OA18941A - In-situ process to produce hydrogen from underground hydrocarbon reservoirs - Google Patents

Abstract

A hydrocarbon reservoir is treated with heat to induce gasification, water-gas shift, and/or aquathermolysis reactions to generate gases including hydrogen. The hydrogen alone is produced to the surface by using hydrogen-only membranes in the production wells.

Description

IN-SITU PROCESS TO PRODUCE HYDROGEN FROM UNDERGROUND HYDROCARBON RESERVOIRS

FIELD OF THE INVENTION

The present invention relates to the production of hydrogen from subsurface sources.

BACKGROUND OF THE INVENTION

Hydrocarbon réservoirs are abundant globally and many technologies are known for use in the production of hydrocarbon to surface from these réservoirs, including primary processes as well as secondary recovery processes such as water flooding and Chemical flooding to produce additional hydrocarbon.

For heavy oil and extra heavy oil (bitumen), the hydrocarbon is usualiy too viscous at original reservoir conditions to be produced to surface using conventional methods, and so heavy oil and bitumen are commonly thermally treated to lower the viscosity so that the resource flows more easily in the reservoir and can be produced to the surface.

After heavy oil and bitumen is extracted, it has to be upgraded to synthetic crude oil which in tum is refmed into transportation fuels and feedstocks for the petrochemical industry.

However, it is known that the production of hydrocarbon resources results in eventual génération of carbon dioxide since the resources or their products are generally combusted to harvest their energy.

There is thus an ongoing desire to produce fuels such as hydrogen that are more carbon dioxide neutral, which can also be used as Chemical feedstock for industries such as upgraders and fertilizer production. However, conventional means of generating hydrogen (e.g., steam methane reforming or electrolysis) are also known to be carbon-intensive or undesirably expensive to implement.

SUMMARY OF THE INVENTION

The present invention therefore seeks to provide methods and Systems for generating hydrogen, a potentially carbon dioxide neutral energy source and industrial feedstock, from hydrocarbon réservoirs.

According to embodiments of the présent invention, in situ gasification, water-gas shift and /or aquathermolysis are employed to produce synthesis gas in the subsurface reservoir, such synthesis gas comprising steam, carbon monoxide, carbon dioxide, and hydrogen, where the carbon oxides are rejected from being produced to the surface by means of a hydrogen-only permeable membrane in the wellbore. The process then produces a gas product largely comprising hydrogen tothe surface.

The produced hydrogen is an alternative energy vector that can be produced to the surface from hydrocarbon réservoirs. The produced hydrogen can then be combusted on surface to generate power or heat or consumed in fuel cell devices for production of power or as an industrial feedstock.

In a first broad aspect of the présent invention, there is provided a method for producing hydrogen from a hydrocarbon reservoir, the method comprising:

a. providing a well from surface to the reservoir;

b. locating at least one hydrogen-permeable membrane in the well,

c. heating the reservoir to facilitate at least one of gasification, water-gas shift, and aquathermolysis reactions to occur between hydrocarbon and water within the reservoir to generate a gas stream comprising hydrogen, and

d. engaging the gas stream and the at least one hydrogen-permeable membrane, such that the at least one hydrogen-permeable membrane permits passage of only the hydrogen in the gas stream to the surface.

In some exemplary embodiments of the first aspect, the step of heating the reservoir comprises: injecting an oxidizing agent into the reservoir to oxidize at least some of the hydrocarbon within the reservoir; generating electromagnetic or radio-frequency waves with an electromagnetic or radio-frequency antenna placed within the reservoir; injecting a hot material into the reservoir; or generating heat by using a resistance-based (ohmic) heating System located within the réservoir. It will be clear to those skilled in the art that other heating means may be applicable for applications of the present invention.

In some exemplary embodiments, the at least one hydrogen-permeable membrane may comprise at least one of: palladium (Pd), vanadium (V), tantalum (Ta) or niobium (Nb). The at least one hydrogen-permeable membrane may also comprise a palladîum-copper alloy, or potentially a palladium-silver alloy. The at least one hydrogen-permeable membrane may comprise a ceramic layer, and most preferably a ceramic layer on the inside or the outside of a palladium-copper alloy. The at least one hydrogen-permeable membrane may comprise a ceramic layer and a non-ceramic layer selected from the group consisting of palladium, vanadium, tantalum, niobium, copper, alloys of these materials, and combinations thereof, and the non-ceramic layer may comprise a palladium-copper alloy.

