Catalyst for reducing in-situ conversion activation energy of kerogen, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a catalyst for reducing the in-situ conversion activation energy of kerogen, and a preparation method therefor and the use thereof. The catalyst comprises: a first component, which comprises a composite system of an acid-treated natural mineral and an alcohol or an alcohol solution; and a second component, which comprises a system containing a phytic acid and metal ion chelate. The catalyst is mixed with an oil shale powder, and a catalytic pyrolysis reaction is performed in simulated formation conditions, thereby effectively reducing the catalytic activation energy and temperature of the pyrolysis of kerogen.

Description

A catalyst for reducing the activation energy of kerogen in-situ conversion and its preparation method and application TECHNICAL FIELD

[0001] The present application relates to a catalyst for reducing the activation energy of kerogen in-situ conversion and its preparation method and application, belonging to the technical field of oil shale in-situ conversion. BACKGROUND

[0002] Oil shale is a kind of sedimentary rock rich in solid combustible organic matter with high ash content. When heated at high temperature, it is converted into light shale oil and shale gas through thermal chemical reactions such as cracking, cyclization and polycondensation. Oil shale in-situ conversion is a new and efficient and environmentally friendly technology for developing deep underground oil shale. Its principle is to place an electric heater in the heating well and heat the oil shale reservoir by heat conduction, and then collect the produced shale oil and hydrocarbon gas. However, oil shale in-situ conversion must meet certain geological conditions and the oil shale needs to be heated to a high temperature of about 500℃ for a long time to produce oil and gas products. This restricts the in-situ conversion of oil shale.

[0003] Oil shale pyrolysis catalysts can accelerate the breaking of long-chain molecular bonds in organic matter, converting solid or heavy organic matter into flowable light petroleum hydrocarbons. Through catalytic technology, it is expected to solve the problems of high pyrolysis temperature and long heating time of oil shale, and realize the in-situ conversion of oil shale. Currently, the commonly used catalysts mainly include transition metal salt catalysts and non-transition metal salt catalysts.

[0004] Song et al. used natural clay, attapulgite and 3-mercaptopropyl trimethoxysilane (MPTMS) to prepare catalyst SO3H-APG, which reduced the pyrolysis temperature and activation energy of oil shale, improved the hydrocarbon yield in the oil shale conversion process, and reduced the content of oxygen-containing compounds and nitrogen-containing compounds (Oil shale in-situ up grading with natural clay-based catalysts: enhancement of oil yield and quality [J]. Fuel, 2022, 314: 123076.).

[0005] Chang et al. found that the use of transition metal salts CoCl2 and NiCl2 can promote the pyrolysis and secondary cracking of oil shale, but the catalysts used are poor in reducing the pyrolysis temperature of oil shale, which prevents the application of in-situ underground conversion technology of oil shale to commercial development (Investigation of the effect of selected transition metal salts on the pyrolysis of Huadian oil shale, China[J]. Oil Shale, 2017, 34:354.).

[0006] Sun Jinsheng et al. studied the catalytic pyrolysis behavior of chromium chloride on oil shale, showing that chromium chloride can reduce the pyrolysis temperature by about 50℃ and the activation energy by 44.4% (Catalytic pyrolysis of oil shale by chromium chloride and molecular simulation mechanism [J]. Journal of China University of Petroleum (Natural Science Edition), 2023, 47(1):74-80).

[0007] CN114522722A discloses a molecular sieve-containing catalyst for catalytic cracking of oil shale, comprising a rare earth mesoporous molecular sieve, a quaternary ammonium base, supported metal nano-alumina, ethyl cyclohexane, and a surfactant. The pore size of the rare earth mesoporous molecular sieve is 3–7 nm. This catalyst accelerates the conversion of oil source material to oil and gas and lowers the cracking conversion temperature of oil shale through the use of rare earth mesoporous molecular sieves. However, the catalyst has too many components, its preparation process is complex, and the compatibility of the components is poor, which limits its practical application.

