Subterranean hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons and methods of making and using the same

Abstract

The present application relates to oil and gas field development technical field, disclose a kind of underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbon and its preparation method and use method.The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbon contains: (a) rare earth-based complex, the rare earth-based complex is the complex of hydrocarbon liquid and one or more rare earth compounds;And (b) naphthalene.The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbon described in the application in the process of use, in illite-containing high-temperature porous medium, by the action of rare earth compound, light hydrocarbon and naphthalene, hydrogen and hydrogenation product (such as tetrahydro naphthalene, decalin etc.) of naphthalene can be generated, that is, hydrogen production and hydrogen storage effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil and gas field development, in particular to an underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons and a preparation method and use method thereof. BACKGROUND

[0002] In-situ upgrading is to convert heavy oil into light oil and greatly improve the recovery rate through catalytic upgrading in the oil reservoir, and to upgrade poor resources into high-quality resources, so as to realize the primary energy utilization and cost reduction and emission reduction of the whole industry chain, which is equivalent to an "underground refinery", and is expected to solve the benefit and environmental problems of mining, gathering and refining, and its scientific problems are clear, the technical route is clear and has been verified by field test.

[0003] One of the core reactions of in-situ upgrading of high-viscosity crude oil is catalytic hydrogenation of heavy crude oil components, and the selection of hydrogen source is the key to determine the technical route and cost-effectiveness. At present, the hydrogen source for catalytic hydrogenation of petroleum products mainly has two types, hydrogen and tetrahydro naphthalene / decalin. Among them, there are three types of hydrogen production technologies in the petroleum industry, the first type is gaseous hydrocarbon hydrogen production, mainly natural gas steam reforming technology, which needs more than 800 DEG C; the second type is light oil hydrogen production, mainly naphtha steam reforming technology, which needs 500 DEG C; the third type is heavy oil hydrogen production, mainly heavy oil partial oxidation steam reforming technology, which needs 600-1000 DEG C. The hydrogen production cost of the above routes is very high, the high temperature condition is harsh, the generated hydrogen is gaseous, and the requirements for storage and reactor are high, especially in the field of catalytic hydrogenation, which will face the complex heterogeneous reaction of gaseous hydrogen source-solid catalyst-liquid substrate, which needs a temperature as high as 350-400 DEG C, which corresponds to a water vapor pressure of more than 16 MPa, which is higher than the fracture pressure of most high-viscosity crude oil reservoirs, so it is not a good hydrogen source. The hydrogen-rich polycyclic compounds represented by tetrahydro naphthalene and decalin can provide hydrogen for catalytic hydrogenation reaction under relatively mild conditions, and because they are liquid, there is no gas-liquid and gas-solid interface, the reaction efficiency is higher, and it can meet the use in underground oil reservoirs, so it is a good hydrogen source for underground catalytic hydrogenation upgrading. However, the industrial synthesis route of the good hydrogen source is mainly derived from the hydrogenation reduction reaction of naphthalene, and the raw material is still high-pressure hydrogen, which is expensive. If it is directly injected as a hydrogenation agent, although it is technically feasible, it is economically unfeasible, and the low-cost production of good hydrogen source in the oil reservoir is one of the key scientific problems to be solved in the in-situ upgrading of high-viscosity crude oil.

[0004] It can be seen that the hydrogen production temperature of the above route is harsh and the cost is high, which is difficult to be used in the field of in-situ upgrading. Therefore, there is an urgent need for a new good hydrogen source, a preparation method and a use method to overcome the defects in the prior art. SUMMARY

[0005] The present application aims to provide a low-temperature catalytic hydrogen transfer based underground hydrogen source, a preparation method and a use method thereof, which can provide a low-cost high-quality hydrogen source for in-situ modified catalytic hydrogenation reaction, ingeniously avoids the high-temperature condition required by hydrogen as a hydrogen source, directly solves the cost problem of high-quality hydrogen source, and can be produced in place in an oil reservoir.

[0006] To achieve the above-mentioned purpose, the present application provides a low-temperature catalytic hydrogen transfer based underground hydrogen source in one aspect, which contains:

[0007] (a) a rare earth-based complex, which is a complex of one or more rare earth compounds and a hydrocarbon liquid; and

[0008] (b) naphthalene.