The at least one hydrogen-permeable membrane is preferably located in the well within the réservoir, but it may also be positioned in the well proxi mate to the réservoir, or at other points in the well.

In some exemplary embodiments, a porous material is located in the well to support the at least one hydrogen-permeable membrane within the well. The porous material is preferably but not necessarily porous Steel.

In some exemplary embodiments of the present invention, methods comprise the further step, after the step of heating the réservoir, of delaying engaging the gas stream and the at least one hydrogen-permeable membrane to allow for further génération of the hydrogen. This step of delaying may comprise delaying for a period in the range of l week to 12 months, and most preferably in the range of I week to 4 weeks.

In exemplary embodiments where dielectric heating is used for the step of heating the réservoir, electromagnetic radiation may hâve a frequency in the range of about 60 Hz to 1000 GHz, and preferably in the range of 10 MHz to 10 GHz.

Where a resistance-based (ohmic) heating System is used to heat the reservoir, heating is preferably to températures in the range of 200 to 800 degrees C, and most preferably in the range of 400 to 700 degrees C.

In a second broad aspect of the present invention, there is provided a system for recovering hydrogen from a subsurface reservoir, the System comprising:

an apparatus for heating the reservoir to generate a gas stream comprising hydrogen;

a well located in the reservoir, and a hydrogen-permeable membrane in the well adapted to permit passage therethrough of hydrogen in the gas stream but disallow passage therethrough of other gases in the gas stream, to allow production of the hydrogen through the well to surface.

In some exemplary embodiments ofthe second aspect, the apparatus for heating the reservoir comprises at least one of an oxidizing-agent injector, an electromagnet, a radio-frequency antenna, and a hot material injector.

The produced hydrogen may be consunied in a fuel eiectrochemical cell device, combusted to generate steam for power génération or steam for oil recovery, or used as industrial feedstock.

A detailed description of exemplary embodiments of the present invention is given in the foilowing. It is to be understood, however, that the invention is not to be construed as being limited to these embodiments. The exemplary embodiments are directed to particular applications of the present invention, while it will be clear to those skilled in the art that the present invention has applicability beyond the exemplary embodiments set forth herein.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings, which illustrate exemplary embodiments of the present invention:

FIG. IA to IC are simplified élévation and sectional diagrams illustrating stages in a System and method whereby a hydrocarbon reservoir is heated by oxidizing a portion of the hydrocarbon within the reservoir.

FIG. 2 is a simplified élévation and sectional diagram illustrating a system and method whereby a hydrocarbon reservoir i s heated using an electroniagnetic/radio frequency antenna placed within the reservoir.

FIG. 3 is a simplified sectional diagram illustrating the use of multiple antennas and production wells.

FIG. 4A to 4C are sectional views illustrating exemplary hydrogen-separating composite membranes.

FIG. 5 is a simplified élévation and sectional diagram illustrating an exemplary system and method whereby an oxidizing agent is continuously injected into the reservoir to produce hydrogen.

FIG. 6 is a simplified élévation and sectional diagram illustrating an exemplary system and method whereby one of the wells has a resistance-heating cartridge within the well to heat the reservoir to produce hydrogen.

FIG.7 is a diagram illustrating some of the reactions that occur in the exemplary methods described herein which occur within the reservoir to produce hydrogen.

FIG. 8A to 8B are diagrams illustrating results of a thermal reactive reservoir simulation, using the reaction scheme illustrated in FIG. 7, of a hydrogen production process in a heavy oil reservoir comprising a cyclic oxidizing agent injection process including periods of noninjection where Chemical reactions are allowed to continue within the reservoir.

FIG. 9A to 9D are diagrams illustrating results of a thermal reactive reservoir simulation, using the reaction scheme illustrated in FIG. 7, of a hydrogen production process in a heavy oil reservoir comprising a continuous oxidizing agent injection process.

Exemplary embodiments of the present invention will now be described with reference to the accompanying drawings.

DETAILED DESCRIPTION OFTHE EXEMPLARY EMBODIMENTS

Throughout the following description, spécifie details are set forth in order to provide a more thorough understanding to pensons skilled in the art. However, well known éléments may not hâve been shown or described in detail to avoid unnecessarily obscuring the disclosure The following description of examples of the invention is not intended to be exhaustive or to Iimit the invention to the précisé form of any exemplary embodiment. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.

