CN115853492A - In-situ hydrogen production and utilization method for oil and gas reservoir - Google Patents
In-situ hydrogen production and utilization method for oil and gas reservoir Download PDFInfo
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- CN115853492A CN115853492A CN202211461209.9A CN202211461209A CN115853492A CN 115853492 A CN115853492 A CN 115853492A CN 202211461209 A CN202211461209 A CN 202211461209A CN 115853492 A CN115853492 A CN 115853492A
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000001257 hydrogen Substances 0.000 title claims abstract description 73
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 73
- 239000007789 gas Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003345 natural gas Substances 0.000 claims abstract description 13
- 239000012041 precatalyst Substances 0.000 claims abstract description 8
- 238000010248 power generation Methods 0.000 claims abstract description 7
- 230000005484 gravity Effects 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 33
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000005674 electromagnetic induction Effects 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
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- 238000010792 warming Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses an in-situ hydrogen production and utilization method for an oil and gas reservoir, which comprises the following steps: selecting an oil and gas reservoir with a good cover layer; injecting a pre-catalyst into a hydrocarbon region of a hydrocarbon reservoir; raising the temperature of the oil and gas reservoir to a temperature at which hydrocarbons are oxidized, hydrothermally cracked or reformed and converted into hydrogen; closing the production well for a period of time to allow the reaction to fully occur and the produced gas to undergo gravity separation; extracting hydrogen from an upper production well of the reservoir; and treating the gas recovered from the production well, and then mixing the treated gas into a natural gas pipeline and performing distributed power generation of a hydrogen gas turbine.
Description
Technical Field
The invention belongs to the field of oil and gas field exploitation, and particularly relates to an in-situ hydrogen production and utilization method for an oil and gas reservoir.
Background
With the influence of human beings on global climate, the world is warming, and human beings are experiencing a series of disastrous weather and climate events such as heat waves, floods, drought, forest fires and sea level rises. Most of oil and gas resources are burned as fuel, a large amount of carbon dioxide is generated by the combustion, and if the generated carbon dioxide is completely discharged into the atmosphere, the greenhouse effect is further intensified, and more climate problems are caused.
The hydrogen energy is called as ultimate energy by the advantages of cleanness, environmental protection, high efficiency, wide source, energy storage and the like, is the best choice for replacing mineral energy in the future, and can effectively solve the consumption problem of renewable energy so as to solve the problems of global fossil energy crisis, global warming, environmental pollution and the like.
At present, the hydrogen production raw materials mainly comprise petroleum, natural gas, coal and other stone resources, and compared with other hydrogen production methods, the hydrogen production process by fossil energy reforming is more mature, and the price of the raw materials is relatively low.
The original purpose of hydrogen energy development is to reduce carbon emission, the main raw materials for global hydrogen production mainly adopt coal for hydrogen production, which is in addition to the goal of developing hydrogen energy to realize green low-carbon transformation of energy, and if the application of 1 hundred million hydrogen terminals is realized, fossil energy such as coal, natural gas and the like is required to be consumed by more than 5 hundred million tons of standard coal, and the emission of carbon dioxide is close to 12 hundred million-18 hundred million tons, so that the hydrogen energy industry can become the largest energy consumption and carbon emission field.
Disclosure of Invention
Aiming at the problems of the hydrogen production technology, the invention provides an in-situ hydrogen production and utilization method of an oil-gas reservoir, which aims at oil-gas resources which cannot be produced under the existing economic technology conditions, can recycle the residual oil-gas resources to produce hydrogen, and can effectively solve the problem of high carbon emission in the existing hydrogen production technology.
The invention utilizes the in-situ conversion of the oil-gas reservoir to generate hydrogen, can stop the emission of carbon dioxide while producing hydrogen, mixes the produced hydrogen into a natural gas pipe network or performs distributed power generation of a hydrogen turbine, efficiently utilizes the hydrogen on site, and has great significance for promoting the carbon peak reaching and carbon neutralization in the world.
An in-situ hydrogen production and utilization method for an oil and gas reservoir comprises the following steps:
optionally but preferably a reservoir with a good cap;
injecting a pre-catalyst into a hydrocarbon zone of a hydrocarbon reservoir;
raising the temperature of the oil and gas reservoir to a temperature at which hydrocarbons are oxidized, hydrothermally cracked or reformed and converted into hydrogen;
closing the production well for a period of time to allow the reaction to fully occur and the produced gas to undergo gravity separation; extracting hydrogen from an upper production well of the reservoir;
and treating the gas recovered from the production well, and then mixing the treated gas into a natural gas pipeline and performing distributed power generation of a hydrogen gas turbine.