[0009] Preferably, the content of the rare earth-based complex is 70-99.9wt% and the content of naphthalene is 0.1-30wt% based on the total amount of the underground hydrogen source.

[0010] Further preferably, the content of the rare earth-based complex is 80-99wt% and the content of naphthalene is 1-20wt% based on the total amount of the underground hydrogen source.

[0011] Preferably, the content of the rare earth element in the rare earth complex is 0.1-5% based on the total mass of the rare earth complex.

[0012] 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.

[0013] Preferably, the rare earth compound is selected from at least one of a metallocene rare earth metal organic complex and a rare earth metal aromatic organic acid complex, preferably at least one of a metallocene rare earth metal organic complex and a naphthalene-based organic acid rare earth complex.

[0014] Preferably, the hydrocarbon liquid is a petroleum hydrocarbon liquid or a petroleum refining product.

[0015] Preferably, the hydrogen-carbon atomic ratio of the hydrocarbon liquid is not less than 1.62, preferably more than 1.78.

[0016] The present application provides a method for preparing the above-mentioned low-temperature catalytic hydrogen transfer based underground hydrogen source in a second aspect, which comprises the following steps:

[0017] (1) reacting one or more rare earth compounds with one or more hydrocarbon liquids, and separating a liquid from the reaction mixture;

[0018] (2) mixing the liquid separated in step (1) with naphthalene, and separating the liquid from the mixture.

[0019] Preferably, in step (1), the reaction temperature is 60-100℃, and the reaction time is 1-8h.

[0020] Preferably, in step (2), the operating temperature of the mixing process is 60-72℃, and the time is 1-10h.

[0021] The third aspect of the present application provides a method for using the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons as described above or prepared according to the method as described above, which comprises:

[0022] (1) injecting the underground hydrogen source into a porous medium containing illite to form a hydrogen production and storage system;

[0023] (2) increasing the temperature and pressure of the hydrogen production and storage system to 150-350℃ and 1-16MPa, respectively, to generate hydrogen and hydrogenated products of naphthalene, and realize hydrogen production and storage;

[0024] wherein, in the porous medium containing illite, the mass fraction of illite is not less than 0.2%.

[0025] Through the above technical solution, using the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons, in the high-temperature porous medium containing illite, through the action of rare earth compounds, light hydrocarbons and naphthalene, hydrogen and hydrogenated products of naphthalene (such as tetrahydronaphthalene, decahydronaphthalene, etc.) can be generated, that is, the effect of hydrogen production and storage is produced. Compared with the prior art, not only the hydrogen production and storage integration is realized, but also the process difficulty and cost of high-quality hydrogen source are significantly reduced. DETAILED DESCRIPTION

[0026] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0027] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. For ranges comprising a start and end value, any intervening value and this intervening value are understood to be included in the range. For ranges having a minimum and maximum value and including any intervening value, the intervening values are understood to be included in the range are understood to be individually disclosed as well as in combination with each other value falling within the range. For ranges having a minimum value, a maximum value, and including any intervening value, the intervening values are understood to be individually disclosed as well as in combination with each other value falling within the range.

[0028] The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons contains:

[0029] (a) a rare earth based complex, which is a complex of a hydrocarbon liquid and one or more rare earth compounds; and

[0030] (b) naphthalene.

[0031] In the underground hydrogen source based on the low-temperature catalytic hydrogen transfer of hydrocarbon according to the present application, the content of the rare earth based complex can be 70-99.9wt%, preferably 80-99wt%, based on the total amount of the underground hydrogen source; and the content of naphthalene can be 0.1-30wt%, preferably 1-20wt%, for example, 1wt%, 5wt%, 10wt%, 15wt% or 20wt%.

[0032] In the underground hydrogen source based on the low-temperature catalytic hydrogen transfer of hydrocarbon according to the present application, the content of the rare earth element in the rare earth complex is 0.1-5% of the total mass of the rare earth complex, for example, 0.1%, 1%, 2%, 3%, 4% or 5%.

[0033] In the underground hydrogen source based on the low-temperature catalytic hydrogen transfer of hydrocarbon according to the present application, 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. In a preferred case, the rare earth element is lanthanum, cerium or a combination of light rare earth elements, i.e. lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.

