US2104360 A US 2104360A US 3127935 A US3127935 A US 3127935A
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well
combustion
injection
gas
front
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Fred H Poettmann
Bert K Larkin
Jr Harry W Milton
John C Bixel
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Marathon Oil Co
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Marathon Oil Co
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    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E21B43/243Combustion in situ

Description

Aprll 7, 1964 F, H. POETTMANN ETAL 3,127,935

1N SITU coMEUsToN FoR OIL RECOVERY 1N TAR SANDS, on. sHALEs AND coNvENToNAE PETROLEUM RESERVOIRS Filed April 8, 1960 fg 3 INvENToRs, FRED H. POETTMANN BERT K.LARK|N HARRY W, MILTON jl: JOHN C.BIXEL ATTORNEYS United States Patent O 3,127,935 IN SlTU COMBUSTION FOR OIL RECOVERY IN TAR SANDS, OIL SHALES AND CONVENTIONAL PETROLEUM RESERVOIRS Fred H. Poettnlann and Bert K. Larkin, Littleton, and Harry W. Milton, Jr., and John C. Bixel, Denver, Colo., assigner-s to Marathon Oil Company, Findlay, Ohio, a corporation of Ohio Filed Apr. 8, 196i), Ser. No. 21,043 19 Claims. (Cl. 1mi- 11) This invention relates to underground combustion processes in porous media having organic content, such as oil reservoirs and fractured oil shale structures. Oil shale has no fluid hydrocarbon present and in its natural formation is not suficiently permeable to support in situ combustion. Consequently, the area being worked requires some type of initial preparation or conditioning, such as shattering or fracturing. These procedures are well known in the art and any suitable method may be utilized. The practice of the present invention as applied to oil shale, involves treatment of a porous media, however produced.

This invention also is useful in the treatment of tar sands and petroleum reservoirs, particularly those containing heavy oils. It may utilize but is not limited to a two-pass combustion front movement through the structure being worked, and this may involve either separate front movements in the same direction, or reverse combustion followed by forward combustion, as preferred.

The practice of utilizing a reverse combustion as a first pass followed by introduction of additional oxygen to reverse the front movement and direct it in concurrent ow with the gas is well known. One of the defects is that the increase in available oxygen produces higher temperatures with the result that the residual coke or other hydrocarbon remaining on the rocks or sand grains after the first pass is burned in the second pass to such an extent that a substantial amount of valuable material is lost, which otherwise might be a product of the extraction. v

Our invention departs from prior practices in several respects, all of which improve the eiciency of the treatment and provide higher yields. Of perhaps greatest importance is the reduction of available oxygen after the initial temperature limits have been reached so as to permit continuing extraction without oxidation, due to the elimination of combustion, or through utilization of gas combustion at temperatures below the minimum for burning coke, with product removal by the inert gas flow to the production well.

In either oil reservoirs or oil shale structures, a two pass treatment may be utilized in which the front movement of both passes is in the same direction. To do this, surface changes are made to convert a former injection well or wells into a production well or wells and a former production well into an injection well to direct flow into one or a plurality of production Wells which were injection wells. Particularly in oil shale, this is of considerable value in that the rst pass front movement may be controlled to move rapidly through the deposit at substantially non-coking temperatures to bring the temperature in the area being worked to a distilling temperature, and in so doing, the permeability of the area is increased substantially.

3,127,935 Patented Apr. 7, 1964 Due to the fact that there is substantially no heat loss in the oil shale deposit, the second pass movement is beneted by holding combustion to a minimum. When reversing heat front movement is employed, additional oxygen is introduced to cause the front reversal when it approaches or reaches the injection wells and the eifect of this is to produce excessively high temperatures and sustain combustion in the second pass. The optimum condition is attained if suflicient heat is available to distill the kerogen content for its removal as an oil. A substantial ga-s flow is required as the conveying vehicle, but combustion no longer is required after the minimum temperature requirement is established.