The reservoir may be selected by three-dimensional or four-dimensional seismic exploration techniques in combination with well interpretation or electromagnetic induction techniques, optionally but preferably with a good seal, more particularly all around, and in particular with a cap layer capable of trapping hydrogen. The oil-gas reservoir with good sealing property at the periphery can be used as a hydrogen storage reservoir. Three-dimensional or four-dimensional seismic exploration techniques in combination with well logging interpretation or electromagnetic induction techniques may also be used to obtain reservoir water and gas distribution and to optimize production well locations.
Most of the oil and gas reservoirs can not be sealed all around, and for example, limestone oil and gas reservoirs and carbonate oil and gas reservoirs can develop natural cracks and karst caves. For the oil and gas reservoir, the produced hydrogen can be produced and injected into the oil and gas reservoir with good sealing performance at the periphery.
The process provided by the present invention comprises introducing a pre-catalyst into the hydrocarbon reservoir, said catalyst consisting of a plurality of catalysts, generally not less than two, more specifically not less than three, and especially not less than four. For example, the catalyst is composed of a catalyst which can catalyze the gasification of crude oil into carbon monoxide, catalyze the water-gas shift conversion, catalyze the partial oxidation of methane, and catalyze the reforming of methane to produce hydrogen. For a part of hydrocarbon reservoirs, clay minerals of the oil reservoirs have part of required metal elements (such as iron and copper), so that the component types of the catalyst can be reduced.
The injection catalyst is a metal-based material (e.g., iron-based, copper-based, nickel-based catalysts), and many catalysts that have been studied to catalyze the conversion of oil gas to hydrogen gas can also be used in the present invention (Logan Gradisher, bryce Dutcher, maohong Fan, catalytic hydrogen production from gas fuels via the water gas shift reaction [ J ]. Applied Energy, volume 139,2015, pages 335-349.).
The injected catalyst precursor is in the form of a solution, such as a metal salt (nitrate, sulfate, acetate, etc.), which forms a metal oxide upon reaction with air at high temperature in the earth.
The present invention provides methods comprising raising the temperature of a hydrocarbon reservoir to a temperature at which hydrocarbon oxidation, hydrothermal cracking, or reforming is converted to hydrogen. Generally not less than 350 deg.C, especially not less than 450 deg.C, especially not less than 600 deg.C.
The method for raising the temperature of the oil and gas reservoir comprises but is not limited to injecting steam to heat the oil and gas reservoir, injecting air to burn the oil and gas in a downhole ignition mode, injecting air to burn the oil and gas, and injecting low-ignition-point substances and then injecting air to burn. When injecting air to heat the reservoir, water is optionally, but not necessarily, injected at the same time.
When injecting air to heat a hydrocarbon reservoir, the wellbore tubing material selected should be resistant to oxygen-enriched air, typically having an oxygen concentration of 30%, more particularly 40%, particularly 70%, and especially 90%.
In the method for in-situ hydrogen production and high-efficiency utilization, the in-situ hydrogen production conversion region does not occur at the combustion front edge, but occurs in a region which extends to the temperature of at least 280 ℃ from the combustion front edge to the periphery.
The method for heating the oil and gas reservoir can be selected but is preferably realized by injecting air for combustion, injecting air and/or water after injecting the catalyst, stopping injecting the air after a period of combustion, continuing injecting the catalyst after the air is consumed, and injecting the air again to ensure that the oil and gas can be spontaneously combusted.
The disclosed method comprises shutting down the production well for a period of time sufficient for the reaction to occur and gravity separation of the produced gas, optionally but preferably for a period of time such that the production well pressure reaches the reaction zone pressure.
The hydrogen production reaction of oil gas can produce hydrogen, oxycarbide, nitrogen oxide, sulfur oxide, hydrocarbon gas and the like, because the hydrogen mass density is minimum and the molecular size is small, the hydrogen can reach a production well firstly, and because of the action of gravity and pressure, the hydrogen can be independently gathered above the oil gas reservoir, and the oxycarbide, the nitrogen oxide, the sulfur oxide and the like can be buried below the oil gas reservoir, so that the atmosphere is not polluted.
