CN116409748A - Hydrogen production composition, preparation method thereof and hydrogen production method - Google Patents
Hydrogen production composition, preparation method thereof and hydrogen production method Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 107
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 107
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 52
- -1 rare earth compounds Chemical class 0.000 claims abstract description 37
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000002734 clay mineral Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 17
- 150000002910 rare earth metals Chemical class 0.000 claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010779 crude oil Substances 0.000 claims description 4
- FYUFTDQZCVVFRO-UHFFFAOYSA-H europium(3+) phthalate Chemical compound [Eu+3].[Eu+3].[O-]C(=O)c1ccccc1C([O-])=O.[O-]C(=O)c1ccccc1C([O-])=O.[O-]C(=O)c1ccccc1C([O-])=O FYUFTDQZCVVFRO-UHFFFAOYSA-H 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910001919 chlorite Inorganic materials 0.000 claims description 3
- 229910052619 chlorite group Inorganic materials 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 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 description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- VPQDJSGQSNLEJE-UHFFFAOYSA-L [Cl-].[Cl-].[Ce+2] Chemical compound [Cl-].[Cl-].[Ce+2] VPQDJSGQSNLEJE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005504 petroleum refining Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 238000005516 engineering process Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003502 gasoline Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- FZUDMFCCNVDITF-UHFFFAOYSA-N 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid Chemical compound OC1=C(C(O)=O)C=CC2=C(O)C(C(=O)O)=CC=C21 FZUDMFCCNVDITF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003756 stirring 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
- 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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A hydrogen-generating composition containing one or more rare earth compounds and one or more hydrocarbon liquids is disclosed. The invention can realize hydrogen production under the action of water vapor at the temperature of below 350 ℃ in the sandstone porous medium containing clay minerals through the action of rare earth compounds and hydrocarbon liquid. The rare earth compound and hydrocarbon liquid hydrogen-producing composition and the hydrogen-producing composition are used for producing hydrogen under the combined action of clay minerals, sandstone porous media and water vapor, and compared with the prior art, the hydrogen-producing composition has the advantages of obviously reducing the reaction temperature, lowering the hydrogen-producing cost and improving the safety.
Description
Technical Field
The invention relates to the technical field of petroleum processing, in particular to a hydrogen production composition, a preparation method thereof and a hydrogen production method.
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 heavy strategic resource, has a revolutionary opportunity, and is expected to bring about great changes in oil gas yield and safety situation once a new breakthrough of theoretical technology is obtained. In-situ modification is carried out in an oil reservoir through catalytic modification, so that heavy oil is irreversibly converted into light oil, the recovery ratio is greatly improved, poor resources are upgraded into high-quality resources, and the energy once utilization, consumption reduction and emission reduction of the whole industrial chain are realized. In-situ upgrading technology requires that heavy oil and an upgrading agent system undergo a series of chemical reactions such as catalytic cracking, catalytic hydrogenation and the like under the conditions of 100-350 ℃ and 0.1-20 MPa to produce lighter oil and gas. One of the core reactions is the catalytic hydrogenation of heavy crude oil components, but if a process of injecting hydrogen or other gases is chosen, there is a safety risk and a high cost challenge, and there is a need for a composition that can generate hydrogen in situ under the reservoir conditions that can be achieved by current processes.