[0034] In the underground hydrogen source based on the low-temperature catalytic hydrogen transfer of hydrocarbon according to the present application, the rare earth compound is preferably selected from at least one of a metallocene rare earth metal organic complex and a rare earth metal aromatic organic acid complex, more preferably at least one of a metallocene rare earth metal organic complex and a naphthalene-based organic acid rare earth complex. In a specific embodiment, the rare earth compound is selected from at least one of Cp2CeCl, Cp2CeTIBu (wherein the rare earth element is a combination of light rare earth elements, i.e. lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium), 2,3-naphthalene dicarboxylic acid cerium and 1,5-dihydroxy-2,6-naphthalene dicarboxylic acid rare earth (wherein the rare earth element is a combination of light rare earth elements, i.e. lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium).

[0035] In the underground hydrogen source based on the low-temperature catalytic hydrogen transfer of hydrocarbon according to the present application, the hydrocarbon liquid can be a petroleum hydrocarbon liquid or a petroleum refining product. In a further preferred embodiment, the hydrogen-carbon atom (mole) ratio of the hydrocarbon liquid is not less than 1.62, preferably 1.78-2.2. In a specific embodiment, the hydrocarbon liquid is selected from at least one of naphtha, catalytic diesel, coking diesel and straight-run gasoline.

[0036] The method for preparing the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbon according to the present application can comprise:

[0037] (1) reacting one or more rare earth compounds with one or more hydrocarbon liquids, and separating the liquid (i.e. rare earth-based complex) from the reaction mixture;

[0038] (2) mixing the liquid separated in step (1) with naphthalene, and separating the liquid from the mixture.

[0039] In step (1), the reaction temperature is 60-100°C, and the reaction time is 1-8h.

[0040] In step (2), the operating temperature for the mixing process is 60-72°C, and the time is 1-10h.

[0041] In the method according to the present application, in step (1), the amount of the rare earth compound and the hydrocarbon liquid is such that the content of rare earth element in the prepared rare earth-based complex is 0.1-5wt%.

[0042] In the method according to the present application, 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. In a preferred case, the rare earth element is lanthanum, cerium or a combination of light rare earth elements, i.e. lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.

[0043] In the method according to the present application, preferably, the rare earth compound is selected from at least one of metallocene rare earth metal organic complex and rare earth metal aromatic organic acid complex, and more preferably at least one of metallocene rare earth metal organic complex and naphthalene-based organic acid rare earth complex. In a specific embodiment, the rare earth compound is selected from Cp2CeCl, Cp2CeT (wherein the rare earth element is a combination of light rare earth elements, i.e. lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium), 2,3-naphthalene dicarboxylic acid cerium and 1,5-dihydroxy-2,6-naphthalene dicarboxylic acid rare earth (wherein the rare earth element is a combination of light rare earth elements, i.e. lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium).

[0044] In the method according to the present application, the hydrocarbon liquid can be a petroleum hydrocarbon liquid or a petroleum refining product. In a further preferred embodiment, the hydrogen-carbon atomic (molar) ratio of the hydrocarbon liquid is not less than 1.62, and preferably 1.78-2.2. In a specific embodiment, the hydrocarbon liquid is selected from at least one of naphtha, catalytic diesel, coking diesel and straight-run gasoline.

[0045] In the method of the present application, in step (2), the rare earth-based complex and naphthalene are used in an amount such that the content of the rare earth-based complex in the underground hydrogen source prepared is 70-99.9 wt%, preferably 80-99 wt%; and the content of naphthalene is 0.1-30 wt%, preferably 1-20 wt%.

[0046] In a more preferred embodiment, the method for preparing the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons comprises:

[0047] (1) mixing one or more rare earth compounds with one or more hydrocarbon liquids, and stirring and reacting at 60-100°C for 1-8 hours;

[0048] (2) ultrasonic treatment under stirring for 1-8 hours;

[0049] (3) cooling and filtering to obtain a liquid, which is the rare earth-based complex, wherein the rare earth element accounts for 0.1-5% of the total mass of the product;

[0050] (4) mixing the rare earth-based complex with naphthalene at 60-72°C under stirring for 1-10 hours;

[0051] (5) cooling and filtering to obtain a liquid, which is the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons of the present application.

[0052] The present application also provides a method for using the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons described above or prepared according to the method described above, which comprises:

[0053] (1) injecting the underground hydrogen source into a porous medium containing illite at normal temperature and pressure to form a hydrogen production and storage system;

[0054] (2) increasing the temperature and pressure of the hydrogen production and storage system to 150-350°C and 1-16 MPa, respectively, to generate hydrogen and hydrogenated products of naphthalene, and realize hydrogen production and storage.

