A catalyst for low-temperature catalytic cracking of crude oil, a preparation method and application thereof

Abstract

The present application relates to the technical field of oil and gas field development, and discloses a crude oil low-temperature catalytic cracking catalyst as well as a preparation method and application thereof.The crude oil low-temperature catalytic cracking catalyst contains naphthalene sulfonate or naphthalene sulfonate derivative salt, naphthalene sulfonic acid or naphthalene sulfonic acid derivative, hydroxynaphthoic acid, transition metal organic acid salt, 1,10-phenanthroline, internal olefin sulfonate, rare earth metal compound and solvent.The crude oil low-temperature catalytic cracking catalyst can produce olefin hydrogenation precursors below 350 DEG C by the action of naphthalene sulfonate, hydroxynaphthoic acid metal, internal olefin sulfonic acid rare earth and other components on heavy crude oil in the presence of clay mineral porous medium.

Description

Technical Field

[0001] This invention relates to the field of oil and gas field development technology, specifically to a low-temperature catalytic cracking catalyst for crude oil, its preparation method, and its application. Background Technology

[0002] Global proven reserves of high-viscosity crude oil are 815 billion tons, accounting for 70% of the remaining oil reserves. It is a large-scale strategic resource and presents a revolutionary opportunity. Once new theoretical and technological breakthroughs are achieved, it is expected to bring about tremendous changes in my country's oil and gas production and security situation, which deserves high attention.

[0003] In-situ refining transforms heavy oil into light oil irreversibly through catalytic refining within the reservoir, significantly improving recovery rates and upgrading inferior resources into high-quality resources. This enables the entire industry chain to utilize energy in a single step and reduce energy consumption and emissions, essentially creating an "underground refinery." It is expected to solve the efficiency and environmental issues of extraction, gathering, transportation, and refining. Its scientific questions are clear, its technical route is well-defined, and it has been verified by field tests.

[0004] One of the core reactions in in-situ reforming is the catalytic cracking and hydrogenation of heavy component macromolecules. The ability to efficiently produce hydrogenation precursors through catalytic cracking is crucial to the success of the process. Currently, there are two main technologies for producing olefin hydrogenation precursors through cracking. The first is conventional thermal cracking, which requires very high temperatures (700-900℃) and is accompanied by severe coking (dehydrogenation producing elemental carbon), making it unsuitable for in-situ reforming. The second is catalytic pyrolysis (CPP), which uses heavy oil as feedstock and employs a proprietary catalyst to lower the temperature to 500-700℃, producing ethylene and propylene under milder operating conditions than steam cracking. This broadens the feedstock sources for ethylene and propylene production, and due to the milder operating conditions, the equipment and material requirements are lower, resulting in relatively lower investment and high economic value. However, even with this technology, it is difficult to reach temperatures above 500℃ in oil reservoirs, thus limiting its use for in-situ reforming. The common technical bottleneck of the two routes mentioned above is that the required temperature is much higher than the temperature that can be easily achieved when heating the reservoir. Even if the reservoir is heated to above 500°C by electric heating or air injection to burn the oil layer, it is not economically feasible.

[0005] Therefore, there is an urgent need for a catalyst, preparation method, and application method that can cause heavy crude oil to crack at a lower temperature to produce olefin hydrogenation precursors, in order to overcome the shortcomings of existing technologies. Summary of the Invention

[0006] The purpose of this invention is to overcome the problem that the reaction temperature of existing catalytic cracking catalysts is too high, making them unsuitable for in-situ reforming of oil reservoirs. This invention provides a low-temperature catalytic cracking catalyst for crude oil, its preparation method, and its application. This low-temperature catalytic cracking catalyst can be used to provide hydrogenation precursors such as small molecule olefins for in-situ reforming catalytic hydrogenation reactions. The required temperature is significantly lower than that of the CPP process, and it can be generated in-situ within the oil reservoir.

[0007] To achieve the above objectives, the present invention provides a low-temperature catalytic cracking catalyst for crude oil, which contains the following components:

[0008] (a) One or more naphthalene sulfonates or naphthalene sulfonic acid derivative salts;

[0009] (b) One or more naphthalenesulfonic acids or naphthalenesulfonic acid derivatives;

[0010] (c) One or more hydroxynaphthoic acids;

[0011] (d) Transition metal organoacid salts;

[0012] (e)1,10-phenanthroline;

[0013] (f) One or more internal olefin sulfonates;

[0014] (g) rare earth metal compounds; and

[0015] (h) Solvent.

[0016] Preferably, the mass ratio of components (a) to (h) is (1-10):(1-10):(1-20):(0.5-10):(0.1-5):(1-10):(1-10):100.

[0017] More preferably, the mass ratio of components (a) to (h) is (2-5):(3-8):(2-10):(0.8-5):(0.3-3):(2-5):(3-6):100.

[0018] Preferably, the naphthalene sulfonate or naphthalene sulfonic acid derivative salt is selected from at least one of α-naphthalene sulfonate, β-naphthalene sulfonate, hydroxylated α-naphthalene sulfonate and hydroxylated β-naphthalene sulfonate, and is more preferably cobalt β-naphthalene sulfonate and / or nickel 6-hydroxy-2-naphthalene sulfonate.

[0019] Preferably, the naphthalenesulfonic acid or naphthalenesulfonic acid derivative is selected from at least one of α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, hydroxylated α-naphthalenesulfonic acid, and hydroxylated β-naphthalenesulfonic acid.

[0020] Preferably, the hydroxynaphthoic acid is selected from at least one of 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-6-naphthoic acid.

[0021] Preferably, the transition metal organophosphate is manganese acetate and / or molybdenum acetate.

[0022] Preferably, the olefin sulfonate is a C8-C26 olefin sulfonate, and more preferably a C18-C24 olefin sulfonate sodium salt.

[0023] Preferably, the rare earth metal compound is a light rare earth metal compound, wherein the light rare earth metal is selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium.

