CN117985651A - Underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer and preparation method and application method thereof - Google Patents
Underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer and preparation method and application method thereof Download PDFInfo
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- CN117985651A CN117985651A CN202211329958.6A CN202211329958A CN117985651A CN 117985651 A CN117985651 A CN 117985651A CN 202211329958 A CN202211329958 A CN 202211329958A CN 117985651 A CN117985651 A CN 117985651A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 268
- 239000001257 hydrogen Substances 0.000 title claims abstract description 268
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 71
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 71
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 69
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 51
- 150000002431 hydrogen Chemical class 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000012546 transfer Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 172
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 123
- 239000007788 liquid Substances 0.000 claims abstract description 54
- -1 rare earth compounds Chemical class 0.000 claims abstract description 47
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- 229910052900 illite Inorganic materials 0.000 claims abstract description 36
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000003860 storage Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052693 Europium Inorganic materials 0.000 claims description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 10
- 229910052773 Promethium Inorganic materials 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 10
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 10
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 10
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000003209 petroleum derivative Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 abstract description 24
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 abstract description 16
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007789 gas Substances 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 20
- 239000003921 oil Substances 0.000 description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 13
- 239000010779 crude oil Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 7
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- GIVPVKBSJYTRMO-UHFFFAOYSA-K cerium(3+) naphthalene-1-carboxylate Chemical compound [Ce+3].[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12.[O-]C(=O)c1cccc2ccccc12 GIVPVKBSJYTRMO-UHFFFAOYSA-K 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- VPQDJSGQSNLEJE-UHFFFAOYSA-L [Cl-].[Cl-].[Ce+2] Chemical compound [Cl-].[Cl-].[Ce+2] VPQDJSGQSNLEJE-UHFFFAOYSA-L 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000005504 petroleum refining Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000005487 naphthalate group Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/47—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing ten carbon atoms
- C07C13/48—Completely or partially hydrogenated naphthalenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/47—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing ten carbon atoms
- C07C13/48—Completely or partially hydrogenated naphthalenes
- C07C13/50—Decahydronaphthalenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of oil-gas field development, and discloses an underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, and a preparation method and a use method thereof. The underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer contains: (a) A rare earth-based composite, wherein the rare earth-based composite is a composite of hydrocarbon liquid and one or more rare earth compounds; and (b) naphthalene. In the use process of the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, hydrogen and hydrogenation products of naphthalene (such as tetrahydronaphthalene, decalin and the like) can be generated through the actions of rare earth compounds, light hydrocarbons and naphthalene in a high-temperature porous medium containing illite, namely, the effects of hydrogen generation and hydrogen storage are generated.
Description
Technical Field
The invention relates to the technical field of oil and gas field development, in particular to an underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, and a preparation method and a use method thereof.
Background
The global high viscosity crude oil is used for ascertaining 8150 hundred million tons of reserves, accounting for 70 percent of the residual reserves of the petroleum, is a large-scale major strategic resource, has a revolutionary opportunity, and is expected to bring great changes of oil gas yield and safety situation in China once a new breakthrough of theoretical technology is obtained, so that the method is worth paying high attention to.
In-situ modification is carried out in an oil reservoir through catalytic modification, heavy oil is irreversibly converted into light oil, recovery ratio is greatly improved, poor resources are upgraded into high-quality resources, the energy of the whole industrial chain is utilized once, consumption is reduced, emission is reduced, the method is equivalent to an underground refinery, benefits and environmental problems of exploitation, gathering, transportation and refining are hopefully solved, scientific problems are clear, technical routes are clear, and field test verification is carried out.
One of the core reactions for in situ upgrading of high viscosity crude oil is the catalytic hydrogenation of heavy crude oil components, and the choice of hydrogen source is critical in determining technical routes and cost effectiveness. At present, the hydrogen sources for catalytic hydrogenation of petroleum products mainly comprise two types, namely hydrogen and tetrahydronaphthalene/decalin. Among them, the petroleum industry produces hydrogen gas by 3 kinds of technology, the first kind is hydrogen production by gaseous hydrocarbon, mainly natural gas steam reforming technology, and it needs above 800 ℃; the second type is light oil hydrogen production, mainly naphtha steam conversion technology, and the temperature is 500 ℃; the third category is hydrogen production by heavy oil, mainly the partial oxidation steam conversion technology of heavy oil, which requires 600-1000 ℃. The hydrogen obtaining cost of the route is very high, the high temperature condition is harsh, the generated hydrogen is in a gaseous state, the requirements on storage and a reactor are high, the method is particularly used in the field of catalytic hydrogenation, the temperature is required to be up to 350-400 ℃ in the face of complex heterogeneous reaction of a gaseous hydrogen source, a solid catalyst and a liquid substrate, the pressure of water vapor corresponding to the temperature is more than 16MPa, the rupture pressure of a middle-shallow reservoir is higher than the rupture pressure of most of high-viscosity crude oil, and the method is difficult to meet the reservoir conditions of most of high-quality crude oil, so the method is not a high-quality hydrogen source. The hydrogen-rich polycyclic compound represented by tetrahydronaphthalene and decalin can provide hydrogen for catalytic hydrogenation reaction under milder conditions, is liquid, does not have gas-liquid-gas-solid interfaces, has higher reaction efficiency, can meet the use in underground oil reservoirs, and is a high-quality hydrogen source for underground catalytic hydrogenation modification. However, the industrial synthesis route of the high-quality hydrogen source mainly comes from hydrogenation reduction reaction of naphthalene, the raw material is still high-pressure hydrogen, the price is high, if the high-quality hydrogen source is directly injected as a hydrogenation agent, the technology is feasible but is not economically feasible, and the low-cost production of the high-quality hydrogen source under the oil reservoir condition is one of the key scientific problems to be solved in-situ modification of the high-viscosity crude oil.
