CA2803985A1

CA2803985A1 - In situ combustion process with reduced co2 emissions

Info

Publication number: CA2803985A1
Application number: CA2803985A
Authority: CA
Inventors: Pentti Paurola; Harald Vindspoll; Knut Vebjorn Grande; Karina Heitnes Hofstad
Original assignee: Statoil ASA
Current assignee: Equinor ASA
Priority date: 2010-06-28
Filing date: 2011-06-28
Publication date: 2012-01-05
Anticipated expiration: 2031-06-28
Also published as: GB2481594A; US9470077B2; CA2803985C; RU2564425C2; RU2013103479A; GB2481594B; US20140196895A1; WO2012001008A1; GB201010855D0

Abstract

The present invention provides a method of recovering a hydrocarbon mixture from a subterranean formation comprising: (i) injecting an oxygen-rich gas into said formation; (ii) combusting said oxygen-rich gas in said formation thereby heating and reducing the viscosity of said hydrocarbon mixture and generating CO2-rich gas; (iii) recovering said heated hydrocarbon; and (iv) capturing at least a portion of CO2 from said CO2-rich gas.

Description

FIELD OF THE INVENTION

The present invention relates to a method of recovering a hydrocarbon mixture, especially a heavy hydrocarbon mixture, from a subterranean formation by an in situ combustion method using an oxygen-rich gas. An important feature of the method is that at least a portion of C02 from the C02-rich gases produced in the combustion process is captured. A preferred feature of the method of the invention is that at least a portion of C02 from the C02-rich gases produced in the combustion process is stored in a formation for future use.

BACKGROUND
Heavy hydrocarbons, e.g. bitumen, represent a huge natural source of the world's total potential reserves of oil. Present estimates place the quantity of heavy hydrocarbon reserves at several trillion barrels, more than 5 times the known amount of the conventional, i.e. non-heavy, hydrocarbon reserves. This is partly because heavy hydrocarbons are generally difficult to recover by conventional recovery processes and thus have not been exploited to the same extent as non-heavy hydrocarbons.
Heavy hydrocarbons possess very high viscosities and low API (Americal Petroleum Institute) gravities which makes them difficult, if not impossible, to pump in their native state.
Additionally heavy hydrocarbons are characterised by high levels of unwanted compounds such as asphaltenes, trace metals and sulphur that need to be processed appropriately during recovery and/or refining.
Some methods have been developed to extract and process heavy hydrocarbon mixtures. The method that is used most often commercially today for heavy hydrocarbon recovery from subterranean reservoirs is steam assisted gravity drainage (SAGD). In this method two horizontal wells are drilled approximately five meters apart then steam is injected into the reservoir through the upper wellbore permeating the oil sand. Steam softens the heavy hydrocarbon (e.g. bitumen) and enables it to flow out of the reservoir and into the lower well. From there it is pumped to the surface facilities. Significant improvements have been made in SAGD
processes in recent years, and further optimizations continue to be driven by cost and environmental issues. These improvements include more efficient methods for steam

2 generation and a general reduction in the steam to bitumen ratio. Both of these improvements are aimed at reducing the amount of steam that needs to be produced which is an energy consuming process that also generates vast amounts of C02.
Another recent development has been the injection of about 10% solvents (sometimes called diluents) with the steam. The idea of this improvement is that the diluent condenses and mixes into the hydrocarbon in the formation and thereby decreases its viscosity and increases its API gravity and thus enhances its recovery.
Nevertheless the SAGD process still suffers from inherent drawbacks. These include:
(i) the use of natural gas for steam generation causes high C02 emissions (ii) diluent must still be added to transport the recovered hydrocarbon to refineries users and then separated therefrom. The latter causes C02 emissions (iii) asphaltenes are present in the recovered hydrocarbon and their removal at refineries causes yet further C02 emissions.
Overall the SAGD process leads to the production of vast amounts of C02 whereas it has already been recognised in the energy industry that C02 emissions must be managed better. The concentration of C02 in the Earth's atmosphere has already risen from about 280 to 370 parts per million since the industrial revolution and if current trends are not changed may reach at least twice the preindustrial level by 2100. The possible environmental impact of such a change is well documented.
More recently a number of in situ combustion bitumen recovery processes have been developed and a few of these are in the pilot plant phase. In these methods the injection and production wells are only preheated using steam. Once the oil sands reservoir has been heated to a sufficient ignition temperature, air is injected into the injection wells and ignites to ultimately form a combustion front driving the bitumen recovery. Hot combustion gases contact the bitumen ahead of the combustion zone and heat the bitumen to temperatures greater than about 300 to 400 C. An example of such a process is described in US 5,456,315.
In the method disclosed in US 5,456,315 a row of vertical injection wells are completed in the upper part of the reservoir, at least one gas production well, spaced laterally from the row of injection wells, is also provided and a horizontal production well is positioned below the injection interval. Oxygen-containing gas, typically air, is injected through each injection well and ignites. Initially a discrete combustion chamber exists around the base of each injection well but as combustion proceeds a common combustion chamber forms between each of the injection wells. The