[0055] In the method for using the present application, the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons can flow, can not flow, or can partially flow and partially not flow in the porous medium containing illite.

[0056] In the method for using the present application, water, crude oil, etc. can exist in the porous medium containing illite.

[0057] In the process of the application, the mass fraction of illite in the illite-containing porous medium is not less than 0.2%, preferably 0.4%-4%. In a specific embodiment, the mass fraction of illite in the illite-containing porous medium is 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.2%, 3.5% or 4%.

[0058] In the use method of the application, the hydrogenation product of naphthalene is a mixture of different hydrogenation degrees, mainly tetrahydro-naphthalene and decahydro-naphthalene.

[0059] The technical ideas of the application mainly include three aspects: 1. "Gas hydrogen to liquid hydrogen", in order to ensure safety and sustainable development, instead of the international common gas hydrogen source technical route, a new liquid hydrogen source is sought; 2. "From oil", under the current technical conditions, the cost of liquid hydrogen source is much higher than that of gas hydrogen source, therefore, the application adopts the technical route of obtaining electrons from liquid hydrocarbon, and the electrons are transferred to the hydrogen storage medium to generate a cheap liquid hydrogen source; 3. "Hydrogen in situ", the hydrogen transfer reaction occurs underground, and the liquid hydrogen source is generated in situ, which is more conducive to participating in the subsequent hydrogenation reaction. Through the above set of technical ideas, the three major technical challenges of safety, low cost and in-situ hydrogen generation are solved, and the application can be directly used for in-situ upgrading of high-viscosity crude oil.

[0060] The underground hydrogen source based on the low-temperature catalytic hydrogen transfer of hydrocarbons in the application is used for in-situ upgrading of high-viscosity crude oil, on the one hand, the upgrading and viscosity reduction effect is good, the viscosity reduction rate of the produced crude oil is more than 99%, and the yield is significantly increased; on the other hand, the catalytic hydrogen transfer reaction of hydrocarbons can occur at a low temperature below 350℃, hydrogen and the hydrogenation product of naphthalene are generated, and in-situ upgrading in the underground reservoir becomes possible.

[0061] There are three types of existing catalytic hydrogen production technologies based on hydrocarbons, namely gaseous hydrocarbon hydrogen production, light oil hydrogen production and heavy oil hydrogen production, mainly using composite catalysts of transition metals such as molybdenum, cobalt and iron, and the reaction temperature is as high as 500-1000℃, which is difficult to achieve in the underground reservoir for a long time, so it is not feasible in the field of oilfield development. Compared with the prior art, the technical scheme of the application has the following advantages:

[0062] (1) The reaction temperature of the catalytic hydrogen production based on hydrocarbon raw materials is reduced from more than 500℃ to within 350℃, which makes it possible to achieve conditions that were not possible underground, which is a milestone;

[0063] (2) The required hydrocarbon raw material can be crude oil (thick oil), which changes the originally high-priced purchased hydrogen source into a cheap self-produced one, which has great practical significance;

[0064] (3) The reaction can occur in a porous medium underground, avoiding the high-risk process of injecting high-risk dangerous hydrogen source from the wellhead, which has strong practicality.

[0065] The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons and the preparation method and use method thereof according to the present application are further illustrated by examples below. The examples are implemented on the premise of the technical solutions of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the examples below.

[0066] In the experimental methods in the following examples, if no special instructions are given, they are all conventional methods in the field. The experimental materials used in the examples below can be commercially available if no special instructions are given.

[0067] In the following examples, the content of rare earth elements in the rare earth-based composite is analyzed according to the X-ray fluorescence spectrometry (XRF), and the content of naphthalene in the underground hydrogen source is detected according to the gas chromatography.

[0068] Example 1

[0069] This example is used to illustrate the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons and the preparation method thereof according to the present application.

[0070] The underground hydrogen source prepared in this example contains a composite of Cp2CeCl and naphtha and naphthalene, and the preparation process is as follows:

[0071] (1) Mix Cp2CeCl and naphtha, and stir the mixture at 60°C for 2 hours to obtain a mixture.

[0072] (2) Ultrasonically treat the mixture under stirring for 2 hours.