Consequently, this practice of the present invention permits effective utilization of the established heat and utilizes a ow of gas from a hot zone to the ultimate discharge point. The heat loss due to lower temperatures of the injected gas is almost a negligible factor and distillation continues over a long period after combustion is terminated. lBy eliminating secondary burning of carbonaceous matter, a substantially greater proportion of the kerogen content is recovered as oil than is possible in a treatment where two stage combustion is utilized over a substantial time interval.

Another feature of the practice of the present invention is the utilization of accelerated frontal velocity providing what may be termed a high velocity front movement. An advantage of this velocity control is to maintain lower maximum temperatures in the area being worked and by proper control of gas velocity, gas composition and catalyst, frontal temperatures and velocities may be maintained at predetermined standards. With rapid front movement, the available oxygen is rapidly removed from the areas where distilling temperatures persist, and at the completion of the initial pass, the introduction of inert or relatively inert gases provides a control against detrimental combustion in the second stage treatment.

Another innovation of the present invention is the selection and use of catalysts permitting temperature development by gas combustion rather than burning a substantial amount of the organic content in attaining the required temperature.

It is an object of our invention to provide a simple, efcient and economical in situ combustion treatment in porous media having organic content which gives a higher recovery.

Another object of our invention is to provide a simple, economical and efficient in situ combustion treatment for oil shale deposits which utilizes a high velocity combustion front movement to initially attain distillation ternperatures within the area being worked and thereafter maintains distillation conditions over a protracted period Without repetition of combustion.

-A furthe-r object of .the invention is to provide a simple, economical and efficient .treatment in porous media havring organic content in which an initial combustion front movement is `directed through the area being worked in yan atmospheric having available oxygen in substantial quantity, and fol-lowing such initial front movement with a second fron-t movement comprising gas combustion maintained at temperatures at which deposited coke is not burned to any substantial degree.

The accompanying drawings illustrates typical instala lations tor the practice of our invention. In the drawlngs:

FIG. l is a schematic plan View of a typical iive-spot Iwell pattern utilized in a treatment according to the present invention;

=FIG. 2 is a schematic top plan View lof another Well pattern :which may be utilized in the practice of your invention; and

FIG. 3 is a vertical section .through a typical deposit in which the treatment oi the present invention is practiced and illustrates in more or less schematic arrangement, the components of the surface and underground installations.

When a five-spot Well pattern of the type shown in FIG. l is employed, a series of injection Wells Will be utilized 4to introduce air .or other oxygen-containing gas into a structure being worked, represented in general area by the circumferential line 7, land these injection Wells 5 `direct flow of gases ltoward a substantially central production well 6. Usually in initiating combustion in such .a structure, substantial amounts `of oxygen Will be introduced through the production vvell 6 to condition a circumferential area 8 for initiating combustion, and yafter being properly conditioned, combustion will be initiated through Well 6 in any suitable manner, causing a heat front movement away from well 6 and toward the injection Wells 5. When combustion is progressing satisfactorily, air is introduced .through the injection Wells 5 and supply through Well 6 is terminated with the result that reverse combustion is maintained lwith the hot gases passing the combustion front to carry evolved products to and out of production well 6.

The arrangement shown in FIG. 2 involves linear flow paths With a row of injection Wells 5a supplying the air or other oxygen-containing gas and a row of production 'wells 6a arranged at substantially the same spacing as .the wells 5a with heat iront movement from the producftion Wells toward the injection wells. After an operation `of this type is completed, the surface installation can be changed so that the Wells 5a become production wells `6a and fron-t movement is continued in the same way through an additional area to be Worked. FIG. 3 illustrates `an arrangement of :Wells in the form-ation which may be either the five-spot pattern of FIG. 1 or the linear pattern of FIG. 2. The surface is indicated at 12 and a porous media to be Worked is shown at 13 -With overburden 14 overlying the porous media and such overburden may be of varying composition as indicated Iby the shading dilerences. One or more injection Wells 15, here shown as one, extend 'from a point above the surface through the overburden 14 to the bottom of the porous media layer 113. One or more production Wells, here shown as a single well `16, extend from a point above the surface to the bottom of the porous media structure y13:. A lateral line 17 -is provided to conduct the output of Well 16 past la normally open valve 18 into a collection and storage system 19. Oxygen-containing gas, preferably a fuel and catalyst mix-ture, as will be described hereinafter, is delivered through a supply -line Z1 past a normally open valve 22 into the injection well or wells and this supply is established and maintained throughout the course of the front movement.