[0008] CN114477317A discloses a needle-like nano-iron-based bimetallic hydroxide, in which the metal cations in the layers are composed of Fe 3+ and from Ni 2+ Mn 2+ With Co 2+ It is composed of a divalent metal cation selected from the middle, and its interlayer anion is composed of OH. - CO3 2- and OCN - Composition. This needle-shaped nano-iron-based bimetallic hydroxide possesses abundant active sites, high-temperature resistance, and structural stability. When used to catalyze the pyrolysis of oil shale, it can lower the pyrolysis temperature, achieve controllable distribution of oil shale pyrolysis products, and convert oil shale pyrolysis products into low- and medium-carbon hydrocarbon organic matter. However, although this needle-shaped nano-iron-based bimetallic hydroxide can reduce the pyrolysis temperature and activation energy during the conversion of oil shale kerogen, it is prepared by interprecipitation, which presents problems such as complex preparation process and poor catalyst stability.

[0009] CN115703076A discloses a catalyst applied in processing fossil energy substances. The catalyst contains an active component, and the active component is selected from phthalocyanine and / or its derivatives, and / or, porphyrin and / or its derivatives. The catalyst can reduce the activation energy of the pyrolysis process of fossil energy substances. However, the catalyst contains various organic substances, and adding these organic substances into the formation will pollute the formation.

[0010] CN107178350A discloses a method for in-situ extraction of hydrocarbons from oil shale. The method comprises: adding a transition metal catalyst into a supercritical fluid; injecting the supercritical fluid dissolving the transition metal catalyst into a heated well; controlling the temperature and pressure of the injected supercritical fluid to form a supercritical environment in the oil shale reservoir; heating the oil shale reservoir by the supercritical fluid, and cracking kerogen into a mixture under the action of the transition metal catalyst. The transition metal catalyst is selected from at least one of a cobalt compound and a chromium compound. However, the process of the method is complex, and is not environmentally friendly to the formation. More importantly, the effect of the transition metal catalyst used in the method in reducing the pyrolysis temperature is not ideal, and the stability of the catalyst is poor.

[0011] At present, the development of catalysts for reducing the activation energy and pyrolysis temperature of in-situ conversion of kerogen mainly focuses on the use of metal salts and organic substances. This has many problems such as the effect of reducing the activation energy and pyrolysis temperature is not ideal, the organic substances are not environmentally friendly to the formation, and the catalyst preparation process is complex.

[0012] Therefore, developing a new catalyst for reducing the activation energy of in-situ conversion of kerogen is still one of the problems to be solved in the field. SUMMARY

[0013] To solve the above technical problems, the purpose of the present application is to provide a catalyst for reducing the activation energy of in-situ conversion of kerogen, and a preparation method and application thereof. The catalyst of the present application can reduce the activation energy and pyrolysis temperature of in-situ conversion of kerogen when used for pyrolyzing oil shale.

[0014] To achieve the above purpose, the first aspect of the present application provides a catalyst for reducing the activation energy of in-situ conversion of kerogen, which comprises: a first component and a second component; the first component comprises a composite system of an acid-treated natural mineral and an alcohol or an alcohol solution, the natural mineral is a natural mineral containing magnesium and / or calcium, and the acid-treated natural mineral comprises a solid phase and a liquid phase; the second component comprises a system containing a phytic acid-metal ion chelate, and the metal ion comprises an alkaline earth metal ion and / or a transition metal ion.

[0015] In the above-mentioned catalyst, preferably, the mass ratio of the first component to the second component is 9-1:1-9.

[0016] In the above-mentioned catalyst, preferably, the acid-treated natural mineral is prepared by mixing and reacting the natural mineral containing magnesium and / or calcium with an acid solution.

[0017] In the above-mentioned catalyst, preferably, the mixing mass ratio of the natural mineral containing magnesium and / or calcium to the acid solution is 1:2-20.

[0018] In the above-mentioned catalyst, preferably, the total mass of magnesium and / or calcium in the liquid phase of the acid-treated natural mineral (calculated as the mass of the element) accounts for 20-95% of the total mass of the metal in the natural mineral containing magnesium and / or calcium. It should be noted that when both magnesium and calcium are present in the liquid phase, the total mass of magnesium and calcium is calculated.

[0019] In the above-mentioned catalyst, preferably, the composite system is prepared by mixing and reacting the acid-treated natural mineral with an alcohol or an alcohol solution.