[0073] (3) Cool and filter to obtain a liquid, which is the cerium-based composite, wherein the content of cerium element in the composite is 0.1% of the total mass of the composite.

[0074] (4) Mix the cerium-based composite with naphthalene, and stir the mixture at 70°C for 4 hours.

[0075] (5) Cool and filter to obtain a liquid, which is the cerium-based underground hydrogen source A1, wherein the content of naphthalene in the composition is 5% of the total mass of the composition.

[0076] Example 2

[0077] This example is used to illustrate the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons and the preparation method thereof according to the present application.

[0078] The underground hydrogen source prepared in this example contains a composite of Cp2CeCl and naphtha and naphthalene, and the preparation process is as follows:

[0079] (1) Mix the metallocene t-butyl rare earth (wherein the rare earth element is a mixture of light rare earth elements) with catalytic diesel oil, stir at 100°C for 4 hours to obtain a mixture.

[0080] (2) Ultrasonically treat the mixture under stirring for 4 hours.

[0081] (3) Cool and filter to obtain a liquid, which is a metallocene rare earth-based complex, wherein the light rare earth element accounts for 2% of the total mass of the complex.

[0082] (4) Mix the metallocene rare earth-based complex with naphthalene, stir at 60°C for 8 hours.

[0083] (5) Cool and filter to obtain a liquid, which is a metallocene rare earth-based underground hydrogen source A2, wherein naphthalene accounts for 10% of the total mass of the composition.

[0084] Example 3

[0085] This example is used to illustrate the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons and its preparation method according to the present application.

[0086] The underground hydrogen source prepared in this example contains a complex of 2,3-naphthalene dicarboxylic acid cerium and coking diesel oil and naphthalene, and its preparation process is as follows:

[0087] (1) Mix 2,3-naphthalene dicarboxylic acid cerium with coking diesel oil, stir at 90°C for 8 hours to obtain a mixture.

[0088] (2) Ultrasonically treat the mixture under stirring for 8 hours.

[0089] (3) Cool and filter to obtain a liquid, which is a naphthalene dicarboxylic acid cerium-based complex, wherein the cerium element accounts for 5% of the total mass of the complex.

[0090] (4) Mix the naphthalene dicarboxylic acid cerium-based complex with naphthalene, stir at 72°C for 2 hours.

[0091] (5) Cool and filter to obtain a liquid, which is a naphthalene dicarboxylic acid cerium-based underground hydrogen source A3, wherein naphthalene accounts for 1% of the total mass of the composition.

[0092] Example 4

[0093] This example is used to illustrate the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons and its preparation method according to the present application.

[0094] The underground hydrogen source prepared in this example contains a complex 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:

[0095] (1) Mix 1,5-dihydroxy-2,6-naphthalene dicarboxylic acid rare earth (wherein the rare earth element is a mixture of light rare earth elements) with straight-run gasoline, and stir at 70°C for 8 hours to obtain a mixture.

[0096] (2) Ultrasonically treat the mixture under stirring for 8 hours.

[0097] (3) Cool and filter to obtain a liquid, which is a naphthalene dicarboxylic acid rare earth-based complex, wherein the light rare earth elements account for 2% of the total mass of the complex.

[0098] (4) Mix the naphthalene dicarboxylic acid rare earth-based complex with naphthalene, and stir at 70°C for 1 hour.

[0099] (5) Cool and filter to obtain a liquid, which is a naphthalene dicarboxylic acid rare earth-based underground hydrogen source A4, wherein naphthalene accounts for 20% of the total mass of the composition.

[0100] Example 5

[0101] This example is used to illustrate the application of the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons as an underground hydrogen source according to the present application.

[0102] The cerocene-based underground hydrogen source A1 prepared in Example 1 is injected into a high-temperature porous medium containing illite as an underground hydrogen source to generate hydrogen and hydrogenated products of naphthalene, so as to realize hydrogen production and storage, and the use method is as follows:

[0103] (1) At normal temperature and pressure, 10 g of the cerocene-based underground hydrogen source A1 is injected into a porous sandstone containing illite, so that the underground hydrogen source is in full contact 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 the pores before the underground hydrogen source is injected, and the diameter of the porous sandstone is 3.8 cm, the length is 10 cm, and the porosity is 24%.