[0024] More preferably, the rare earth metal compound is selected from at least one of lanthanum acetate, cerium acetate, light rare earth acetate, lanthanum chloride, cerium chloride, and light rare earth chloride.

[0025] Preferably, the solvent is selected from at least one of petroleum products and crude oil.

[0026] A second aspect of the present invention provides a method for preparing the above-mentioned low-temperature catalytic cracking catalyst for crude oil, the method comprising the following steps:

[0027] (1) Disperse naphthalenesulfonic acid or naphthalenesulfonic acid derivatives in a solvent to obtain a first dispersion;

[0028] (2) Disperse naphthalene sulfonate or naphthalene sulfonic acid derivative salt in the first dispersion to obtain a second dispersion;

[0029] (3) Disperse hydroxynaphthoic acid in the second dispersion to obtain a third dispersion;

[0030] (4) Disperse the transition metal organophosphate in the third dispersion to obtain the fourth dispersion;

[0031] (5) Mix 1,10-phenanthroline with the fourth dispersion, heat and stir, and then separate after cooling;

[0032] (6) Disperse the rare earth metal compound in the upper oil phase separated in step (5) to obtain the fifth dispersion;

[0033] (7) Mix the inner olefin sulfonate, water and the fifth dispersion, heat, stir, cool and then separate the upper oil phase.

[0034] Preferably, in step (5), the temperature is heated to 85-95°C and the stirring time is 1-20 hours.

[0035] Preferably, in step (7), the temperature is heated to 55-65°C and the stirring time is 1-20 hours.

[0036] The third aspect of this invention provides the application of the crude oil low-temperature catalytic cracking catalyst described above or the crude oil low-temperature catalytic cracking catalyst prepared according to the method described above in the in-situ upgrading process of underground oil reservoirs.

[0037] Preferably, the application process includes:

[0038] (1) The crude oil low-temperature catalytic cracking catalyst is mixed with heavy crude oil in a porous medium containing clay minerals;

[0039] (2) Heat the mixture to 220-350℃ and react for 1-200h.

[0040] Preferably, the mass fraction of the clay mineral in the porous medium is not less than 0.2%.

[0041] Preferably, the clay mineral is one or more of illite, kaolinite, chlorite, montmorillonite, and vermiculite.

[0042] Preferably, the porous medium is one or more of natural rock, granular deposits, and solids containing internal pores.

[0043] Preferably, the mass ratio of the crude oil low-temperature catalytic cracking catalyst to the heavy crude oil is 1:10-1000.

[0044] Through the above technical solution, the crude oil low-temperature catalytic cracking catalyst of the present invention is used in porous media containing clay minerals. By reacting components such as naphthalene sulfonate, metal hydroxynaphthoic acid, and rare earth sulfonates with heavy crude oil, olefin hydrogenation precursors can be generated at temperatures below 350°C. Compared with existing technologies, this not only enables in-situ generation of olefin hydrogenation precursors from underground reservoirs but also significantly reduces the required process temperature. Detailed Implementation

[0045] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0046] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0047] The crude oil low-temperature catalytic cracking catalyst of the present invention contains the following components:

[0048] (a) One or more naphthalene sulfonates or naphthalene sulfonic acid derivative salts;

[0049] (b) One or more naphthalenesulfonic acids or naphthalenesulfonic acid derivatives;

[0050] (c) One or more hydroxynaphthoic acids;

[0051] (d) Transition metal organoacid salts;

[0052] (e)1,10-phenanthroline;

[0053] (f) One or more internal olefin sulfonates;

[0054] (g) rare earth metal compounds; and

[0055] (h) Solvent.

[0056] In the crude oil low-temperature catalytic cracking catalyst of the present invention, the mass ratio of components (a) to (h) can be (1-10):(1-10):(1-20):(0.5-10):(0.1-5):(1-10):(1-10):100, preferably (2-5):(3-8):(2-10):(0.8-5):(0.3-3):(2-5):(3-6):100.

[0057] In the crude oil low-temperature catalytic cracking catalyst of the present invention, the content of the naphthalene sulfonate or naphthalene sulfonic acid derivative salt (i.e., component (a)) relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 2-5 parts by weight, specifically, for example, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or 5 parts by weight. The naphthalene sulfonate or naphthalene sulfonic acid derivative salt can be selected from at least one of α-naphthalene sulfonate, β-naphthalene sulfonate, hydroxylated α-naphthalene sulfonate, and hydroxylated β-naphthalene sulfonate, preferably cobalt β-naphthalene sulfonate and / or nickel 6-hydroxy-2-naphthalene sulfonate, most preferably a mixture of cobalt β-naphthalene sulfonate and nickel 6-hydroxy-2-naphthalene sulfonate, and the mixing ratio of the two can be 1:0.5-2, most preferably 1:1.

[0058] In one embodiment, the naphthalene sulfonate or naphthalene sulfonic acid derivative salt can be a rare earth naphthalene sulfonic acid, which is a mixture of α-naphthalene sulfonate and β-naphthalene sulfonate, and the rare earth element therein is a mixture of light rare earth elements, wherein the light rare earth element refers to at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.

[0059] In the crude oil cryogenic catalytic cracking catalyst of the present invention, the content of naphthalenesulfonic acid or naphthalenesulfonic acid derivative (i.e., component (b)) relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 3-8 parts by weight, specifically, for example, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, or 8 parts by weight. The naphthalenesulfonic acid or naphthalenesulfonic acid derivative can be selected from at least one of α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, hydroxylated α-naphthalenesulfonic acid, and hydroxylated β-naphthalenesulfonic acid, preferably naphthalenesulfonic acid (i.e., α-naphthalenesulfonic acid and / or β-naphthalenesulfonic acid).

[0060] In the crude oil cryogenic catalytic cracking catalyst of the present invention, the content of hydroxynaphthoic acid (i.e., component (c)) relative to 100 parts by weight of the solvent can be 1-20 parts by weight, preferably 2-10 parts by weight, specifically, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight. The hydroxynaphthoic acid can be selected from at least one of 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-6-naphthoic acid.