In initiating combustion, it will be satisfactory to deliver .the oxygen content through production well 16 in which event valve 1S is closed, valve 22 is closed and air or other oxygen-containing gas is delivered from a source of supply 23` past an open valve 24 in line 25 for discharge at ythe bottom of Well 16. When sufficient oxygen is introduced in this manner to support combustion, the structure adjoining Well 16 is ignited by any suitable method initiating a `combustion front movement represented at 27 which travels toward the injection Well or fwells 15. After front movement is progressing satisfactorily, the air supply through line 25 will be terminated by closing valve Z4, valve 1.8 will be open to deliver the output of Well 16 into collection system 19, and tuel and catalyst or other oxygen supply will resume through line 21 by opening of valve 212.

This `arrangement serves to maintain a iioW in media `13 from the injection wells to the production Well With a reveiise heat front movement maintained to provide the desired recovery. Hot gases passing yfront 27 carry products ot combustion and .other evolved materials into and through the well 16 for delivery into the collection system 19.

When combustion iront movement is initiated adjacent production Well 16, it is preferable to arrange the associated injection well 15 as an exhaust or production Well. In such event, valve 2.2 will be closed so that all outflow from :Well `15 Will be directed into a line 26 past an open valve 2S for discharge into the collection System A19. With such an arrangement, it is possible to sarnple the composition of the gas passing from Well 15, and when an appreciable amount of CO2 gas is noted, the combustion .front movement will have progressed to a point Where it is advantageous `to rearrange the Wells, mak-ing Well 15 .the injection well yand Well 16 the production fvvell. vIn such event, valve 23 is closed, valve 18 is `open and valve 22, is .open to deliver uel and catalyst lfroni supply 20 into well 15 While the outflow of Well 116 will pass through line 17 into collection system 19.

The feature of reversing the Well functioning may be utilized effectively in a later stage of the treatment. For example, if porous media 13 represents an oil shale deposit, such deposit will be suitably prepared for in situ combustion by shattering of the structure according to Well known methods so that sucient permeability will be provided to permit the flow of gases through the area being worked and thus permit development and maintenance of a combustion front as required. The portions of the shale structure 13x shown in FIG. 3 represent pyrolyzed or partially pyrolyzed shale and the position of the combustion front 27 between the Wells 15 and 16 is indicated. The shale 13 in advance of the front will be shattered, but at its natural temperature, Whereas the pyrolyzed shale section 13x between front 27 and Well 16 will be a high temperature zone in Which combustion has terminated, but distillation temperatures are maintained to continue extract of shale oil from the kerogen of the deposit.

The practice of the present invention contemplates a departure from prior practices, in that the initial combustion front movement represented by 27 is maintained under temperature control to produce distillation temperatures Within a non-coking temperature range and the movement of the front through the shale effectively increases permeability so that as the combustion progresses beyond a point where distillation continues, the iiow of gases into and through the hot zone serves to maintain the required distillation temperature and to carry products of combustion and other evolved matter to the production Well and then to the surface. Coking temperatures for tar sands, oil shales and conventional oil reservoirs vary widely according to diiierent oil properties and coking rates. As noted in the May 1960, Journal of Petroleum Technology, page 14, coking of heavy oils of tar sands will commence at 450 to 500 F., while in relinery operations coking will begin at S50-900 F., as noted n Advances in Petroleum Chemistry and Refining 2, page 371 (1959) Interscience Publishers, Inc., New York. The non-Coking limits for various materials are well known in the art and available in numerous publications, and therefore have not been detailed herein.