For most of the hydrocarbon reservoirs which cannot be exploited by the existing economic technology, enough water exists, and hydrogen conversion reaction can occur when the catalyst and the temperature and pressure are proper. Thus, if the reservoir is heated by means of ignition or auto-ignition of injected air, it may be selected not to inject water.
The reaction mechanism includes, but is not limited to:
oil+O 2 +H 2 O→CH 4 +CO+CO 2
CO+H 2 O→H 2 +CO 2
CH 4 +0.5O 2 →CO+2H 2
CH 4 +H 2 O→CO+3H 2
2CH 4 +3O 2 →2CO+4H 2 O
the method provided by the invention comprises extracting hydrogen from an upper production well of the reservoir. The position optimization of the production well can be realized by three-dimensional and four-dimensional seismic exploration and electromagnetic induction technology.
The tubular column material of the production well needs to be hydrogen embrittlement resistant, and particularly is a high-strength hydrogen embrittlement resistant material.
In particular, if the reservoir has good containment around it, the production well may also act as an injection well for hydrogen gas which is injected into the reservoir for storage.
The method provided by the invention comprises the steps of treating the gas recovered from the production well, then mixing the treated gas into a natural gas pipeline and carrying out distributed power generation of the hydrogen turbine.
The natural gas pipe network hydrogen doping can solve the problem of hydrogen transportation, and the concentration of the doped hydrogen is generally not less than 10%, particularly not less than 20%, and particularly not less than 30%. The maximum utilization of energy can also be realized by controlling parameters such as production pressure difference, well opening time and the like of a production well, so that certain hydrocarbon gases (such as methane and ethane) with molecular mass between that of hydrogen and carbon oxides, nitrogen oxides and sulfur oxides are produced together and then mixed into a natural gas pipeline.
The distributed power generation of the hydrogen gas turbine can be connected to the grid, and peak regulation and frequency modulation are realized. The gas to be combusted in the hydrogen turbine may be selected from a mixed gas of high-concentration hydrogen gas, particularly a hydrogen gas concentration of not less than 20%. The mixed gas produced as described above is also applicable to a hydrogen gas turbine.
Heating an oil-gas reservoir (particularly a heavy oil reservoir) by injecting air can lead substances with polycyclic aromatic hydrocarbons, such as asphaltene, colloid and the like in the heavy oil to generate reactions such as thermal cracking, high-temperature oxidation, hydrothermal cracking, hydrocatalysis and the like to generate modification, so that the fluidity is increased, and the recovery ratio of the reservoir is improved.
The invention is particularly suitable for oil and gas reservoirs which cannot be exploited by the existing economic technology, including but not limited to oil reservoirs after tertiary oil recovery, heavy oil reservoirs and water-locked gas reservoirs. The recovery ratio of the oil deposit after tertiary oil recovery is generally not more than 50% because the oil deposit is heterogeneous, the recovery ratio of the heavy oil deposit is generally not more than 65% because the crude oil has poor mobility and the oil deposit is heterogeneous, and the gas cannot be produced because of the water in the gas deposit and the water produced in the process of exploitation in the water-locked gas deposit.
Compared with the prior art, the invention has the following advantages: the hydrogen production is carried out underground, so that not only can the oil gas resources which cannot be exploited in the prior art be reused, but also the emission of greenhouse gases is inhibited or even eliminated while clean energy hydrogen is obtained, and the hydrogen is utilized on site or injected into an oil gas reservoir with a good cover layer, so that the problems of hydrogen transportation and storage are solved, and the invention has wide application prospect.
Drawings
FIG. 1 is a schematic illustration of the process implementation of the present invention.
In the figure: 1. an oxygen-rich/oxygen-lean air injection system; 2. an injection well; 3; an implant; 4. a hydrogen accumulation zone; 5. a production well; 6. a natural gas pipe network; 7. a gas turbine.
Wherein the oxygen-enriched/depleted air system 1 includes, but is not limited to, a high pressure gas injection pump, an oxygen generator, an ISC pump.