The hydrogen production process using petroleum hydrocarbon as raw material is an important source of industrial hydrogen at present, and is classified into three types according to the types of raw materials, the first type of technology is gaseous hydrocarbon hydrogen production, the main raw material is methane, the core technology is natural gas steam conversion technology, and the principle is that methane and water steam are firstly converted into carbon monoxide and hydrogen under the action of different catalysts, and then carbon monoxide is converted into carbon dioxide and hydrogen. Wherein the first reaction requires a high temperature of 800 ℃ to 900 ℃ and the second reaction also requires a high temperature of 300 ℃ to 400 ℃; the second technology is light oil hydrogen production, wherein the main raw material is naphtha, the core technology is naphtha steam conversion technology, the principle is similar to that of natural gas steam conversion, and the catalyst is different, so that the high temperature of 500 ℃ is needed; the third technology is that the heavy oil is used for producing hydrogen, the main raw material is heavy oil, the core technology is that the heavy oil is partially oxidized and steam converted, the principle is that under the action of different catalysts, partial components react with oxygen to generate carbon monoxide and a large amount of heat, the main components are initiated to react with water to generate carbon monoxide, and then the carbon monoxide is converted into carbon dioxide and hydrogen, and the temperature is required to be higher than 1000 ℃. The existing hydrogen production technology has high requirements on reaction temperature, is difficult to meet the process requirements of in-situ modification subsurface reaction, and is especially limited by the highest heating temperature of water vapor.
Disclosure of Invention
In order to at least partially solve the technical problems or disadvantages of the prior art, the present application contemplates a gas-free composition that can generate a hydrogen source in situ at a lower temperature for a catalytic hydrogenation reaction. The composition can generate hydrogen under the working condition that the temperature is within 350 ℃.
The present invention provides a hydrogen-generating composition comprising one or more rare earth compounds and one or more hydrocarbon liquids.
In the hydrogen-generating composition, the content of the rare earth compound is based on the mass ratio of the rare earth element in the composition of 0.1-5 percent.
The rare earth compound and the hydrocarbon liquid react to produce hydrogen under the limiting condition of the invention, and the proportion of the rare earth compound and the hydrocarbon liquid only affects the final hydrogen production amount, but does not affect whether the hydrogen production occurs.
In a specific embodiment, the rare earth compound is any one of lanthanum, cerium and europium or a light rare earth compound.
In a specific embodiment, the rare earth compound is a rare earth metal organic compound.
Further, the rare earth metal organic compound is one or a combination of a plurality of rare earth metal organic complexes and rare earth metal aromatic organic acid complexes. Specifically, the rare earth compound can be cerium dichloride, or lanthanum methyl dichloride, or lanthanum di-tert-butyl light rare earth, or europium phthalate, or cerium 2, 3-naphthalene dicarboxylate, or 1, 5-dihydroxy-2, 6-naphthalene dicarboxylate light rare earth.
The hydrocarbon liquid has a hydrogen-carbon atomic ratio of not less than 1.62, preferably not less than 1.78, and further, the hydrocarbon liquid is a petroleum hydrocarbon liquid. The petroleum hydrocarbon liquid refers to various hydrocarbon liquids produced in crude oil and petroleum refining processes.
The invention provides a preparation method of the hydrogen-generating composition, which comprises the following steps:
mixing one or more rare earth compounds with one or more hydrocarbon liquids and stirring for reacting for 1 to 8 hours to obtain a mixture, wherein the addition amount of the rare earth compounds and the hydrocarbon liquids is required to be 0.1 to 5 percent of the mass of the mixture of rare earth metal elements;
the above mixture was treated with ultrasonic waves for 1 to 8 hours while being vigorously stirred, and the reaction temperature was controlled at 60 to 100 ℃.
The invention provides application of the composition in hydrogen production.
The invention provides a method for producing hydrogen by using the hydrogen-producing composition, which comprises the steps of injecting the hydrogen-producing composition into a sandstone porous medium containing clay minerals, and increasing the temperature under the action of water vapor to realize hydrogen production.