Therefore, the hydrogen obtaining temperature condition of the route is harsh, the cost is high, and the route is difficult to be used in the field of in-situ modification. Accordingly, there is a strong need for new sources of high quality hydrogen, methods of manufacture and methods of use that overcome the deficiencies described in the prior art.
Disclosure of Invention
The invention aims to provide an underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, a preparation method and a use method thereof, wherein the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer can provide a low-cost high-quality hydrogen source for in-situ modified catalytic hydrogenation reaction, skillfully avoids the high-temperature condition of hydrogen as the hydrogen source, directly solves the cost problem of the high-quality hydrogen source, and can be generated in situ in an oil reservoir.
In order to achieve the above object, the present invention provides, in one aspect, a subsurface hydrogen source based on hydrocarbon low temperature catalytic hydrogen transfer, comprising:
(a) A rare earth-based composite, wherein the rare earth-based composite is a composite of hydrocarbon liquid and one or more rare earth compounds; and
(B) Naphthalene.
Preferably, the rare earth-based compound is contained in an amount of 70 to 99.9wt% and naphthalene is contained in an amount of 0.1 to 30wt% based on 100wt% of the total amount of the underground hydrogen source.
Further preferably, the rare earth-based compound is contained in an amount of 80 to 99wt% and naphthalene is contained in an amount of 1 to 20wt% based on 100wt% of the total amount of the underground hydrogen source.
Preferably, in the rare earth composite, the rare earth element accounts for 0.1-5% of the total mass of the rare earth composite.
Preferably, the rare earth element in the rare earth compound is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium.
Preferably, the rare earth compound is selected from at least one of a rare earth metallocene organic complex and a rare earth aromatic organic acid complex, preferably at least one of a rare earth dicyclopentadiene organic complex and a naphthalene-based organic acid rare earth complex.
Preferably, the hydrocarbon liquid is a petroleum hydrocarbon liquid or a petroleum refining product.
Preferably, the hydrocarbon liquid has a hydrogen to carbon atomic ratio of not less than 1.62, preferably not less than 1.78.
In a second aspect, the present invention provides a method for preparing the above-described underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, comprising the steps of:
(1) Reacting one or more rare earth compounds with one or more hydrocarbon liquids, and separating the liquids from the reaction mixture;
(2) Mixing the liquid separated in step (1) with naphthalene, and then separating the liquid from the mixture.
Preferably, in step (1), the reaction temperature is 60-100℃and the reaction time is 1-8 hours.
Preferably, in step (2), the mixing process is operated at a temperature of 60-72℃for a period of 1-10 hours.
In a third aspect, the present invention provides a method of using a hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source as described hereinbefore or prepared in accordance with the method described hereinbefore, the method comprising:
(1) Injecting the underground hydrogen source into a porous medium containing illite to form a hydrogen production and storage system;
(2) Raising the temperature and pressure of the hydrogen producing and storing system to 150-350 ℃ and 1-16MPa respectively to generate hydrogen and naphthalene hydrogenation products, so as to realize hydrogen producing and storing;
Wherein the mass fraction of illite in the illite-containing porous medium is not less than 0.2%.
Through the technical scheme, the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer can generate hydrogenation products (such as tetrahydronaphthalene, decalin and the like) of hydrogen and naphthalene through the actions of rare earth compounds, light hydrocarbons and naphthalene in a high-temperature porous medium containing illite, namely, the effects of generating hydrogen and storing hydrogen are generated. Compared with the prior art, the integrated hydrogen generation and hydrogen storage is realized, and the process difficulty and cost of a high-quality hydrogen source are obviously reduced.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer comprises:
(a) A rare earth-based composite, wherein the rare earth-based composite is a composite of hydrocarbon liquid and one or more rare earth compounds; and
(B) Naphthalene.
