WO2015180992A1

WO2015180992A1 - Method for the thermal treatment of an underground oil reservoir

Info

Publication number: WO2015180992A1
Application number: PCT/EP2015/060916
Authority: WO
Inventors: Vladimir Stehle
Original assignee: Wintershall Holding GmbH
Priority date: 2014-05-26
Filing date: 2015-05-18
Publication date: 2015-12-03

Abstract

The invention relates to a method for the thermal treatment of an underground oil reservoir, comprising the steps of a) drilling a well (B) into the underground oil reservoir, b) injecting a flowable composition (FZ), which contains a molded catalyst (FK), through the well (B) into the underground oil reservoir, c) injecting a combustible mixture (BM) through the well (B) into the underground oil reservoir, d) bringing the combustible mixture (BM) in contact with the molded catalyst (FK) in the underground oil reservoir, wherein the molded catalyst (FK) catalyzes an exothermic reaction of the combustible mixture (BM).

Description

The present invention relates to a process for the thermal treatment of an underground oil reservoir and to a process for the production of oil from a subterranean oil reservoir. Moreover, the present invention relates to a catalytic heat generator. In natural petroleum reservoirs, petroleum is generally present in the voids of porous reservoirs which are closed to the surface by impermeable facings. In addition to crude oil and natural gas, underground oil reservoirs generally contain more or less saline water. This water is also called deposit water or formation water. In the cavities in which the petroleum is present, it may be very fine cavities, capillaries, pores or the like. The cavities may, for example, have a diameter of only 1 μm.

In order to extract crude oil and / or natural gas from underground oil reservoirs, at least one well is usually first drilled (drilled) into the underground oil reservoir. After sinking the well into the subterranean oil reservoir, oil generally initially flows to the surface through the borehole due to the natural intrinsic pressure of the subsurface oil reservoir. The intrinsic pressure of the underground oil reservoir can be caused, for example, by gases present in the reservoir, such as methane, ethane or propane. This phase of oil production is also referred to as primary oil production.

In addition to primary oil production methods for secondary and tertiary mineral oil production are known. In secondary and tertiary oil production, additional drilling is being drilled (sunk) into the underground oil reservoir. A distinction is generally made between so-called production wells and so-called injection wells. The production wells are used to extract oil from the underground oil reservoir to the surface. Through the injection well, a flood agent is injected into the underground oil reservoir to maintain or increase the pressure of the underground oil reservoir. The injected flooding agent forces petroleum through the cavities of the underground oil reservoir from the injection well toward the production wells. In the secondary and tertiary processes for the production of crude oil, flooding agents include, for example, water, water vapor and water, to which additives are added. used. In addition, gases such as carbon dioxide or nitrogen are also used as flooding agents.

In order to increase the flow of oil from the underground oil reservoir, at least part of the underground oil reservoir is generally hydraulically fractured. For this purpose, suitable tail liquors (FF) are pressed under high pressure into the underground oil reservoir. The pressure is usually in the range of 500 to 1000 MPa. As a result, parts of the underground oil reservoir (the underground rock formation) are broken hydraulically. This process is also referred to as hydraulic fracturing. "Hydraulic fracturing" is the occurrence of a fracture event in the surrounding rock of a well in a subterranean oil reservoir as a result of the hydraulic action of a liquid or gas pressure on the rock of the underground oil reservoir.

The fracking liquid (FF) described in the prior art are liquids which contain water, gel formers and optionally proppants (S) such as sand. The fraying increases the permeability of the underground oil reservoir. This increases the delivery rate of petroleum trapped in cavities. The fracture of the underground oil reservoir will facilitate the flow of oil to the production wells. The proppants (S) contained in the fraying fluid (FF) serve to stabilize the fracture tears formed during fraying, so that these cracks remain open after the completion of the fraying.

Another known method for increasing the production rates of oil from an underground oil reservoir is the thermal treatment of the underground oil reservoir. Thermal treatment processes are particularly used in underground oil reservoirs containing high viscosity petroleum. In addition, thermal treatment of oil shale deposits is used.

For this purpose, a fuel and an oxidant are generally injected into the underground oil reservoir. The fuel and the oxidizer react exothermally in the subterranean oil reservoir with evolution of heat. The heat development modifies the rheological properties of the petroleum contained in the subterranean oil reservoir, thereby increasing the production rate. Depending on the intensity of the exothermic reaction, it is also possible to effect a pyrolysis of the petroleum or the matrix of the underground Erdöllagerstätte. Pyrolysis occurs preferentially in the thermal treatment of oil shale deposits. The prior art describes various methods for this purpose. These generally inject the fuel and oxidizer and then an initiator solution which initiates the exothermic reaction of the fuel and oxidant into the underground oil reservoir. This often leads to large losses of the injected fuel and the oxidant, since they do not completely abreact but remain in partially unreacted state in the underground Erdöllagerstätte.

Therefore, processes have been developed in which the thermal treatment of the underground oil reservoirs is carried out by combusting combustible mixtures catalyzed by a solid catalyst, the so-called shaped catalyst, in the well, the hot products of the burning then being injected into the underground oil reservoir. RU 2 447 276 describes a process for the thermal treatment of an underground oil reservoir with a vapor-gas mixture, which results from the burning of a liquid or gaseous combustible mixture. For this purpose, a tubular reactor containing a shaped catalyst is introduced into a bore. The molded article catalysts typically have dimensions of 1 to 6 mm and contain ceramic materials such as alumina, zeolite or silica as support materials.

As a catalytically active component, the shaped-body catalysts contain platinum or palladium. The liquid or gaseous combustible mixture is injected through a separate tubing string into the tubular reactor where the shaped catalyst catalyst initiates and catalyzes the combustion of the combustible mixture.

The steam-gas mixture produced in the tubular reactor used for the thermal treatment is continuously removed therefrom.

A disadvantage of the method described in RU 2 447 276, in which the thermal treatment of the underground oil reservoir is carried out by the burning of a combustible mixture in the well and the subsequent pressing of the hot combustion products into the underground oil reservoir, is the high thermal load of the well. This leads to the loss of the strength of the casing and the fracturing of the cementing of the bore. In addition, not all the heat developed can be used to treat the underground oil reservoir, as part of it also heats the well. The use of the additional reactor which is introduced into the bore is also associated with high costs. Furthermore, the method described in RU 2 447 276 is not suitable for deflected bores because the tubular reactor can not be inserted into the horizontal portion of a deflected bore. The present invention is therefore based on the object to provide a method for the thermal treatment of a subterranean Erdöllagerstätte that does not have the disadvantages of the prior art described above, or only to a reduced extent. It should also be feasible as possible. In the method according to the invention, the bore should be exposed to the lowest possible thermal load and overheating of the bore should be precluded. In addition, it should be possible to dispense with complicated and expensive additional apparatuses such as the reactor described in RU 2 447 276. In addition, the method according to the invention should be feasible with the usual equipment used for crude oil production and well researched.

In addition, the method for the thermal treatment of an underground Erdöllagerstätte should also be used in combination with a Frackverfahren. In addition, the flowable composition (FZ) should be able to be safely introduced into tailing cracks in the underground oil reservoir and possibly also take over the function of a proppant (S).

This object is achieved by a method for the thermal treatment of an underground oil reservoir, comprising the steps of a) bringing down a bore (B) in the underground Erdöllagerstätte, b) injecting a flowable composition (FZ) containing a molded article catalyst (FK) through which Bore (B) into the underground

(C) injecting a combustible mixture (BM) through the well (B) into the underground well deposit; d) contacting the combustible mixture (BM) with the shaped catalyst (FK) in the underground well deposit, wherein the shaped catalyst (FK) catalyzes an exothermic reaction of the combustible mixture (BM), the subterranean crude oil deposit after process step b) and before process step c) with a Frackflüssigkeit (FF), optionally containing a proppant (S) is treated, wherein the Frackflüssigkeit (FF) with a pressure greater than the minimum local rock stress injected into the underground oil reservoir to form fracture cracks in the underground oil reservoir.

The subject of the present invention is also a process for the thermal treatment of an underground oil reservoir, comprising the steps Sinking a hole (B) in the underground oil reservoir,

Injecting a flowable composition (FZ) containing a shaped catalyst (FK) through the well (B) into the underground well deposit; (c) injecting a combustible mixture (BM) through the well (B) into the underground well deposit; Contacting the Combustible Mixture (BM) with the Shaped Catalyst (FK) in the underground well deposit, wherein the Shaped Catalyst (FK) catalyzes an exothermic reaction of the combustible mixture (BM).

With the method according to the invention for thermal treatment of an underground oil reservoir, it is possible to form cavities in the underground oil reservoir and by the heat and gas evolution occurring in the thermal treatment in conjunction with the resulting pressure, it can in the underground Erdöllagerstätte to form further cracks come. In addition, for example, deposits can be removed from the underground oil reservoir. The deposits may be, for example, high-viscosity substances such as paraffins, high-viscosity petroleum oils or bitumen (asphaltenes).

The process according to the invention is particularly suitable for the thermal treatment of fissures and fractures in subterranean formations formed by hydraulic fracturing and in which, in the further course of mineral oil production, a decrease in permeability has been registered by the deposition of the abovementioned highly viscous substances. With the aid of the method according to the invention, the above-described high-viscosity substances from the gaps, fractures and the deposit itself can be effectively removed. In addition, it is possible to produce new fractures and gaps with the method according to the invention. With the aid of the method according to the invention is thus an effective increase in the permeability of possibly in the bore (B) existing perforation (6) and an effective improvement of the communication between productive layer and bore (B) possible.

The inventive method for thermal treatment of an underground oil reservoir, it is also possible to modify the rheological properties of the present in the underground oil reservoir deposits and petroleum. By warming the deposits and the oil liquid, the viscosity decreases. In addition, it is possible to produce temperatures at which the oil and the deposits can be thermally split (cracking). This also reduces the viscosity of the petroleum and the deposits.

In addition, the process according to the invention ensures contact between the shaped catalyst (FK) and the combustible mixture (BM) in the underground oil reservoir. The substances used in the process of the invention, the combustible mixture (BM), the flowable composition (FZ), optionally the exothermic mixture (EM) and optionally the second flowable composition (FZ2) are also good and safe to handle.