The well type of the injection well 2 and the production well 5 includes, but is not limited to, a vertical well and a horizontal well.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The injectant 3 comprises a catalyst forebody, air and water; specifically, as shown in fig. 1, a catalyst precursor is injected into a hydrocarbon reservoir through an injection well 2 by an oxygen-rich/oxygen-poor air injection system 1, then oxygen-rich/oxygen-poor air is injected into the hydrocarbon reservoir through the injection well 2, and the hydrocarbon is combusted by means of ignition or spontaneous combustion. At this point, the production well 5 is shut-in. The hydrogen conversion reaction will take place in a region extending around the combustion front to a temperature of at least 280 c. Because the hydrogen density and the molecular volume are small, the hydrogen can be independently gathered in the hydrogen gathering area 4, and meanwhile, the carbon dioxide and other greenhouse gases can be buried at the bottom of the oil and gas reservoir. When the pressure near the production well 4 rises to coincide with the combustion zone pressure, the production well 4 is opened to begin hydrogen production.
The produced hydrogen is mixed into a natural gas pipe network 6 for residents to use or is added into a gas turbine 7 for on-site power generation and grid connection. In particular, hydrocarbon gases (such as methane and ethane) having molecular masses between those of hydrogen and carbon oxides, nitrogen oxides, sulfur oxides, can be produced and incorporated into the natural gas pipeline network 6 or fed into the gas turbine 7 to maximize energy use.
Claims (9)
1. An in-situ hydrogen production and utilization method for an oil and gas reservoir is characterized by comprising the following steps:
injecting a pre-catalyst into a hydrocarbon region of a hydrocarbon reservoir;
raising the temperature of the oil and gas reservoir to a temperature at which hydrocarbons are oxidized, hydrothermally cracked or reformed and converted into hydrogen;
closing the production well for a period of time to allow the reaction to fully occur and the produced gas to undergo gravity separation;
extracting hydrogen from an upper production well of the reservoir;
and treating the gas recovered from the production well, and then mixing the treated gas into a natural gas pipeline and performing distributed power generation of a hydrogen gas turbine.
2. The method as claimed in claim 1, wherein the reservoir has a cap layer capable of trapping hydrogen.
3. The method as claimed in claim 1, wherein the pre-catalyst is injected in the form of a metal salt solution that can be oxidized to a metal oxide catalyst.
4. The method for in-situ hydrogen production and utilization of oil and gas reservoirs according to claim 1, wherein the pre-catalyst is composed of a pre-catalyst for catalyzing multiple reactions.
5. The method for in-situ hydrogen production and utilization of oil and gas reservoirs according to claim 1, wherein the pre-catalyst is injected in a mode of being alternately injected with air.
6. The method as claimed in claim 1, wherein the raising of the temperature of the hydrocarbon reservoir is generated by injecting air to initiate the combustion of the hydrocarbon.
7. The method for in situ production of hydrogen and utilization of a hydrocarbon reservoir as claimed in claim 1, wherein the shut-in time is the time for the formation pressure around the production well to reach the combustion zone pressure.
8. The method for in-situ hydrogen production and utilization of oil and gas reservoirs according to claim 1, wherein the gas mixed into a natural gas pipe network and a gas turbine is a mixture of hydrogen, methane and ethane.
9. The method for in situ production of hydrogen and utilization of a hydrocarbon reservoir as claimed in claim 1, wherein the hydrocarbon reservoir is a hydrocarbon reservoir that cannot be produced under existing economic and technical conditions.
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| CN202211461209.9A CN115853492A (en) | 2022-11-21 | 2022-11-21 | In-situ hydrogen production and utilization method for oil and gas reservoir |
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| CN202211461209.9A CN115853492A (en) | 2022-11-21 | 2022-11-21 | In-situ hydrogen production and utilization method for oil and gas reservoir |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149898A (en) * | 2008-09-08 | 2011-08-10 | 艾瑞斯福斯基尼投资公司 | Process for generating hydrogen |
| CN112196505A (en) * | 2020-09-04 | 2021-01-08 | 中国石油工程建设有限公司 | Oil reservoir in-situ conversion hydrogen production system and hydrogen production process thereof |
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- 2022-11-21 CN CN202211461209.9A patent/CN115853492A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149898A (en) * | 2008-09-08 | 2011-08-10 | 艾瑞斯福斯基尼投资公司 | Process for generating hydrogen |
| CN112196505A (en) * | 2020-09-04 | 2021-01-08 | 中国石油工程建设有限公司 | Oil reservoir in-situ conversion hydrogen production system and hydrogen production process thereof |
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