In the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer according to the present invention, the content of the rare earth-based complex may be 70 to 99.9wt%, preferably 80 to 99wt%, based on 100wt% of the total amount of the underground hydrogen source; the naphthalene content may be 0.1 to 30wt%, preferably 1 to 20wt%, and specifically, for example, may be 1wt%, 5wt%, 10wt%, 15wt% or 20wt%.
In the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer according to the present invention, the rare earth element in the rare earth composite may be 0.1 to 5% by weight, specifically, for example, 0.1%, 1%, 2%, 3%, 4% or 5% by weight of the total mass of the rare earth composite.
In the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer according to the invention, the rare earth element in the rare earth compound is preferably a light rare earth element. In a specific embodiment, the rare earth element in the rare earth compound is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium. Preferably, the rare earth element is lanthanum, cerium, or a combination of light rare earth elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium.
In the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer according to the present invention, preferably, the rare earth compound is at least one selected from the group consisting of rare earth metallocene organic complexes and rare earth aromatic organic acid complexes, and more preferably at least one selected from the group consisting of rare earth dicyclopentadiene organic complexes and naphthalene based organic acid rare earth complexes. In particular embodiments, the rare earth compound is selected from the group consisting of cerium dichloride (Cp 2 CeCl), tert-butyl rare earth dicyclopentadiene (wherein the rare earth elements are combinations of the light rare earth elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium), cerium 2, 3-naphthalene dicarboxylate, and rare earth 1, 5-dihydroxy-2, 6-naphthalene dicarboxylate (wherein the rare earth elements are combinations of the light rare earth elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium).
In the hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source of the present invention, the hydrocarbon liquid may be a petroleum hydrocarbon liquid or a petroleum refining product. In a further preferred embodiment, the hydrocarbon liquid has a hydrogen to carbon atom (molar) ratio of not less than 1.62, preferably 1.78 to 2.2. In a specific embodiment, the hydrocarbon liquid is selected from at least one of naphtha, catalytic diesel, coker diesel, and straight run gasoline.
The preparation method of the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer can comprise the following steps:
(1) Reacting one or more rare earth compounds with one or more hydrocarbon liquids, and separating the liquids (i.e., rare earth-based complexes) from the reaction mixture;
(2) Mixing the liquid separated in step (1) with naphthalene, and then separating the liquid from the mixture.
In the step (1), the reaction temperature is 60-100 ℃ and the reaction time is 1-8h.
In the step (2), the operation temperature of the mixing process is 60-72 ℃ and the time is 1-10h.
In the method of the present invention, in the step (1), the rare earth compound and the hydrocarbon liquid are used in such an amount that the rare earth element content in the prepared rare earth-based composite is 0.1 to 5wt%.
In the method of the present invention, the rare earth element in the rare earth compound is preferably a light rare earth element. In a specific embodiment, the rare earth element in the rare earth compound is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium. Preferably, the rare earth element is lanthanum, cerium, or a combination of light rare earth elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium.
In the method of the present invention, the rare earth compound is preferably selected from at least one of a rare earth metallocene organic complex and a rare earth aromatic organic acid complex, and more preferably at least one of a rare earth dicyclopentadienyl organic complex and a naphthalene-based organic acid rare earth complex. In particular embodiments, the rare earth compound is selected from the group consisting of cerium dichloride (Cp 2 CeCl), tert-butyl rare earth dicyclopentadiene (wherein the rare earth elements are combinations of the light rare earth elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium), cerium 2, 3-naphthalene dicarboxylate, and rare earth 1, 5-dihydroxy-2, 6-naphthalene dicarboxylate (wherein the rare earth elements are combinations of the light rare earth elements lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium).
In the process of the present invention, the hydrocarbon liquid may be a petroleum hydrocarbon liquid or a petroleum refining product. In a further preferred embodiment, the hydrocarbon liquid has a hydrogen to carbon atom (molar) ratio of not less than 1.62, preferably 1.78 to 2.2. In a specific embodiment, the hydrocarbon liquid is selected from at least one of naphtha, catalytic diesel, coker diesel, and straight run gasoline.
In the process according to the invention, in step (2), the rare earth-based compound and naphthalene are used in amounts such that the content of rare earth-based compound in the prepared underground hydrogen source is 70 to 99.9wt%, preferably 80 to 99wt%; the naphthalene content is 0.1 to 30 wt.%, preferably 1 to 20 wt.%.
In a more preferred embodiment, the method for preparing a hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source comprises:
(1) Mixing one or more rare earth compounds with one or more hydrocarbon liquids, and stirring at 60-100 ℃ for reaction for 1-8 hours;
(2) Ultrasonic treatment is carried out for 1 to 8 hours under stirring;
(3) Cooling and filtering to obtain liquid, namely the rare earth-based compound, wherein rare earth elements account for 0.1-5% of the total mass of the product;
(4) Stirring and mixing the rare earth-based compound and naphthalene at 60-72 ℃ for 1-10h;
(5) Cooling and filtering to obtain liquid, namely the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer.