Throughout this spécification, numerous ternis and expressions are used in accordance with their ordinary meanings. Provided below are définitions of some additional tenus and expressions that are used in the description that follows.

“Oil” is a naturally occurring, unrefined petroleum product composed of hydrocarbon components. Bitumen and heavy oil are nonnally distinguished from other petroleum products based on their densities and viscosities. Heavy oil is typically classified with densîty of which is between 920 and 1000 kg/m3. Bitumen typically has densîty greater than 1000 kg/m3. For purposes of this spécification, the tenus “oil”, bitumen and heavy oil are used interchangeably such that each one includes the other. For example, where the term bitumen is used alone, it includes within its scope heavy oil.

As used herein, petroleum réservoir refers to a subsurface formation that is primarily composed of a porous matrix which contains petroleum products, nainely oil and gas. As used herein, heavy oil réservoir refers to a petroleum réservoir that is primarily composed of porous rock containing heavy oil. As used herein, oil sands réservoir refers to a petroleum réservoir that is primarily composed of porous rock containing bitumen.

Cracking refers to the splitting of larger hydrocarbon chains into smaller-chained compounds.

The tenu in situ refers to the environment of a subsurface oil sand réservoir.

In broad aspects, the exemplary methods and Systems described herein use oil sand reservoirs as a hydrogen source, both the bitumen and the formation water.

In general, the present spécification describes Systems and methods to treat oil reservoirs (conventional oil, heavy oil, oil sands reservoirs, carbonate oil reservoirs) to recover hydrogen. The methods include injection of oxygen or an oxygen-rich stream into the reservoir to combust a portion of the hydrocarbons in the réservoir.

In some preferred exemplary embodiments, during injection of the oxidizing agent no fluids are produced to the surface. After the target température is achieved in the reservoir, injection stops and during this time the remaining oxygen in the reservoir is consumed and gasification reactions and the water-gas shift reaction takes place. During these reactions, hydrogen is produced within the reservoir. The production well is compieted with a hydrogen-only permeable membrane, which when opened for production only produces hydrogen to the surface. After the hydrogen production rate drops below a threshold value, oxygen injection starts once again and the process is repeated multiple times until the overall hydrogen production rate drops below a threshold value. The threshold value can be determined from a minimum hydrogen production rate that is économie which will be set by the costs of oxygen injection, price of hydrogen production, storage, transportation, and consumption (e.g., in a fuel cell for power), and the costs of operation. The hydrogen-only permeable membrane prevents the production of carbon oxides to the surface. Thus, the process yields hydrogen from the hydrocarbons and water that are situated within the reservoir. If needed to enable the desired reactions, water may be injected into the reservoir with the oxygen.

Oxidation of the reservoir fluids by injecting oxygen into the reservoir is one means to generate heat within the reservoir. The reactions that occur in the reservoir at elevated températures can include low and high température oxidation, pyrolysis (thermal cracking), aquathermolysis (hydrous pyrolysis or thermal cracking reactions in the presence of water), gasification reactions, and the water-gas shift reaction.

FIG. IA to IC illustrate a System 10 wherein a steam-assisted gravity drainage (SAGD) well pair 12 comprising an injection well 14 and a production well 16 is used for implémentation of an exemplary embodiment of the present invention in a reservoir 18, over three stages. It will be clear to those skilled in the art that exemplary methods may employ an existing steamassisted gravity drainage (SAGD) well pair or a well pair that is simply using a SAGD well configuration or pattern of SAGD well pairs, for example, a pad of SAGD well pairs. Furthermore, it will be clearto those skilled in the art that exemplary methods may employ an existing cyclic steam stimulation (CSS) well or a well that is simply using a CSS well configuration or pattern of CSS wells, for example, a pad of CSS wells. In Stage l (illustrated in FIG. I A), oxygen is injected into the réservoir 18 through an open injection well 14, resulting in combustion of a portion of the bitumen in a combustion zone 20 of the réservoir 18 to generate the températures (for a non-Iimiting example, >700 degrees C) required for the gasification, water-gas shift, and aquathermolysis reactions. The production well 16 remains closed at this stage. In Stage 2, oxygen injection is stopped and the injection well 14 is closed, and the remaining oxygen in the réservoir 18 is consumed by the ongoing reactions in the combustion zone 20. Since the réservoir 18 in the near well région is at sufficiently elevated températures, gasification, water-gas shift, and aquathermolysis reactions continue. The gas products from the reactions accumulate in the reservoir 18 Thereafter, Stage 3 is initiated, when the production well 16 containing the hydrogen séparation membrane (not shown) is opened which then produces hydrogen to surface. After the hydrogen production has dropped to non-commercial rates, the process can then be re-started with Stage l. The method is not limited to horizontal wells but also can be done with vertical and deviated and multilatéral wells. The method can be equally applied in a gas reservoir. The method may be applied where oil is produced from the reservoir in addition to hydrogen. The method may be applied where synthesis gas is produced from the reservoir.