When the heat front movement has progressed to a point adjoining the injection Well, the function of the Wells may be reversed by surface changes involving closing of valves 18 and 22 and opening of valves 24 and 28. As a consequence, well 16 then becomes an injection well and Well 15 becomes a production well discharging through line 26 past open valve 28 into collection system 19. At this stage, it is preferable to introduce a fuel and catalyst mixture, the details of which will be described hereinafter, and direct the flow of such gas into the pyrolyzed shale 13x from the bottom of well 16, causing it to flow toward well 15 now functioning as the production Well. As there is almost no heat loss to surrounding structure, the required distillation temperatures are maintained in the material behind the advancing initial combustion front movement and the fuel and catalyst mixture provides a convenient means for directing a second combustion front movement from well 16 to well 15, which is primarily gas combustion with temperatures maintained sufficiently low that no appreciable amount of valuable constituent is consumed by such front movement. Any reabsorbed shale oil from the first front movement is directed through the hot zone in advance of the second front and carries to the then production well 15 for delivery into collection system 19 and such second movement may be a forward or reverse movement. This procedure eliminates the excessive combustion effect which results from reversing heat front movement and allows a sufficient time interval at any point in the area being Worked between the contact with the first heat front and the contact with the second heat front to permit a substantial amount of distillation to continue in such interval.

This procedure permits utilization of special controls between the termination of the first heat front pass and the start of the second front pass. For example, an inert gas may be injected to reduce temperature to a predetermined value and at a predetermined rate for holding the desired heat. Inert gases from the products of combustion, nitrogen, steam or CO2 may be used. When inert gas alone is circulated, distillation continues with product removal and no combustion is maintained in the area being worked. By introducing such gas at a higher velocity than in the first combustion front movement, an accelerated temperature reduction is attained with product removal continuing as previously described.

By utilizing a mixture of such gas and a liquid such as Water, an even more rapid temperature reduction may be effected. Organic liquids also may be used in lieu of water, which have the further advantage of diluting heavy immobile oils of the deposit to provide sufficient mobility to direct their removal in free-flowing condition to the production Well.

The preceding description refers to treatments in porous media having organic content, and this terminology is intended to include tar sands, oil shale deposits and conventional petroleum reservoirs containing heavy oils. While oil shale in its natural formation is not permeable, it can be rendered sufliciently permeable by fracturing or shattering to permit distribution and flow of gases through the shattered portion to such a degree that it becomes4 permeable porous media within the requirements of this invention. V

In its general application, the present invention provides an innovation in in situ combustion practices through controls which eliminate the requirement for burning all of the coke deposited on the sand grains. This is of particular importance in heavy oil reservoirs where the fuel laid down may be as high as three to tive pounds per cubic foot of reservoir space. Such control is provided by use of certain air-gas mixtures, alone, or in conjunction with certain catalysts. The rate of combustion front movement is controlled as detailed hereinafter (column 6, lines 32-4-3) and a substantial amount of gas combustion is substituted to reduce consumption of contained fuel. The gas combustion is maintained at noncoking temperatures and with a lesser oxygen requirement.

The heavy metal oxidation catalysts are Well suited for use in the practice of this invention. These include copper, silver, platinum, vanadium, iron, manganese, nickel, cobalt, chromium, molybdenum, osmium and titanium. Many of these will be present in the sandstones and associated waters of underground porous media having organic content, but usually not in sutiicient concentration and chemical composition to be effective in the treatment. Consequently, it is advantageous to introduce a sufficient quantity of catalyst prior to or during the combustion front movement to satisfy the requirements of the operation.