In addition, compared with the methods described in the prior art for the thermal treatment of an underground oil reservoir, higher temperatures in the underground oil reservoir are achieved with the method according to the invention. In addition, soot formation can be avoided, thereby avoiding deterioration of the permeability of the underground Erdöllagerstätte soot. In addition, due to the high temperatures that are achieved with the method according to the invention, micro and macro-fractures can be generated.

A further advantage of the process according to the invention is that the shaped-body catalyst (FK) contained in the flowable composition (FZ) can be introduced into any fracture cracks which may be present and is also trapped therein and thus simultaneously acts as a proppant (S). When the molded article catalyst (FK) is trapped in the fracture cracks, it is not washed away by the combustible mixture (BM). Therefore, the heated by the inventive method area of the underground oil reservoir is precisely predictable. Moreover, with the method according to the invention, the heat generated can penetrate deeper into the subterranean crude oil deposit, whereby a larger area in the underground oil reservoir is thermally treated.

Underground oil deposit

The method according to the invention for the thermal treatment of an underground oil reservoir can in principle be used in all underground oil reservoirs containing crude oil. However, the process according to the invention is preferably used in unconventional underground oil reservoirs. According to the invention, unconventional subterranean oil reservoirs are deposits which have a dense deposit matrix and / or contain crude oil with a high viscosity. Unconventional underground oil deposits are, for example, shale oil deposits, bitumen deposits, heavy oil deposits or oil shale deposits. The unconventional underground oil reservoirs generally have a permeability of less than 10 mD. The viscosity of the petroleum is generally in the range of 10 to 10,000 mPas. The viscosity of the bitumen can be well over 10,000 mPas. In unconventional shale-oil deposits, oil production is only possible after massive thermal treatment of the reservoir rock (pyrolysis).

The underground oil reservoir can have cracks, crevices and clefts. In the context of the present invention, cracks, crevices and fractures are summarized under the generic term "cracks." In the context of the present invention, the term "cracks" therefore also includes cracks and clefts, as well as tail cracks.

The cracks may be of natural origin or may have been generated by treatment of the underground oil reservoir, for example by a fracking process.

Process Step a) In process step a), a well (B) is drilled into the underground oil reservoir. Preferably, the bore (B) is drilled in the petroleum bearing layer. Techniques for drilling down wells into underground oil reservoirs are known to those skilled in the art and are described, for example, in EP 0 952 300. The hole (B) is generally stabilized and sealed. This can be done for example by cementing the borehole wall of the bore (B) or by introducing a casing into the bore (B).

In process step a) exactly one hole (B) can be drilled into the underground oil reservoir. In addition, it is also possible to bring down in process step a) two or more holes (B) in the underground Erdöllagerstätte. The term "a bore (B)" includes both exactly one bore (B) and two or more holes (B).

The bore (B) can be configured as a vertical, horizontal or deflected bore. Preferably, a deflected bore is drilled as the bore (B).

The term "vertical" is generally understood to mean an axis (perpendicular direction) which is directed at the center of the earth or at right angles to the surface of the earth. According to the invention, "vertical" also means a section of a bore (B) which is less than +/- 30 ° C, preferably less than +/- 20 ° C and in particular less than +/- 10 ° C deviates from the Lotrichtung. "Horizontal" is generally understood to mean a plane (horizontal plane) which is aligned parallel to the earth's surface or at right angles to the vertical direction.According to the invention, "horizontal" also means a section of a bore (B) which is less than +/- 30 ° C, preferably less than +/- 20 ° C and more preferably less than +/- 10 ° C deviates from the horizontal plane.

In the case of a deflected bore (B), the bore (B) has a vertical portion and a horizontal portion (11), these portions being interconnected by a bent portion. For the vertical portion and the horizontal portion (1 1) of the hole (B), the above definitions apply mutatis mutandis to horizontal and vertical.

Preferably, the bore (B) is a deflected bore. The horizontal section (1 1) of the bore (B) is preferably downed in a petroleum-bearing layer of the underground Erdöllagerstätte.

The subject of the present invention is therefore also a method in which the bore (B) is a deflected bore comprising a vertical portion and a horizontal portion (11), the horizontal portion (11) in the petroleum-carrying layer and is arranged parallel to this.

In order to ensure the hydrodynamic connection between the bore (B) and the oil-carrying layer, in a preferred embodiment a part of the bore (B) is perforated in method step a), whereby perforation openings (6) are produced.

"Hydrodynamic compound" is understood according to the invention to mean that liquids can be introduced (exchanged) via this compound, in particular the flowable composition (FZ) and the combustible mixture (BM).

In a preferred embodiment, a portion of the bore (B) is thus perforated in step a) after drilling down the well bore (B) into the subterranean crude oil deposit, preferably into the petroleum-carrying layer of the underground oil reservoir, to obtain perforation openings (6).

The subject matter of the present invention is thus also a method in which, in method step a), a section of the bore (B) is perforated to obtain perforation openings (6).

The perforation openings (6) are preferably arranged in the petroleum-carrying layer. The length of the portion of the perforation openings (6) can in wide Ranges vary. In the case of a vertical hole (B), the length of the portion of the perforation holes (6) is generally in the range of 1 m to 100 m. The length of the section of the perforation openings (6) normally corresponds to the thickness of the petroleum-carrying layer. In the event that the perforation openings (6) in the horizontal region (1 1) of the bore (B) are arranged, the length of the portion of the perforation openings (6) is not limited by the thickness of the petroleum-bearing layer. In this embodiment, the length of the portion of the perforation openings (6) may also be in the range of 1 to 100 m. In addition, the length can also be significantly above 100 m, for example in the range of> 100 to 1000 m.

The perforation to form the perforation openings (6) can be carried out by methods known per se. The ball perforation is preferably used here, as described for example in RU 2 358 100. In case the well (B) is stabilized with a well casing, the well casing is also perforated.

The perforation openings (6) are preferably arranged in a petroleum-carrying layer. In the event that the subterranean oil deposit has multiple oil-bearing layers separated by non-oil bearing layers, in the case of a vertical well (B), the perforations (6) preferably extend through all the oil-bearing layers and through all non-oil-bearing layers. In the event that the bore (B) is designed as a deflected bore, the perforation openings (6) are preferably arranged in the horizontal portion (1 1) of the bore (B).

Moreover, it is possible to treat the surrounding area of the perforation openings (6) by a fracking process in order to further improve the hydrodynamic connection between the bore (B) and the petroleum-bearing layer.

This creates cracks in the underground oil reservoir. The cracks produced by a fraying process are also referred to as fracking cracks. Suitable tailing methods are known in principle to the person skilled in the art. In conventional tailing processes for forming tailing cracks in the subterranean petroleum deposit, usually a tailing liquid (FF), which may contain a proppant (S), is injected at high pressure (generally 500 to 1000 MPa) into the subterranean crude oil deposit. As a result, fracture cracks are formed in the underground oil reservoir. The fracturing fluid (FF) is injected into the well (B) at a pressure greater than the minimum local rock stress of the subsurface oil reservoir to create the fracture cracks. The minimum in-situ rock stress of the subterranean formation is also referred to as the minimum principal stress. This is understood to mean the pressure that is necessary to form tailings cracks in the underground oil reservoir. The pressure required depends on the geological and geomechanical conditions of the underground oil reservoir. These conditions include, for example, rock pressure / depth, reservoir pressure, stratification, and rock strength of the underground oil reservoir.

In practice, the pressure during the fracking process is increased until the formation of fracking cracks occurs. The pressures which are necessary for this purpose are usually in the range from 100 to 10000 bar or 100 to 1000 bar, preferably in the range from 400 to 1000 bar, more preferably in the range from 600 to 1000 bar and particularly preferably in the range from 700 to 1000 bar. At the same time, the pumping rates can rise to 1000 square meters per minute. As fracking liquid (FF), water is frequently used, to which other additives such as thickening agents are optionally added. Suitable additives are known to the person skilled in the art, for example the additives which are described below for the carrier liquid (T) are suitable, so that the statements there and preferences apply accordingly.

The process, which uses water as the tailing liquid (FF), is also referred to as "hydraulic fracturing." In this process, the fracture cracks and matrix deposits formed are contaminated with water, which can swell clay and clay particles in the underground oil reservoir This is particularly the case when the deposit matrix, that is the surrounding rock, consists of clayey rocks.

Particularly in the development of unconventional underground oil reservoirs, this effect is very disadvantageous, since the unconventional underground oil reservoirs, as described above, in any case have a low permeability and / or contain petroleum with a high viscosity.

Suitable fracking liquids (FF) and fracking processes are described, for example, in WO 2008/106695 and US Pat. No. 7,213,651. The spatial extent of the fracture cracks depends heavily on the geological conditions of the underground oil reservoir. In addition, the spatial extent of the fracture tears depends on the applied pressure and the duration of the fracking process. The fracture cracks generally have a radial extent (length) in the range of 10 to 200 m, preferably in the range of 15 to 150 m, and more preferably in the range of 20 to 70 m, each measured from the center of the bore (B) in the Perforation openings (6).

To carry out the fracking process, an injection strand is introduced into the bore (B). The area of the bore (B) above the perforation openings (6) is closed with a packer. Subsequently, a fraying liquid (FF) is injected at a pressure in the range of 100 to 10,000 bar through the injection line into the underground oil reservoir. Under the influence of the pressure of the tailing fluid (FF), fracture cracks develop in the underground oil reservoir.

In the fracking liquid (FF), a proppant (S) may be included. In addition, it is possible to use a Frackflüssigkeit (FF), which contains no proppant (S).

The proppant (S) is also called proppant. The terms "proppants (S)" and "proppant" are used synonymously in the context of the present invention. Suitable proppants (S) are known to the person skilled in the art. Suitable proppants (S) are, for example, particulate ceramic materials, such as sand, bauxite or glass beads. The particle size of the proppant (S) depends on the geometry of the fracture cracks that are to be supported. Suitable particle sizes are generally in the range of 0.15 mm to 3.0 mm.

For each subsurface formation (underground deposit) the particle size and other parameters of the proppant (S) are optimized.

The permeability / permeability of the tailings fractions filled with proppant should be greater by 10 ³ to 10 ⁸ than the permeability of the deposit, this ensures optimum conditions for oil production.

The support means (S) serves to keep the fracture cracks formed during hydraulic fraying open. That the proppant (S) prevents the fracking cracks from closing again when the fracking process is completed and the hydraulic pressure built up by the fraying fluid (FF) decreases again.