[0061] In the low-temperature catalytic cracking catalyst for crude oil described in this invention, the content of the transition metal organophosphate (i.e., component (d)) relative to 100 parts by weight of the solvent can be 0.5-10 parts by weight, preferably 0.8-5 parts by weight. Specifically, for example, it can be 0.8 parts by weight, 0.92 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.3 parts by weight, 4.5 parts by weight, or 5 parts by weight. The transition metal in the transition metal organophosphate can be a Group IVB metal, Group VB metal, Group VIB metal, Group VIIB metal, or Group VIII metal, preferably a Group VIB metal or Group VIIB metal, more preferably Mn or Mo. The organic acid in the transition metal organophosphate can be a C1-C8 monocarboxylic acid or dicarboxylic acid, preferably acetic acid. In a preferred embodiment, the transition metal organophosphate is manganese acetate and / or molybdenum acetate.

[0062] In the crude oil low-temperature catalytic cracking catalyst of the present invention, the content of 1,10-phenanthroline (i.e., component (e)) relative to 100 parts by weight of the solvent can be 0.1-5 parts by weight, preferably 0.3-3 parts by weight, specifically, for example, 0.3 parts by weight, 0.4 parts by weight, 0.47 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.25 parts by weight, 2.5 parts by weight, 2.8 parts by weight, or 3 parts by weight.

[0063] In the crude oil low-temperature catalytic cracking catalyst of the present invention, the content of the inner olefin sulfonate (i.e., component (f)) relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 2-5 parts by weight. Specifically, for example, it can be 2 parts by weight, 2.5 parts by weight, 2.97 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 3.83 parts by weight, 4 parts by weight, 4.5 parts by weight, or 5 parts by weight. The inner olefin sulfonate can be a C8-C26 inner olefin sulfonate, preferably an inner olefin sulfonate with a high content of C18-C24 β-hydroxysulfonate, and more preferably a C18-C24 inner olefin sulfonate sodium salt.

[0064] In the crude oil low-temperature catalytic cracking catalyst of the present invention, the content of the rare earth metal compound (i.e., component (g)) relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 3-6 parts by weight, specifically, for example, 3 parts by weight, 3.17 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 4.8 parts by weight, 5 parts by weight, 5.2 parts by weight, 5.5 parts by weight, or 6 parts by weight. In a preferred embodiment, the rare earth metal compound is a light rare earth metal compound, wherein the light rare earth metal is selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium. The rare earth metal compound can be an inorganic acid salt and / or an organic acid salt of a rare earth metal. In a more preferred embodiment, the rare earth metal compound is selected from at least one of lanthanum acetate, cerium acetate, light rare earth acetate (wherein light rare earth refers to a combination of multiple light rare earth metals), lanthanum chloride, cerium chloride, and light rare earth chloride (wherein light rare earth refers to a combination of multiple light rare earth metals).

[0065] In the low-temperature catalytic cracking catalyst for crude oil described in this invention, the solvent can be selected from at least one of petroleum products and crude oil. The petroleum product can be, for example, diesel oil.

[0066] The above-mentioned low-temperature catalytic cracking catalyst for crude oil can be prepared by simple mixing.

[0067] In a preferred embodiment, to obtain better performance, the preparation method of the crude oil low-temperature catalytic cracking catalyst includes:

[0068] (1) Disperse naphthalenesulfonic acid or naphthalenesulfonic acid derivatives in a solvent to obtain a first dispersion (also known as naphthalenesulfonic acid dispersion);

[0069] (2) Disperse naphthalene sulfonate or naphthalene sulfonic acid derivative salt in the first dispersion to obtain a second dispersion (also known as naphthalene sulfonate composition);

[0070] (3) Disperse hydroxynaphthoic acid in the second dispersion to obtain a third dispersion (also known as naphthalene sulfonate-hydroxynaphthoic acid dispersion);

[0071] (4) Disperse the transition metal organophosphate in the third dispersion to obtain the fourth dispersion (also known as naphthalene sulfonate-hydroxynaphthoic acid metal dispersion);

[0072] (5) Mix 1,10-phenanthroline with the fourth dispersion, heat and stir, and then separate after cooling;

[0073] (6) Disperse the rare earth metal compound in the upper oil phase (also known as naphthalene sulfonate-hydroxynaphthoic acid metal composition) separated in step (5) to obtain the fifth dispersion (also known as naphthalene sulfonate-hydroxynaphthoic acid metal-rare earth composition);

[0074] (7) Mix the inner olefin sulfonate, water and the fifth dispersion, heat, stir, cool, and then separate the upper oil phase, which is the crude oil low-temperature catalytic cracking catalyst of the present invention.

[0075] In the above method, the dispersion process in step (1) is carried out under stirring, and the stirring time can be 10-60 minutes.

[0076] In the above method, the dispersion process in step (2) is carried out under stirring, and the stirring time can be 10-60 minutes.

[0077] In the above method, the dispersion process in step (3) is carried out under stirring, and the stirring time can be 5-30 minutes.

[0078] In the above method, the dispersion process in step (4) is carried out under stirring, and the stirring time can be 10-60 minutes.

[0079] In the above method, in step (5), the temperature is heated to 85-95°C and the stirring time is 1-20 hours.

[0080] In the above method, the dispersion process in step (6) is carried out under stirring, and the stirring and mixing time can be from 30 minutes to 3 hours.

[0081] In the above method, in step (7), the temperature is heated to 55-65°C and the stirring time is 1-20h.