Another exemplary system 30 according to the present invention is illustrated in FIG. 2. In this implémentation, heat is provided to the reservoir 18 using an electromagnetic / radio frequency antenna 32 to form a heated zone 36. The heated reservoir 18 undergoes gasification, water-gas shift, and aquathermolysis reactions which generate hydrogen and other gases within the reservoir 18. The generated hydrogen is produced to the surface through the hydrogen-only permeable membrane within a production well 34. This approach is not limited to horizontal wells as illustrated but also can be done with vertical and deviated and multilatéral wells. The method can be equally applied in a gas reservoir.

Another related embodiment is illustrated in FIG. 3 in sectional or cross-well view, wherein a

System 40 comprises multiple production wells 42 and multiple electromagnetic/radio frequency antennas/heaters 44. The electromagnetic/radio frequency heaters 44 are positioned between the hydrogen production wells 42 in the reservoir 18, and create a heated zone 46. The method is not limited to horizontal wells but also can be done with vertical and deviated and multilatéral wells. The method can be equally applied in a gas reservoir. Wells with résistance (ohmic) heaters may also be used.

The reactions generate gas which then enables gravity drainage (due to density différence) of hot mobilized oil and steam condensate towards the base of the gasification reaction chamber. Thus, additional source material for further reaction is provided by moving mobilized oil towards the reactive zone above and around the injection well or antenna. This helps with gasification reactions and maintains the 700+ degrees C zone near the well. The in-well membrane allows hydrogen to pass but holds other gas molécules in the reservoir.

FIG. 5 illustrâtes a further exemplary embodiment of a system 50 according to the présent invention. Similar to the embodiment of FIG. IA to IC, the System 50 comprises a SAGD well pair 52 (an injection well 54 and a production well 56). However, instead of allowing for a post-injection chemical reaction period in the heated zone 58 before production, the injection and production wells 54, 56 remain open and allow a continuous flow of injected oxidizing agent and produced hydrogen. The method may be applied where oil is produced from the reservoir in addition to hydrogen. The method may be applied where synthesis gas is produced from the reservoir.

FIG. 6 illustrâtes a further exemplary embodiment of a system 60 according to the présent invention. In this embodiment, comprising a well pair 62 (an injection well 64 and a production well 66), one of the wells 64, 66 is provided with a resistance-heatîng cartridge which is used to heat a pyrolysis zone 68 in the reservoir 18 to produce hydrogen through the production well 66.

In other embodiments, not illustrated, a single-well configuration could be used wherein oxygen is injected along one part of the well and hydrogen-only production occurs along another part of the well. The well can be vertical, deviated, horizontal or multilatéral.

In further non-illustrated embodiments, heating of the réservoir can be done by electromagnetic or radio frequency waves. Altematively, heating of the reservoir can be done using high pressure, high température steam.

The présent method can also be used in oil and gas réservoirs where the water content of the reservoir is considered high such that in normal practice, these réservoirs would not be produced for oil or gas, respectively. Methods and system according to the présent invention could be used in high water content hydrocarbon reservoirs since hydrogen is sourced not only from the hydrocarbon but also the water within the reservoir. Thus, the methods taught herein may be capable of use in reservoirs where the high water content renders them less vaiuable than oil saturated reservoirs, converting previously less vaiuable petroleum reservoirs to vaiuable energy sources since the hydrogen is sourced from both the petroleum as well as the water in the reservoir.

The present invention relates to treatment of an oil or gas reservoir for production of hydrogen from the hydrocarbon and water within the reservoir. The treatment includes heating the reservoir to enable gasification and water-gas shift reaction to produce hydrogen within the reservoir and then using a hydrogen-only production well, equipped with a hydrogen membrane, to produce hydrogen from the reservoir.