The invention also provides a method of using the hydrocarbon-based low temperature catalytic hydrogen transfer underground hydrogen source described above or prepared according to the method described above, the method comprising:
(1) Injecting the underground hydrogen source into a porous medium containing illite at normal temperature and normal pressure to form a hydrogen production and storage system;
(2) And respectively raising the temperature and the pressure of the hydrogen production and storage system to 150-350 ℃ and 1-16MPa to generate hydrogenation products of hydrogen and naphthalene, thereby realizing hydrogen production and storage.
In the method of use of the invention, the hydrocarbon-based subsurface hydrogen source that catalyzes hydrogen transfer at low temperature may or may not flow in the illite-containing porous medium, or may not flow partially while not flowing partially.
In the method of use of the present invention, water, crude oil, etc. may be present in the illite-containing porous medium.
During the application, the mass fraction of illite in the illite-containing porous medium is not less than 0.2%, preferably 0.4% -4%. In specific embodiments, the mass fraction of illite in the illite-containing porous media is 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.2%, 3.5% or 4%.
In the method of use of the invention, the hydrogenation products of naphthalene are mixtures of different hydrogenation degrees, mainly tetrahydronaphthalene and decalin.
The technical idea of the invention mainly comprises three aspects: firstly, the gas hydrogen is converted into liquid hydrogen, so that the international general technical route of the gas hydrogen source is not needed for safety and sustainable development, and a new liquid hydrogen source is sought; secondly, the cost of a liquid hydrogen source is far higher than that of a gas hydrogen source under the current technical condition because of taking oil, and the method adopts a technical route for acquiring electrons from liquid hydrocarbon and transfers the electrons to a hydrogen storage medium to generate a low-cost liquid hydrogen source; thirdly, hydrogen is generated in situ, hydrogen transfer reaction occurs underground, and a liquid hydrogen source is generated in situ, so that the subsequent hydrogenation reaction is facilitated. Through the whole set of technical thought, three important technical challenges of safety, low cost and in-situ hydrogen generation are solved, and the method can be directly used for in-situ modification of high-viscosity crude oil.
The high-viscosity crude oil is subjected to in-situ modification by adopting the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer, so that on one hand, the modification and viscosity reduction effects are good, the viscosity reduction rate of the produced crude oil is more than 99%, and the yield is remarkably increased; on the other hand, the method can catalyze hydrocarbon to generate hydrogen transfer reaction at the low temperature below 350 ℃ to generate hydrogen and hydrogenation products of naphthalene, so that in-situ modification in an underground oil reservoir is possible.
The existing hydrocarbon-based catalytic hydrogen production technologies are three types, namely gaseous hydrocarbon hydrogen production, light oil hydrogen production and heavy oil hydrogen production, mainly adopt transition metal composite catalysts such as molybdenum, cobalt, iron and the like, and have the reaction temperature of 500-1000 ℃ and are difficult to realize in an underground oil reservoir for a long time, so that the technology has no feasibility in the field of oilfield development. Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The reaction temperature of the catalytic hydrogen production based on hydrocarbon raw materials is reduced from more than 500 ℃ to less than 350 ℃, so that the condition which cannot be achieved underground becomes possible, and the catalytic hydrogen production has a milestone meaning;
(2) The needed hydrocarbon raw material can be crude oil (thick oil), and the hydrogen source which is originally required to be purchased from high price is changed into low-price self-production, so that the practical significance is great;
(3) The reaction can occur in an underground porous medium, so that the process of injecting the high-risk dangerous chemical hydrogen source from the wellhead is avoided, and the practicability is very strong.
The hydrocarbon-based low temperature catalytic hydrogen transfer underground hydrogen source, and methods of making and using the same, according to the present invention, are further described by way of example below. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below are commercially available unless otherwise specified.
In the following examples, the rare earth element content of the rare earth based composite was analyzed according to X-ray fluorescence spectroscopy (XRF), and the naphthalene content of the subsurface hydrogen source was detected according to gas chromatography.
Example 1
This example illustrates a hydrocarbon low temperature catalytic hydrogen transfer-based underground hydrogen source and method of making the same according to the present invention.
The underground hydrogen source prepared in this example contains a combination of dicyclopentadienyl cerium chloride (Cp 2 CeCl) and naphtha and naphthalene, and is prepared as follows:
(1) The mixture was obtained by mixing the cerium dichloride (Cp 2 CeCl) with naphtha and reacting at 60℃for 2 hours with stirring.
(2) The above mixture was sonicated with stirring for 2 hours.
(3) Cooling and filtering to obtain liquid, namely the dicyclopentadienyl cerium-based compound, wherein cerium element accounts for 0.1 percent of the total mass of the compound.