Various gaseous mixtures may be utilized in the practice of our invention, including the use of inert gases at certain stages of the treatment. Such mixtures may include air and natural gas, air and butane, air and propane, air and methane, air and ethane, air and acetylene, or complex mixtures of the foregoing. The gaseous mixture may be fed separately and such feed may be continuous or intermittent. With a distribution system such as shown in FIG. 3, it will be preferable to initially supply a catalyst composition or mixture from storage supply station 20 in water as a carrier vehicle through the several injection Wells 15 for distribution throughout area 7. The required property for the catalyst seems to be that it forms unstable oxides which can be oxidized from one state to another. It also is possible to inject a solution containing a soluble catalyst salt. The salt would decompose to an oxide when heated by the approaching combustion front. Gaseous carrier vehicles and catalysts may be used and have the advantage of bringing the catalyst to a treatment site at the time its use is required. When used, such compositions will comprise the gas introduction through an injection well, and such supply may be intermittent or continuous.

After the catalyst has been distributed as aforesaid, the porous media is charged with sufficient oxygen to establish and maintain combustion, usually through production Well 16 as previously described. Combustion is initiated in the manner described hereinbefore and both frontal temperature and velocity are controlled by varying total gas velocity, gas composition and catalyst. It is desirable to have a high frontal velocity in this stage, and We have found that by proper conrol in conjunction with catalyst use, frontal velocities may be increased as much as two and one-half times normal velocities and with a lowering of frontal temperatures.

The use of the catalyst will be effective in oil reservoirs, tar sands and oil shale deposits. Utilization of a rapid combustion front advance in the first pass treatment with temperature of the front maintained at essentially a noncoking temperature benefits the operation in changing the pour point of the heavy oil causing it to flow freely to the production well. However, combustion moves fast enough that burning of contained organic content is avoided to a large degree, and yet produces sufficient heat so that cracking and extraction may continue for a long iuterval after passage of the front. The continuous flew of hot gases and products of combustion from the front to the production well offsets any tendency toward heat loss in the area in between and makes possible a considerable amount of cracking or distillation after combustion is terminated.

Another feature of the practice of this invention as applied to oil shale structures is the recognition that until a temperature of about ll00 F. is attained, there is no CO2 evolution from the carbonate minerals of the deposit. Therefore, it is possible to utilize a first front pass to develop the main oil shale extraction with distillation temperatures maintained after passage of the front to attain an essentially complete extraction from various parts of the working area before arrival of a second front. The second combustion front will be controlled to develop temperatures approximating l500 F. so as t0 obtain CO2 extraction for process use. The second front movement may involve reversing of frontal movement as previously described, or changing wells as previously described so as to establish uniform treatment time between frontal passes throughout the entire area.

lthe downstream side of the front.

It is also intended that retort off gases may be utilized in such an operation. They are introduced at substantially higher temperatuers than the air normally supplied and preheat the portion of the shale in advance of the front. While the fuel value of the return gas is usually not enough to be significant, establishing a high pressure preheated zone in advance of the front assists in developing the rapid frontal advance and assists distillation on In this way, only a negligible amount of the extracted organic content is used as fuel and most of it passes to the production well and is recovered in the treatment.

The catalysts described hereinbefore may be utilized in other types of treatments with effective results. For instance, in reservoirs having no appreciable quantity of catalyst material occurring naturally, the introduction of such catalysts will serve to reduce temperature in the combustion front with increased velocity of its movement, all of which produces higher extraction. Also, in light oil reservoirs, the reduced ignition temperatures deriving from catalyst introduction make otherwise volatile constituents available as fuel and support in situ combustion where it would not be feasible to use it otherwise.

What we claim is:

1. In a method for the recovery of hydrocarbons from underground formations penetrated at spaced points by an injection well and a producing well wherein combustion is initiated in such a formation prepared for in situ combustion and a combustion front is propagated through a prepared portion of said formation having an oxidation catalyst distributed therein, the improvement which comprises propagating a combustion front through the formation by varying, in relation to oxidation catalyst concentration in the prepared portion, the velocity and oxygen content of a continuous flow of a gas mixture introduced through the injection well for directing said frontal movement, so as to establish a maximum temperature in said frontal movement capable of maintaining distillation temperatures but insufficient to cause coking of an appreciable amount of the hydrocarbons within the prepared portion during recovery of a major portion of the hydrocarbon content of said prepared portion, and recovering evolved products through the producing well.