High water content in oil and gas reservoirs is typically thought to be disadvantageous for oil or gas production. However, it has been found that high water content may be a benefit for the production of hydrogen since water supplies hydrogen due to the water-gas shift reaction. It has been fbund that many of the reactions that produce hydrogen source the hydrogen from the water in the reservoir - under the températures of the reactions, the formation water is converted to steam which then participâtes in the steam reforming reactions with the hydrocarbons in the reservoir.

Following is further detailed description regarding certain exemplary embodiments of the present invention.

A. Heating the reservoir

In certain exemplary embodiments, the reservoir is heated to a température where gasification and water-gas shift reactions take place between the oil and water within the reservoir.

The heat can be delivered to the reservoir through a variety of methods commonly known in the art. Typical methods used in the art include a combustion step where oxygen is injected into the reservoir for a period of time where a portion of the hydrocarbon is combusted to generate heat within the reservoir to achieve températures on the order of 400 to 700 degrees C. Other modes of heating including electromagnetic or radio frequency based heating. Other modes of heating include injecting hot materials into the reservoir.

After the heat is injected to the reservoir, if done by combustion, oxygen injection is stopped and the Chemical reactions are allowed to continue within the reservoir at the elevated température achieved by the combustion step. If heated by electromagnetic heating, then this heating can continue to keep the reservoir at the desired reaction température.

B. Gasification, Water-Gas Shift, and Aquathermolysis Réactions Period

During the period of time at the which the reservoir is at elevated température, gasification and water-gas shift and aquathermolysis reactions may occur with conséquent génération of hydrogen, hydrogen sulphide, carbon monoxide, carbon dioxide, and steam (water vapour), and possibly other gases. As the reactions occur in the reservoir, the gas components collect within the reservoir pore spaces and any fractures or other void spaces in the reservoir.

FIG. 7 illustrâtes some of the reactions that occur in the reservoir. As can be seen, the fuel for oxidation and gasification is the bitumen and coke that forms from reactions that occur during the process. Bitumen can be represented as a mixture of maltenes (saturates, aromatics, and resins) and asphaltenes (large cyclic compounds with large viscosity). During oxidation, maltenes can be converted into asphaltenes. Asphaltenes can be converted, via both low and high température oxidation as well as thermal cracking into a variety of gas products including methane, hydrogen, carbon monoxide, carbon dioxide, hydrogen sulphide, and high molecular weight gases (e.g., propane, etc.) and coke. The coke can then be converted, through oxidation

H and gasification reactions to methane, water (vapour), carbon monoxide, carbon dioxide, and hydrogen. Also, methane can be converted, via gasification reactions, to hydrogen and carbon dioxide and carbon monoxide. Carbon monoxide and water (vapour) can be converted, via the water-gas shift reaction, to hydrogen and carbon dioxide. In general, fuel components in the system (e.g., oil, coke, methane) can be gasified to produce mixtures of carbon monoxide, carbon dioxide, and hydrogen.

C. Production of Hydrogen

After enough time has elapsed for the génération of hydrogen, the hydrogen is produced from the reservoir through the hydrogen-only membranes within the production well. In this manner, the hydrogen sulphide, carbon monoxide, carbon dioxide, steam, and other gas components remain in the reservoir white the hydrogen alone is produced to surface. Since hydrogen is removed from the reservoir, this promotes the reactions to generate more hydrogen.

For the hydrogen-only membrane to be placed in the production well, meta!lie membranes, for example, constructed from palladium (Pd), vanadium (V), tantalum (Ta) or niobium (Nb), are mechanically robust but with limited ranges of optimal performance with respect to température. These membranes work by a solubility-diffusion mechanism, with the hydrogen dissolving in the membrane materiai and diffusing to the other side where it is released; this mechanism yields hydrogen flux (moles transport rate per unit area) proportional to the square root of the pressure. To i11ustrate, vanadium and titanium permeability to hydrogen drops at high températures and also forms métal oxide layers that prevent efficient hydrogen séparation. Pd-based membranes hâve the advantage since their hydrogen pemieability rises with increasing température. However, Pd membranes are poisoned by hydrogen sulfide (H2S) and carbon monoxide (CO) which are created by aquathermolysis when steam and oil, e.g. bitumen, are contacted at elevated températures. This can be countered by using Pd-Copper alloys. For cost réduction, multilayer membranes consisting of Pd-Cu alloy and V, Ta, and Nb could be constructed. Other alloys such as palladium-silver alloys may also be useful for certain embodiments of the present invention.