The method specifically comprises the following steps:
injecting the hydrogen-generating composition into a sandstone porous medium containing clay minerals at normal temperature and normal pressure to enable the hydrogen-generating composition to fully contact with the clay minerals and sandstone mineral particles;
injecting hot water vapor into the sandstone porous medium containing the hydrogen-producing composition and clay minerals to form a hydrogen-producing system;
raising the temperature of the hydrogen production system to 150-350 ℃, the pressure to 1-20 MPa, and maintaining for 1-1000 hours to finish hydrogen production;
in the above method for producing hydrogen, the clay mineral is one or more of illite, kaolinite, chlorite, montmorillonite, vermiculite and the like, and is generally natural clay mineral contained in sandstone;
the mass fraction of the clay mineral in the sandstone porous medium containing the clay mineral is not less than 1.5%.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
the invention provides a hydrogen production composition, a preparation method and a use method thereof, which can realize hydrogen production under the action of water vapor at the temperature of below 350 ℃ in a sandstone porous medium containing clay minerals through the action of rare earth compounds and hydrocarbons. The rare earth compound and hydrocarbon hydrogen-producing composition and the hydrogen-producing composition are used for producing hydrogen under the combined action of clay minerals, sandstone porous media and water vapor, and compared with the prior art, the hydrogen-producing composition has the advantages of obviously reducing the reaction temperature, lowering the hydrogen-producing cost and improving the safety.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below. It should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Example 1
The hydrogen-generating composition provided in example 1 of the present invention was prepared from a cyclopentadienyl cerium chloride (Cp 2 CeCl) is compounded with naphtha.
The preparation method of the hydrogen-producing composition comprises the following steps:
the dicyclopentadienyl cerium chloride (Cp) 2 CeCl) was thoroughly mixed with naphtha, wherein cerium element was 0.1% by mass of the mixture, and the mixing temperature was controlled at 60 ℃.
Example 2
The hydrogen-generating composition provided in example 2 of the present invention was prepared from lanthanum methyl dicyclopentadienyl (Cp 2 LnMe) and catalytic diesel oil.
The preparation method of the hydrogen-producing composition comprises the following steps:
lanthanum methyl dicyclopentadienyl (Cp) 2 LnMe) and catalytic diesel oil, wherein lanthanum element accounts for 1% of the mass of the mixture, and the mixing temperature is controlled at 80 ℃.
Example 3
The hydrogen-generating composition provided in the embodiment 3 of the invention is formed by compounding cyclopentadienyl di-tert-butyl rare earth (wherein rare earth element is a light rare earth element mixture) and coked gasoline.
The preparation method of the hydrogen-producing composition comprises the following steps:
fully mixing the cyclopentadienyl di-tert-butyl rare earth with the coked gasoline, wherein the rare earth element accounts for 5% of the mass of the mixture, and the mixing temperature is controlled at 100 ℃.
Example 4
The hydrogen-generating composition provided in the embodiment 4 of the invention is formed by compounding europium phthalate and catalytic gasoline.
The preparation method of the hydrogen-producing composition comprises the following steps:
europium phthalate and coked gasoline are fully mixed, wherein europium element accounts for 0.5% of the mass of the mixture, and the mixing temperature is controlled at 100 ℃.
Example 5
The hydrogen-generating composition provided in the embodiment 5 of the invention is formed by compounding 2, 3-cerium naphthalene dicarboxylate and coked diesel.
The preparation method of the hydrogen-producing composition comprises the following steps:
cerium 2, 3-naphthalene dicarboxylate and coked diesel oil are fully mixed, cerium element accounts for 0.5% of the mass of the mixture, and the mixing temperature is controlled at 90 ℃.
Example 6
The hydrogen-generating composition provided in the embodiment 6 of the invention is formed by compounding 1, 5-dihydroxy-2, 6-naphthalene dicarboxylic acid rare earth (wherein the rare earth element is a light rare earth element mixture) and straight-run gasoline.
The preparation method of the hydrogen-producing composition comprises the following steps:
fully mixing 1, 5-dihydroxyl-2, 6-naphthalene dicarboxylic acid rare earth with straight-run gasoline, wherein rare earth elements account for 2% of the mass of the mixture,
the mixing temperature was controlled at 70 ℃.
Example 7
The methods of using the hydrogen-generating compositions in the various embodiments described above are as follows:
the hydrogen-producing compositions described in examples 1 to 6 were injected into a sand-filling pipe (sand-filling pipe diameter 5cm, length 20cm, internal filling mass ratio: 95% quartz sand and 5% natural clay mineral, natural clay mineral including 54% kaolinite, 31% illite, 7% montmorillonite, 6% chlorite, 2% vermiculite, and hydrogen production was achieved by increasing the temperature under the action of steam.