3 combustion zone or area has fronts comprising hot gases that serve to heat up hydrocarbon in their vicinity. This results in the production of heated heavy hydrocarbon of lower viscosity than the native hydrocarbon that drains downwardly through the chamber under the influence of gravity. Thus hydrocarbon is produced from the horizontal production well lying below the injection interval. The gases produced from the in situ combustion flow through the reservoir toward the gas production wells.
This process, however, also suffers from a major disadvantage. Air is the preferred gas for injection into the well to establish and maintain combustion, thus vast quantities of nitrogen-containing compounds including NOx gases are produced in the combustion gases along with C02. These have to be removed from the gases produced from the gas production wells in order for it to be disposed which is an expensive process. Morever, as with SAGD, significant volumes of C02 are simply emitted into the atmosphere.
US 4,410,042 and US 4,498,537 disclose modified in situ combustion methods wherein oxygen or a mixture of oxygen and C02 is used instead of air as the oxidant for combustion. US 4,410,042 discloses a method wherein combustion is initiated with a mixture of C02 and 02 but after the combustion front has advanced away from the wellbore, the C02/02 mixture is replaced with pure 02. The method is designed to reduce the risk of ignition in the wellbore. US 4,498,537 discloses a method wherein pure 02 or a C02/02 mixture containing at least 75% 02 is used. It teaches that the use of oxygen or an 02/CO2 mixture is advantageous because the increased levels of C02 produced in the reservoir acts as a local pressurising agent as well as a solvent in the oil phase to lower the viscosity of the oil, which together with the thermal effects of combustion, stimulates the reservoir and increases the production of oil.
Compared to the method disclosed in US 5,456,315, however, even greater concentrations of C02 are produced in the processes of US 4,410,042 and US

4,498,537 and are simply emitted to the atmosphere. As mentioned above, the increase in C02 levels in the Earth's atmosphere is a growing environmental concern and many options are currently being explored to reduce its production.
Considerable attention is, for example, being focussed on energy generation from alternative energy sources such as solar and wind power. However about 85% of the world's present energy needs are still met by burning fossil fuels therefore technologies are still needed that enable hydrocarbons to be recovered and then utilised more efficiently and with lower environmental impact, in particular, with the release of less C02.

In particular a need exists for recovery processes for hydrocarbon mixtures, and especially heavy hydrocarbon mixtures, that enables the C02 produced to be managed. In particular, methods are required that reduce the C02 emitted to the atmosphere compared to currently available techniques. Methods resulting in superior feedstock for delivery to refineries would of course also be advantageous.
The present inventors have devised an in situ combustion process wherein an oxygen-rich gas, for instance, a mixture of oxygen and C02, is used for the injection that generates and maintains combustion in the reservoir. This generates the hot combustion gases that serve to soften the heavy hydrocarbon and ease its recovery. A
C02-rich atmosphere is simultaneously created during combustion from which the can easily be captured and optionally recycled and/or stored. Consequently little, if any, C02 is emitted into the Earth's atmosphere.

SUMMARY OF INVENTION
Thus viewed from a first aspect the present invention provides a method of recovering a hydrocarbon mixture from a subterranean formation comprising:
(i) injecting an oxygen-rich gas into said formation;
(ii) combusting said oxygen-rich gas in said formation thereby heating and reducing the viscosity of said hydrocarbon mixture and generating C02-rich gas;
(iii) recovering said heated hydrocarbon; and (iv) capturing at least a portion of C02 from said C02-rich gas.
Preferred methods of the invention comprise the further step of:
(va) using said captured C02 in a method of recovering a hydrocarbon mixture.
For instance, the C02 may be used to form oxygen-rich gas for injection in step (i).
Alternatively at least a portion of the captured C02 may be used in other well treatment processes, e.g. enhanced oil recovery operations.
Particularly preferred methods of the invention comprise the further step of:
(vb) storing at least a portion of the captured C02 from said C02-rich gas in a formation.
Viewed from a further aspect the present invention provides the use of an oxygen and C02 mixture in a method of recovering hydrocarbon from a subterranean formation wherein said oxygen and C02 mixture is combusted thereby heating and reducing the viscosity of said hydrocarbon and generating a C02-rich gas, wherein at least a portion of C02 from said C02-rich gas is captured.

In a preferred embodiment at least a portion of the captured C02 is used to form oxygen-rich gas for use in a method of recovering a hydrocarbon mixture.
In a preferred embodiment at least a portion of the captured C02 from said C02-rich gas is stored in a formation.

5 Viewed from a further aspect the invention provides a well arrangement comprising:
(a) a vertical injection well having an inlet for injecting an oxygen-rich gas into a formation;
(b) a substantially horizontal production well for recovering a hydrocarbon mixture; and (c) a vertical vent well having an outlet for recovering C02 rich gas; wherein said outlet of said vertical vent well is connected to a C02 purifier.
DETAILED DESCRIPTION