Ceramic membranes are inert to H2S and CO and can be used at températures achieved by in situ gasi fi cation processes. Microporous ceramic membranes for hydrogen séparation hâve several advantages over metallic membranes: the flux is directly proportional to the pressure; the pemieabiiity of ceramic microporous membranes rises signifîcantly with température, and the cost of the raw materials for ceramic membranes is much iess than that of metallic membranes. Since they are porous, they tend not to produce pure hydrogen aithough they can be hydrogen-selective with relativeiy high hydrogen permeability. In some embodiments, the membrane can hâve a ceramic layer to not only provide ability to separate hydrogen from gas components generated from the reactions but to also strengthen the membrane.

In some embodiments, the hydrogen membrane is configured to be highly sélective to hydrogen (especially if the hydrogen gas is to be used for power génération from a fuel cell at surface), highly permeable to hydrogen, capable of withstanding heating up to 700 degrees C, able to withstand H2S and CO gas, robust mechanically given the issues of placing the membranes in the well, and/or capable of being manufactured with diameters and lengths that can fit in wells (between 20-30 cm in diameter and 700-1000 m in length). In some embodiments, the membranes can also withstand the partial oxidation stage which will consume carbon and other solid buildup on the exterior surface of the composite membrane.

Turning now to FIG. 4A to 4C, exemplary embodiments of membranes according to the present invention are illustrated FIG. 4A illustrâtes a membrane arrangement 70, wherein the arrangement 70 is located within a well liner 72. The arrangement 70 comprises a porous steel support layer 74, an overiying Pd-Cu alloy layer 76, and an outer ceramic layer 78. In FIG. 4B, the support layer is absent and the arrangement 80 comprises an inner alloy layer 86 and an outer ceramic layer 88 disposed within the well liner 82. FIG, 4C illustrâtes an arrangement 90 comprising only an alloy layer 96 tn a well liner 92

D. New cycle

If the heating is done in a cyclic manner, for example, from in situ combustion, then after the température of the réservoir has dropped such that the gasification, water-gas shift, and aquathermolysis reaction rates hâve dropped so that hydrogen production drops below a threshold value, then a new cycle of oxygen injection and conséquent in situ combustion will start leading to renewed heating of the réservoir. Thereafter, Steps A to C above are repeated. If continuous heating is done by oxidization agent injection or electromagnetic or radio frequency or résistive heating methods, then continuous hydrogen production can occur from the reservoir.

EXAMPLES

FIG. 8A to 8B illustrate results of a first thermal reactive reservoir simulation conducted usine the CMG STARS ™ reservoir simulation software (a software product that is the industry standard for thermal reactive reservoir production process simulation - it solves energy and material balances in the context of phase equilibrium and Darcy flow within porous media) for a cyclical process according to the present invention. In this case, a single vertical well is used for both injection and production within the reservoir. In this example, the operation is done cyclical [y where oxygen is injected for a period of time after which it is shut in and then it is opened for production for a period after which it is shut in. This cycle of injection and production is repeated until the overall process is no longer productive at predetermined levels. The reservoir properties used in this three-dimensional reservoir simulation model has properties typical of that of an oil sands reservoir (porosity 0.3, horizontal permeability 2200 mD, vertical permeability 1100 mD, thickness 37 m, oil saturation 0.7, initial pressure 2800 kPa, initial température 13 degrees C, initial solution gas gas-to-oil ratio 10 m³/m³). In the model the reaction scheme illustrated in FIG. 7 is used. FIG. 8A shows that on injection of oxygen in a cyclic manner, hydrogen is generated in the reservoir via the reactions described in FIG. 7. FIG. 8B displays the température distributions in the vertical plane of the injection/production well. The results show that the température reaches as high as 500 degrees C in the reservoir surrounding the vertical well after the injection of oxygen into the reservoir. As a conséquence of this température rise, the reactions described in FIG. 7 occur with conséquent génération of hydrogen in the reservoir. After the oxygen injection step is complété, the well is converted to production mode and the hydrogen alone is produced from the reservoir. The cycles are continued until the amount of hydrogen produced per cycle is no longer économie.