For this purpose, the proppant (S) must be introduced into the fracture cracks formed. The proppant (S) is therefore generally suspended in the fracking fluid (FF).

The fracking liquid (FF) serves as a carrier or transport to transport the proppant (S) in the tailoring cracks. The proppant (S) is generally contained in amounts of from 1 to 65% by weight, preferably in amounts of from 10 to 40% by weight and more preferably in amounts of from 25 to 35% by weight, in the fracturing fluid (FF) , based on the total weight of the fraying liquid (FF) and the proppant (S). The amount of proppant used (S) depends on the properties of the underground oil reservoir.

Preferred proppants (S) have a density in the range of 1.5 to 2.5 g / cm ³ . The density of the proppant (S) is preferably in the range of the density of the fracking liquid (FF), thereby preventing the sedimentation of the proppant (S). Suitable proppants (S) are described for example in US 201 1/077176. In the event that proppants (S) are used with a density greater than 2.5 g / cm ³ , optionally, the density of the fracturing fluid (FF) by the addition of thermally stable powders, such as quartz sand, can be increased. Due to the amount of thermally stable powder used, the viscosity of the fracking liquid (FF) can be varied within wide limits.

In the event that the fracking liquid (FF) contains no proppant (S), the fracking liquid (FF) is partially pressed out of the fracking cracks after generation of the fracking cracks after pressure decrease. In this embodiment, the generated tailing cracks partially close again after pressure decrease. However, this is not disadvantageous because the partially closed tailings cracks are reopened by injecting the flowable composition (FZ). The pressure that must be used for this is significantly lower than the pressure that had to be used to generate the fracture cracks.

In the case that the fraying liquid (FF) contains a proppant (S) dispersed therein, the proppant (S) stabilizes the generated fracture cracks so that the fracture cracks remain open even after the pressure has been decreased.

As stated above, after the fracking process has been carried out, the fracking cracks are generally heavily contaminated with the water contained in the fraying liquor (FF). Before injecting the flowable composition (FZ) and / or the combustible mixture (BM), the fraying liquid (FF) may be removed from the fracture tears. This process is also referred to as remediation. Suitable methods for remedying the fracture cracks are known to the person skilled in the art.

One common method for remediating the fracture cracks of a subsurface oil reservoir involves simple "draining" or back pumping of the tailing fluid (FF). However, a remediation of the fracture cracks before carrying out the method according to the invention is not absolutely necessary. In one embodiment, the method according to the invention is thus carried out without a prior refurbishment of the fracture cracks.

Process step b)

In process step b), a flowable composition (FZ) is injected through the bore (B) into the underground oil reservoir. "Flowable" in this context means that the flowable composition (FZ) can be pumped by conventional pumps.

In the context of the present invention, "a flowable composition (FZ)" is understood to mean both precisely a flowable composition (FZ) and two or more flowable compositions (FZ).

According to the invention, the flowable composition (FZ) contains a shaped-body catalyst (FK) and a carrier liquid (T).

In the context of the present invention, "a shaped-body catalyst (FK)" means both exactly one shaped-body catalyst (FK) and two or more shaped-body catalysts (FK). The same applies to "a carrier liquid (T)". "A carrier liquid (T)" means exactly one carrier liquid (T) as well as mixtures of two or more carrier liquids (T).

The flowable composition (FZ) generally contains 5 to 70% by weight of the shaped-body catalyst (FK) and 30 to 95% by weight of the carrier liquid (T), in each case based on the total weight of the flowable composition (FZ), the sum of the Weight information gives 100%.

Suitable carrier liquids (T) are known to those skilled in the art. According to the invention, the carrier liquid (T) used is preferably water or a mixture of water and other solvents, for example glycerol. The carrier liquid (T) may moreover contain further additives in dissolved form.

Additives which may optionally be present in dissolved form in the carrier liquid (T) are, for example, thickeners, surfactants, urea, oxidants, acids and alkalis.

Suitable thickeners are, for example, synthetic polymers, such as polyacrylamide or copolymers of acrylamide and other monomers, especially monomers containing sulfonic acid groups, and also polymers of natural origin such as glucosylglucans, xanthan, diuthane or glucan. Preferred thickener is glucan. Through the use of thickening agents, the viscosity of the flowable composition (FZ) can be increased in order to prevent sedimentation of the shaped-body catalyst (FK) and of an optionally present proppant (S). The content of thickener in the carrier liquid (T) may generally be in the range of 0.01 to 5 wt .-%, based on the total weight of the carrier liquid (T).

The viscosity of the flowable composition (FZ) is generally in the range from 100 to 1500 mPas, preferably in the range from 200 to 1000 mPas and particularly preferably in the range from 300 to 800 mPas. Of course, the flowable composition (FZ) may also have higher or lower viscosities.

As surfactants anionic, cationic and nonionic surfactants can be used.

Common nonionic surfactants are, for example, ethoxylated mono-, di- and trialkylphenols, ethoxylated fatty alcohols and polyalkylene oxides. In addition to the unmixed polyalkylene oxides, preferably C ₂ -C ₄ -alkylene oxides and phenyl-substituted C ₂ -C ₄ -alkylene oxides, in particular polyethylene oxides, polypropylene oxides and poly (phenylethylene oxides), especially block copolymers, in particular polypropylene oxide and polyethylene oxide blocks or poly (phenylethylene oxide) and Polyethylene oxide blocks having polymers, and also random copolymers of these alkylene oxides suitable. Such Alkylenoxidblockcopolymerisate are known and commercially z. B. under the name Tetronic ^® and Pluronic ^® (BASF) available.

Typical anionic surfactants are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ -C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (alkyl radical: C ₁₂ -C ₁₈ ) and ethoxylated alkylphenols (alkyl radicals: C ₄ -C ₁₂ ) and of alkylsulfonic acids ( Alkyl radical: Ci ₂ -Ci ₈ ).

Suitable cationic surfactants are, for example, C ₆ -C ₁₈ -alkyl, alkylaryl or heterocyclic radicals, primary, secondary, tertiary or quaternary ammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, propylium salts, sulfonium salts and phosphonium salts. Examples of its dodecylammonium acetate or the corresponding sulfate, disulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinsäure- esters, N-Cetylpyridiniumsulfat and N-Laurylpyridiniumsalze, cetyltrimethylammonium bromide and sodium lauryl sulfate called. The content of surfactant in the carrier liquid (T) may generally be in the range of 0.01 to 5 wt .-%, based on the total weight of the carrier liquid (T). The flowable composition (FZ) contains a shaped catalyst (FK) and a carrier liquid (T). As the carrier liquid (T), it is also possible, for example, to use a composition as described above for the fracking liquid (FF).

With regard to the carrier liquid (T), therefore, the above-described embodiments and descriptions for the fracking liquid (FF) apply accordingly. The flowable composition (FZ) may contain as the carrier liquid (T) in one embodiment of the invention, the fracking liquid (FF). With regard to the fracking liquid (FF), the previously described embodiments and preferences apply. The present invention thus also relates to a process in which the flowable composition (FZ) contains a carrier liquid (T), the carrier liquid (T) being the fracking liquid (FF).

Shaped catalysts (FK) are known in the art as such, they usually contain an active metal (A) and a ceramic support (KT).

The molded body catalyst (FK) contained in the flowable composition (FZ) contains, in one embodiment according to the invention, a ceramic support (KT) and an active metal (A).

The term "a ceramic support (KT)" according to the invention means both exactly one ceramic support (KT) and mixtures of two or more ceramic supports (KT) .Also, "active metal (A)" means both exactly one active metal (A) as well as mixtures of two or more active metals (A) understood.

The present invention thus also relates to a process in which the shaped-body catalyst (FK) contains a ceramic support (KT) and an active metal (A). In one embodiment, the molded article catalyst (FK) contains from 0.1 to 20% by weight of the active metal (A), preferably from 0.2 to 15% by weight and more preferably from 0.5 to 10% by weight of the Active metal (A), in each case based on the total weight of the shaped body catalyst (FK). As a ceramic carrier (KT), in principle, all known to the expert ceramic carrier (KT) are suitable. Preferably, a ceramic carrier (KT) having a large inner surface and a high porosity is used. Preferably, the should ceramic supports (KT) also have high heat resistance and high strength, even at high pressures. Under high pressures are particularly to be understood pressures up to 70 MPa. In a preferred embodiment, the ceramic support (KT) contains at least one compound selected from the group consisting of aluminum oxide, aluminum silicate, zirconium dioxide and silicon dioxide. As aluminum silicate zeolites are preferred. In a particularly preferred embodiment, the ceramic support (KT) contains alumina, particularly preferably contains the ceramic support (KT) as alumina a-alumina.

The present invention thus also provides a process in which the shaped-body catalyst (FK) contains a ceramic support (KT) selected from the group consisting of aluminum oxide, aluminum silicate, zirconium dioxide and silicon dioxide.

The preparation of such ceramic supports (KT) are known in the art. They are described, for example, in US Pat. No. 6,565,825. In general, the ceramic support (KT) has a porosity in the range from 35 to 70% by volume, preferably from 40 to 65% by volume and particularly preferably from 45 to 60% by volume, in each case based on the total volume of the ceramic support ( KT). The specific surface area of the ceramic support (KT) is generally in the range from 4 to 50 m ² / g, preferably in the range from 6 to 45 m ² / g and particularly preferably in the range from 8 to 40 m ² / g.

In a further embodiment of the present invention, the ceramic support (KT) used is the proppant (S). For the proppant (S) apply the previously described designs and preferences.

In the process according to the invention, the ceramic support (KT) can in principle be used in all known forms. For example, the ceramic carrier (KT) may be in the form of rings, balls and / or cylinders. Preferably, the ceramic support (KT) is in the form of spheres.

In general, the ceramic support (KT) has a diameter in the range of 0.1 to 10 mm, preferably in the range of 0.5 to 8 mm and particularly preferably in the range of 1 to 6 mm. The active metal (A) contained in the molded article catalyst (FK) is generally applied to the ceramic support (KT). If the support (S) is used as the ceramic support (KT), the active metal (A) is applied to the support (S).

For applying the active metal (A) on the ceramic support (KT) are all known in the art methods. Preferably, the active metal (A) is wet-chemically or dry-chemically applied by impregnation on the ceramic support (KT). Methods for this are known to the person skilled in the art.