[0020] In the above-mentioned catalyst, preferably, the mass ratio of the mass of magnesium and / or calcium in the liquid phase of the acid-treated natural mineral (calculated as the total mass of magnesium and calcium when both magnesium and calcium are present in the liquid phase) to the mass of the alcohol or the alcohol solution (calculated as the mass of the solution when an alcohol solution is used) is 8-2:2-8.

[0021] In the catalyst of the present application, the first component includes a composite system of an acid-treated natural mineral and an alcohol or an alcohol solution, wherein the acid-treated natural mineral includes a solid phase and a liquid phase. Magnesium ions and / or calcium ions in the liquid phase can form alcoholates with the alcohol; the solid phase can act as a porous and high specific surface area "reaction bed", which can fully adsorb and accommodate the alcohol and continuously provide metal ions to combine with the alcohol, thus playing a slow-release role and having strong stability. Therefore, the composite system of the present application also includes a solid phase and a liquid phase and contains alcoholates. Under the in-situ conversion conditions of oil shale formation, the alcoholates in the composite system of the present application will slowly undergo chemical reactions to form complexes of magnesium and / or calcium and alcohol, while continuously releasing water molecules, which are in a supercritical state under the in-situ conversion conditions of oil shale formation, can efficiently dissolve hydrocarbons and salts in the rock formation, enter the voids of the reticulate structure of kerogen in oil shale, and promote the discharge of generated oil and gas, thus achieving the effect of energy enhancement and oil displacement.

[0022] In the above-mentioned catalyst, preferably, the alkaline earth metal ions and / or transition metal ions include one or a combination of several of vanadium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, zinc ions, yttrium ions, zirconium ions, silver ions, magnesium ions, calcium ions and barium ions.

[0023] In the above-mentioned catalyst, preferably, the system containing the phytic acid-metal ion chelate is prepared by mixing and reacting an alkaline earth metal compound and / or a transition metal compound with a phytic acid solution.

[0024] In the above-mentioned catalyst, preferably, the mixing mass ratio of the alkaline earth metal compound and / or the transition metal compound to the phytic acid solution is 1:1-10.

[0025] In the catalyst of the present application, the second component includes a system containing a phytic acid-metal ion chelate, which has high stability. Under the conditions of in-situ conversion of oil shale formation, the present application exerts catalytic action by the metal ion in the first component and the second component, and exerts action together with the water molecules released by the alcohol compound in the first component, thereby reducing the pyrolysis temperature and reducing the activation energy of in-situ conversion of kerogen.

[0026] The second aspect of the present application provides a preparation method of the above-mentioned catalyst for reducing the activation energy of in-situ conversion of kerogen, which includes the following steps:

[0027] (1) mixing and reacting a natural mineral containing magnesium and / or calcium with an acid solution for a period of time to obtain an acid-treated natural mineral system, the acid-treated natural mineral system including a solid phase and a liquid phase;

[0028] (2) mixing and reacting the acid-treated natural mineral system obtained in step (1) with an alcohol or an alcohol solution for a period of time to obtain a composite system;

[0029] (3) mixing and reacting an alkaline earth metal compound and / or a transition metal compound with a phytic acid solution for a period of time to obtain a system containing a phytic acid-metal ion chelate;

[0030] (4) mixing the composite system obtained in step (2) with the system containing the phytic acid-metal ion chelate obtained in step (3) to obtain the catalyst for reducing the activation energy of in-situ conversion of kerogen.

[0031] In the above-mentioned preparation method, preferably, in step (1), the natural mineral containing magnesium and / or calcium includes one or a combination of magnesite, calcite, dolomite and montmorillonite. More preferably, the natural mineral containing magnesium and / or calcium is a natural mineral containing magnesium and calcium.

[0032] In the above-mentioned preparation method, preferably, in step (1), the acid solution includes an inorganic acid solution and / or an organic acid solution, the inorganic acid solution including one or a combination of sulfuric acid solution, hydrochloric acid solution, nitric acid solution and phosphoric acid solution, and the organic acid solution including one or a combination of formic acid solution, citric acid solution, oxalic acid solution and acetic acid solution; the concentration of the acid solution is 0.1-20 mol / L.