FIG. 9A to 9D illustrâtes the results of a second simulation using the CMG STARS ™ reservoir simulation software, for an exemplary embodiment of the present invention wherein a lower injection well is placed in the reservoir near the base of the reservoir and an upper production well is placed above the injection well. In this case, the production well is inclined within the reservoir, as can best be seen in FIG. 9A. In this example, the length ofthe injection well is equal to 105 m. The reservoir properties used in this three-dimensional reservoir simulation model has properties typical of that of an oil sands reservoir (porosity 0.3, horizontal permeability 2200 mD, vertical permeability 1100 mD, thickness 37 m, oil saturation 0.7, initial pressure 2800 kPa, initial température 13 degrees C, initial solution gas gas-to-oil ratio 10 m /ni ). In the model the reaction scheme illustrated in FIG. 7 is used.

FIG. 9B illustrâtes operations where three different flow rates of oxygen are injected into the reservoir. in Cases A, B, and C, the oxygen injection rates are 17.5, i .05, and i.75 million scf/day, respectively.

FIG. 9C shows the resulting hydrogen production volumes from the reservoir corresponding to Cases A, B, and C. The cumulative volumes of hydrogen produced after 700 days of operation are 104, 37, and 44 million scf of hydrogen.

FIG. 9D présents an example of the température distributions in the horizontal-vertical plane of the injection and production wells for Case A. The results show that as oxygen is injected into the reservoir, a reactive zone is created within the reservoir. The reactive zone is characterized by the zone with température that is higher than the original reservoir température. The results demonstrate that the température rises above 450 degrees C and at the reaction front, the température reaches as high as 900 degrees C. With températures more than 400 degrees C, gasification reactions occur within the hot zone which generate hydrogen which is exclusively produced by the upper production well to the surface. Within the hot zone around the injection well, heated oil drains and accumulâtes around the injection well thus supplying more fuel for the reactions that occur around the injection well.

The above exampies illustrate exemplary methods of conducting in situ gasification reactions within a réservoir where a membrane is used in the production well to produce hydrogen to the surface.

The hydrogen generated from the methods taught here can be used in fuel cells at surface to generate power, or combusted to produce steam which can be used to generate power or for other in situ oit recovery processes, or sold as industrial feedstock.

As will be clear from the above, those skilled in the art would be readily able to détermine obvious variants capable of providing the described functionality, and ail such variants and functional équivalents are intended to fall within the scope of the present invention.

Unless the context clearly requires otherwise, throughout the description and the claims:

• comprise , “comprising”, and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not lîmited to”.

connected , coupled , or any variant thereof, means any connection or coupling, either direct or indirect, between two or more éléments; the coupling or connection between the éléments can be physical, logical, or a combination thereof.

• “herein”, “above”, “below”, and words of similar import, when used to describe this spécification shall refer to this spécification as a whole and not to any particular portions of this spécification.

or , in reference to a list of two or more items, covers ail of the following interprétations of the word: any of the items in the list, ail of the items in the list, and any combination of the items in the list.

• the singular fomis “a”, “an” and “the” also include the meaning of any appropriate plural fbrms.

Words that indicate directions such as “vertical”, “transverse”, “horizontal”, “upward”, “downward”, “forward”, “backward”, “inward”, “outward”, “vertical”, “transverse”, “left”, “right “front”, “back”, “top”, “bottom”, “below”, “above”, “under”, and the like, used in this description and any accompanying claims (where present) dépend on the spécifie orientation of the apparatus described and illustrated. The subject matter described herein may assume various alternative orientations Accordingly, these directîonal terms are not strictly defined and should not be interpreted narrowly.

Spécifie examples of methods and Systems hâve been described herein for purposes of illustration. These are only examples. The technology provided herein can be applied to contexts other than the exemplary contexts described above. Many alterations, modifications, additions, omissions and permutations are possible within the practice of this invention. This invention includes variations on described embodiments that would be apparent to the skiiled person, including variations obtained by: replacing features, éléments and/or acts with équivalent features, éléments and/or acts; mixing and matching of features, éléments and/or acts from different embodiments, combining features, éléments and/or acts from embodiments as described herein with features, éléments and/or acts of other technology; and/or omitting combining features, éléments and/or acts from described embodiments.

The foregoing is considered as illustrative only of the principles of the invention. The scope of the daims should not be limited by the exemplary embodiments set forth in the foregoing, but should be given the broadest interprétation consistent with the spécification as a whole.