The active metal (A) is applied, for example by impregnation on the ceramic support (KT). For this purpose, for example, the ceramic support (KT) with an aqueous solution of a salt of the active metal (A) are added. In this case, the salt of the active metal (A) is adsorbed on the ceramic support (KT). Subsequently, the ceramic support (KT), which then contains the salt of the active metal (A), dried and then calcined. The salt of the active metal (A) is thereby converted into the elemental metal or the metal oxide.

As active metal (A) are in principle all known in the art active metals (A), which catalyze the exothermic reaction of the combustible mixture (BM). Active metals (A) are therefore metals which are catalytically active towards the combustible mixture (BM).

Preferably, the active metal (A) contains at least one metal selected from groups 5, 8, 9, 10, 11 and 12 of the Periodic Table of the Elements according to IUPAC nomenclature of the groups, more preferably the active metal (A) contains at least one metal, selected from the group consisting of copper, cadmium, iron, gold, silver, nickel, vanadium, palladium and platinum and most preferably contains the active metal (A) palladium and / or platinum.

The active metal (A) can be used in the process according to the invention as an elemental metal, as a metal oxide or as a metal salt. The active metal (A) is preferably used as elemental metal or as metal oxide. The present invention thus also provides a process in which the shaped-body catalyst (FK) contains an active metal (A) selected from groups 5, 8, 9, 10, 11 and 12 of the Periodic Table of the Elements.

In a preferred embodiment, the shaped-body catalyst (FK) contains at least one further metal as doping. "Another metal" means exactly one more metal as well as two or more further metals.The further metal is preferably selected from the group consisting of chromium, manganese, iron, Cobalt, nickel, copper, vanadium, zinc, zirconium and gallium. In particular, the further metal is selected from the group consisting of iron, cobalt, nickel and copper. The further metal can be used in the process according to the invention as an elemental metal, as a metal oxide or as a metal salt. The additional metal is preferably used as elemental metal or as metal oxide. For applying the further metal to the ceramic support (KT), the same methods as described for the active metal (A) are suitable.

According to another embodiment of the present invention, the ceramic support (KT) to which the active metal (A) and optionally the further metal is applied may be mixed with a binder to obtain a catalyst composition. Suitable binders are the customary binders known to the person skilled in the art, such as aluminum oxide and / or Si-containing binders. Particularly preferred are Si-containing binders; In particular, tetraalkoxysilanes, polysiloxanes and colloidal Si0 ₂ sols are suitable.

The binder is then generally in a concentration of 5 to 80 wt .-%, preferably from 10 to 50 wt .-%, particularly preferably from 10 to 30 wt .-% before, based on the total weight of the catalyst composition.

After addition of the binder, a shaping step takes place in this embodiment, in which the catalyst composition is processed into the shaped-body catalyst (FK) in accordance with processes known to those skilled in the art. As a method, for example, spraying a suspension containing the ceramic support (KT) or the catalyst composition, spray drying, tableting, pressing in the wet or dry state and extruding be mentioned. Two or more of these methods can also be combined. Auxiliaries such as pore formers and pasting agents or else other additives known to the person skilled in the art can be used for shaping.

Pore formers and / or pasting agents are preferably removed after deformation by at least one suitable drying and / or calcining step from the resulting molded article catalyst (FK).

The geometry of the shaped-body catalysts (FK) produced in this way can be, for example, spherical (hollow or full), cylindrical (hollow or full), ring-shaped, saddle-shaped, star-shaped, honeycomb-shaped or tablet-shaped. Furthermore, extrudates are for example in strand, Trilob, Quatrolob, star or hollow cylindrical shape in question. Furthermore, the catalyst mass to be molded can be extruded, calcined and the extrudates thus obtained broken and processed into a split or powder. The split can be in different sieve fractions are separated. According to a preferred embodiment of the invention, the shaped-body catalyst (FK) is used in spray-dried form, preferably spray powder. These are preferably balls. The molded article catalyst (FK) preferably has a size of 0.1 to 10 mm.

In one embodiment of the invention, the underground oil reservoir is subjected to a fracking process during process step b), that is, the underground oil reservoir is being cracked. The flowable composition (FZ) in process step b) is injected into the subterranean crude oil deposit at a pressure greater than the minimum local rock stress to form fracture cracks in the underground oil reservoir.

The subject matter of the present invention is therefore also a process in which the flowable composition (FZ) is injected into the subterranean crude oil deposit in step b) at a pressure greater than the minimum local rock load, to form fracture cracks in the underground oil reservoir ,

In an embodiment in which the subterranean crude oil deposit is scrubbed in process step b), the flowable composition (FZ) as the carrier liquid (T) contains the fracking liquid (FF). The flowable composition (FZ) then generally contains from 30 to 70 wt .-% of Frackflüssigkeit (FF), preferably from 30 to 50 wt .-% of Frackflüssigkeit (FF) and particularly preferably from 30 to 40 wt .-% of Tie liquid (FF), based on the total weight of the flowable composition (FZ). Particularly preferably, in this embodiment, the carrier liquid (T) consists of fracking liquid (FF).

In a further embodiment in which the subterranean crude oil deposit is scrubbed in process step b), the flowable composition (FZ) contains the fracking liquid (FF) and the shaped catalyst (FK) and does not contain proppant (S). In this embodiment, therefore, the shaped body catalyst (FK) serves as a proppant. In other words, in this embodiment, the flowable composition (FZ) contains no proppant (S) other than the molded article catalyst (FK). As a proppant so only the shaped body catalyst (FK) is used.

In this embodiment, the flowable composition (FZ) generally contains from 30 to 70% by weight of the molded article catalyst (FK), preferably from 50 to 70% by weight of the molded article catalyst (FK), and more preferably from 60 to 70% by weight. % of the shaped-body catalyst (FK), in each case based on the total weight of the flowable composition (FZ). In a preferred embodiment in which the subterranean crude oil deposit is scrubbed in process step b), the flowable composition (FZ), the molded article catalyst (FK) and the proppant (S). For the shaped-body catalyst (FK) and the proppant (S), the above-described embodiments and preferences apply. In this embodiment, both the proppant (S) itself and the molded article catalyst (FK) may function as a proppant.

The subject matter of the present invention is therefore also a process in which the flowable composition (FZ) in process step b) contains the proppant (S) and is injected into the subterranean oil reservoir at a pressure greater than the minimum local rock stress Formation of fracture cracks in the underground oil reservoir.

The subject matter of the present invention is therefore also a process in which the flowable composition (FZ) contains the proppant (S).

When the flowable composition (FZ) contains the molded article catalyst (FK) and the proppant (S), it is particularly preferable that the molded article catalyst (FK) as the ceramic carrier (KT) also contains the proppant (S).

In this embodiment, the flowable composition (FZ) contains the fracking liquid (FF) as the carrier liquid (T). The flowable composition (FZ) also contains the molded article catalyst (FK) and the proppant (S).

The subject matter of the present invention is therefore also a process in which the underground crude oil deposit is scrubbed during process step b) and the flowable composition (FZ) contains the shaped catalyst (FK) and the proppant (S), wherein the shaped catalyst (FK) as a ceramic carrier (KT) also contains the proppant (S).

In this embodiment, the flowable composition (FZ) generally contains from 10 to 50% by weight of the molded article catalyst (FK) and from 10 to 70% by weight of the proppant (S), preferably from 10 to 40% by weight of the Shaped body catalyst (FK) and from 20 to 60 wt .-% of the proppant (S) and particularly preferably from 10 to 30 wt .-% of the shaped body catalyst (FK) and from 30 to 50 wt .-% of the proppant (S), respectively based on the total weight of the flowable composition (FZ).

This embodiment is particularly advantageous since the shaped-body catalyst (FK) of the support means (S) only by the in Formkörperkatalysator (FK) contained active metal (A) differs. The physical properties of the molded article catalyst (FK) and the proppant (S) are therefore very similar. Therefore, they make equal demands on the carrier liquid (T), for example with respect to the necessary viscosity of the carrier liquid (T), in order to avoid settling of the shaped-body catalyst (FK) and of the proppant (S). In addition, the proppant (S) and the shaped catalyst (FK) behave the same way for example when pumping. In addition, compared to the method in which only the molded article catalyst (FK) is used as the proppant (S), the advantage is that it is less expensive since there is generally less molded article catalyst (FK) and thus less of the active metal (A) contained therein. must be used. Moreover, in this embodiment, the molded article catalyst (FK) is particularly evenly distributed in the subterranean crude oil deposit, particularly in the fracture cracks. In a further embodiment according to the invention, the underground oil reservoir between process step a) and process step b) and / or between process step b) and process step c) is treated by a fracking process. With regard to the fracking process, the previously described embodiments and preferences apply.

The subject matter of the present invention is thus also a process in which the underground oil reservoir after process step a) and before process step b) and / or after process step b) and before process step c) is treated with a fracking liquid (FF) which optionally contains a proppant (S). wherein tailing fluid (FF) is injected into the subterranean oil reservoir at a pressure greater than the minimum local rock stress to form fracture tears in the subterranean oil reservoir.

The subject matter of the present invention is also a process in which the subterranean crude oil deposit after process step a) and before process step b) is treated with a fracking fluid (FF) optionally containing a proppant (S), the fracking fluid (FF) being treated with a Pressure greater than the minimum local rock stress injected into the underground oil reservoir to form fracture cracks in the underground oil reservoir.

Of course, it is also possible according to the invention that the underground oil reservoir between process step a) and process step b) and / or between process step b) and process step c) and during process step b) is treated by a fracking process. Likewise, it is possible according to the invention to repeat the fracking process between process step a) and process step b) and / or between process step b) and process step c) and during process step b) several times. In a particularly preferred embodiment, the underground oil reservoir is treated with a fracking process between process step a) and process step b). Subsequently, method step b) is performed. As a result, a quasi-ring-shaped region is formed in the borehole near zone which contains the shaped-body catalyst (FK). According to the invention, the term "well area" is understood to mean the area in the underground oil reservoir at a distance of 0 to 50 m around the bore (B), preferably from 0 to 20 m around the bore (B) and in particular from 1 to 10 m around the bore (FIG. B) understood.

The present invention thus also relates to a process in which the underground oil reservoir between process step a) and process step b) with a Frackflüssigkeit (FF), optionally containing the proppant (S) is treated, wherein the Frackflüssigkeit (FF) with a Pressure greater than the minimum local rock stress injected into the subterranean oil reservoir to form fracture cracks in the subsurface oil reservoir.