[0082] In the above method, the amount of naphthalene sulfonate or naphthalene sulfonic acid derivative salt used relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 2-5 parts by weight. The naphthalene sulfonate or naphthalene sulfonic acid derivative salt can be selected from at least one of α-naphthalene sulfonate, β-naphthalene sulfonate, hydroxylated α-naphthalene sulfonate, and hydroxylated β-naphthalene sulfonate, preferably cobalt β-naphthalene sulfonate and / or nickel 6-hydroxy-2-naphthalene sulfonate, most preferably a mixture of cobalt β-naphthalene sulfonate and nickel 6-hydroxy-2-naphthalene sulfonate, and the mixing ratio of the two can be 1:0.5-2, most preferably 1:1.

[0083] In one embodiment, the naphthalene sulfonate or naphthalene sulfonic acid derivative salt can be a rare earth naphthalene sulfonic acid, which is a mixture of α-naphthalene sulfonate and β-naphthalene sulfonate, and the rare earth element therein is a mixture of light rare earth elements, wherein the light rare earth element refers to at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.

[0084] In the above method, the amount of naphthalenesulfonic acid or naphthalenesulfonic acid derivative used relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 3-8 parts by weight. The naphthalenesulfonic acid or naphthalenesulfonic acid derivative can be selected from at least one of α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, hydroxylated α-naphthalenesulfonic acid, and hydroxylated β-naphthalenesulfonic acid, preferably naphthalenesulfonic acid (i.e., α-naphthalenesulfonic acid and / or β-naphthalenesulfonic acid).

[0085] In the above method, the amount of hydroxynaphthoic acid used relative to 100 parts by weight of the solvent can be 1-20 parts by weight, preferably 2-10 parts by weight. The hydroxynaphthoic acid can be selected from at least one of 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-6-naphthoic acid.

[0086] In the above method, the amount of the transition metal organometallic acid salt relative to 100 parts by weight can be 0.5-10 parts by weight, preferably 0.8-5 parts by weight. The transition metal in the transition metal organometallic acid salt can be a Group IVB, Group VB, Group VIB, Group VIIB, or Group VIII metal, preferably a Group VIB or Group VIIB metal, more preferably Mn or Mo. The organic acid in the transition metal organometallic acid salt can be a C1-C8 monocarboxylic acid or dicarboxylic acid, preferably acetic acid. In a preferred embodiment, the transition metal organometallic acid salt is manganese acetate and / or molybdenum acetate.

[0087] In the above method, the amount of 1,10-phenanthroline used relative to 100 parts by weight of the solvent can be 0.1-5 parts by weight, preferably 0.3-3 parts by weight.

[0088] In the above method, the amount of the inner olefin sulfonate relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 2-5 parts by weight. The inner olefin sulfonate can be a C8-C26 inner olefin sulfonate, preferably an inner olefin sulfonate with a high content of C18-C24 β-hydroxysulfonate, and more preferably sodium C18-C24 inner olefin sulfonate.

[0089] In the above method, the amount of the rare earth metal compound used relative to 100 parts by weight of the solvent can be 1-10 parts by weight, preferably 3-6 parts by weight. In a preferred embodiment, the rare earth metal compound is a light rare earth metal compound, wherein the light rare earth metal is selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and europium. The rare earth metal compound can be an inorganic acid salt and / or an organic acid salt of a rare earth metal. In a more preferred embodiment, the rare earth metal compound is selected from at least one of lanthanum acetate, cerium acetate, light rare earth acetate (wherein light rare earth refers to a combination of multiple light rare earth metals), lanthanum chloride, cerium chloride, and light rare earth chloride (wherein light rare earth refers to a combination of multiple light rare earth metals).

[0090] In the above method, in step (7), the amount of water used relative to 100 parts by weight of the solvent can be 10-50 parts by weight, preferably 20-40 parts by weight. The water can be purified water, deionized water, etc.

[0091] In the above method, the solvent can be selected from at least one of petroleum products and crude oil. The petroleum product can be, for example, diesel oil.

[0092] This invention also provides the application of the crude oil low-temperature catalytic cracking catalyst described above or the crude oil low-temperature catalytic cracking catalyst prepared according to the method described above in the in-situ upgrading process of underground oil reservoirs.

[0093] In a preferred embodiment, the application process includes:

[0094] (1) The crude oil low-temperature catalytic cracking catalyst is mixed with heavy crude oil in a porous medium containing clay minerals;

[0095] (2) Heat the mixture to 220-350℃ and react for 1-200h.

[0096] During the application, the mass fraction of the clay mineral in the porous medium is not less than 0.2%, preferably more than 1%, and more preferably more than 2% (e.g., 2-10%). In specific embodiments, the mass fraction of the clay mineral in the porous medium is 2%, 3%, 2.7%, 3%, 4%, 5%, 5.3%, 6%, 7%, 8%, 9%, or 10%.

[0097] In the application process, the clay mineral can be one or more of illite, kaolinite, chlorite, montmorillonite, and vermiculite.

[0098] In the application, the porous medium can be one or more of natural rock, granular deposits, and solids with internal pores.

[0099] In the application process, the mass ratio of the crude oil low-temperature catalytic cracking catalyst to the heavy crude oil can be 1:10-1000, preferably 1:20-800, and more preferably 50-500.

[0100] The main technical idea of ​​this invention is to abandon traditional petroleum refining catalysis theories and commonly used techniques. It does not rely on external factors such as alumina and calcium oxide, nor on the low activation energy of catalytic centers formed by alumina lattice defects and the empty outer orbitals of transition metals to accommodate and decompose chemical bonds (electron clouds) such as CC, CS, CN, and CO. Instead, it shifts the focus from "artificial external defects" to "utilizing internal structures," that is, taking the "internal factors" of the high-viscosity crude oil molecular structure as the starting point. By matching the catalyst with the typical molecular structure of high-viscosity crude oil, and through the synergistic effect of intermolecular forces, the activation energy is significantly reduced, thereby significantly lowering the reaction temperature. Specifically, in a porous medium containing clay minerals, catalytic cracking of crude oil can occur at temperatures below 350°C through the interaction of naphthalene sulfonate, hydroxynaphthoic acid metal, and rare earth sulfonates with heavy crude oil, producing olefin hydrogenation precursors.