The methods of the present invention are concerned with the recovery of a hydrocarbon mixture. As used herein, the term "hydrocarbon mixture" is used to refer to a combination of different hydrocarbons, i.e. to a combination of various types of molecules that contain carbon atoms and, in many cases, attached hydrogen atoms. A
"hydrocarbon mixture" may comprise a large number of different molecules having a wide range of molecular weights. Generally at least 90 % by weight of the hydrocarbon mixture consists of carbon and hydrogen atoms. Up to 10% by weight may be present as sulfur, nitrogen and oxygen as well as metals such as iron, nickel and vanadium (i.e.
as measured sulfur, nitrogen, oxygen or metals). These are generally present in the form of impurites of the desired hydrocarbon mixture.
The methods of the present invention are particularly useful in the recovery of heavy hydrocarbon mixtures. A heavy hydrocarbon mixture comprises a greater proportion of hydrocarbons having a higher molecular weight than a relatively lighter hydrocarbon mixture. As used herein a heavy hydrocarbon mixture preferably has an API gravity of less than about 15 , preferably less than 12 , still more preferably less than 10 , e.g. less than 8 . It is particularly preferred if the API gravity of the heavy hydrocarbon mixture to be recovered is from about 5 to about 15 , more preferably from about 6 to about 12 , still more preferably about 7 to about 12 , e.g.
about 7.5-9 . Examples of heavy hydrocarbon mixtures that typically have API gravities falling in these ranges are bitumens, tars, oil shales and oil sand deposits.

6 The methods of the present invention facilitate the recovery of a hydrocarbon mixture and, at the same time, reduce the amount of C02 emissions associated with recovery of the hydrocarbon compared to conventional processes. The methods of the invention are based on an in situ combustion process wherein a gas is injected into the oil-bearing formation where it combusts with hydrocarbon present therein. A
combustion front forms and the area of formation adjacent to the combustion front is heated, therefore the viscosity of any hydrocarbon present in this zone is reduced. As the hydrocarbon softens and becomes flowable, gravity forces it downwards towards a production well from where it can be produced.
In the methods of the present invention, the gas injected into the formation is an oxygen-rich gas. As used herein, the term "oxygen-rich gas" is used to refer to an oxygen-containing gas comprising at least 25% by volume oxygen and/or 002.
Air, which comprises about 20% by volume oxygen and less than 1 % by volume 002, is not an oxygen rich gas.
A preferred oxygen-rich gas for use in the methods of the present invention comprises at least 25% by volume oxygen. Particularly preferred oxygen-rich gases comprise at least 30 % by volume, more preferably at least 40 % by volume oxygen.
Particularly preferred oxygen-rich gas comprises 25-100 % by volume oxygen, more preferably 30-90 % by volume oxygen, still more preferably 40-85 % by volume oxygen, e.g. about 50 to 80 % by volume oxygen or about 50 to 70 % by volume oxygen.
In preferred methods of the invention, the oxygen-rich gas additionally comprises 002. Particularly preferably the oxygen-rich gas consists essentially of (e.g.
consists of) oxygen and 002. Particularly preferably the oxygen-rich gas does not comprise nitrogen or any nitrogen-containing gas, especially nitrogen.
Preferably the oxygen-rich gas comprises less than 10% by volume nitrogen, more preferably less than 5% by volume nitrogen, still more preferably less than 2 % by voluume nitrogen, e.g. less than 1 % by volume nitrogen.
In preferred methods of the invention, the oxygen-rich gas comprises at least % by volume 002, more preferably at least 10 % by volume C02 and still more preferably at least 15 % by volume 002. Particularly preferably the amount of C02 in the oxygen-rich gas is in the range 0-50 % by volume, more preferably 5 to 30 % by volume, still more preferably 10 to 20 % by volume.
Preferably the oxygen-rich gas is an oxygen and C02 mixture. Preferred oxygen and C02 mixtures consist of oxygen and 002. Particularly preferred oxygen

7 and C02 mixtures comprise 50-95 % by volume oxygen and 50-5 % by volume 002, more preferably 60-85 % oxygen and 40-15 % by volume 002, still more preferably 70-80 % by volume oxygen and 30-20 % by volume 002. An example of a preferred oxygen and C02 mixture is 60-70 % oxygen and 40-30 % C02 % by volume.
Particularly preferably the oxygen-rich gas comprises oxygen and C02 in a ratio of 50:50 to 99:1 by volume, more preferably 70:30 to 95:5 by volume.
In the methods of the present invention the oxygen-rich gas combusts when it is injected into the formation. Preferably the combustion generates a temperature of 300-1000 C, more preferably 500-800 C, still more preferably 600-750 C in the reservoir.
The temperatures achieved in the methods of the present invention are generally higher than the reservoir temperatures achieved using SAGD. This is advantageous because the higher temperatures achieved by the methods of the invention mean that the heavy hydrocarbon is upgraded during the recovery process.
Moreover the reservoir temperatures achieved in the methods of the present invention may advantageously be controlled. Temperature control may be accomplished by varying the flow rate of oxygen injected into the formation and/or by varying the proportion of oxygen present in the oxygen-rich gas that is injected into the formation. Preferably temperature control is achieved by varying both the flow rate of oxygen injected into the formation and the proportions of oxygen and C02 present in the oxygen-rich gas.
Typically the oxygen-rich gas (e.g. oxygen or an oxygen and C02 mixture) is injected into the formation at a flow rate that is sufficient to achieve combustion of about 5 to 15% of the hydrocarbon present therein. A decrease in the flow rate of oxygen is expected to decrease the temperature achieved in the reservoir.
Additionally, or alternatively, the proportion of oxygen and C02 present in the oxygen-rich gas may be varied to control the reservoir temperature. Whilst an oxygen-rich gas comprising 100% oxygen would generally be expected to create a reservoir temperature in the region of 800-1000 C, an oxygen-rich gas comprising a 90:10 by volume mixture of oxygen and C02 would be expected to create a lower reservoir temperature at the same flow rate. The use of C02 in the oxygen-rich gas thus provides an additional mechanism by which to potentially control reservoir temperature.
Having an ability to control the temperature achieved in the reservoir by combustion is advantageous because it impacts upon the nature of the hydrocarbon mixture produced from the recovery process. Generally the higher the temperature achieved by the combustion in the reservoir the greater the amount of upgrading of