Figure 1 shows a vertical section through an underground well deposit treated with a method according to this embodiment. A vertical hole (1; B) has been drilled into the subterranean crude oil deposit. The bore (1; B) is in hydrodynamic connection via perforation openings (6) with fracking cracks (2) in the underground deposit. The tailing cracks (2) were produced by a fracking liquid (FF) tailing process containing the proppant (3; S) before the flowable composition (FZ) was injected. The Frackrisse (2) therefore contain the proppant (3; S). As a result of the subsequent injection of the flowable composition (FZ), a quasi-ring-shaped region containing the shaped-body catalyst (4, FK) has formed in the borehole near zone. When the combustible mixture (BM) injected with process step c) is in contact with the shaped body catalyst (4, FK), the exothermic reaction of the combustible mixture (BM) is catalyzed (process step d)). The reaction products released during the exothermic reaction of the combustible mixture (BM) and heat of reaction (5) are introduced into the subterranean crude oil deposit.

In a further particularly preferred embodiment, the subterranean crude oil deposit is first treated between process step a) and process step b) by a fracking process, then injected according to process step b) the flowable composition (FZ) and finally the underground Erdöllagerstätte between process step b) and process step c) again treated with a fracking process. As a result, the molded body catalyst (FK) contained in the flowable composition (FZ) is displaced deeper into the underground oil reservoir. It forms a quasiringförmiger range containing the shaped body catalyst (FK), with an inner ring radius (R). Of the Inner ring radius (R) corresponds to the distance (R) of the inner ring from the center of the hole (B). The molded article catalyst (FK) is present between the inner ring and the outer ring of the quasi-annular region with the inner ring radius (R) and the outer ring radius (R1). "Quasi-ring-shaped" means that neither the inner ring radius (R) nor the outer ring radius (R1) must be the same size at all points, so the distance (R) of the inner ring can vary.

The inner ring radius (R) is generally in a range of 1 to 10 m, preferably in a range of 5 to 10 m, and more preferably in a range of 7 to 10 m.

The outer ring radius (R1) of the quasi-annular region containing the molded article catalyst (FK) is generally in a range of 2 to 20 m, preferably in a range of 5 to 15 m, and more preferably in a range of 10 to 15 m.

It goes without saying that the outer ring radius (R1) is greater than the inner ring radius (R). Preferably, the quasi-annular region containing the shaped-body catalyst (FK) has a width (BR) in the range of 0.5 to 10 m, preferably in the range of 1 to 8 m and particularly preferably in a range of 2 to 5 m.

The width (BR) of the quasi-ring-shaped region is the difference between the outer ring radius (R1) and the inner ring radius (R). So BR = R1 - R.

The subject matter of the present invention is therefore also a process in which the underground oil reservoir between process step a) and process step b) and between process step b) and process step c) with a Frackflüssigkeit (FF), optionally containing the proppant (S) is treated wherein the fracking fluid (FF) is injected into the subterranean oil reservoir at a pressure greater than the minimum local rock stress to form fracture cracks in the subterranean oil reservoir.

The above-described embodiments and preferences with regard to the fracking process apply. In this embodiment, it is particularly preferred if the fracking liquid (FF) used for the fracking process between process step b) and process step c) contains a proppant (S) which has an increased permeability (conductivity), since then the flow in process step c ) injected combustible mixture (BM) is facilitated. FIG. 2a) shows by way of example a vertical section through an underground oil reservoir which has been subjected to a fracking process between process step a) and process step b) and between process step b) and process step c). A vertical hole (1; B) has been drilled into the subterranean crude oil deposit. The bore (1; B) is in hydrodynamic communication via perforation openings (6) with fracking cracks (2) in the underground deposit. The fracture tears (2) were produced by a fracking liquid (FF) tailing process containing the proppant (3; S) before the flowable composition (FZ) was injected. Following the injection of the flowable composition (FZ) further tailing liquid (FF), which also contains the proppant (3; S), was injected. The Frackrisse (2) therefore contain proppant (3; S). As a result of the subsequent injection of the flowable composition (FZ), a quasi-ring-shaped region containing the shaped-body catalyst (4, FK) has formed in the borehole near zone. This was further introduced into the fracking cracks (2) by further injection of fracking liquid (FF) around the inner ring radius (R). A quasi-ring-shaped region containing the shaped-body catalyst (4, FK) forms with an inner ring radius (R) and an outer ring radius (R1). The inner ring of the quasi-annular region is removed from the bore (1; B) by the inner ring radius (R). When the combustible mixture (BM) injected with process step c) is in contact with the shaped body catalyst (4, FK), the exothermic reaction of the combustible mixture (BM) is catalyzed (process step d)). The reaction products released in the exothermic reaction of the combustible mixture (BM) and heat of reaction (5) are transferred to the underground oil reservoir. It is advantageous in this embodiment that overheating of the bore (B) is precluded, since the combustible mixture (BM) is brought into contact with the shaped body catalyst (FK) only at a distance (R) from the bore (B) in method step d) becomes. In addition, with this embodiment, a large area of the underground oil deposit can be thermally treated.

In a further particularly preferred embodiment of the method according to the invention, first in method step b), the flowable composition (FZ) is injected through the bore (B) into the underground oil reservoir. Subsequently, the underground Erdöllagerstätte between process step b) and process step c) is treated by a fracking process. As a result, fracture cracks are generally generated which are between 5 and 50 m long and have a width in the range of 5 to 50 mm. Since the fracture cracks thus formed are relatively short, this fracking process is also referred to as mini-fracking process and the fracture cracks formed as mini-Frackrisse. For the mini-tailoring process, the same designs and preferences apply as for the tailoring process. In the mini-fracking process, it is particularly preferred that the tailing liquid (FF) used contains a proppant (S) which increases one Having conductivity (conductivity), since then the flow of the injected in step c) combustible mixture (BM) is facilitated.

The subject matter of the present invention is therefore also a process in which the underground oil reservoir between process step b) and process step c) is treated with a fracking liquid (FF) which optionally contains the proppant (S), the fracking liquid (FF) being treated with a Pressure greater than the minimum local rock stress injected into the underground oil reservoir to form fracture cracks in the underground oil reservoir.

Figure 3 shows a vertical section through an underground well deposit treated by this mini-fracking process. A vertical hole (1; B) has been drilled into the subterranean crude oil deposit. The hole (1; B) is in hydrodynamic communication via perforations (6) with mini-fracture cracks (22) in the underground deposit. The Mini-Frackrisse (21) were generated by a mini-Frackverfahren after the flowable composition (FZ) was injected. The fracking liquid (FF) used for the mini-fracking process, which contains the proppant (3; S), further introduces the shaped body catalyst contained in the previously injected flowable composition (FZ) into the subterranean crude oil deposit. This forms a quasi-ring-shaped area with an inner ring radius (R) around the hole (1, B). Upon contact of the combustible mixture (BM) injected with process step c) with the shaped body catalyst (4, FK), the exothermic reaction of the combustible mixture (BM) is catalyzed (process step d)). The reaction products released in the exothermic reaction of the combustible mixture (BM) and heat of reaction (5) are transferred to the underground oil reservoir.

In a further embodiment according to the invention, during process step b) and / or between process step b) and process step c), a second flowable composition (FZ2) is injected through the bore (B) into the underground oil reservoir.

The second flowable composition (FZ2) contains a second carrier liquid (T2) and a second shaped body catalyst (FK2).

According to the invention, "a second carrier liquid (T2)" means exactly one second carrier liquid (T2) as well as a mixture of two or more second carrier liquids (T2). "According to the invention, a second shaped body catalyst (FK) means both exactly one second shaped body catalyst (FK ), as well as a mixture of two or more second molded catalysts (FK). With respect to the second carrier liquid (T2), the same designs and preferences apply as for the carrier liquid (T) contained in the flowable composition (FZ).

The second molded article catalyst (FK2) contains a second ceramic support (KT2) and a second active metal (A2).

"A second ceramic support (KT2)" according to the invention means both exactly a second ceramic support (KT2), as well as a mixture of two or more second ceramic support (KT2).

"A second active metal (A2)" according to the invention means both exactly one second active metal (A2) and a mixture of two or more second active metals (A2).

With respect to the second ceramic carrier (KT2), the same embodiments and preferences as previously described for the ceramic carrier (KT) contained in the molded article catalyst (FK) apply. The second molded article catalyst (FK2) may also contain the additional metal.

In general, the second active metal (A2) is applied to the second ceramic support (KT2). For this purpose, for example, the wet chemical and dry chemical processes for impregnation can be used, as they are known in the art and have previously been described for the application of the active metal (A) on the ceramic support (KT).

The second active metal (A2) preferably contains a metal selected from Groups 6 and 7 of the Periodic Table of the Elements. Preferably, the second active metal (A2) contains a metal selected from the group consisting of manganese and chromium.

The present invention thus also provides a process in which the second shaped-body catalyst (FK2) contains a second active metal (A2) selected from groups 6 and 7 of the Periodic Table of the Elements. The second active metal (A2) can be used in the process according to the invention as an elemental metal, as a metal oxide or as a metal salt. The second active metal (A2) is preferably used as elemental metal or as metal oxide.

Following the injection of the second flowable composition (FZ2) and before process step c), the following steps are generally carried out: b2) injecting an exothermic mixture (EM) through the well (B) into the underground well deposit,

b3) contacting the exothermic mixture (EM) with the second

Shaped Catalyst (FK2) in the underground deposit, the second Shaped Catalyst (FK2) exotherms the exothermic reaction

Catalysed mixture (EM).

By an exothermic mixture (EM) is meant a mixture capable of exothermic reaction. The exothermic reaction of the exothermic mixture (EM) is catalyzed by the second molded article catalyst (FK2) according to the invention.

In one embodiment according to the invention, the second flowable composition (FZ2) is injected together with the flowable composition (FZ) in process step b) through the bore (B). In other words, during step b), the second flowable composition (FZ2) is injected through the well (B) into the subterranean well deposit. In this embodiment, it is particularly preferred that the carrier liquid (T) is used as the second carrier liquid (T2).