The method comprises the following specific steps:
(1) 10g of the hydrogen-producing composition described in examples 1 to 6 was injected into the above sand filling pipe at normal temperature and pressure, so that the hydrogen-producing composition was in sufficient contact with the clay-containing quartz sand porous medium in the sand filling pipe;
(2) Injecting hot water vapor with the temperature of 150 to 400 ℃ into the hydrogen production composition and the clay-containing quartz sand porous medium containing the components of the embodiments 1 to 6 respectively to form a hydrogen production system;
(3) Raising the temperature of the hydrogen production system to 150-350 ℃, maintaining the pressure to 1-20 MPa for 1-1000 hours, collecting the generated gas and detecting the hydrogen yield by gas chromatography;
(4) Control experiment a: repeating the steps (1) to (3) but not containing clay component in the hydrogen production system;
(5) Control experiment B: repeating steps (1) to (3) above, but wherein the hydrogen-generating composition of examples 1 to 6 does not contain hydrocarbon liquid in the hydrogen-generating system;
(6) Control experiment C: repeating steps (1) to (3) above, but the hydrogen-generating composition of examples 1 to 6 in the hydrogen-generating system does not contain a rare earth compound;
example 8
Embodiment 8 of the present invention provides a method for producing hydrogen using the above-described hydrogen-producing composition, the method comprising: the hydrogen-generating compositions described in examples 1 to 6 were injected into the clay-containing outcrop sandstone core (core diameter 3.8cm, core length 9.5 cm) of the Jurassic family of the northwest edge of the Soshould basin, and the temperature was raised under the action of steam to effect hydrogen generation.
The method comprises the following specific steps:
(1) 10g of the hydrogen-producing composition described in examples 1 to 6 was injected into the sandstone core at normal temperature and pressure, so that the hydrogen-producing composition was in sufficient contact with the sandstone core;
(2) Injecting hot water vapor with the temperature of 150 to 400 ℃ into the hydrogen-producing composition and the sandstone core containing the components of the embodiments 1 to 6 respectively to form a hydrogen-producing system;
(3) Raising the temperature of the hydrogen production system to 150-350 ℃, the pressure to 1-20 MPa, and maintaining for 1-1000 hours to finish hydrogen production;
example 9
Example 8 of the present invention provides a method of producing hydrogen using a hydrogen-producing composition, the method comprising: the hydrogen-producing compositions described in examples 1 to 6 were injected into oil-impregnated sandstone cores (cores obtained by drilling from 500m underground, core diameter 2.54cm, core length 8cm, original oil saturation 62%) of dwarf clay-containing oil-fields of northwest wind city of the Pascal basin, and the temperature was raised under the action of steam to produce hydrogen.
The method comprises the following specific steps:
(1) 10g of the hydrogen-producing composition described in examples 1 to 6 was injected into the sandstone core at normal temperature and pressure, so that the hydrogen-producing composition was in sufficient contact with the sandstone core;
(2) Injecting hot water vapor with the temperature of 150 to 400 ℃ into the hydrogen-producing composition and the sandstone core containing the components of the embodiments 1 to 6 respectively to form a hydrogen-producing system;
(3) Raising the temperature of the hydrogen production system to 150-350 ℃, the pressure to 1-20 MPa, and maintaining for 1-1000 hours to finish hydrogen production;
as can be seen by comparing the above examples and experimental results: (1) The hydrogen-generating compositions of examples 1 to 6 all produced hydrogen at a temperature of not higher than 350 ℃; (2) Examples 1-6 hydrogen production of the hydrogen-producing composition at a temperature no greater than 350 ℃ may occur in three different types of sandstone porous media, quartz sand filled tubes, outcrop sandstone cores, oil-immersed sandstone cores; (3) In the hydrogen-producing composition and the hydrogen-producing conditions, if one of the clay, hydrocarbon liquid and rare earth compound is arbitrarily removed, hydrogen cannot be produced at 400 ℃, the higher the reaction temperature is, the easier the hydrogen production is, and the larger the hydrogen production is, depending on the rule of influence of the temperature on hydrogen production, that is, in the case of using the same hydrogen-producing composition, it can be judged that the same cannot be produced at 350 ℃. Therefore, the clay, hydrocarbon liquid and rare earth compound are all necessary conditions for hydrogen production under the condition of the claims; (4) The higher the temperature of the hydrogen-generating compositions of examples 1 to 6 in the range of 150 to 400 ℃, the greater the hydrogen production amount; the minimum hydrogen production temperature that can be demonstrated is as low as 150 ℃.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (15)
1. A hydrogen-generating composition, characterized by: contains one or more rare earth compounds and one or more hydrocarbon liquids.