[0101] Using the crude oil low-temperature catalytic cracking catalyst described in this invention for in-situ upgrading of high-viscosity crude oil has two advantages: firstly, it has a good viscosity reduction effect, with a viscosity reduction rate of over 99% and a significant increase in production; secondly, it can catalytically crack at temperatures below 350°C to produce olefin hydrogenation precursors, making in-situ upgrading possible in underground reservoirs.

[0102] Current crude oil (heavy oil) catalytic cracking technologies mainly use molecular sieves doped with precious metals and metal oxides as catalysts, with reaction temperatures exceeding 500°C. To produce olefins, the reaction temperature reaches even higher levels, exceeding 600°C. Furthermore, these catalysts are expensive, cannot be injected into the wellbore, and are unsuitable for heavy oil and oil sands production. Compared to existing technologies, the technical solution of this invention has the following advantages:

[0103] (1) The reaction temperature of catalytic cracking is reduced from above 500℃ to below 350℃, making it practically valuable for oilfield development;

[0104] (2) The catalytic cracking products contain a large amount of olefins, which are deep cracking products with high economic value;

[0105] (3) The catalyst is no longer a solid particle or cluster, but can flow and be injected into the reservoir with the liquid, which is practical.

[0106] The following examples further illustrate the crude oil low-temperature catalytic cracking catalyst, its preparation method, and its application according to the present invention. The examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0107] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0108] Example 1

[0109] This embodiment is used to illustrate the crude oil low-temperature catalytic cracking catalyst and its preparation method according to the present invention.

[0110] The crude oil low-temperature catalytic cracking catalyst prepared in this embodiment contains: cobalt β-naphthalenesulfonate, nickel 6-hydroxy-2-naphthalenesulfonate, naphthalenesulfonic acid, 3-hydroxy-2-naphthoic acid, manganese acetate, 1,10-phenanthroline, sodium sulfonate of C18-C24 olefins, cerium acetate, and diesel oil. Its preparation process is as follows:

[0111] (1) Add 5g of naphthalenesulfonic acid to 100g of diesel oil and stir for 30 minutes until completely dissolved to form a naphthalenesulfonic acid dispersion;

[0112] (2) Add 1g of cobalt β-naphthalenesulfonate and 1g of nickel 6-hydroxy-2-naphthalenesulfonate to the above naphthalenesulfonic acid dispersion, stir for 30 minutes, and it will be completely dissolved to form a naphthalenesulfonate composition;

[0113] (3) Add 10g of 3-hydroxy-2-naphthoic acid to the above naphthalene sulfonate composition and stir for 10 minutes to obtain naphthalene sulfonate-hydroxynaphthoic acid dispersion;

[0114] (4) Add 4.3g of manganese acetate to the above naphthalene sulfonate-hydroxynaphthoic acid dispersion and stir for 30 minutes to obtain naphthalene sulfonate-hydroxynaphthoic acid metal dispersion;

[0115] (5) Add 2.25g of 1,10-phenanthroline (purchased from Aladdin) to the above naphthalene sulfonate-hydroxynaphthoic acid metal dispersion, heat to 90°C and stir for 8 hours, cool and separate to obtain the upper oil phase, which is the naphthalene sulfonate-hydroxynaphthoic acid metal composition.

[0116] (6) Add 3.17g of anhydrous cerium acetate (purchased from Aladdin) to the above naphthalene sulfonate-hydroxynaphthoic acid metal composition and stir for 1 hour to obtain naphthalene sulfonate-hydroxynaphthoic acid metal-rare earth composition;

[0117] (7) Add 3.83g of sodium sulfonate of C18-C24 inner olefins and 25mL of purified water to the above naphthalene sulfonate-hydroxynaphthoic acid metal-rare earth composition, heat to 60°C and stir for 8 hours, and then separate the upper oil phase after cooling. This is the crude oil low-temperature catalytic cracking catalyst Cat-1 of the present invention.

[0118] Example 2

[0119] This embodiment is used to illustrate the crude oil low-temperature catalytic cracking catalyst and its preparation method according to the present invention.

[0120] The crude oil low-temperature catalytic cracking catalyst prepared in this embodiment contains: rare earth naphthalene sulfonate (a mixture of α-naphthalene sulfonate and β-naphthalene sulfonate, wherein the rare earth elements are a mixture of light rare earth elements), naphthalene sulfonic acid, 2-hydroxy-6-naphthoic acid, molybdenum acetate, 1,10-phenanthroline, sodium sulfonate of C8-C18 inner olefins, light rare earth acetate (wherein the rare earth elements are a mixture of light rare earth elements), and diesel oil. The preparation process is as follows:

[0121] (1) Add 5g of naphthalenesulfonic acid to 100g of diesel oil and stir for 30 minutes until completely dissolved to form a naphthalenesulfonic acid dispersion;

[0122] (2) Add 5g of rare earth naphthalene sulfonic acid to the above naphthalene sulfonic acid dispersion, stir for 30 minutes and it will be completely dissolved to form a naphthalene sulfonate composition;

[0123] (3) Add 2g of 2-hydroxy-6-naphthoic acid to the above naphthalene sulfonate composition and stir for 10 minutes to obtain naphthalene sulfonate-hydroxynaphthoic acid dispersion;

[0124] (4) Add 0.92 g of molybdenum acetate to the above naphthalene sulfonate-hydroxynaphthoic acid dispersion and stir for 30 minutes to obtain naphthalene sulfonate-hydroxynaphthoic acid metal dispersion;

[0125] (5) Add 0.47 g of 1,10-phenanthroline to the above naphthalene sulfonate-hydroxynaphthoic acid metal dispersion, heat to 90°C and stir for 8 hours, and after cooling, separate the upper oil phase to obtain the naphthalene sulfonate-hydroxynaphthoic acid metal composition.