8 PCT/EP2011/060847 hydrocarbon mixture occurs. As used herein, the term "upgrading" generally refers to the process of altering a hydrocarbon mixture to have more desirable properties, e.g. to reduce the average molecular weight of the hydrocarbons present in the mixture and correspondingly its viscosity. Upgrading during the recovery process is therefore generally desirable. In in situ combustion processes, upgrading is believed to occur by thermal cracking. At the same time, however, the temperature of the reservoir needs to be controlled so that the combustion area, as well as the combustion gases, is contained in the part of the formation where they are desired.
An additional factor that may impact upon the extent of upgrading, as well as on overall recovery of hydrocarbon mixture, is the extent to which the oxygen-rich gas injected into the formation mixes with the hydrocarbon. The injection of oxygen within C02 enables oxygen to be delivered more efficiently throughout the formation and hence may lead to a higher recovery of hydrocarbon.
Additionally at least some of the C02 present in the oxygen-rich gas may mix with the hydrocarbon present in the formation and thereby decrease its viscosity and increase its API. In other words, the C02 may function as a diluent. This also leads to a higher recovery of hydrocarbon and may avoid the need for use of other diluents.
The C02 is believed to dissolve in the hydrocarbon present in the reservoir and thereby act as a solvent lowering the viscosity of the oil. The amount of dissolution depends on a number of factors, e.g. the local formation pressure and temperaure, but is nevertheless greater than that experienced when air is used as the oxidant because of the much greater concentration of C02 produced.
Water is additionally formed in the combustion reaction in the form of steam.
It may aid in conveying the heat of combustion further into the formation, further enhancing the effect of the heat achieved. Additionally water may optionally be injected into the formation. If injection of water is carried out, the injection preferably occurs at the same time as injection of oxygen-rich gas.
The oxygen-rich gas injected into the formation may be produced by any method conventional in the art. Oxygen, for instance, may be produced by separation of air into its components using an air separator. Preferably the oxygen used has a purity of at least 95% by volume, preferably at least 97 % by volume, still more preferably at least 99% by volume. When present, C02 may be commercially available C02, C02 obtained from the C02-rich gas resulting from combustion and/or C02 from carbon storage. Preferably the C02 used is commercially available C02 or C02 obtained from the C02 rich gas resulting from combustion. Particularly preferably at

9 least a portion of the C02 used is obtained from the C02-rich gas resulting from combustion. In other words at least a portion of C02 is recycled 002.
The oxygen-rich gas is typically injected into the formation using conventional equipment for the handling of gases. Preferably the oxygen-rich gas is injected into the formation at a pressure less than the fracturing pressure of the formation.
Preferably the oxygen-rich gas is injected into the formation at a pressure that is greater than the reservoir pressure. Generally the oxygen-rich gas is injected at a pressure that is 5-20 bar, e.g. about 10 bar, greater than the reservoir pressure. When the oxygen-rich gas comprises a mixture, e.g. of oxygen and 002, the gases may be mixed prior to injection or co-injected. Preferably the gases are mixed prior to injection.
Prior to the injection of the oxygen-rich gas, the formation is preferably heated.
This ensures that ignition and combustion will occur when the oxygen-rich gas is injected. Preferably the formation is heated prior to injection by steam, in particular, by cyclic steam stimulation. Steam may be injected into the formation using conventional techniques. The preheating stage is preferably continued until the reservoir reaches a high enough temperature to maintain combustion. Preferably the preheating step achieves a reservoir temperature of 150-300 C, still more preferably 200-250 C.
The generation of steam is, however, an energy consuming and C02 producing process, therefore the amount of steam used is preferably minmised. The C02 produced during steam generation may optionally be captured and stored in a formation and/or incorporated into the oxygen-rich gas injected into the formation.
The methods of the present invention may also employ an ignition device. Any commercially available device may be used, e.g. a downhole burner. When present, the ignition device is preferably placed in the injection well. Preferred ignition devices achieve temperatures of at least 300 C, e.g. 300-500 C.
When the formation is sufficiently heated to enable auto-ignition and/or an ignition device (e.g. a downhole burner) is operated, oxygen-rich gas is injected into the formation. Preferably the injection is via at least one injection well, still more preferably via at least one vertical injection well. Preferably the injection wells are drilled though the overburden and completed in the upper portion of the reservoir. By upper portion is meant the upper 50% of the total height of the oil-bearing reservoir.
Particularly preferably a plurality of injection wells (e.g. 2, 3, 4 or more) is utilised.
When more than one injection well is used, the wells are preferably arranged in a row. Thus after injection is carried out in each well and combustion progresses, a common combustion front will form along the row of wells that subsequently progresses through the formation.
Combustion may be continued until the combustion zone has advanced a certain distance away from the injection well, after which time the combustion is 5 terminated. Termination is typically achieved by stopping the injection of oxygen-rich gas into the formation. The formation may be allowed to soak or it may be put back onto production. If a soak is used, its length will vary depending on the nature of the formation and the wells therein, e.g. the well depth, the rate of production, number of times the well has been stimulated etc. After the soak is completed, the well is put