[0033] In the above preparation method, preferably, in step (1), the mixing mass ratio of the natural mineral containing magnesium and / or calcium to the acid solution is 1:2-20.

[0034] In the above preparation method, preferably, in step (1), the reaction temperature of the natural mineral containing magnesium and / or calcium to the acid solution is 20-100℃, and the reaction time is 10-60 minutes.

[0035] In the above preparation method, preferably, in step (1), the total mass of magnesium and / or calcium (in terms of the mass of the element) in the liquid phase of the natural mineral system after acid treatment accounts for 20-95% of the total mass of the metal in the natural mineral containing magnesium and / or calcium. It should be noted that when both magnesium and calcium are present, the total mass of magnesium and calcium is used.

[0036] In step (1) of the present application, the natural mineral containing magnesium and / or calcium is treated with an acid solution, which not only increases the specific surface area and pore volume of the natural mineral, but more importantly, the metal ions in the free state are obtained through acid treatment, which lays the foundation for the subsequent combination of magnesium ions and / or calcium ions with alcohol to form crystalline alcoholates. At the same time, the solid phase in the natural mineral system after acid treatment can act as a porous "reaction bed" with high specific surface area, which can fully adsorb and accommodate alcohol, and can continuously provide metal ions to combine with alcohol, play a slow-release role and have strong stability. Moreover, when used for catalytic pyrolysis of oil shale, it is also beneficial to the mass transfer and diffusion of hydrocarbons obtained after in-situ conversion of oil shale.

[0037] In the above preparation method, preferably, in step (2), the mixing ratio of the natural mineral system after acid treatment to the alcohol or alcohol solution is: the mass ratio of magnesium and / or calcium (when both magnesium and calcium are present, the total mass of magnesium and calcium is used) in the liquid phase of the natural mineral system after acid treatment to the mass of the alcohol or alcohol solution (when an alcohol solution is used, the mass of the solution is used) is 8-2:2-8.

[0038] In the above preparation method, preferably, in step (2), the alcohol includes one or a combination of several of methanol, ethanol and propanol, and the alcohol solution includes one or a combination of several of methanol aqueous solution, ethanol aqueous solution and propanol aqueous solution, and the mass concentration of the alcohol solution is 10-90%.

[0039] In the above preparation method, preferably, in step (2), the reaction temperature of the natural mineral system after acid treatment to the alcohol or alcohol solution is 20-60℃, and the reaction time is 10-60 minutes.

[0040] In step (2) of the present application, the acid-treated natural mineral system is mixed and reacted with an alcohol or an alcohol solution. Since the magnesium ions and / or calcium ions in the liquid phase of the system have empty orbitals, and the alcohol has lone pair electrons of oxygen, the magnesium ions and / or calcium ions form stable crystalline alcohol complexes with the alcohol. The alcohol complex and the acid-treated natural mineral system form a composite system, which lays the foundation for subsequent structural transformation to form a complex of magnesium and / or calcium and alcohol.

[0041] In the above preparation method, preferably, in step (3), the alkaline earth metal compound and / or the transition metal compound include one or more of salts of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, silver, magnesium, calcium, and barium.

[0042] In the above preparation method, preferably, in step (3), the mass concentration of the phytic acid solution is 5-80%.

[0043] In the above preparation method, preferably, in step (3), the mixing mass ratio of the alkaline earth metal compound and / or the transition metal compound to the phytic acid solution is 1:1-10.

[0044] In the above preparation method, preferably, in step (3), the reaction temperature of the alkaline earth metal compound and / or the transition metal compound with the phytic acid solution is 30-100°C, more preferably 50-80°C, and the reaction time is 0.5-6 hours, more preferably 1-4 hours.

[0045] In step (3) of the present application, the alkaline earth metal ions and / or the transition metal ions are complexed by the phytic acid solution to obtain a system containing a phytic acid-metal ion chelate. Phytic acid has a strong complexation with most metal ions, and has strong antioxidant properties. The alkaline earth metal compound and / or the transition metal compound treated by the phytic acid solution can form a stable phytic acid-metal ion chelate.