[0126] (6) Add 6g of anhydrous acetic acid light rare earth (purchased from Inner Mongolia Rare Earth Group Co., Ltd.) to the above naphthalene sulfonate-hydroxynaphthoic acid metal composition and stir for 1 hour to obtain naphthalene sulfonate-hydroxynaphthoic acid metal-rare earth composition.

[0127] (7) Add 2.97g of sodium sulfonate of C8-C18 inner olefins and 25mL of purified water to the above naphthalene sulfonate-hydroxynaphthoic acid metal-rare earth composition, heat to 60°C and stir for 8 hours, and then separate the upper oil phase after cooling. This is the crude oil low-temperature catalytic cracking catalyst Cat-2 of the present invention.

[0128] Example 3

[0129] This embodiment is used to illustrate the crude oil low-temperature catalytic cracking catalyst and its preparation method according to the present invention.

[0130] The low-temperature catalytic cracking catalyst for crude oil prepared in this embodiment contains: nickel 6-hydroxy-2-naphthalenesulfonate, naphthalenesulfonic acid, 1-hydroxy-2-naphthoic acid, manganese acetate, molybdenum acetate, 1,10-phenanthroline, sodium sulfonate of C18-C24 olefins, lanthanum chloride, and diesel oil. Its preparation process is as follows:

[0131] (1) Add 3g of naphthalenesulfonic acid to 100g of diesel oil and stir for 30 minutes until completely dissolved to form a naphthalenesulfonic acid dispersion;

[0132] (2) Add 4g of nickel 6-hydroxy-2-naphthalenesulfonate to the above naphthalenesulfonic acid dispersion, stir for 30 minutes, and it will be completely dissolved to form a naphthalenesulfonate composition;

[0133] (3) Add 6g of 1-hydroxy-2-naphthoic acid to the above naphthalene sulfonate composition and stir for 10 minutes to obtain naphthalene sulfonate-hydroxynaphthoic acid dispersion;

[0134] (4) Add 1g of manganese acetate and 1g of molybdenum acetate to the above naphthalene sulfonate-hydroxynaphthoic acid dispersion, and stir for 30 minutes to obtain naphthalene sulfonate-hydroxynaphthoic acid metal dispersion;

[0135] (5) Add 1.5g of 1,10-phenanthroline to the above naphthalene sulfonate-hydroxynaphthoic acid metal dispersion, heat to 90°C and stir for 8 hours, cool and separate to obtain the upper oil phase, which is the naphthalene sulfonate-hydroxynaphthoic acid metal composition.

[0136] (6) Add 4.5g of anhydrous lanthanum chloride (purchased from Aladdin) to the above naphthalene sulfonate-hydroxynaphthoic acid metal composition and stir for 1 hour to obtain naphthalene sulfonate-hydroxynaphthoic acid metal-rare earth composition.

[0137] (7) Add 3g of sodium sulfonate of C18-C24 olefins and 25mL of purified water to the above naphthalene sulfonate-hydroxynaphthoic acid metal-rare earth composition, heat to 60°C and stir for 8 hours, and then separate the upper oil phase after cooling. This is the crude oil low-temperature catalytic cracking catalyst Cat-3 of the present invention.

[0138] Example 4

[0139] This embodiment illustrates the application of the crude oil low-temperature catalytic cracking catalyst of the present invention in the in-situ upgrading process of underground oil reservoirs.

[0140] (1) Add 25 mL of heavy oil (taken from Liaohe Oilfield in Liaoning Province, with a viscosity of 4386 mPa·s (50℃)) to a PARR high-temperature and high-pressure reactor with a maximum capacity of 100 mL, then add 10 g of quartz sand and 1 g of natural clay (separated from underground rock cores in Liaohe Oilfield), heat to 90℃ and stir evenly, then cool to room temperature to simulate a clay-containing porous medium filled with crude oil.

[0141] (2) 1g of the crude oil low-temperature catalytic cracking catalyst prepared in Example 1 was injected into the reactor at room temperature and pressure. After heating to 90°C, the mixture was stirred evenly and cooled to room temperature so that it could be fully mixed with heavy crude oil in the sandstone porous medium.

[0142] (3) The reactor was heated stepwise to 200℃, 220℃, 240℃, 280℃, 300℃ and 350℃ and reacted for 1 hour. After each reaction, the reactor was cooled to room temperature and pressure and 1 mL of crude oil was sampled. 0.8 mL of the crude oil was used to determine the viscosity of the crude oil by HAAKE rheometer and 0.2 mL of the crude oil was used to detect the distribution of light and heavy components by whole oil gas chromatography.

[0143] The results showed that C2-C4 olefins were detected in the produced gas at temperatures ranging from 220 to 350℃, with concentrations of approximately 18-34%. Furthermore, a decrease in crude oil viscosity was observed starting at 220℃, with viscosity reduction rates of 0%, 32%, 38%, 44%, 46%, and 46% at the six temperature groups, respectively.

[0144] Comparative Experiment 1: The experimental equipment, reagents, conditions and operating steps are the same as in this embodiment. The difference is that the addition of clay is cancelled in step (1) of this embodiment. No olefin generation and significant viscosity reduction were observed in any of the 6 temperatures of this experiment, indicating that clay minerals are the key component of the low-temperature catalytic cracking catalyst for crude oil of the present invention to achieve catalytic cracking of heavy crude oil.

[0145] Comparative Experiment 2: The experimental equipment, reagents, conditions and operating steps are the same as in this embodiment. The difference is that when preparing the crude oil low-temperature catalytic cracking catalyst in step (2) of this embodiment, the addition of two types of components, naphthalene sulfonate or naphthalene sulfonic acid derivative salt and naphthalene sulfonic acid or naphthalene sulfonic acid derivative, is cancelled (i.e., the addition of cobalt β-naphthalene sulfonate, nickel 6-hydroxy-2-naphthalene sulfonate and naphthalene sulfonic acid is cancelled). No olefin formation and significant viscosity reduction were observed in any of the 6 temperatures of this group of experiments, indicating that naphthalene sulfonate or naphthalene sulfonic acid derivative salt and naphthalene sulfonic acid or naphthalene sulfonic acid derivative are essential key components for the crude oil low-temperature catalytic cracking catalyst of this invention to achieve catalytic cracking of heavy crude oil.