(4) The ceria-based complex was mixed with naphthalene and stirred at 70 ℃ for 4 hours.
(5) Cooling and filtering to obtain liquid, namely the ceria-based underground hydrogen source A1, wherein naphthalene accounts for 5% of the total mass of the composition.
Example 2
This example illustrates a hydrocarbon low temperature catalytic hydrogen transfer-based underground hydrogen source and method of making the same according to the present invention.
The underground hydrogen source prepared in the embodiment contains a compound of dicyclopentadiene tertiary butyl rare earth (wherein the rare earth element is a light rare earth element mixture) and catalytic diesel oil and naphthalene, and the preparation process is as follows:
(1) The tertiary butyl rare earth of the dicyclopentadiene (wherein the rare earth element is a light rare earth element mixture) is mixed with catalytic diesel oil, and stirred and reacted for 4 hours at 100 ℃ to obtain a mixture.
(2) The mixture was sonicated with stirring for 4 hours.
(3) Cooling and filtering to obtain liquid, namely the dicyclopentadiene rare earth based compound, wherein the light rare earth element accounts for 2 percent of the total mass of the compound.
(4) The rare earth-based half metallocene compound was mixed with naphthalene and stirred at 60℃for 8 hours.
(5) Cooling and filtering to obtain liquid, namely the rare earth-based underground hydrogen source A2 of the dicyclopentadiene, wherein naphthalene accounts for 10% of the total mass of the composition.
Example 3
This example illustrates a hydrocarbon low temperature catalytic hydrogen transfer-based underground hydrogen source and method of making the same according to the present invention.
The underground hydrogen source prepared in this example contains a compound of cerium 2, 3-naphthalene dicarboxylate and coked diesel and naphthalene, and the preparation process is as follows:
(1) Cerium 2, 3-naphthalene dicarboxylate was mixed with coked diesel oil and reacted at 90℃for 8 hours with stirring to obtain a mixture.
(2) The above mixture was sonicated with stirring for 8 hours.
(3) And cooling and filtering to obtain liquid, namely the cerium naphthalate-based compound, wherein cerium element accounts for 5% of the total mass of the compound.
(4) The cerium naphthalate-based complex was mixed with naphthalene and stirred at 72 ℃ for 2 hours.
(5) And cooling and filtering to obtain liquid, namely cerium naphthalate-based underground hydrogen source A3, wherein naphthalene accounts for 1% of the total mass of the composition.
Example 4
This example illustrates a hydrocarbon low temperature catalytic hydrogen transfer-based underground hydrogen source and method of making the same according to the present invention.
The underground hydrogen source prepared in this example contains a compound of 1, 5-dihydroxy-2, 6-naphthalene dicarboxylic acid rare earth (wherein the rare earth element is a mixture of light rare earth elements) and straight run gasoline, and naphthalene, and its preparation process is as follows:
(1) The 1, 5-dihydroxy-2, 6-naphthalene dicarboxylic acid rare earth (wherein the rare earth element is a light rare earth element mixture) is mixed with straight-run gasoline, and stirred and reacted for 8 hours at 70 ℃ to obtain a mixture.
(2) The above mixture was sonicated with stirring for 8 hours.
(3) Cooling and filtering to obtain liquid, namely the naphthalene dicarboxylic acid rare earth-based compound, wherein the light rare earth element accounts for 2% of the total mass of the compound.
(4) The rare earth naphthalate-based complex was mixed with naphthalene and stirred at 70℃for 1 hour.
(5) Cooling and filtering to obtain liquid, namely the naphthalene dicarboxylic acid rare earth-based underground hydrogen source A4, wherein naphthalene accounts for 20% of the total mass of the composition.
Example 5
This example illustrates the use of a hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source according to the present invention as a subsurface hydrogen source.
The ceria-based underground hydrogen source A1 prepared in example 1 is injected as an underground hydrogen source into a high temperature porous medium containing illite to generate hydrogen and hydrogenation products of naphthalene, so as to realize hydrogen production and hydrogen storage, and the use method is as follows:
(1) 10g of the ceria-based underground hydrogen source A1 is injected into porous sandstone containing illite at normal temperature and pressure, so that the underground hydrogen source is fully contacted with the illite to form a hydrogen production and storage system, the mass fraction of illite in the porous sandstone is 3.2%, the porous sandstone is saturated with water in pores before being injected into the underground hydrogen source, and the diameter of the porous sandstone is 3.8cm, the length of the porous sandstone is 10cm, and the porosity of the porous sandstone is 24%.
(2) The above system containing the subsurface hydrogen source was heated to 350 c and the pressure was raised to 16MPa for 18 hours, during which time samples were taken every 3 hours.