[0046] In the above preparation method, preferably, in step (4), the mixing mass ratio of the composite system to the system containing the phytic acid-metal ion chelate is 9-1:1-9.

[0047] The metal ions introduced into the oil shale by the two routes (i.e., the metal ions from the first component and the metal ions from the second component) of the present application have significant lewis acid characteristics, which can fully exert the catalytic effect of the metal, promote the cracking of long-chain aliphatic hydrocarbons into short-chain aliphatic hydrocarbons, and thus rapidly convert kerogen into short-chain flowable hydrocarbons through catalysis. Under this catalytic mechanism, the alkaline earth metal ions and / or the transition metal ions and the water molecules released by the alcohol complex in the composite system jointly play a role, thereby reducing the pyrolysis temperature and reducing the in-situ conversion activation energy of kerogen.

[0048] The present application also provides a catalyst for reducing the activation energy of kerogen in-situ conversion, which is prepared by the above-mentioned method for preparing a catalyst for reducing the activation energy of kerogen in-situ conversion.

[0049] The present application provides an oil shale pyrolysis method, which comprises the following steps: contacting the above-mentioned catalyst for reducing the activation energy of kerogen in-situ conversion with oil shale and performing a pyrolysis reaction to reduce the activation energy of kerogen in-situ conversion of the oil shale, so as to obtain a pyrolysis product.

[0050] In the above-mentioned oil shale pyrolysis method, preferably, the amount of the catalyst for reducing the activation energy of kerogen in-situ conversion is 10-90% of the total mass of the oil shale.

[0051] The present application has at least the following beneficial effects:

[0052] The catalyst of the present application avoids the traditional idea of adding functional components to increase energy and drive oil, but uses a slow-release technology. When the catalyst is used for pyrolyzing oil shale, it can significantly reduce the activation energy of kerogen in-situ conversion and the pyrolysis temperature. Moreover, the catalyst has high metal retention rate, good sustained effectiveness of metal ions, strong stability, good environmental protection, and simple preparation process. BRIEF DESCRIPTION OF DRAWINGS

[0053] Figure 1 is an electron microscope photo of the montmorillonite used in Example 4.

[0054] Figure 2 is an electron microscope photo of the solid phase of the acid-treated natural mineral system obtained in step (1) of Example 4. DETAILED DESCRIPTION

[0055] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail below, but it should not be understood as limiting the scope of the present application.

[0056] In the following examples and comparative examples, the specific experimental steps or conditions are not specified, and can be performed according to the conventional experimental steps described in the existing technical literature. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained by purchase.

[0057] The sources of raw materials or equipment in the following examples and comparative examples are as follows:

[0058] MgO (Mg: 42.02%, Ca: 7.18%), calcite (Mg: 30%, Ca: 50%), dolomite (Mg: 25.32%, Ca: 21.72%) and montmorillonite (Mg: 22%, Ca: 34%): Shandong Xinhai Mining Technology Equipment Co., Ltd. It should be noted that the content of Mg and Ca in these natural minerals is in terms of the mass content of Mg and Ca elements.

[0059] Sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, citric acid, oxalic acid and acetic acid: chemical pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0060] Methanol, ethanol and propanol: National Pharmaceutical Group Chemical Reagent Co., Ltd., analytical pure.

[0061] Phytic acid: chemical pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0062] Vanadium chloride, chromium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, copper chloride, zinc chloride, yttrium chloride, zirconium chloride, silver chloride, magnesium chloride, calcium chloride and barium chloride: chemical pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0063] Oil shale: 80-120 mesh, PetroChina Changqing Oilfield Branch Co., Ltd.

[0064] The content of metal elements such as magnesium and calcium in the minerals of the following examples and comparative examples is determined by EDTA titration.

[0065] The morphology of the surface of the sample is tested by using a scanning electron microscope of Ultra Plus type of German Carl Zeiss Company. The working parameters are: acceleration voltage 5-20 KV, working distance: WD = 8-12 mm, magnification: 86-200 Kx. The specific operation method includes: first, the sample to be tested is treated by gold spraying for 10 minutes twice, and then placed on the observation platform for sample observation.