2. The hydrogen-generating composition according to claim 1, wherein the content of the rare earth compound is based on 0.1 to 5% by mass of the rare earth element in the composition.
3. The hydrogen-generating composition of claim 1, wherein the rare earth compound is any one of lanthanum, cerium, europium, or a light rare earth compound.
4. The hydrogen-generating composition of claim 1, wherein the rare earth compound is a rare earth metal organic compound.
5. The hydrogen-generating composition of claim 4, wherein the rare earth organic compound is one or a combination of rare earth organic complexes, rare earth aromatic organic acid complexes.
6. The hydrogen-generating composition of claim 5, wherein the rare earth metal organic compound is a cerium dichloride, or a lanthanum methyl dichloride, or a light rare earth butyl mono-di-tert-butyl, or europium phthalate, or cerium 2, 3-naphthalate, or a light rare earth 1, 5-dihydroxy-2, 6-naphthalate.
7. The hydrogen-generating composition according to claim 1, wherein the hydrocarbon liquid is a hydrocarbon liquid having a hydrogen to carbon atomic ratio of not less than 1.62.
8. The hydrogen-generating composition of claim 7, wherein the hydrocarbon liquid is a hydrocarbon liquid having a hydrogen to carbon atomic ratio of not less than 1.78.
9. The hydrogen-producing composition of claim 8, wherein the hydrocarbon liquid is derived from crude oil or petroleum refining products.
10. A process for preparing a hydrogen-generating composition according to any one of claims 1 to 9, comprising the steps of:
one or more rare earth compounds and one or more hydrocarbon liquids are fully mixed, the addition amount of the rare earth compounds and the hydrocarbon liquids is required to satisfy that the rare earth metal elements account for 0.1 to 5 percent of the mass of the mixture, and the reaction temperature is controlled between 60 ℃ and 100 ℃.
11. Use of a hydrogen-generating composition according to any one of claims 1 to 9 for the production of hydrogen.
12. A method of producing hydrogen using the hydrogen-producing composition of any one of claims 1-9, comprising: the hydrogen-producing composition is injected into a sandstone porous medium containing clay minerals, and the temperature is increased under the action of steam to realize hydrogen production.
13. The method of producing hydrogen as claimed in claim 12, comprising the steps of:
injecting the hydrogen-generating composition into a sandstone porous medium containing clay minerals at normal temperature and normal pressure to enable the hydrogen-generating composition to fully contact with the clay minerals and sandstone mineral particles;
injecting hot water vapor into the sandstone porous medium containing the hydrogen-producing composition and clay minerals to form a hydrogen-producing system;
raising the temperature of the hydrogen production system to 150-350 ℃, raising the pressure to 1-20 MPa, and maintaining for 1-1000 hours to finish hydrogen production.
14. The method of producing hydrogen according to claim 13, wherein the clay mineral is one or more combinations of illite, kaolinite, chlorite, montmorillonite, vermiculite, and the like.
15. The method of producing hydrogen according to claim 14, wherein the clay mineral in the clay mineral-containing sandstone porous medium is not less than 1.5% by mass.
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