(3) The hydrogen component in the sample gas was detected by gas chromatography, naphthalene and its hydrogenation products were detected in the sample liquid by gas chromatography, and the results are shown in table 1 below, and as can be seen from the data in table 1, this embodiment can produce hydrogen and store hydrogen.
(4) Control experiment 1: according to steps (1) - (3) of this example, the porous sandstone size was similar but the illite content was only 0.08%, and as a result, hydrogen was produced without the formation of naphthalene hydrogenation products.
(5) Control experiment 2: according to the steps (1) - (3) of this example, the heating temperature was reduced to 140 ℃, no hydrogen nor naphthalene hydrogenation products were produced within 18 hours, the temperature was further increased to 150 ℃, and after 14 hours, the hydrogen and naphthalene hydrogenation products were detected.
(6) Control experiment 3: according to steps (1) - (3) of this example, but replacing the subsurface hydrogen source with pure naphthalene, i.e., removing the rare earth based complex therefrom, no hydrogen is produced, nor is the hydrogenation product of naphthalene produced.
TABLE 1
Reaction time (h) | Detecting hydrogen | Detection of tetrahydronaphthalene | Detection of decalin | Naphthalene detection |
0 | Without any means for | Without any means for | Without any means for | Has the following components |
3 | Has the following components | Without any means for | Without any means for | Has the following components |
6 | Has the following components | Without any means for | Without any means for | Has the following components |
9 | Has the following components | Has the following components | Without any means for | Has the following components |
12 | Has the following components | Has the following components | Without any means for | Has the following components |
15 | Has the following components | Has the following components | Has the following components | Has the following components |
18 | Has the following components | Has the following components | Has the following components | Has the following components |
Example 6
This example illustrates the use of a hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source according to the present invention as a subsurface hydrogen source.
Injecting the rare earth-based underground hydrogen source A2 prepared in the example 2 as an underground hydrogen source into a high-temperature porous medium containing illite to generate hydrogen and hydrogenation products of naphthalene so as to realize hydrogen production and hydrogen storage, wherein the using method is as follows:
(1) 10g of the rare earth-based underground hydrogen source A2 is injected into porous sandstone containing illite at normal temperature and normal pressure, the underground hydrogen source is fully contacted with the illite to form an underground hydrogen source system, the mass fraction of illite in the porous sandstone is 1.5%, the porous sandstone is saturated with water in pores before the injection of the underground hydrogen source, and the diameter of the porous sandstone is 3.8cm, the length of the porous sandstone is 10.4cm, and the porosity of the porous sandstone is 24%.
(2) The above-mentioned underground hydrogen source system was heated to 300℃and the pressure was raised to 12MPa for 48 hours, during which samples were taken at irregular intervals.
(3) The hydrogen component in the sampled gas is detected by gas chromatography, naphthalene and hydrogenation products thereof in the sampled liquid are detected by gas chromatography, and the results are shown in the following table 2, and as can be seen from the data in the table 2, the embodiment can produce hydrogen and can completely consume naphthalene to realize hydrogen storage.
(4) Control experiment 1: according to steps (1) - (3) of this example, the porous sandstone size was similar but the illite content was only 0.08%, and as a result, hydrogen was produced without the formation of naphthalene hydrogenation products.
(5) Control experiment 2: according to the steps (1) - (3) of this example, the heating temperature was reduced to 140 ℃, no hydrogen nor naphthalene hydrogenation products were produced within 18 hours, the temperature was further increased to 150 ℃, and after 14 hours, the hydrogen and naphthalene hydrogenation products were detected.
(6) Control experiment 3: according to the steps (1) - (3) of the present example, the mass fraction of naphthalene in the underground hydrogen source was increased from 10% to 50%, hydrogen and naphthalene hydrogenation products were produced at the initial stage of the reaction, and naphthalene could be detected, and after 48 hours, sampling showed no hydrogen and naphthalene, and tetralin and decalin. It follows that in the case of an excess of naphthalene, the hydrogen produced by the subsurface hydrogen source can be completely converted into a hydrogen storage product (naphthalene hydrogenation product).
(7) Control experiment 4: according to steps (1) - (3) of this example, but replacing the subsurface hydrogen source with pure naphthalene, i.e., removing the rare earth based complex therefrom, no hydrogen is produced, nor is the hydrogenation product of naphthalene produced.
TABLE 2
Reaction time (h) | Detecting hydrogen | Detection of tetrahydronaphthalene | Detection of decalin | Naphthalene detection |
0 | Without any means for | Without any means for | Without any means for | Has the following components |
1 | Has the following components | Without any means for | Without any means for | Has the following components |
2 | Has the following components | Trace amount of | Without any means for | Has the following components |
4 | Has the following components | Has the following components | Trace amount of | Has the following components |
8 | Has the following components | Has the following components | Has the following components | Has the following components |
16 | Has the following components | Has the following components | Has the following components | Without any means for |
24 | Has the following components | Has the following components | Has the following components | Without any means for |
32 | Has the following components | Has the following components | Has the following components | Without any means for |
40 | Has the following components | Has the following components | Has the following components | Without any means for |
48 | Has the following components | Has the following components | Has the following components | Without any means for |
Example 7
This example illustrates the use of a hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source according to the present invention as a subsurface hydrogen source.