The subject matter of the present invention is thus also a method in which, during method step b), a second flowable composition (FZ2) is injected through the bore (B) into the subterranean crude oil deposit. The subject matter of the present invention is thus also a process in which, in process step b), the flowable composition (FZ) and the second flowable composition (FZ2) are injected together through the bore (B) into the subterranean crude oil deposit. It is also possible and preferred according to the invention that the second flowable composition (FZ2) after the flowable composition (FZ) and before the combustible mixture (BM) through the hole (B) is injected into the underground Erdöllagerstätte. In other words, this means that the second flowable composition (FZ2) is injected between process step b) and process step c).

The subject matter of the present invention is therefore also a method in which, between method step b) and method step c), the second flowable composition (FZ2) is injected through the bore (B) into the underground oil reservoir. In general, the following steps are then carried out after method step b) and before method step c): b1) injecting the second flowable composition (FZ2) containing the second molded article catalyst (FK2) through the well (B) into the subterranean crude oil deposit,

b2) injecting an exothermic mixture (EM) through the well (B) into the underground well deposit,

b3) contacting the exothermic mixture (EM) with the second molded article catalyst (FK2) in the underground reservoir, wherein the second molded article catalyst (FK2) catalyzes an exothermic reaction of the exothermic mixture (EM).

The subject matter of the present invention is therefore also a process in which, after process step b) and before process step c), the following steps are carried out: b1) injecting a second flowable composition (FZ2) containing a second shaped catalyst (FK2) through the bore (B) into the underground oil reservoir, b2) injecting an exothermic mixture (EM) through the well (B) into the underground well deposit, b3) contacting the exothermic mixture (EM) with the second shaped catalyst (FK2) in the underground well deposit wherein the second molded article catalyst (FK2) catalyzes an exothermic reaction of the exothermic mixture (EM).

In one embodiment of the present invention, it is possible to carry out method step b2) and method step b3) at least temporarily simultaneously. "At least temporarily" in the context of the present invention means that, for example, first process step b2) is carried out, then process step b2) and process step b3) are carried out simultaneously, for example for a period in the range of 1 to 10 days, and then process step b3) Of course it is possible to repeat all process steps b1), b2) and b3) It is likewise possible to repeat only one or two of the process steps b1), b2) and b3).

In one embodiment of the present invention, it is also possible to carry out process step b) and process step b1) at least temporarily simultaneously. "At least temporarily" means, for example, in the context of the present invention hate first, process step b) is performed, then Method step b) and method step b1) are carried out simultaneously, for example for a period of time in the range of 1 to 10 days, and then method step b1) is carried out. The subject matter of the present invention is thus also a method in which method step b) and method step b1) are carried out at least temporarily simultaneously.

In step b2), an exothermic mixture (EM) is injected through the well (B) into the subterranean crude oil deposit.

For injection of the exothermic mixture (EM) through the bore (B) into the underground deposit, in principle, all methods known to those skilled in the art are suitable. The composition of the exothermic mixture (EM) according to the invention is chosen so that it can be pumped by conventional pumps. The exothermic mixture (EM) may be both a solution and a suspension. In a preferred embodiment, the exothermic mixture (EM) is an aqueous solution or aqueous suspension.

According to the invention, the exothermic mixture (EM) preferably contains a peroxide.

In a preferred embodiment, an aqueous hydrogen peroxide solution containing from 10 to 70% by weight, preferably from 10 to 50% by weight and particularly preferably from 20 to 30% by weight, of hydrogen peroxide, based on the invention, is used as exothermic mixture (EM) Total weight of the exothermic mixture (EM).

The present invention thus also provides a process in which the exothermic mixture (EM) contains a peroxide.

In step b3) the exothermic mixture (EM) is contacted with the second molded article catalyst (FK2) in the underground oil reservoir. The second shaped-body catalyst (FK2) catalyses the exothermic reaction of the exothermic mixture (EM). It is possible that also the shaped-body catalyst (FK) at least partially catalyzes the exothermic reaction of the exothermic mixture (EM).

In one embodiment of the present invention, the second molded article catalyst (FK2) contained in the second flowable composition (FZ2) catalyzes an exothermic reaction of the exothermic mixture (EM) which is not combustion. When using peroxides, preferably an aqueous hydrogen peroxide solution, the peroxide decomposes to oxygen and in the case of hydrogen peroxide to water. Preferably, the exothermic reaction of the exothermic mixture (EM) is an exothermic decomposition.

In the exothermic reaction, temperatures in the range of 100 to 800 ° C, preferably in the range of 200 to 700 ° C and more preferably in the range of 300 to 600 ° C are generally achieved. As a result, for example, in the underground oil reservoir existing water, and possibly in the exothermic mixture (EM) contained water, heated or even evaporated. In addition, reaction products of the exothermic reaction of the exothermic mixture (EM) are formed, which are also released together with the heat of reaction. Contains the exothermic mixture (EM), for example, hydrogen peroxide, it forms as the reaction product of the exothermic reaction (decomposition), water and oxygen. These products are also heated and optionally evaporated. This heats the subterranean oil reservoir as well as the substances it contains, such as petroleum, deposits and the shaped catalyst (FK).

The hot and optionally gaseous reaction products are preferably pressed deeper into the underground Erdöllagerstätte. Methods for this are known to the person skilled in the art. Particularly preferably, the hot and optionally gaseous reaction products of the exothermic reaction of the exothermic mixture (EM) are pressed into the newly formed or already present tailings cracks.

An advantage of this method is that the shaped-body catalyst (FK) heats up and thus it can effectively catalyze the exothermic reaction (process step d)) of the combustible mixture (BM) injected in process step c). It is therefore not necessary to heat the combustible mixture (BM) before injection into the underground oil reservoir.

When a second flowable composition (FZ2) is injected into the underground deposit, it is also possible to treat the underground deposit by a fracking process. At the time of the execution of the fracking process as well as for the fracking process itself, the previously described designs and preferences apply. Particularly preferably, the underground oil reservoir is first treated by process step a) and before process step b) by a fracking process. Subsequently, in process step b) the flowable composition (FZ) injected together with the second flowable composition (FZ2). If appropriate, the underground oil reservoir between process step b) and process step c) can be treated again by a fracking process. Particularly advantageous in this embodiment is that the shaped-body catalyst (FK) and the second shaped-body catalyst (FK2) are very evenly distributed in the underground Erdöllagerstätte. The heating of the molded article catalyst (FK) by the exothermic reaction of the exothermic mixture (EM), which is catalyzed by the second molded article catalyst (FK2), is therefore particularly uniform.

More preferably, the subterranean crude oil deposit is first treated by process step a) and prior to process step b) by a fracking process, i. between method step a) and method step b). Subsequently, in process step b), the flowable composition (FZ) is injected and then in process step b1) the second flowable composition (FZ2) is injected. If appropriate, the underground oil reservoir between process step b) and process step c) can be treated again by a fracking process. In all embodiments, the molded article catalyst (FK) and the second molded article catalyst (FK2) are preferably distributed in a quasi-annular region around the well (B) in the underground deposit.

The present invention thus also provides a process in which the shaped-body catalyst (FK) and optionally the second

Shaped body catalyst (FK2) is distributed in a quasi-annular region around the bore (B) in the underground oil reservoir.

Process step c)

In step c), the combustible mixture (BM) is injected through the well (B) into the subterranean crude oil deposit. In principle, all combustible mixtures (BM) known to the person skilled in the art, whose exothermic reaction is catalyzed by the shaped-body catalyst (FK), are suitable as the combustible mixture (BM).

Before and / or during the injection, the combustible mixture (BM) can be heated if necessary.

In principle, all methods known to the person skilled in the art are suitable for injecting the combustible mixture (BM) through the bore (B) into the underground deposit. The composition of the combustible mixture (BM) is chosen according to the invention so that it can be pumped by means of conventional pumps. In general, the combustible mixture (BM) contains a fuel and an oxidizer. By "one fuel" is meant both a single fuel and a mixture of two or more fuels "an oxidizer" means both an oxidizer and a mixture of two or more oxidizers.

Suitable oxidizing agents are, for example, selected from the group consisting of air, oxygen, water and hydrogen peroxide.

Suitable fuels are, for example, selected from the group consisting of hydrocarbons and alcohols. As hydrocarbons both liquid and gaseous hydrocarbons can be used. Gaseous hydrocarbons are, for example, selected from the group consisting of methane, ethane, propane, butane and natural gas. For example, liquid hydrocarbons are selected from the group consisting of naphtha, diesel distillate, and petroleum.

Suitable alcohols are, for example, selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.

The subject matter of the present invention is thus also a process in which the combustible mixture (BM) in process step c) contains a fuel selected from the group consisting of hydrocarbons and alcohols.

The combustible mixture (BM) injected in process step c) can be liquid or gaseous. The terms "liquid" and "gaseous" refer to the physical state of the combustible mixture (BM) at room temperature (20 ° C) and room pressure (1013 mbar). It is possible that the combustible mixture (BM) has a different state of aggregation in the subterranean oil reservoir and / or already during injection. The gaseous combustible mixtures (BM) preferably contain methane and air. Optionally, the gaseous combustible mixture (BM) contains inert gases. Suitable inert gases are, for example, nitrogen and / or carbon dioxide. The combustible mixture generally contains 0 to 50 wt .-% inert gases, preferably 0 to 30 wt .-% inert gases and particularly preferably 0 to 20 wt .-% inert gases, each based on the total weight of the gaseous combustible mixture (BM). In a preferred embodiment, the gaseous combustible mixture (BM) contains 5 to 50% by weight of methane and 50 to 95% by weight of air, more preferably 10 to 40% by weight of methane and 60 to 90% by weight of air and in particular preferably 15 to 35% by weight of methane and 65 to 85% by weight of air, in each case based on the total weight of the gaseous combustible mixture (BM). The sum of the wt .-% of methane and air generally give 100%.

Particularly preferably, the gaseous combustible mixture (BM) injected in process step c) contains methane and air if the exothermic mixture (EM) injected in process step b2) contains a peroxide.

The present invention thus also provides a process in which the exothermic mixture (EM) in process step b2) contains a peroxide and / or the combustible mixture (BM) in process step c) contains methane and air.

A preferred liquid combustible mixture (BM) contains water and a fuel selected from the group consisting of natural gas, propane, naphtha, diesel distillate, petroleum and methanol. In a particularly preferred embodiment, the liquid combustible mixture (BM) contains water, hydrogen peroxide and at least one fuel selected from the group consisting of natural gas, propane, naphtha, diesel distillate, petroleum and methanol. In a most preferred embodiment, the liquid combustible mixture (BM) contains water, hydrogen peroxide and methanol.