2. A process as defined in claim 1, in which the ca-talyst is a copper composition.

3. A process as defined in claim 1, in which the catalyst is an iron composition.

4. A process as defined in claim l, in which the catalyst is a manganese composition.

5. In a method for the recovery of hydrocarbons from underground formations penetrated at spaced points by an injection well and a producing well wherein combustion is initiated in such a formation prepared for in situ combustion and a combustion front is propagated through a prepared portion of said formation having an oxidation catalyst distributed therein, the improvement which comprises propagating a combustion front through the formation, inclusive of gas combustion, by varying, in relation to oxidation catalyst concentration in the prepared portion, the velocity and oxygen content of a continuous flow of a gas mixture introduced through the injection well for supporting combustion and directing said frontal movement, so as to establish a maximum temperature in said frontal movement capable of maintaining distillation temperatures but insufficient to cause coking of an appreciable amount of the hydrocarbons within the prepared portion during recovery of a major portion of the hydrocarbon content of said prepared portion, and recovering evolved products through the producing well.

6. In a method for the recovery of hydrocarbons from underground formations penetrated at spaced points by an injection well and a producing well wherein combustion is initiated in such a formation prepared for in situ combustion and a combustion front is propagated through a prepared portion of said formation having an Voxidation catalyst distributed therein, the improvement which comprises propagating a rst combustion front through the formation by varying, in relation to oxidation catalyst concentration in the prepared portion, the velocity and oxygen content of a continuous flow of a gas mixture introduced through the injection well for directing said frontal movement, so as to establish a maximum temperature in said frontal movement insufficient to cause coking of any appreciable amount of the hydrocarbons within the prepared portion, directing a second combustion front movement through said prepared portion by introduction through the injection well of a continuous flow of a gas mixture capable of establishing distillation temperatures in a combustion-free atmosphere in advance of said second front movement, and recovering evolved products through the producing well.

7. In a method for the recovery of hydrocarbons from underground formations penetrated at spaced points by an injection well and a producing well wherein combustion is initiated in such a formation prepared for in situ combustion and a combustion front is propagated through a prepared portion of said formation having an oxidation catalyst distributed therein, the improvement which comprises propagating a combustion front through the formation by varying, in relation to oxidation catalyst concentration in the prepared portion, the velocity, oxidation catalyst and oxygen content of a continuous ow of a gas mixture introduced through the injection well for directing said frontal movement, so as to establish a maximum temperature in said frontal movement capable of maintaining distillation temperatures but insulcient to cause coking of an appreciable amount of the hydrocarbons Within the prepared portion during recovery of a major portion of the hydrocarbon content of said prepared portion, and recovering evolved products through the producing well.

8. In a method for the recovery of hydrocarbons from underground formations penetrated at spaced points by an injection well and a producing well wherein combustion is initiated in such a formation prepared for in situ combustion and a combustion front is propagated through a prepared portion of said formation having an oxidation catalyst distributed therein, the improvement which comprises propagating a combustion front through the formation by varying, in relation to oxidation catalyst concentration in the prepared portion, the input velocity and oxygen content of a combustion-supporting gas mixture introduced through the injection well so as to establish a maximum temperature in the frontal movement capable of maintaining distillation temperatures but insufficient to cause coking of an appreciable amount of the hydrocarbons within the prepared portion of the formation during recovery of a major portion of the hydrocarbon content of said prepared portion, and recovering evolved products through the producing well.