[0066] The performance evaluation method of the catalysts of the following examples and comparative examples includes:

[0067] The Rock-eval 6 pyrolysis instrument produced by the French VINCI company is used to evaluate the pyrolysis catalytic performance of the catalyst. The standard for performing the pyrolysis reaction is GB / T 18602-2012. The test process includes: heating the mixture of the catalyst and the oil shale sample to 300°C at a temperature rise rate of 10°C / min, holding for 3 minutes, analyzing S1 by using a gas chromatograph, and performing programmed temperature rise in the temperature range of 300°C-800°C at a temperature rise rate of 10°C / min, analyzing S2 by using a gas chromatograph. S1 refers to the content of free hydrocarbons (mg / g) generated by pyrolysis of unit mass of the oil shale sample below 300°C, and S2 refers to the content of hydrocarbons (mg / g) generated by pyrolysis of unit mass of the oil shale sample in the temperature range of 300-800°C. The pyrolysis temperature is obtained by the temperature corresponding to the highest point of the S2 peak in the gas chromatogram. The classical Arrhenius formula is used to calculate the activation energy:

[0068] The thermal decomposition of a substance is described by formula (4.1):

[0069] Where f(α) is a function whose type depends on the reaction mechanism;

[0070] α is the conversion degree, which is a normalized form of the weight loss data of the oil shale sample, and can be defined as formula (4.2)

[0071] Where m is the initial mass of the sample, mg; m f is the final mass of the sample, mg; m i is the mass of the sample at temperature T i , mg;

[0072] k is the reaction rate constant related to temperature, which is usually defined by the Arrhenius formula as:

[0073] Where A is the pre-exponential factor of the decomposition reaction, min -1 ; E is the activation energy of the pyrolysis reaction, kJ / mol; R is the universal gas constant, 8.134 J·mol -1 ·K -1 ; T is the thermodynamic temperature, K;

[0074] Substituting formula (4.3) into formula (4.1) can obtain:

[0075] According to the uniform kinetics of the reaction, f(α) can be defined as:

[0076] f(α)=(1-α) n (4.5), where n is the order of the reaction;

[0077] Substituting equation (4.5) into equation (4.4), the expression of reaction rate is:

[0078] For non-isothermal measurement of linear heating rate procedure, equation (4.4) can be rewritten into final form:

[0079] Finally, plot the data, the values of activation energy E and pre-exponential factor A can be obtained from the slope and intercept of the linear fitting line respectively.

[0080] Example 1

[0081] The present embodiment provides a catalyst for reducing activation energy of kerogen in-situ conversion, and a preparation method thereof, which comprises the following steps:

[0082] (1) 50 grams of magnesite and a sulfuric acid solution with a concentration of 0.1 mol / L are mixed at a mass ratio of 1:2 at 20°C, and after reacting for 60 minutes at 20°C, an acid-treated natural mineral system is obtained; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0083] The total mass (in terms of the mass of the element) of magnesium and calcium in the liquid phase of the acid-treated natural mineral system accounts for 60% of the mass of the metals in the magnesite;

[0084] (2) 3.69 grams of a methanol aqueous solution with a mass concentration of 10% is slowly added to the acid-treated natural mineral system, and the mixture is reacted for 60 minutes at 20°C under stirring to obtain a composite system;

[0085] (3) 0.09 grams of vanadium chloride is mixed with 0.09 grams of a phytic acid solution with a mass concentration of 5% at 30°C and reacted for 6 hours to obtain a system containing a phytic acid-metal ion chelate;

[0086] (4) the composite system obtained in step (2) is mixed with the system containing the phytic acid-metal ion chelate obtained in step (3) at a mass ratio of 9:1 to obtain the catalyst for reducing activation energy of kerogen in-situ conversion.