[0104] (2) Heat the system containing the underground hydrogen source to 350°C, and increase the pressure to 16 MPa, and maintain for 18 hours, during which sampling is performed every 3 hours.

[0105] (3) Detect the hydrogen content in the sampled gas by gas chromatography, and detect the naphthalene and hydrogenated products thereof in the sampled liquid by gas chromatography, and the results are shown in Table 1 below, and it can be seen from the data in Table 1 that the embodiment can produce hydrogen and store hydrogen.

[0106] (4) Control experiment 1: according to steps (1)-(3) of this example, the size of the porous sandstone is approximately the same but the illite content is only 0.08%, and the results show that hydrogen is produced but no hydrogenated products of naphthalene are generated.

[0107] (5) Control Experiment 2: According to the steps (1)-(3) of this example, the heating temperature is reduced to 140°C, and no hydrogen gas is generated and no hydrogenation product of naphthalene is generated within 18 hours. The temperature is continuously increased to 150°C, and hydrogen gas and hydrogenation product of naphthalene are detected after 14 hours.

[0108] (6) Control Experiment 3: According to the steps (1)-(3) of this example, but the underground hydrogen source is replaced by pure naphthalene, i.e. the rare earth-based complex is removed therefrom. As a result, neither hydrogen gas is generated nor hydrogenation product of naphthalene is generated.

[0109] Table 1

[0110]

[0111] Example 6

[0112] This example is used to illustrate the application of the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to the present application as an underground hydrogen source.

[0113] The di-rare earth-based underground hydrogen source A2 prepared in Example 2 is injected into a high-temperature porous medium containing illite as an underground hydrogen source to generate hydrogen gas and hydrogenation product of naphthalene to realize hydrogen production and hydrogen storage, and the use method is as follows:

[0114] (1) At normal temperature and pressure, 10 g of the di-rare earth-based underground hydrogen source A2 is injected into a porous sandstone containing illite to make the underground hydrogen source fully contact 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 the pores before the underground hydrogen source is injected, and the diameter of the porous sandstone is 3.8 cm, the length is 10.4 cm, and the porosity is 24%.

[0115] (2) The above underground hydrogen source system is heated to 300°C, and the pressure is increased to 12 MPa, which is maintained for 48 hours, and sampling is taken at irregular intervals during the period.

[0116] (3) The hydrogen content in the sampled gas is detected by gas chromatography, and the naphthalene and its hydrogenation product in the sampled liquid are detected by gas chromatography, and the results are shown in Table 2 below. As can be seen from the data in Table 2, the present embodiment can produce hydrogen and completely consume naphthalene to realize hydrogen storage.

[0117] (4) Control Experiment 1: According to the steps (1)-(3) of this example, the size of the porous sandstone is approximately the same, but the illite content is only 0.08%. As a result, hydrogen gas is generated but no hydrogenation product of naphthalene is generated.

[0118] (5) Control Experiment 2: According to the steps (1)-(3) of this example, the heating temperature is reduced to 140°C, and no hydrogen gas is generated and no hydrogenation product of naphthalene is generated within 18 hours. The temperature is continuously increased to 150°C, and hydrogen gas and hydrogenation product of naphthalene are detected after 14 hours.

[0119] (6) Control Experiment 3: According to steps (1)-(3) of this example, the mass fraction of naphthalene in the underground hydrogen source was increased from 10% to 50%. Hydrogen and the hydrogenation product of naphthalene were generated at the initial stage of the reaction, and naphthalene could be detected. Sampling after 48 hours showed that there was no hydrogen and naphthalene, but there were tetrahydro-naphthalene and decahydro-naphthalene. It can be seen that, in the case of excess naphthalene, the hydrogen generated by the underground hydrogen source can be completely converted into hydrogen storage products (hydrogenation products of naphthalene).

[0120] (7) Control Experiment 4: According to steps (1)-(3) of this example, but the underground hydrogen source was replaced with pure naphthalene, i.e. the rare earth-based complex in it was removed. As a result, neither hydrogen nor the hydrogenation product of naphthalene was generated.

[0121] Table 2

[0122]

[0123] Example 7

[0124] This example is used to illustrate the application of the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to the present application as an underground hydrogen source.