Particularly preferably, the liquid combustible mixture (BM) contains 45 to 55 wt .-% water, 30 to 40 wt .-% methanol and 5 to 25 wt .-% hydrogen peroxide, each based on the total weight of the liquid combustible mixture (BM).

More preferably, the liquid combustible mixture (BM) contains 45 to 55% by weight of water, 25 to 45% by weight of methanol and 10 to 20% by weight of hydrogen peroxide, each based on the total weight of the liquid combustible mixture (BM).

Most preferably, the liquid combustible mixture (BM) contains 40 to 60% by weight of water, 20 to 50% by weight of methanol and 10 to 20% by weight of hydrogen peroxide, based in each case on the total weight of the liquid combustible mixture (BM). ,

The sum of the wt% of water, methanol and hydrogen peroxide in the liquid combustible mixture (BM) generally gives 100%. Process step d)

In process step d), the combustible mixture (BM) is brought into contact with the 5-shaped catalyst (FK) in the underground oil reservoir.

The molded article catalyst (FK) catalyses the exothermic reaction of the combustible mixture (BM). During the exothermic reaction of the combustible mixture (BM), the fuel contained in the combustible mixture (BM) reacts exothermically with the oxidant also contained in the combustible mixture (BM). In this case, the fuel is oxidized by the oxidizing agent. This exothermic reaction is generally a combustion, it can be done with or without flames.

In the exothermic reaction of the liquid combustible mixture (BM), the subsurface oil reservoir is generally at temperatures in the range of 15-200 to 1200 ° C, preferably in the range of 300 to 1000 ° C and particularly preferably in the range of 400 to 1000 ° C, elevated. It forms a heated zone.

Due to the high temperatures, for example, the oil present in the underground 0 oil reservoir can be thermally split. It is also possible that the rocks and petroleum in the underground oil reservoir are pyrolyzed. In addition, the viscosity of the petroleum contained in the underground oil reservoir and other deposits is reduced, thereby facilitating the extraction of oil, and in some cases is even possible.

5

Due to the temperature increase due to the exothermic reaction, the fracture cracks that may be present in the underground oil reservoir can also be remediated.

The water obtained, in particular, after the completion of a fracking process in the underground oil reservoir, and in particular in the fracking cracks produced in the fraying process, is heated or even vaporized by the thermal treatment (temperature rise) in the heated zone, thereby increasing the mobility of the water contained in the fracking cracks. in the case of evaporation that becomes

35 Water even removed from the fracking cracks. Additives which have been added to the fracking fluid (FF) used to form the fracture tears, such as thickeners, are destroyed during the thermal treatment. In the event that an aqueous fracturing fluid (FF) containing thickening agents (gel-forming additives) was used to produce the fracture cracks, the viscosity 0 of the fracturing fluid (FF) decreases as a result of the thermal treatment process according to the invention. This phenomenon is also referred to as "yellowing." In the event that the heated zone after performing the thermal treatment Temperatures of> 100 ° C, for example, temperatures in the range of 150 to 1200 ° C, the Frackflüssigkeit (FF) is evaporated. The thickening agents contained in the fracking liquid (FF) are thermally decomposed. It is also possible that with the thermal treatment according to the invention in the underground Erdöllagerstätte further Frackrisse be generated.

In one embodiment according to the invention, the method steps c) and d) are carried out at least simultaneously at the same time. Thus, the combustible mixture (BM) is injected through the well (B) into the underground well deposit while the combustible mixture (BM) is simultaneously contacted with the shaped catalyst (FK) in the underground well deposit.

"At least temporarily" means in the context of the present invention that, for example, process step c) is performed, then process step c) and process step d) are carried out simultaneously, for example for a period in the range of several days to several weeks and then process step d) is performed The subject matter of the present invention is thus also a method in which method step c) and method step d) are carried out at least simultaneously at the same time.

In a further embodiment according to the invention, at least one of process steps a), b), c) and d) is repeated.

In one embodiment of the invention, after process step d), oil from the underground oil reservoir is conveyed through a production well. The subject of the present invention is therefore also a process in which, after process step d), oil is taken from the underground oil reservoir through a production well.

For the production well, the same embodiments and preferences apply as previously described for the well (B).

As a production hole, for example, the bore (B) are used.

Figure 4 shows a vertical section through a subterranean crude oil deposit having tailings cracks for production (22). In the underground Erdöllagerstätte a deflected bore (B) with a horizontal section (1 1) is brought down. By a fracking process with a fracking liquid (FF) containing the proppant (3; S), Tail cracks (2, 22) were generated before the flowable composition (FZ) was injected. The flowable composition (FZ) was injected only in individual fracture tears (2). Processes for this are known to the person skilled in the art. Following the injection of the flowable composition (FZ) further tailing liquid (FF), which also contains the proppant (3; S), was injected. The tailoring cracks (2; 22) therefore contain proppants (3; S). By injecting the flowable composition (FZ) into individual fracture cracks (2), a quasi-ring-shaped region containing the shaped-body catalyst (4, FK) has formed in the fracture flaws (2) in the well region. This was further introduced into the fracking cracks (2) by further injection of fracking liquid (FF) around the inner ring diameter (R). A quasi-ring-shaped region containing the shaped-body catalyst (4, FK) forms with an inner ring radius (R) and an outer ring radius (R1). The inner ring of the quasi-annular region is removed from the bore (1; B) by the inner ring radius (R). Upon contact of the subsequently injected combustible mixture (BM) with the shaped-body catalyst (4, FK), the exothermic reaction of the combustible mixture (BM) is catalyzed. The reaction products released during the exothermic reaction of the combustible mixture (BM) and heat of reaction (5) are introduced into the subterranean crude oil deposit. As a result, the oil contained in the underground oil reservoir (7) is mobilized and can be promoted via the tailings cracks for production (22).

The present invention furthermore relates to a process for the extraction of crude oil from the underground oil reservoir, comprising the steps of: i) thermal treatment of the underground oil reservoir by the process according to the invention,

ii) extraction of petroleum through a production well.

In a further embodiment of the invention, after process step d), a flood is injected through the well (B) into the subterranean crude oil deposit to extract petroleum from the underground oil reservoir.

The subject matter of the present invention is thus also a process in which after step d) the flooding agent is injected into the underground deposit and oil is taken out through the production well.

The present invention furthermore relates to a process for the extraction of crude oil from the underground oil reservoir, comprising the steps of: i) thermal treatment of the underground oil reservoir by the process according to the invention, ii) Injecting the flooding agent through the well (B) into the underground well deposit and extracting oil through the production well.

Suitable flooding agents are known to the person skilled in the art. Preferred flours are flours which contain at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and especially preferably at least 90% by weight of water, in each case based on the total weight of the flooding agent. It is also possible to use only water as flooding agent. Pure water, partially desalinated seawater, seawater or formation water can be used here as water. The flooding agent may contain 0 to 50 wt .-%, preferably 0 to 30 wt .-%, particularly preferably 0 to 20 wt .-% and particularly preferably 0 to 10 wt .-% further conventional additives, each based on the total weight of flood agent. Thickeners, surfactants or glycerol, for example, can be used as further customary additives. With regard to the thickeners and the surfactants, the embodiments and preferences described above apply.

As soon as the preferred aqueous flooding agent hits the heated zone, the water contained in the aqueous flocculent is heated or evaporated. The heated aqueous flooding agent mobilizes the oil in the underground oil reservoir and displaces it in the direction of the production well. The oil is taken from the production well. Depending on the temperature of the heated zone, the aqueous flooding agent may also be evaporated to water vapor.

By means of the method according to the invention for crude oil production, the aqueous flooding agent is heated or evaporated in situ in the heated zone in situ. This has over conventional methods in which water vapor is used as a flood, the advantage that the heat loss is minimal and that can be dispensed with costly and technically complex generators for steam generation on the surface of the underground oil reservoir.

It is known that the use of conventional steam flooding is limited by the depth of the deposit. For deposits> 1000 m, steam flooding is normally not used. The inventive method allows the steam generation directly in the underground Erdöllagerstätte and at any Teufe.

By injecting the aqueous flooding agent through the well (B) into the heated zone of the underground well deposit, the heated zone is cooled. In one embodiment of the method according to the invention for the production of crude oil, the injection of the aqueous flooding agent is carried out until the temperature of the heated zone to temperatures below 80 ° C, preferably below 100 ° C, cooled. Subsequently, the inventive method for the thermal treatment of the underground Erdöllagerstätte is performed again to form a heated zone again. Subsequently, the injection of an aqueous flooding agent can be made again.

Catalytic heat generator

The subject of the present invention is also a catalytic heat generator. According to the invention, the catalytic heat generator comprises the shaped body catalyst (FK) and a subterranean oil deposit into which is drilled a bore (B) having perforations (6) with a petroleum bearing layer and cracks in the subsurface oil reservoir, the perforation openings (6) having inlet openings of the catalytic heat generator are. Through the inlet openings, the combustible mixture (BM) and optionally the exothermic mixture (EM) can be injected.

The subject of the present invention is thus also a catalytic heat generator, comprising the shaped body catalyst (FK) and an underground oil deposit, in which a bore (B) is drilled having perforation openings (6) with a petroleum-bearing layer and cracks in the subterranean Petroleum deposit, wherein the perforation openings (6) are inlet openings of the catalytic heat generator.

In a preferred embodiment, the catalytic heat generator comprises the molded article catalyst (FK), the second molded article catalyst (FK2), and a subterranean well deposit into which is drilled a bore (B) having perforations (6) with a petroleum-bearing layer and cracks in the underground oil reservoir, wherein the perforation openings (6) are inlet openings of the catalytic heat generator.

In another preferred embodiment, the catalytic heat generator comprises the molded article catalyst (FK), the proppant (S), and a subterranean petroleum deposit into which is drilled a bore (B) having perforations (6) with a petroleum bearing layer and cracks in the underground oil reservoir, wherein the perforation openings (6) are inlet openings of the catalytic heat generator.

In a particularly preferred embodiment, the catalytic heat generator comprises the molded article catalyst (FK), the second molded article catalyst (FK2), the proppant (S) and a subterranean crude oil deposit into which a bore (B) is drilled Perforation openings (6), with a petroleum-bearing layer and cracks in the underground Erdöllagerstätte, wherein the perforation openings (6) are inlet openings of the catalytic heat generator.