10 back onto production.
In preferred methods of the invention, the hydrocarbon mixture is produced via a production well, particularly preferably via a substantially horizontal (e.g.
horizontal) production well. Preferably the production well is oriented perpindicularly to the injection wells. Preferably the production well is positioned in spaced relation below said injection well. When the injection wells form a row, preferably the production well is located or aligned below the row. Preferably the distance between the bottom of the injection well and the production well is about 2-20 metres, more preferably about 5-10 metres. Preferably the production well is located in the lower portion of the reservoir. By lower portion is meant the lower 50% of the total height of the oil-bearing reservoir. Preferably the production well is fitted with a slotted liner conventional in the art to permit ingress of hydrocarbon mixture from the reservoir.
Preferably the hydrocarbon mixture is pumped from the production well to the surface.
In the methods of the present invention, a gas layer forms around and above the bottom of the injection wells. This gas layer comprises uncombusted oxygen-rich gas (e.g. CO2 present in the gas) and the gases produced by combustion, i.e.
CO2 and water vapour. Unlike when air is used as the oxidant, the gas layer does not comprise sifnificant amounts of nitrogen or nitrogen containing compounds. The gas present in the gas layer is preferably removed from the formation via at least one vent well, especially at least one vertical vent well. Preferably a plurality, e.g. 2, 3 or more, vent wells are provided. The vent wells are preferably drilled though the overburden and completed in the upper portion of the reservoir. Preferably the vent wells are parallel to the injection wells. Preferably the vent wells are located remotely to (e.g.
at least 5 metres away from) the injection wells. Particularly preferably the vent wells are spaced far enough away from the injection wells so that the produced gases are sufficiently cooled prior to arrival at the vent well to avoid damage thereto. If necessary, however,

11 the vent wells may be cooled, e.g. by water circulation. When C02 is present in the oxygen-rich gas injected into the formation, the majority of unreacted injection gas is C02 and thus is considerably less dangerous than if oxygen is present in the vent well gas. The vent wells may direct the gases to the surface or to a formation for storage.
Preferably the vent wells direct the gases to the surface so they can be treated or conditioned prior to capture and optional storage in a formation.
Thus a particularly preferred method of the invention comprises:
(i) injecting an oxygen-rich gas into said formation via a vertical injection well;
(ii) combusting said oxygen-rich gas in said formation thereby heating and reducing the viscosity of said hydrocarbon mixture and generating C02-rich gas;
(iiia) recovering said hydrocarbon mixture via a substantially horizontal production well;
(iiib) recovering said C02 rich gas via a vertical vent well; and (iv) capturing at least a part of said C02 from said C02-rich gas.
Particularly preferred methods of the invention comprise the further step of:
(va) using said captured C02 in a method of recovering a hydrocarbon mixture, e.g. to form oxygen-rich gas for injection in step (i).
Alternatively at least a portion of the captured C02 may be used in other well treatment processes, e.g. in enhanced oil recovery methods. For instance the may be used in a process for simultaneously extracting and upgrading a heavy hydrocarbon mixture as described in W02011/007172. This process comprises:
i) injecting supercritical or near-supercritical C02 at a temperature of around the critical temperature and a pressure of around the critical pressure into a heavy hydrocarbon deposit; and ii) removing a stream of C02 from the deposit, which stream is charged with a hydrocarbon mixture having a lower average molecular weight than that of the heavy hydrocarbon deposit.
Particularly preferred methods of the invention comprise the further step of:
(vb) storing at least a portion of captured C02 from said C02-rich gas in a formation.
The C02-rich gas produced from a vent well preferably comprises at least 50 %
by volume C02, more preferably at least 70 % by volume C02, still more preferably at least 80 % by volume C02. The amount of C02 in the C02-rich gas is preferably 100% by volume, preferably 60-95 % by volume, still more preferably 70-90 % by volume C02. The remainder of the gas generally comprises water vapour, SOx and NOx gases and hydrocarbons.

12 Advantages of the processes of the invention compared to conventional in situ combustion therefore include:
= The combustion process in situ yields a gas that is more C02-rich and which has a significantly lower concentration of NOx gases compared to the gas produced from the combustion of air = Sufficiently high levels of C02 are present in the resulting C02-rich gas to enable it to be recycled and reinjected into the formation = Sufficiently high levels of C02 are present in the resulting C02-rich gas to enable C02 to be captured and stored in an efficient process in a formation for use in the future.
Preferably the C02-rich gas produced from a vent well is purified prior to reinjection or storage. Particularly preferably the C02-rich gas is treated to remove water vapour, SOx and NOx gases and other impurities. This may be done by any conventional techniques, e.g. water separation. Preferably the C02-rich gas is also treated to remove hydrogen and/or hydrocarbons. The removal of hydrocarbon is preferably carried out using a cold-box arrangement or a membrane system.
Preferably the C02-rich gas produced in the method is captured in a C02 purifier. The C02 purifier may be, for example, a C02 capture apparatus comprising an absorption tower and a regeneration tower. Such towers are conventional in the art.
Preferably the C02-rich gas is contacted, typically in counter flow, with an aqueous absorbent in an absorber column. The gas leaving the absorber column is preferably C02 depleted and can be released to the atmosphere. The C02 preferably leaves the absorber column together with the absorbent. Typically the absorbent is subsequently regenerated in a regenerator column and returned to the absorber column. The separated from the absorbent is preferably sent for reinjection or storage, e.g. in a subterranean formation.
The C02 obtained is preferably of high purity, e.g. the C02 may have a purity of 95-100%, e.g. 96-99%. Preferably at least a portion of C02 from the C02 rich gas is used to recover a hydrocarbon mixture from a formation. Preferably at least a portion of C02 from the C02-rich gas is used to form an oxygen-rich gas for injection in step (i).
Preferably a portion of C02 from said C02-rich gas is pressurised, condensed and pumped to a formation for storage.
Thus in preferred well arrangements of the present invention, the C02 purifier is connected to the inlet of said injection well. In further preferred arrangements, the C02 purifier is connected to a means for transporting C02 into a formation for storage.