9. In a method for underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection well and a producing well, the improvement which comprises injecting an oxygen-containing gas through one of said wells into said media, initiating a moving Zone of combustion therein at a point remote from the injection well, supplying oxygen-containing gas carrying an oxidation catalyst through the injection well at a regulated velocity capable of maintaining said combustion zone at an accelerated rate of advance toward said injection well and at a non-coking temperature until said zone has reached an area adjacent the injection well, subsequently introducing an oxygendeficient fuel gas into said media for maintaining distillation temperatures in the porous media by gas cornbustion, and removing evolved products through said production well.

l0. In a methor of underground combustion in oil shale having an organic content, said shale being penetrated at spaced points by an injection well and a producing well, the improvement which comprises injecting an oxygen-containing gas through one of said wells into a permeable portion of the oil shale structure, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygen-containing gas carrying an oxidation catalyst through said injection well, varying the total oxygen-containing gas velocity and oxygencontaining gas composition so as to maintain said combustion zone at an accelerated rate of advance toward said injection well and at a non-coking temperature until said zone has reached an area adjacent the injection Well, subsequently introducing an oxygen-deficient fuel gas into said shale for maintaining distillation temperatures in the pyrolyzed shale, and removing evolved products through said production Well.

11. In a method of underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection well and a producing well, the improvement which comprises injecting an oxygen-containing gas through one of said wells into said media, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygencontaining gas carrying an oxidation catalyst through the injection well at a regulated velocity capable of maintaining said combustion zone at an accelerated rate of advance toward said injection well and at a noncoking temperature until said zone has reached an area adjacent the injection Well, subsequently introducing an inert gas into said media for maintaining distillation ternperatures in the porous media by gas combustion, and removing evolved products through said production well.

12. In a method of undeground combustion in oil shale having an organic content, said shale being penetrated at spaced points by an injection well and a producing well, the improvement which comprises injecting an oxygen-containing gas through one of said Wells into a permeable portion of the oil shale structure, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygen-containing gas carrying an oxidation catalyst through said injection Well, varying the total oxygen-contaning gas velocity, amount of catalyst and oxygen-containing gas composition so as to maintain said combustion zone at an accelerated rate of advance toward said injection well and at a non-coking temperature until said zone has reached an area adjacent the injection Well, subsequently introducing an oxygen-deficient fuel gas into said shale for maintaining distillation temperatures in the pyrolyzed shale, and removing evolved products through said production Well.

13. In a method of underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection well and a producing well, the improvement which comprises injecting an oxygen-containing gas through one of said wells into such a porous media, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygen-containing gas carrying an oxidation catalyst through said injection Well, varying the total oxygen-containing gas velocity, amount of catalyst and oxygen-containing gas composition so as to maintain said combustion zone at an accelerated rate of advance toward said injection well and at a non-Coking temperature until said zone has reached an area adjacent the injection well, subsequently introducing an oxygen-deficient fuel gas into said media for maintaining distillation temperatures in the media, and removing evolved products through said production Well.

14. In a method of underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection well and a producing Well, the improvement which comprises injecting an oxygen-containing gas through one of said Wells into such a porous media, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygen-containing gas carrying an oxidation catalyst through said injection well, varying the total oxygen-containing gas velocity, amount of catalyst and oxygen-containing gas composition so as to maintain said combustion zone at an accelerated rate of advance toward said injection Well and at a non-coking temperature until said zone has reached an area adjacent the injection well, subsequently introducing an inert gas into said media for maintaining distillation temperatures in the media, and removing evolved products through said production well.

15. In a method of underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection Well and a producing well, the improvement Which comprises injecting an oxygen-containing gas through one of said Wells into such a porous media, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygen-containing gas carrying a vapor phase combustion catalyst through said injection Well, varying the total oxygen-containing gas velocity, amount of catalyst and oxygen-containing gas composition so as to maintain said combustion zone at an accelerated rate of advance toward said injection Well and at a non-coking temperature until said zone has reached an area adjacent the injection Well, subsequently introducing an inert gas into said media for maintaining distillation temperatures in the media, and removing evolved products through said production Well.