The cerium naphthalate-based underground hydrogen source A3 prepared in example 3 is used as an underground hydrogen source to be injected into a high-temperature porous medium containing illite to generate hydrogen and hydrogenation products of naphthalene so as to realize hydrogen production and hydrogen storage, and the using method is as follows:
(1) 10g of the cerium naphthalate-based underground hydrogen source A3 is injected into porous sandstone containing illite at normal temperature and normal pressure, the underground hydrogen source is fully contacted with the illite to form an underground hydrogen source system, the mass fraction of illite in the porous sandstone is 0.4%, the porous sandstone simultaneously contains crude oil and water in pores before the injection of the underground hydrogen source, the water content is 40%, the oil content is 60%, and the diameter of the porous sandstone is 3.8cm, the length is 10.7cm and the porosity is 26%.
(2) The above-mentioned underground hydrogen source system was heated to 200℃and the pressure was raised to 7MPa for 240 hours, during which samples were taken at irregular intervals.
(3) The hydrogen component in the sampled gas was detected by gas chromatography, and naphthalene and its hydrogenation products in the sampled liquid were detected by gas chromatography, the results are shown in Table 3 below, and it can be seen from the data in Table 3 that this embodiment can produce hydrogen at a lower temperature and can completely consume naphthalene to realize hydrogen storage.
(4) Control experiment 1: according to the steps (1) - (3) of the present example, the heating temperature was lowered to 140 ℃, no hydrogen was generated nor naphthalene was generated as a hydrogenation product within 48 hours, the temperature was further raised to 150 ℃, hydrogen generation was detected after 42 hours, and tetrahydronaphthalene generation was detected after 72 hours.
(5) Control experiment 2: according to steps (1) - (3) of this example, but replacing the subsurface hydrogen source with pure naphthalene, i.e., removing the rare earth based complex therefrom, no hydrogen is produced, nor is the hydrogenation product of naphthalene produced.
TABLE 3 Table 3
Reaction time (h) | Detecting hydrogen | Detection of tetrahydronaphthalene | Detection of decalin | Naphthalene detection |
0 | Without any means for | Without any means for | Without any means for | Has the following components |
1 | Without any means for | Without any means for | Without any means for | Has the following components |
10 | Has the following components | Has the following components | Without any means for | Has the following components |
40 | Has the following components | Has the following components | Has the following components | Has the following components |
120 | Has the following components | Has the following components | Has the following components | Has the following components |
240 | Has the following components | Has the following components | Has the following components | Has the following components |
Example 8
This example illustrates the use of a hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source according to the present invention as a subsurface hydrogen source.
The rare earth naphthalate-based underground hydrogen source A4 prepared in example 4 is injected into a high-temperature porous medium containing illite to generate hydrogen and hydrogenation products of naphthalene so as to realize hydrogen production and hydrogen storage, and the using method is as follows:
(1) 10g of the rare earth naphthalene dicarboxylic acid-based underground hydrogen source A4 is injected into porous sandstone containing illite at normal temperature and normal pressure, the underground hydrogen source is fully contacted with the illite to form an underground hydrogen source system, the mass fraction of illite in the porous sandstone is 0.4%, the porous sandstone simultaneously contains crude oil and water in pores before the injection of the underground hydrogen source, the water content is 40%, the oil content is 60%, and the diameter of the porous sandstone is 3.8cm, the length is 10.3cm and the porosity is 26%.
(2) The above-mentioned underground hydrogen source system was heated to 150℃and the pressure was raised to 2MPa for 12 hours, during which samples were taken at irregular intervals.
(3) The hydrogen component in the sampled gas was detected by gas chromatography, and naphthalene and its hydrogenation products in the sampled liquid were detected by gas chromatography, the results are shown in Table 4 below, and it can be seen from the data in Table 4 that this embodiment can produce hydrogen at a lower temperature and can completely consume naphthalene to realize hydrogen storage.
(4) Control experiment 1: according to the steps (1) - (3) of this example, the heating temperature was reduced to 140 ℃, no hydrogen nor naphthalene was produced as a hydrogenation product within 12 hours, the temperature was further increased to 150 ℃, and after 12 hours, the formation of hydrogen and tetrahydronaphthalene was detected.
(5) Control experiment 2: according to steps (1) - (3) of this example, but replacing the subsurface hydrogen source with pure naphthalene, i.e., removing the rare earth based complex therefrom, no hydrogen is produced, nor is the hydrogenation product of naphthalene produced.