[0125] The naphthalene dicarboxylic acid cerium-based underground hydrogen source A3 prepared in Example 3 was injected into a high-temperature porous medium containing illite as an underground hydrogen source to generate hydrogen and the hydrogenation product of naphthalene, so as to realize hydrogen production and storage. The method is as follows:

[0126] (1) 10 g of the naphthalene dicarboxylic acid cerium-based underground hydrogen source A3 was injected into a porous sandstone containing illite at normal temperature and pressure, so that the underground hydrogen source was in full contact with the illite to form an underground hydrogen source system. The mass fraction of illite in the porous sandstone was 0.4%, and the porous sandstone contained crude oil and water in the pores before the underground hydrogen source was injected, with a water content of 40% and an oil content of 60%. The diameter of the porous sandstone was 3.8 cm, the length was 10.7 cm, and the porosity was 26%.

[0127] (2) The above underground hydrogen source system was heated to 200°C, and the pressure was increased to 7 MPa, which was maintained for 240 hours, during which sampling was performed at irregular intervals.

[0128] (3) The hydrogen content in the sampled gas was detected by gas chromatography, and the naphthalene and its hydrogenation products in the sampled liquid were detected by gas chromatography. The results are shown in Table 3 below. As can be seen from the data in Table 3, this embodiment can produce hydrogen at a lower temperature, and can completely consume naphthalene to achieve hydrogen storage.

[0129] (4) Control Experiment 1: According to the steps (1)-(3) of this example, the heating temperature is lowered to 140°C, and no hydrogen gas is generated and no hydrogenation product of naphthalene is generated within 48 hours. The temperature is continuously increased to 150°C, and hydrogen gas is detected after 42 hours and tetrahydro-naphthalene is detected after 72 hours.

[0130] (5) Control Experiment 2: According to the steps (1)-(3) of this example, but the underground hydrogen source is replaced by pure naphthalene, i.e. the rare earth-based complex is removed therefrom. As a result, neither hydrogen gas is generated nor hydrogenation product of naphthalene is generated.

[0131] Table 3

[0132]

[0133] Example 8

[0134] This example is used to illustrate the application of the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to the present application as an underground hydrogen source.

[0135] The rare earth-based naphthalene dicarboxylic acid underground hydrogen source A4 prepared in Example 4 is injected into a high-temperature porous medium containing illite to generate hydrogen gas and hydrogenation product of naphthalene to achieve hydrogen production and hydrogen storage, and the use method is as follows:

[0136] (1) 10 g of the rare earth-based naphthalene dicarboxylic acid underground hydrogen source A4 is injected into porous sandstone containing illite at normal temperature and pressure to make the underground hydrogen source fully contact with the illite to form an underground hydrogen source system, the mass fraction of illite in the porous sandstone is 0.4%, and the porous sandstone contains crude oil and water in the pores before the injection of the underground hydrogen source, wherein the water content is 40% and the oil content is 60%, the diameter of the porous sandstone is 3.8 cm, the length is 10.3 cm, and the porosity is 26%.

[0137] (2) The above underground hydrogen source system is heated to 150°C, and the pressure is increased to 2 MPa, and maintained for 12 hours, and samples are taken at irregular intervals during the period.

[0138] (3) The hydrogen content in the sampled gas is detected by gas chromatography, and the naphthalene and its hydrogenation product in the sampled liquid are detected by gas chromatography, and the results are shown in Table 4 below. As can be seen from the data in Table 4, the present embodiment can produce hydrogen at a lower temperature and completely consume naphthalene to achieve hydrogen storage.

[0139] (4) Control Experiment 1: According to the steps (1)-(3) of this example, the heating temperature is lowered to 140°C, and no hydrogen gas is generated and no hydrogenation product of naphthalene is generated within 48 hours. The temperature is continuously increased to 150°C, and hydrogen gas is detected after 42 hours and tetrahydro-naphthalene is detected after 72 hours.

[0140] (5) Control Experiment 2: According to the steps (1)-(3) of the present example, but the underground hydrogen source is replaced by pure naphthalene, i.e. the rare earth-based complex is removed therefrom, as a result, neither hydrogen gas nor hydrogenated product of naphthalene is generated.

[0141] Table 4

[0142]

[0143] As can be seen from the above examples, for the underground hydrogen source based on cyclopentadienyl cerium, cyclopentadienyl rare earth, naphthalene dicarboxylic acid cerium, and naphthalene dicarboxylic acid rare earth, all of them can be used as the underground hydrogen source, and after being injected into the porous sandstone containing 0.4-3.2% illite, under the conditions of temperature 150-350℃ and pressure 2-16 MPa, hydrogen gas, tetrahydronaphthalene, and decahydronaphthalene can be detected within 12-240 hours.