13 Methods for carbon capture and storage are well established in the art and are well known to the skilled man.
The hydrocarbon mixture recovered from the production well preferably has an API of 9-200, more preferably 10-17 , still more preferably 11-15 . Thus in preferred methods of the invention, the hydrocarbon mixture undergoes upgrading during recovery that increases the API of the hydrocarbon mixture by up to 5 , e.g.
by 1 to 5 .
In particularly preferred methods of the invention, the recovered hydrocarbon is deasphalted in a deasphalting unit. Conventional deasphalting techniques may be used. For instance, solvent deasphalting (e.g. with butane or pentane) may be used or the ROSE process may be employed. Alternatively deasphalting may be carried out using supercritical CO2. In this latter case, the CO2 used in the process may be obtained from the C02-rich gas produced by combustion.
Preferably the deasphalted hydrocarbon has an API in the range 16-25 .
Preferably the deasphalted hydrocarbon comprises less than 5% wt, more preferably less than 3 %wt, e.g. 0-2 %wt asphaltenes. Preferably the sulfur content of the deasphalted hydrocarbon is less than 3 %wt, more preferably less than 2.5 %
wt.
Optionally the deasphalted hydrocarbon is transferred to an upgrading unit to undergo thermal cracking or visbreaking, preferably visbreaking. This step may, for example, be used when the API of the deasphalted hydrocarbon mixture is 16 to 20 .
Thermal cracking and/or visbreaking may be carried out by any conventional procedure known in the art. The API of the upgraded product is preferably in the range 18 to 25 .
Such a hydrocarbon mixture is transportable, i.e. it can easily be pumped to a refinery for processing.
The asphaltenes recovered in the deasphalting process are preferably combusted in an oxycombustion process. This process generates CO2 that is preferably captured as hereinbefore described. The combustion also generates steam and power. Preferably the steam and power are used in a stimulation process to heat a formation prior to in situ combustion and/or in a SAGD procedure.

BRIEF DESCRIPTION OF THE DRAWINGS

Figures 1a and 1b are schematic views of a section of an oil-bearing formation with vertical injection wells, vertical vent wells and a horizontal production well;
Figures 2a and 2b are schematic diagrams of a cross section of the oil-bearing formation perpindicular to the horizontal production well;

14 Figure 3 is a flow diagram of a method of the present invention showing the flow of C02; and Figure 4 is a comparative flow diagram for a SAGD method currently in use showing the flow of C02-DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Referring to Figures 1 a and 1 b, they show two views of an oil-bearing formation and the arrangement of wells therein used to carry out the methods of the present invention.
A covering of overburden 1 lies above the oil-bearing formation 2. A row of vertical injection wells 3 are drilled downward through the overburden 1. The injection wells 3 are completed in the oil-bearing formation 2. Vent wells 4 are also drilled through the overburden and are completed in the oil-bearing formation, preferably in an upper portion thereof. Preferably the vent wells 4 are drilled laterally spaced from the injection wells 3 so that the rows of injection wells 3 and rows of vent wells 4 are parallel.
The production well 5 is substantially horizontal and is preferably aligned with, and positioned below, the row of injection wells 3. Preferably the production well is located in a lower region of the oil-bearing formation. The production well is preferably provided with a liner (not shown) as is conventional in the art.
In most cases it will be desirable to preheat the formation prior to commencing in situ combustion. This prepares the cold heavy hydrocarbon for ignition and develops enhanced hydrocarbon mobility in the reservoir. Preheating may be achieved by injecting steam through the injection wells 3 and optionally through the vent wells 4 and/or the production well 5. It is generally desirable to inject steam through all types of wells so fluid communication between the injection well 3, vent well 4 and production well 5 is achieved. Oil may be recovered in production well 5 during this preheating step. When the reservoir is sufficiently heated, combustion may be started.
Referring to Figure 2a, it shows a cross-section of an oil-bearing formation in which combustion has begun. Features that are also shown in Figure 1 are designated by the same reference numeral. Oxygen-rich gas is injected into injection wells 3 to initiate combustion. Thereafter a combustion chamber forms around each injection well 3. The combustion chambers naturally spread and eventually form a continuous chamber that links all of the injection wells 3. The front of the combustion zone heats heavy hydrocarbon in its vicinity thereby increasing the hydrocarbon mobility and enabling it to flow. Under the forces of gravity, the heavy hydrocarbon 6 flows downwards towards production well 5. From there the partially upgraded heavy hydrocarbon is pumped to the surface facilities.
5 At the start of combustion the combustion front is located very close to the injection wells 3 therefore the heavy hydrocarbon 6 that is heated and recovered is from this portion of the reservoir. As the combustion front spreads, however, heavy hydrocarbon that is located further away from the injection wells becomes sufficiently heated to begin to flow. Thus Figure 2a shows a cross section of a well shortly after 10 combustion has been initiated and Figure 2b shows a cross section the same well some time later.
At the same time as combustion, a gas layer 7 forms at the upper surface of the oil-bearing formation. This gas layer comprises highly C02 rich combustion gases (their flow is represented by arrows 8) as well as C02 injected as part of the oxygen-