Claims (26)

1. A method for producing hydrogen from a petroleum réservoir, the method comprising:

a. providing a well from surface to the réservoir;

b. locating at least one hydrogen-permeable membrane in the well;

c. heating the réservoir to facilitate at least one of gasification, water-gas shift, and aquathemiolysis reactions to occur between petroleum hydrocarbons and water within the réservoir to generate a gas stream comprising hydrogen; and

d. engaging the gas stream and the at least one hydrogen-permeable membrane, such that the at least one hydrogen-permeable membrane permits passage of only the hydrogen in the gas stream to the surface.

2. The method of claim 1 wherein the step of heating the réservoir comprises injecting an oxidizing agent into the réservoir to oxidize at least some ofthe petroleum hydrocarbons within the réservoir.

3. The method of claim 1 wherein the step of heating the réservoir comprises generating electromagnetic or radio-frequency waves with an electromagnetic or radio-frequency antenna placed within the réservoir

4. The method of claim 1 wherein the step of heating the réservoir comprises injecting a hot material into the réservoir.

5. The method of claim 1 wherein the step of heating the réservoir comprises generating heat by using a resistance-based (ohmic) heating system iocated within the réservoir.

6. The method of claim 1 wherein the at least one hydrogen-permeable membrane comprises at least one of: palladium (Pd), vanadium (V), tantalum (Ta) or niobium (Nb).

7. The method of any of daims 1 to 6 wherein the at least one hydrogen-permeable membrane comprises a palladiiim-copper alloy.

8. The method of any of daims l to 7 wherein the at least one hydrogen-permeable membrane comprises a ceramic layer.

9. The method of daim 7 wherein the at least one hydrogen-permeable membrane comprises a ceramic layer on the inside or the outside of the palladium-copper alloy.

10. The method of any of daims 1 to 5 wherein the at least one hydrogen-permeable membrane comprises a ceramic layer and a non-ceramic layer selected from the group consisting of palladium, vanadium, tantalum, niobium, copper, alloys of these materials, and combinations thereof.

11. The method of daim 10 wherein the non-ceramic layer comprises a palladium-copper alloy.

12. The method of any of daims 1 to 5 wherein the at least one hydrogen-permeable membrane is located in the well within the reservoir.

13. The method of any of daims 1 to 5 wherein the at least one hydrogen-permeable membrane is positioned in the well proximale to the reservoir.

14. The method of any of daims 1 to 5 wherein a porous material is located in the well to support the at least one hydrogen-permeable membrane within the well.

15. The method of daim 14 wherein the porous material is porous Steel.

16. The method of any of daims 1 to 5, comprising the further step, after the step of heating the reservoir, of delaying engaging the gas stream and the at least one hydrogen-permeable membrane to allow for further génération of the hydrogen.

17. The method of daim 16 wherein the step of delaying comprises delaying for a period in the range of l week to 12 months.

18. The method of claim 17 wherein the delaying is for a period in the range of l week to 4 weeks.

19. The method of claim 3 wherein dielectric heating is used for the step of heating the réservoir, where electromagnetic radiation has a frequency in the range of about 60 Hz to 1000 GHz.

20. The method of claim 19 wherein the electromagnetic radiation has a frequency in the range of 10 MHz to 10 GHz.

21. The method of claim 5 wherein the resistance-based (ohmic) heating system is used to heat the reservoir to températures in the range of 200 to 800 degrees C,

22. The method of claim 21 wherein the température is in the range of 400 to 700 degrees C.

23. A system for recovering hydrogen from a petroleum subsurface reservoir, the system comprising:

an apparatus for heating the reservoir to generate a gas stream comprising hydrogen;

a well located in the reservoir; and a hydrogen-penneable membrane in the well adapted to permit passage therethrough of hydrogen in the gas stream but disallow passage therethrough of other gases in the gas stream, to allow production of the hydrogen through the well to surface.

24. The system of claim 23 wherein the apparatus for heating the reservoir comprises at least one of an oxidizing-agent injecter, an electromagnet, a radio-frequency antenna, and a hot material injector.

25. The system of claim 23 wherein the produced hydrogen is consumed in a fuel electrochemical cell device or combusted to generate steam for power génération or stearn for oil recovery.

26. The system of claims 23 wherein the carbon oxides produced from the process remain in the reservoir and are sequestered there yielding a zéro carbon energy production process.