16. In a method of underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection Well and a producing well, the improvement which comprises injecting an oxygen-containing gas through one of said Wells into said media, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygencontaining gas carrying an oxidation catalyst through the injection well at a regulated velocity capable of maintaining said combustion zone at an accelerated rate of advance toward said injection Well and at a non-coking ternperature until said zone has reached an area adjacent the injection Well, subsequently introducing an inert gas in a liquid carrier vehicle into said media for maintaining distillation temperatures in the media, and removing evolved products through said production Well.

17. In a method of underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection Well and a producing Well, the improvement which comprises injecting an oxygen-containing gas through one of said Wells into said media, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygencontaining gas carrying an oxidation catalyst through the injection Well at a regulated velocity capable of maintaining said combustion zone at an accelerated rate of advance toward said injection Well and at a non-coking temperature until said zone has reached an area adjacent the injection Well, subsequently introducing an inert gas and Water into said media for maintaining distillation temperatures in the media, and removing evolved products through said production Well.

18. In a method of underground combustion in porous media having an organic content, said media being penetrated at spaced points by an injection Well and a producing Well, the improvement which comprises injecting an oxygen-containing gas through one of said Wells into said media, initiating a moving zone of combustion therein at a point remote from the injection Well, supplying oxygencontaining gas carrying an oxidation catalyst through the injection well at a regulated velocity capable of'maintaining said combustion zone at an accelerated rate of advance toward said injection Well and at a non-coking temperature until said zone has reached an area adjacent the injection Well, subsequently introducing an inert gas and an organic liquid into said media for maintaining distillation temperatures in the media, and removing evolved products through said production well.

19. In a method for the recovery of hydrocarbons from underground formations penetrated at spaced points by an injection Well and a producing Well wherein combustion is initiated in such a formation prepared for in situ combustion and a combustion front is propagated through a prepared portion of said formation having an oxidation catalyst distributed therein, the improvemnet which cornprises propagating a combustion front through the formation by varying, in relation to oxidation catalyst concentration in the prepared portion, the velocity and oxygen content of a continuous flow of a gas mixture introduced through the injection well for directing said frontal movement, so as to establish a maximum temperature in said frontal movement capable of maintaining distillation temperatures but insucient to cause appreciable CO2 evolution, directing a second frontal movement through the prepared portion with enough oxygen-containing gas supplied so as to obtain substantial CO2 extraction through- Vout the prepared portion, and recovering evolved products through the producing Well.

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Claims (1)

1. IN A METHOD FOR THE RECOVERY OF HYDROCARBONS FROM UNDERGROUND FORMATIONS PENETRATED AT SPACED POINTS BY AN INJECTION WELL AND A PRODUCING WELL WELL WHEREIN COMBUSTION IS INITIATED IN SUCH A FORMATION PREPARED FOR IN SITU COMBUSTION AND A COMBUSTION FRONT IS PROPAGATED THROUGH A PREPARED PORTION OF SAID FORMATION HAVING AN OXIDATION CATALYST DISTRIBUTED THEREIN, THE IMPROVEMENT WHICH COMPRISES PROPAGATING A COMBUSTION FRONT THROUGH THE FORMATION BY VARYING, IN RELATION TO OXIDATION CATALYST CONCENTRATION IN THE PREPARED PORTION, THE VELOCITY AND OXYGEN CONTENT OF A CONTINUOUS FLOW OF A GAS MIXTURE INTRODUCED THROUGH THE INJECTION WELL FOR DIRECTING SAID FRONTAL MOVEMENT, SO AS TO ESTABLISH A MAXIMUM TEMPERATURE IN SAID FRONTAL MOVEMENT CAPABLE OF MAINTAINING DISTILLATION TEMPPERATURES BUT INSUFFICIENT TO CAUSE COKING OF AN APPRECIABLE AMOUNT OF THE HYDROCARBONS WITHIN THE PREPARED PORTION DURING RECOVERY OF A MAJOR PORTION OF THE HYDROCARBON CONTENT OF SAID PREPARED PORTION, AND RECOVERING EVOLVED PRODUCTS THROUGH THE PRODUCING WELL.
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