15 rich gas. A small amount of oxygen may also be present in gas layer 7. The gas will establish communication with the vent wells 4. Preferably the C02-rich gases from the vent wells 4 are captured at the surface where they are treated as discussed below.
After the combustion front has advanced a certain distance from the injection wells, the injection of oxygen rich gas is stopped. This will terminate the in situ combustion process.
Referring to Figure 3, it shows the flow of C02 through a preferred method of the present invention. Oxygen may be prepared by separation from air (arrow a) and combined with C02 shipped to a platform for carrying out the methods of the invention (arrow b) and/or recycled C02 from earlier recoveries (arrow c). The oxygen and C02 mixture is injected into the formation (arrow d) via injection well 3. As described above, this leads to the production of heavy hydrocarbon at production well 5 (arrow e) and C02 rich gases at vent wells 4 (arrows f).
Typically the heavy hydrocarbon is pumped from production well 5 to the surface. Preferably a water separation is carried out to remove salts (desalting) (arrow g). The heavy hydrocarbon mixture is then preferably routed to a deasphalting unit where asphaltenes are removed therefrom using conventional processes or more preferably by supercritical C02 processing. If C02 is produced in this process, the C02 is preferably captured and recycled and/or stored. When supercritical C02 processing is used, the C02 required for the process may be obtained from the C02-rich gas produced at the vent wells 4 (arrow h). The deasphalted heavy hydrocarbon mixture is

16 routed to a pipeline without diluent, optionally via a visbreaker (arrow k), and then to downstream users (arrow i).
The preferred properties of the heavy hydrocarbon mixture in the formation and the heavy hydrocarbon mixture recovered after deasphalting are shown in the Table below. The table also lists the typical properties of a heavy hydrocarbon mixture obtained by in situ combustion for comparison purposes.

Parameter Bitumen Bitumen from in situ Bitumen from combustion process of the invention Viscosity at 20C (CP) >555.000 100-1850 <100 S content (wt%) 3.2-5 2.6-4.0 2.2-3.6 API grvity ( ) <7.9 10.6-16.2 16-21 SARA analysis Volatile organics (wt%) 15.9 25.6 28.8 Saturates (wt%) 25.9 23.5 26.5 Aromatics (wt%) 16.6 22.6 25.5 Resins (wt%) 12.7 17.2 19.2 Asphaltenes (wt%) 28.9 11.2 -0 In a preferred process of the invention, the asphaltenes obtained in the deasphalting process are transferred to an oxycombustion unit, e.g. a plasma treatment chamber where they are burned. Oxygen (arrow I) and C02 (arrow m) are fed into the unit and the asphaltenes are burned to generate steam and/or power (arrow n). These are preferably used to stimulate a formation prior to in situ combustion and/or in a SAGD process. The exhaust gas from the oxycombustion process is C02 rich and is preferably collected (arrow o). If it is substantially pure it can be recycled directly into the process (dashed arrow p). Otherwise it is routed to the C02 purifier (arrow q).
The segregated C02-rich gases (arrows f) from the production vent wells 4 and optionally from the oxycombustion of asphaltenes (arrow q) are routed to a C02 purifier. Typically C02 is separated from the gases. Optionally the gases are conditioned by removing hydrogen and light hydrocarbon components by a conventional cold box arrangement. The enriched C02 stream (arrow j) can be pressurized, condensed and pumped to available C02 formation storage sites.

17 Alternatively or additionally the C02 may be reinjected into the formation as part of the oxygen rich gas (arrow c).
The table below lists the properties of the gases produced at vent wells 4 in a conventional in situ combustion using air as the gas and using an oxygen and mixture according to the present invention.

Component (mol %) Produced gas from in situ Produced gas from process combustion of the invention Hydrogen 2.23 2.23 Oxygen 0.18 0.18 Nitrogen/Nitrogen 74.70 -0 containing gas Methane 4.48 4.48 Carbon monoxide 1.08 1.08 Carbon dioxide 15.81 90.51 Hydrocarbons C1_5 1.13 1.13 H2S 0.39 0.39 The methods of the present invention therefore yield a C02-rich gas that facilitates the capture and recycling or storage of C02 in a formation.
Figure 4 is a comparative C02 flow diagram for a SAGD method currently in use. Natural gas is used for the generation of steam (arrow z) and this generates huge quantities of C02. The recovered heavy hydrocarbon is also too viscous to pump to a refinery because the reservoir temperature achieved in SAGD does not lead to significant upgrading. A diluent must therefore be added (arrow x) to allow the virgin hydrocarbon to be transported. At the refinery, however, the diluent must first be separated from the heavy hydrocarbon (arrow w) and then the asphaltenes from the hydrocarbon (arrow v). Both of these separation processes generate huge volumes of C02. The refinery also tends to be located remotely to formations and thus a long way from potential C02 subterranean storage.
The methods of the present invention therefore have numerous advantages over the SAGD process including:
= A significant reduction in water usage for steam generation since steam is only required for a short start up period.