In one embodiment of the present invention, the catalytic heat generator contains 40 to 85% by volume of the molded article catalyst (FK), preferably 60 to 85% by volume, and more preferably 70 to 85% by volume of the molded article catalyst (FK) Total volume of the catalytic heat generator.

In a preferred embodiment of the present invention, the catalytic heat generator contains 5 to 20% by volume of the shaped body catalyst (FK) and 60 to 80% by volume of the proppant (S), preferably 10 to 20% by volume of the shaped catalyst (FK). and 60 to 70% by volume of the proppant (S) and particularly preferably 15 to 20% by volume of the shaped body catalyst (FK) and 60 to 65% by volume of the proppant (S), based in each case on the total volume of the catalytic heat generator ,

In a further preferred embodiment of the present invention, the catalytic heat generator contains 40 to 80% by volume of the shaped-body catalyst (FK) and 5 to 10% by volume of the second shaped-body catalyst (FK 2), preferably 40 to 80% by volume of the shaped-body catalyst ( FK) and 5 to 7 vol.% Of the second shaped-body catalyst (FK2), in each case based on the total volume of the catalytic heat generator.

In a particularly preferred embodiment of the present invention, the catalytic heat generator contains 5 to 20% by volume of the molded article catalyst (FK), 1 to 5% by volume of the second molded article catalyst (FK2) and 60 to 80% by volume of the proppant (S ), in each case based on the total volume of the catalytic heat generator.

Usually, the catalytic heat generator contains other substances contained in the underground oil reservoir, such as petroleum and / or the fracking liquid (FF).

According to the invention, the perforation openings (6) of the bore (B) serve as inlet openings of the catalytic heat generator. Through the inlet openings of the catalytic heat generator, the combustible mixture (BM), and optionally the exothermic mixture (EM) can be injected into the catalytic heat generator. The form-body catalyst (FK) catalyzes the exothermic reaction of the combustible mixture (BM). The released during the exothermic reaction heat of reaction is through the catalytic heat generator in the transmit underground oil reservoir. The catalytic heat generator can thus also be used for thermal treatment of the underground oil reservoir.

In a particularly preferred embodiment, the shaped body catalyst (FK) is arranged in the vicinity of the inlet openings. "Near" according to the invention is understood to mean that the shaped body catalyst is arranged in a range of 0 to 50 m, preferably in a range of 0.5 to 20 m and in particular in a range of 1 to 10 m around the inlet opening.

The present invention thus also relates to a catalytic heat generator in which the shaped body catalyst (FK) is arranged in the vicinity of the inlet openings.

With respect to the molded article catalyst (FK), the second

Shaped body catalyst (FK2), the proppant (S), the combustible mixture (BM) and the exothermic mixture (EM) apply the previously described embodiments and preferences.

LIST OF REFERENCE NUMBERS

1 vertical hole (B)

2 Frackriss

3 proppants (S)

4 Shaped Catalyst (FK)

5 reaction products and heat of reaction

6 perforations

7 petroleum

1 1 horizontal hole

21 short tail crack

22 Frack crack for production

R inner ring radius

R1 outer ring radius The figures show in detail

Figure 1: Vertical section through an underground Erdöllagerstätte after process step d), the Formkorperkatalysator (4, FK) forms a quasi-annular region in the Bohrlochnahzone. 2a): Vertical section through an underground oil reservoir after process step d), the shaped-body catalyst (4, FK) forms a quasi-annular region with an inner ring radius (R). FIG. 2b): Horizontal section through the underground oil reservoir according to FIG. 2a).

FIG. 3: A vertical section through an underground oil reservoir after process step d), wherein the underground oil reservoir was subjected to a mini-fracking process.

Figure 4: Vertical section through an underground Erdöllagerstätte, in which subsequent to process step d) petroleum (7) by tail cracks for production (22) is promoted.

The present invention will be further illustrated by the following embodiment, without, however, limiting it thereto.

Embodiment 1

In a subterranean oil deposit (shale oil deposit), which is stored in a depth of 3200 m, several vertical holes (B) are drilled. The productive layer of the underground oil reservoir has a thickness of 80 to 120 m. At least one of the vertical holes (B) is perforated in the region of the productive layer using a conventional cumulative perforator to obtain perforations (6).

The oil deposit is then first scanned. For fraying a fracking liquid (FF) is used, in which ceramic proppant (S) is dispersed. 400 m ^{3 of} tailing liquid (FF), which contains 25% by weight of the ceramic proppant (S) based on the total weight of the fracking liquid (FF), are injected into the subterranean crude oil deposit.

Subsequently, 10 m ^{3 of} the flowable composition (FZ) containing 1.8 t of the molded article catalyst (FK) and 0.7 l of the second molded article catalyst (FK2) are injected into the underground oil reservoir. The shaped-body catalyst (FK) contains a ceramic support (KT), on which palladium is applied as active metal (A). The second shaped-body catalyst (FK2) also contains the ceramic support (KT), to which a manganese salt is applied as the second active metal (A2). The flowable composition (FZ) is distributed in a quasi-annular area around the well zone when injected into the subterranean well deposit.

Subsequently, 15 m ^{3 of} the exothermic mixture (EM) are injected through the hole (B) into the underground oil reservoir. The exothermic mixture (EM) contains a 40 wt .-% solution of hydrogen peroxide in water. The exothermic reaction of the exothermic mixture (EM) is catalyzed by the molded article catalyst (FK) and in particular by the second molded article catalyst (FK2). It forms water vapor and oxygen and the underground Erdöllagerstätte warmed by the released during the exothermic reaction of the exothermic mixture (EM) heat of reaction to temperatures of up to 600 ° C. The shaped-body catalyst (FK) is thus also heated.

In the next step, the gaseous combustible mixture (BM) is injected through hole (B) into the underground oil reservoir for 2 to 3 months. The gaseous combustible mixture (BM) used is a mixture of 30% by volume of methane and 70% by volume of air. The exothermic reaction of the gaseous combustible mixture (BM) is catalyzed by the heated shaped catalyst (FK). The heat of reaction liberated during the exothermic reaction of the combustible mixture (BM) heats the underground oil reservoir to temperatures of up to 1300 ° C. During the exothermic reaction of the combustible mixture (BM), oxidation reactions take place in the underground oil reservoir, the petroleum in the reservoir is thermally cracked (cracked) and at least partially pyrolyzed. Likewise, the reservoir rock is partially pyrolyzed.

Once the gaseous combustible mixture (BM) injection has been stopped, at least one of the holes (B) will be used as a production well to extract petroleum from it.

Claims

claims

A method of thermal treatment of a subsurface oil reservoir, comprising the steps of a) drilling a well (B) into the subsurface oil reservoir, b) injecting a flowable composition (FZ) containing a shaped catalyst (FK) through the well (B) c) injecting a combustible mixture (BM) through the well (B) into the underground well deposit; d) contacting the combustible mixture (BM) with the shaped catalyst (FK) in the underground well deposit, wherein the shaped catalyst (FK) catalyzes an exothermic reaction of the combustible mixture (BM), the subterranean crude oil deposit after process step b) and before process step c) being treated with a fracking fluid (FF) optionally containing a proppant (S), the fracking fluid ( FF) with a pressure greater than the minimum local rock stress i in which subterranean oil deposits are injected, to form fracture cracks in the underground oil reservoir.

2. The method according to claim 1, characterized in that the underground Erdöllagerstätte after process step a) and before process step b) with a Frackflüssigkeit (FF), which optionally contains a proppant (S) is treated, wherein the Frackflüssigkeit (FF) with a Pressure greater than the minimum local rock stress injected into the underground oil reservoir to form fracture cracks in the underground oil reservoir.

3. The method according to any one of claims 1 or 2, characterized in that the flowable composition (FZ) in step b) with a pressure which is greater than the minimum local rock stress is injected into the underground Erdöllagerstätte to form Frackrissen in the underground oil deposit.

4. The method according to claim 3, characterized in that the flowable composition (FZ) contains the proppant (S).

Process according to one of Claims 1 to 4, characterized in that the shaped-body catalyst (FK) contains a ceramic support (KT) selected from the group consisting of aluminum oxide, aluminum silicate, zirconium dioxide and silicon dioxide.

6. The method according to any one of claims 1 to 5, characterized in that the shaped body catalyst (FK) is an active metal (A) selected from the

Groups 5,

Contains 8, 9, 10, 1 1 and 12 of the Periodic Table of the Elements.

Method according to one of claims 1 to 6, characterized in that the combustible mixture (BM) in process step c) contains a fuel selected from the group consisting of hydrocarbons and alcohols.

Method according to one of Claims 1 to 7, characterized in that method step c) and method step d) are carried out at least simultaneously at the same time.

9. The method according to any one of claims 1 to 8, characterized in that after process step b) and before process step c), the following steps are carried out: b1) injecting a second flowable composition (FZ2) containing a second molded article catalyst (FK2), b) injecting an exothermic mixture (EM) through the well (B) into the underground well deposit, contacting the exothermic mixture (EM) with the second shaped catalyst (FK2) in the subterranean well Petroleum deposit, wherein the second shaped catalyst (FK2) catalyzes an exothermic reaction of the exothermic mixture (EM).

10. The method according to claim 9, characterized in that method step b) and process step b1) are carried out at least temporarily simultaneously.

1 1. A method according to any one of claims 9 or 10, characterized in that the exothermic mixture (EM) in process step b2) contains a peroxide and / or the combustible mixture (BM) in process step c) methane and air.

12. The method according to any one of claims 9 to 1 1, characterized in that the second shaped-body catalyst (FK2) contains a second active metal (A2) selected from Groups 6 and 7 of the Periodic Table of the Elements.

13. The method according to any one of claims 1 to 12, characterized in that the shaped-body catalyst (FK) and optionally the second shaped-body catalyst (FK2) is distributed in a quasi-annular region around the bore (B) in the underground Erdöllagerstätte.

14. Method of extracting oil from the underground oil reservoir, comprising the steps of: i) thermal treatment of the underground oil reservoir by the

Method according to one of claims 1 to 13,

ii) extraction of petroleum through a production well.

15. A catalytic heat generator comprising the molded body catalyst (FK) and a subterranean oil deposit into which is drilled a bore (B) having perforations (6) with a petroleum-bearing layer and cracks in the subsurface oil reservoir, characterized in that the perforation openings (6) are inlet openings of the catalytic heat generator.