TABLE 4 Table 4
Reaction time (h) | Detecting hydrogen | Detection of tetrahydronaphthalene | Detection of decalin | Naphthalene detection |
0 | Without any means for | Without any means for | Without any means for | Has the following components |
6 | Has the following components | Without any means for | Without any means for | Has the following components |
12 | Has the following components | Has the following components | Has the following components | Without any means for |
As can be seen from the above examples, the underground hydrogen sources of the ceria base, the dicyclopentadienyl base, the naphthalate base and the naphthalate base can be used as the underground hydrogen sources, and after the porous sandstone containing 0.4 to 3.2% of illite is injected, the generation of hydrogen, tetrahydronaphthalene and decalin can be detected within 12 to 240 hours under the conditions of the temperature of 150 to 350 ℃ and the pressure of 2 to 16 MPa.
And as a comparison: first, after the illite content is reduced to 0.08%, a hydrogenation product with hydrogen generation but no naphthalene is produced, indicating that the lower limit of illite content is a necessary condition; secondly, under the condition that the temperature is reduced to 140 ℃, no hydrogen is generated and no hydrogenation product of naphthalene is generated, and after the temperature is increased to 150 ℃, the generation of the hydrogenation product can be detected, so that the lower limit of the temperature is a necessary condition; thirdly, increasing the mass fraction of naphthalene in the underground hydrogen source from 10% to 50%, generating hydrogen and hydrogenation products of naphthalene in the initial stage of reaction, detecting naphthalene, sampling after 48 hours to show that no hydrogen and naphthalene exist, and generating tetrahydronaphthalene and decalin, which indicates that the hydrogen generated by the underground hydrogen source can be completely converted into hydrogen storage products under the condition of excessive naphthalene; fourth, as a blank experiment, after the rare earth-based compound in the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer is removed, hydrogen and naphthalene hydrogenation products cannot be generated, which indicates that the rare earth-based compound plays an irreplaceable catalytic role therein.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A subsurface hydrogen source based on hydrocarbon low temperature catalytic hydrogen transfer, the subsurface hydrogen source comprising:
(a) A rare earth-based composite, wherein the rare earth-based composite is a composite of hydrocarbon liquid and one or more rare earth compounds; and
(B) Naphthalene.
2. The underground hydrogen source based on hydrocarbon low temperature catalytic hydrogen transfer according to claim 1, wherein the rare earth based composite is 70-99.9wt% and naphthalene is 0.1-30wt%, based on the total amount of the underground hydrogen source being 100 wt%.
3. The underground hydrogen source based on hydrocarbon low temperature catalytic hydrogen transfer according to claim 1 or 2, wherein rare earth elements account for 0.1-5% of the total mass of the rare earth complex.
4. A hydrocarbon low temperature catalytic hydrogen transfer based underground hydrogen source according to any one of claims 1-3, wherein the rare earth element in said rare earth compound is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium.
5. The underground hydrogen source based on hydrocarbon low temperature catalytic hydrogen transfer according to any one of claims 1 to 4, wherein the rare earth compound is selected from at least one of rare earth metallocene organic complexes and rare earth aromatic organic acid complexes, preferably at least one of rare earth dicyclopentadienyl organic complexes and naphthalene based organic acid rare earth complexes.
6. A hydrocarbon low temperature catalytic hydrogen transfer based subterranean hydrogen source according to any of claims 1-5, wherein the hydrocarbon liquid is a petroleum hydrocarbon liquid or petroleum refinery product;
preferably, the hydrocarbon liquid has a hydrogen to carbon atomic ratio of not less than 1.62.
7. A process for preparing a hydrocarbon-based low temperature catalytic hydrogen transfer subsurface hydrogen source according to any one of claims 1-6, comprising the steps of:
(1) Reacting one or more rare earth compounds with one or more hydrocarbon liquids, and separating the liquids from the reaction mixture;
(2) Mixing the liquid separated in step (1) with naphthalene, and then separating the liquid from the mixture.
8. The process according to claim 7, wherein in step (1), the reaction temperature is 60 to 100℃and the reaction time is 1 to 8 hours.
9. The method according to claim 7, wherein in the step (2), the operation temperature of the mixing process is 60 to 72 ℃ for 1 to 10 hours.
10. A method of using a hydrocarbon low temperature catalytic hydrogen transfer-based subsurface hydrogen source as described in any one of claims 1-6 or prepared according to the method of any one of claims 7-9, comprising:
(1) Injecting the underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer into a porous medium containing illite to form a hydrogen production and storage system;
(2) Raising the temperature and pressure of the hydrogen producing and storing system to 150-350 ℃ and 1-16MPa respectively to generate hydrogen and naphthalene hydrogenation products, so as to realize hydrogen producing and storing;
Wherein the mass fraction of illite in the illite-containing porous medium is not less than 0.2%.
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