18 = A significant reduction in natural gas consumption as the methods of the invention use the in situ energy of the heavy hydrocarbon which would otherwise be unrecoverable = An elimination of diluent demand as a result of in situ heavy hydrocarbon upgrading and downstream deasphalting.
= An elimination of C02 emissions because all produced C02 is recycled and/or compressed, condensed and pumped to a formation which can store C02 (Carbon Capture and Storage) = Significantly improved project economics as the heavy hydrocarbon recoveries are estimated to be as much as 50% higher than SAGD recoveries, and capital and operating costs are estimated to be considerably lower than comparable SAGD processes. The beneficial effect of the C02-rich atmosphere in the reservoir is a further viscosity reduction of heavy hydrocarbon in the swept zone and this translates to more recovery.
= The deasphalted heavy hydrocarbon is a superior feedstock to virgin heavy hydrocarbon from SAGD processes for downstream refineries and less C02 is generated in the downstream refinery upgrading processes.
= By changing the oxygen:C02 ratio a desired temperature profile (e.g. between 300-1000 C) can be created in the reservoir and a more selective upgrading of heavy hydrocarbon will result.

Claims

CLAIMS:

1. A method of recovering a hydrocarbon mixture from a subterranean formation comprising:
(i) injecting an oxygen-rich gas into said formation;
(ii) combusting said oxygen-rich gas in said formation thereby heating and reducing the viscosity of said hydrocarbon mixture and generating CO2-rich gas;
(iii) recovering said heated hydrocarbon mixture; and (iv) capturing at least a portion of CO2 from said CO2-rich gas.

2. A method as claimed in claim 1, comprising the further step of:
(va) using said captured CO2 in a method of recovering a hydrocarbon mixture, e.g. to form oxygen-rich gas for injection in step (i).

3. A method as claimed in claim 1 or claim 2, comprising the further step of:
(vb) storing at least a portion of CO2 from said CO2-rich gas in a formation.

4. A method as claimed in any one of claims 1 to 3, wherein said oxygen-rich gas comprises at least 25% by volume oxygen and/or CO2

5. A method as claimed in any one of claims 1 to 4, wherein said oxygen-rich gas comprises CO2-

6. A method as claimed in any one of claims 1 to 5, wherein said oxygen-rich gas comprises at least 30 % by volume oxygen.

7. A method as claimed in any preceding claim, wherein said oxygen-rich gas comprises at least 5 % by volume CO2-

8. A method as claimed in any preceding claim, wherein said formation is heated, e.g. by steam injection, prior to injection of said oxygen-rich gas.

9. A method as claimed in any preceding claim, comprising (i) injecting an oxygen-rich gas into said formation via a vertical injection well;

(ii) combusting said oxygen-rich gas in said formation thereby heating and reducing the viscosity of said hydrocarbon mixture and generating CO2-rich gas;
(iiia) recovering said hydrocarbon mixture via a substantially horizontal production well;
(iiib) recovering said CO2 rich gas via a vertical vent well; and (iv) capturing at least a portion of CO2 from said CO2-rich gas.

10. A method as claimed in any preceding claim, wherein said CO2-rich gas comprises at least 70 % by volume CO2-

11. A method as claimed in any preceding claim, wherein said recovered hydrocarbon mixture has an API of 10-17°.

12. A method as claimed in any preceding claim, wherein said recovered hydrocarbon mixture is deasphalted in a deasphalting unit.

13. A method as claimed in claim 12, wherein said deasphalted hydrocarbon mixture has an API in the range 16-25°.

14. A method as claimed in claim 12 or claim 13, wherein asphaltenes produced in said deasphalting unit are combusted in an oxycombustion process.

15. Use of an oxygen and CO2 mixture in a method of recovering a hydrocarbon mixture from a subterranean formation wherein said oxygen and CO2 mixture is combusted thereby heating and reducing the viscosity of said hydrocarbon mixture and generating a CO2-rich gas, wherein at least a portion of said CO2-rich gas is captured.

16. Use as claimed in claim 15, wherein at least a portion of CO2 from said CO2-rich gas is used in a method of recovering a hydrocarbon mixture.

17. Use as claimed in claim 15 or claim 16, wherein at least a portion of CO2 from said CO2-rich gas is stored in a formation.

18. A well arrangement comprising:
(a) a vertical injection well having an inlet for injecting an oxygen-rich gas into a formation;

(b) a substantially horizontal production well for recovering a hydrocarbon mixture; and (c) a vertical vent well having an outlet for recovering CO2 rich gas;
wherein said outlet of said vertical vent well is connected to a CO2 purifier.

19. A well arrangement as claimed in claim 18, wherein said CO2 purifier is connected to said inlet of said injection well.

20. A well arrangement as claimed in claim 18 or 19, wherein said CO2 purifier is connected to a means for transporting CO2 into a formation for storage.