[0146] Comparative Experiment 3: The experimental equipment, reagents, conditions and operating steps are the same as in this embodiment. The difference is that when preparing the crude oil low-temperature catalytic cracking catalyst in step (2) of this embodiment, the addition of two components, hydroxynaphthoic acid and transition metal organophosphates, is cancelled (i.e., the addition of 3-hydroxy-2-naphthoic acid and manganese acetate is cancelled). No olefin formation and significant viscosity reduction were observed in any of the 6 temperatures of this group of experiments, indicating that hydroxynaphthoic acid and transition metal organophosphates are essential key components for the catalytic cracking of heavy crude oil by the crude oil low-temperature catalytic cracking catalyst of this invention.

[0147] Comparative Experiment 4: The experimental equipment, reagents, conditions and operating steps are the same as in this embodiment. The difference is that when preparing the crude oil low-temperature catalytic cracking catalyst in step (2) of this embodiment, the addition of two types of components, namely, internal olefin sulfonate and rare earth metal compounds, is cancelled (i.e., the addition of C18-C24 internal olefin sulfonate sodium and cerium acetate is cancelled). No olefin formation and significant viscosity reduction were observed in any of the 6 temperatures of this group of experiments, indicating that internal olefin sulfonate and rare earth metal compounds are essential key components for the crude oil low-temperature catalytic cracking catalyst of this invention to achieve catalytic cracking of heavy crude oil.

[0148] Example 5

[0149] This embodiment illustrates the application of the crude oil low-temperature catalytic cracking catalyst of the present invention in the in-situ upgrading process of underground oil reservoirs.

[0150] (1) A 15cm long and 10cm diameter core was drilled from a loose, porous, oil-saturated sandstone with a clay mineral content of 2.7% (taken from a Jurassic heavy oil reservoir on the northwestern margin of the Junggar Basin, with an original crude oil viscosity of 22370mPa·s (50℃), which is classified as extra-heavy oil). The core was placed in an annular stainless steel pressure-resistant clamp and 5g of the crude oil low-temperature catalytic cracking catalyst prepared in Example 2 was injected into it at room temperature and pressure, so that it was mixed with heavy crude oil in the porous sandstone medium.

[0151] (2) The clamp is heated to 350°C in steps at a rate of 2°C / min, starting from 200°C. 1 mL samples are taken at 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, and 350°C. The viscosity is measured by a HAAKE rheometer. The produced gas is collected in a gas bag and then detected by gas chromatography to determine whether it contains gaseous olefins.

[0152] The results are shown in Table 1. As can be seen from Table 1, C2-C4 olefin gas production can be detected starting at 220℃, and crude oil viscosity also begins to decrease at 220℃, with a maximum viscosity reduction rate of 56%.

[0153] Table 1

[0154] 200℃ none 0％ 220℃ have 8％ 240℃ have 13％ 260℃ have 14％ 280℃ have 42％ 300℃ have 46％ 350℃ have 56％

[0155] Example 6

[0156] This embodiment illustrates the application of the crude oil low-temperature catalytic cracking catalyst of the present invention in the in-situ upgrading process of underground oil reservoirs.

[0157] (1) A core sample of 8.2 cm in length and 10 cm in diameter was drilled from a loose, porous, oil-saturated sandstone with a clay mineral content of 5.3% (taken from a Jurassic heavy oil reservoir on the northwestern margin of the Junggar Basin, with an original crude oil viscosity of 20190 mPa·s (50℃), which is classified as extra-heavy oil). The core sample was placed in an annular stainless steel pressure-resistant clamp and 1 g of the low-temperature catalytic cracking catalyst for crude oil prepared in Example 3 was injected into it at room temperature and pressure, so that it was mixed with heavy crude oil in the porous sandstone medium.

[0158] (2) The clamp is heated to 350°C in steps at a rate of 2°C / min, starting from 200°C. 1 mL samples are taken at 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, and 350°C. The viscosity is measured by a HAAKE rheometer. The produced gas is collected in a gas bag and then detected by gas chromatography to determine whether it contains gaseous olefins.

[0159] The results are shown in Table 2. As can be seen from the results in Table 2, C2-C4 olefin gas production can be detected starting at 220℃, and the crude oil viscosity also begins to decrease at 220℃, with a maximum viscosity reduction rate of 54%.

[0160] Table 2

[0161] 200℃ none 0％ 220℃ have 5％ 240℃ have 8％ 260℃ have 22％ 280℃ have 37％ 300℃ have 51％ 350℃ have 54％

[0162] As can be seen from the above embodiments, the crude oil low-temperature catalytic cracking catalyst of the present invention can react with typical heavy crude oil from different oil fields at a temperature range of 220-350°C under conditions of clay content of 2.7%-10%, whether in a high-pressure reactor or a core feeder. The crude oil viscosity is significantly reduced, and C2-C4 olefin gas is generated as a hydrogenation precursor.