[0144] As a comparison: first, when the content of illite is reduced to 0.08%, hydrogen gas is generated but no hydrogenated product of naphthalene is generated, which indicates that the lower limit of the content of illite is a necessary condition; second, when the temperature is reduced to 140℃, neither hydrogen gas nor hydrogenated product of naphthalene is generated, and after being increased to 150℃, the generation of the hydrogenated product can be detected, which indicates that the lower limit of the temperature is a necessary condition; third, when the mass fraction of naphthalene in the underground hydrogen source is increased from 10% to 50%, hydrogen gas and the hydrogenated product of naphthalene are generated in the initial stage of the reaction, and naphthalene can be detected, and the sampling after 48 hours shows that there is no hydrogen gas and naphthalene, but there is tetrahydronaphthalene and decahydronaphthalene, which indicates that in the case of excess naphthalene, the hydrogen gas generated by the underground hydrogen source can be completely converted into the hydrogen storage product; fourth, as a blank experiment, when the rare earth-based complex in the underground hydrogen source based on the low-temperature catalytic hydrogen transfer of hydrocarbons is removed, neither hydrogen gas nor hydrogenated product of naphthalene can be generated, which indicates that the rare earth-based complex plays an irreplaceable catalytic role therein.

[0145] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all of them belong to the protection scope of the present application.

Claims

1. An underground hydrogen source based on low-temperature catalytic hydrogen transfer from hydrocarbons, characterized in that, This underground hydrogen source contains: (a) A rare earth-based complex, wherein the rare earth-based complex is a complex of a hydrocarbon liquid and one or more rare earth compounds, and the rare earth-based complex is prepared by the following method: reacting one or more rare earth compounds with one or more hydrocarbon liquids, separating the liquid from the reaction mixture, which is the rare earth-based complex, wherein the reaction temperature is 60-100°C, and the reaction time is 1-8h. as well as (b) Naphthalene; The rare earth element in the rare earth compound is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium, and the rare earth compound is selected from at least one of rare earth metal organometallic complexes and rare earth metal aromatic organic acid complexes.

2. The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to claim 1, characterized in that, The total amount of the underground hydrogen source is 100wt%, the content of the rare earth-based complex is 70-99.9wt%, and the content of naphthalene is 0.1-30wt%.

3. The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to claim 1, characterized in that, In the rare earth composite, rare earth elements account for 0.1-5% of the total mass of the rare earth composite.

4. The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to any one of claims 1-3, characterized in that, The rare earth compound is at least one of dicerocene rare earth metal organic complexes and naphthalene-based organic acid rare earth complexes.

5. The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to any one of claims 1-3, characterized in that, The hydrocarbon liquid is a petroleum hydrocarbon liquid or a petroleum refining product.

6. The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons according to claim 5, characterized in that, The hydrogen-to-carbon atomic ratio of the hydrocarbon liquid is not less than 1.

62.

7. A method for preparing an underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons as described in any one of claims 1-6, characterized in that, The method includes the following steps: (1) React one or more rare earth compounds with one or more hydrocarbon liquids and separate the liquid from the reaction mixture; (2) Mix the liquid separated in step (1) with naphthalene, and then separate the liquid from the mixture.

8. The method according to claim 7, characterized in that, In step (1), the reaction temperature is 60-100℃ and the reaction time is 1-8h.

9. The method according to claim 7, characterized in that, In step (2), the mixing process is carried out at a temperature of 60-72°C for 1-10 hours.

10. A method of using the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons as described in any one of claims 1-6, or the underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons prepared according to the method described in any one of claims 7-9, characterized in that, The method includes: (1) The underground hydrogen source based on low-temperature catalytic hydrogen transfer of hydrocarbons is injected into a porous medium containing illite to form a hydrogen production and storage system; (2) The temperature and pressure of the hydrogen production and storage system are increased to 150-350℃ and 1-16MPa, respectively, to generate hydrogen and naphthalene hydrogenation products, thereby achieving hydrogen production and storage. In the illite-containing porous medium, the mass fraction of illite is not less than 0.2%.

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