[0163] Based on a series of comparative experiments, the following further conclusions can be drawn: First, after removing the addition of clay, no olefin formation or significant viscosity reduction was observed at any of the six temperatures in this group of experiments, indicating that clay minerals are a key component for the low-temperature catalytic cracking catalyst of this invention to achieve catalytic cracking of heavy crude oil; Second, when preparing the low-temperature catalytic cracking catalyst for crude oil, removing the addition of two types of components (i.e., removing the addition of cobalt β-naphthalenesulfonate, nickel 6-hydroxy-2-naphthalenesulfonate, and naphthalenesulfonic acid), no olefin formation or significant viscosity reduction was observed at any of the six temperatures in this group of experiments, indicating that naphthalenesulfonate or naphthalenesulfonic acid derivative salts and naphthalenesulfonic acid or naphthalenesulfonic acid derivatives are essential key components for the low-temperature catalytic cracking catalyst of this invention to achieve catalytic cracking of heavy crude oil; Third, in the preparation of the low-temperature catalytic cracking catalyst for crude oil... In the preparation of the low-temperature catalytic cracking catalyst, the addition of two components, hydroxynaphthoic acid and transition metal organophosphates (i.e., the addition of 3-hydroxy-2-naphthoic acid and manganese acetate), was eliminated. No olefin formation or significant viscosity reduction was observed at any of the six temperatures in this group of experiments, indicating that hydroxynaphthoic acid and transition metal organophosphates are essential key components for the catalytic cracking of heavy crude oil in the low-temperature catalytic cracking catalyst of this invention. Fourthly, in the preparation of the low-temperature catalytic cracking catalyst for crude oil, the addition of two components, internal olefin sulfonates and rare earth metal compounds (i.e., the addition of C18-C24 internal olefin sulfonate sodium and cerium acetate), was eliminated. No olefin formation or significant viscosity reduction was observed at any of the six temperatures in this group of experiments, indicating that internal olefin sulfonates and rare earth metal compounds are essential key components for the catalytic cracking of heavy crude oil in the low-temperature catalytic cracking catalyst of this invention.

[0164] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A low-temperature catalytic cracking catalyst for crude oil, characterized in that, The raw materials for preparing this low-temperature catalytic cracking catalyst for crude oil contain the following components: (a) One or more naphthalene sulfonates or naphthalene sulfonic acid derivative salts; (b) One or more naphthalenesulfonic acids or naphthalenesulfonic acid derivatives; (c) One or more hydroxynaphthoic acids; (d) Transition metal organoacid salts; (e) 1,10-phenanthroline; (f) One or more internal olefin sulfonates; (g) Rare earth metal compounds; and (h) Solvent; Wherein, the naphthalene sulfonate or naphthalene sulfonic acid derivative salt is selected from at least one of α-naphthalene sulfonate, β-naphthalene sulfonate, hydroxylated α-naphthalene sulfonate, and hydroxylated β-naphthalene sulfonate; The naphthalenesulfonic acid or naphthalenesulfonic acid derivative is selected from at least one of α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, hydroxylated α-naphthalenesulfonic acid, and hydroxylated β-naphthalenesulfonic acid; The transition metal organoacid salt is manganese acetate and / or molybdenum acetate; The internal olefin sulfonate is a C8-C26 internal olefin sulfonate; The rare earth metal compound is selected from at least one of lanthanum acetate, cerium acetate, lanthanum chloride, and cerium chloride; The solvent is selected from at least one of petroleum products and crude oil; The preparation method of the crude oil low-temperature catalytic cracking catalyst includes the following steps: (1) Disperse naphthalenesulfonic acid or naphthalenesulfonic acid derivatives in a solvent to obtain a first dispersion; (2) Disperse naphthalene sulfonate or naphthalene sulfonic acid derivative salt in the first dispersion to obtain a second dispersion; (3) Disperse hydroxynaphthoic acid in the second dispersion to obtain a third dispersion; (4) Disperse the transition metal organophosphate in the third dispersion to obtain the fourth dispersion; (5) Mix 1,10-phenanthroline with the fourth dispersion, heat and stir, and separate after cooling; (6) Disperse the rare earth metal compound in the upper oil phase separated in step (5) to obtain the fifth dispersion; (7) Mix the inner olefin sulfonate, water and the fifth dispersion, heat, stir, cool and then separate the upper oil phase.

2. The low-temperature catalytic cracking catalyst for crude oil according to claim 1, characterized in that, The mass ratio of components (a) to (h) is (1-10):(1-10):(1-20):(0.5-10):(0.1-5):(1-10):(1-10):

100.

3. The low-temperature catalytic cracking catalyst for crude oil according to claim 2, characterized in that, The mass ratio of components (a) to (h) is (2-5):(3-8):(2-10):(0.8-5):(0.3-3):(2-5):(3-6):

100.

4. The crude oil low-temperature catalytic cracking catalyst according to any one of claims 1-3, characterized in that, The naphthalene sulfonate or naphthalene sulfonic acid derivative salt is cobalt β-naphthalene sulfonate and / or nickel 6-hydroxy-2-naphthalene sulfonate.

5. The crude oil low-temperature catalytic cracking catalyst according to any one of claims 1-3, characterized in that, The hydroxynaphthoic acid is selected from at least one of 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 2-hydroxy-6-naphthoic acid.

6. The crude oil low-temperature catalytic cracking catalyst according to any one of claims 1-3, characterized in that, The olefin sulfonate is a C18-C24 olefin sulfonate sodium salt.

7. The low-temperature catalytic cracking catalyst for crude oil according to claim 1, characterized in that, In step (5), the temperature is heated to 85-95°C and the stirring time is 1-20 hours.

8. The low-temperature catalytic cracking catalyst for crude oil according to claim 1, characterized in that, In step (7), the temperature is heated to 55-65°C and the stirring time is 1-20 hours.

9. The application of the crude oil low-temperature catalytic cracking catalyst according to any one of claims 1-8 in the in-situ upgrading process of underground oil reservoirs.

10. The application according to claim 9, characterized in that, The application process includes: (1) The crude oil low-temperature catalytic cracking catalyst is mixed with heavy crude oil in a porous medium containing clay minerals; (2) Heat the mixture to 220-350℃ and react for 1-200h.

11. The application according to claim 10, characterized in that, The mass fraction of the clay mineral in the porous medium is not less than 0.2%.

12. The application according to claim 10, characterized in that, The clay mineral is one or more of illite, kaolinite, chlorite, montmorillonite, and vermiculite.

13. The application according to claim 10, characterized in that, The porous medium is one or more of natural rocks and granular deposits.

14. The application according to claim 10, characterized in that, The mass ratio of the crude oil low-temperature catalytic cracking catalyst to the heavy crude oil is 1:10-1000.