[0087] The performance of the catalyst is evaluated by using a rock pyrolysis instrument: 0.3 grams of the catalyst is mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture is weighed and placed in a rock pyrolysis instrument for pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis products are analyzed by using a gas chromatograph, and then the kerogen pyrolysis temperature is obtained according to the analysis results, and the activation energy is calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0088] It should be noted that the composite system obtained in step (2) of the catalyst preparation method of each embodiment of the present application comprises a solid phase and a liquid phase, and the composite system needs to be uniformly dispersed before being mixed with the system containing the phytic acid-metal ion chelate obtained in step (3). Similarly, the catalyst of each embodiment of the present application comprises a solid phase and a liquid phase, and the catalyst needs to be uniformly dispersed before being mixed with the oil shale sample. In this way, it is ensured that the ratio of the solid phase and the liquid phase in the system is uniform when being weighed.

[0089] Example 2

[0090] The present embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and the preparation method thereof comprises the following steps:

[0091] (1) 20 g of calcite and a hydrochloric acid solution with a concentration of 2.5 mol / L are mixed at a mass ratio of 1:18 at 50°C, and after reacting at 50°C for 40 minutes, an acid-treated natural mineral system is obtained; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0092] The total mass (in terms of the mass of the element) of magnesium and calcium in the liquid phase of the acid-treated natural mineral system accounts for 30% of the mass of the metal in the calcite;

[0093] (2) 2.06 g of ethanol is slowly added to the acid-treated natural mineral system, and the mixture is reacted at 60°C under stirring for 10 minutes to obtain a composite system;

[0094] (3) 2.74 g of chromium chloride is mixed with 27.41 g of a phytic acid solution with a mass concentration of 56% at 100°C and reacted for 0.5 hours to obtain a system containing a phytic acid-metal ion chelate;

[0095] (4) The composite system obtained in step (2) is mixed with the system containing the phytic acid-metal ion chelate obtained in step (3) according to a mass ratio of 8:2 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0096] The performance of the catalyst is evaluated by using a rock pyrolysis instrument: 2.7 g of the catalyst is uniformly mixed with 3 g of an oil shale sample (80-120 mesh), 0.8 g of the mixture is weighed, and then the mixture is placed in a rock pyrolysis instrument for pyrolysis reaction, the specific temperature rising process is as described above, a gas chromatograph is used to analyze the pyrolysis products, and then the pyrolysis temperature of kerogen is obtained according to the analysis results, and the activation energy is calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0097] Example 3

[0098] The present embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and the preparation method thereof comprises the following steps:

[0099] (1) 70 g dolomite and formic acid solution with a concentration of 20 mol / L were mixed at a mass ratio of 1:20 at 30°C, and after reaction at 30°C for 20 min, an acid-treated natural mineral system was obtained; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0100] The total mass of magnesium and calcium (in terms of the mass of the element) in the liquid phase of the acid-treated natural mineral system accounts for 80% of the metal mass in dolomite;

[0101] (2) 17.56 g of an ethanol aqueous solution with a mass concentration of 20% was slowly added to the acid-treated natural mineral system, and the mixture was reacted at 30°C for 20 min under stirring to obtain a composite system;

[0102] (3) 1.77 g of manganese chloride was mixed with 8.84 g of a phytic acid solution with a mass concentration of 72% at 60°C and reacted for 1 h to obtain a system containing a phytic acid-metal ion chelate;

[0103] (4) The composite system obtained in step (2) and the system containing a phytic acid-metal ion chelate obtained in step (3) were mixed at a mass ratio of 7:3 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0104] The performance of the catalyst was evaluated by using a rock pyrolysis instrument: 2.4 g of the catalyst was mixed with 3 g of an oil shale sample (80-120 mesh) to obtain a mixture, 0.8 g of the mixture was weighed and placed in a rock pyrolysis instrument for pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis products were analyzed by using a gas chromatograph, and then the pyrolysis temperature of kerogen was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0105] Example 4

[0106] The present embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and a preparation method thereof comprises the following steps:

[0107] (1) 60 g of montmorillonite and formic acid solution with a concentration of 15 mol / L were mixed at a mass ratio of 1:5 at 70°C, and after reaction at 70°C for 30 min, an acid-treated natural mineral system was obtained; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0108] The total mass of magnesium and calcium (in terms of the mass of the element) in the liquid phase of the acid-treated natural mineral system accounts for 90% of the metal mass in montmorillonite;

[0109] The electron micrographs of the natural mineral before and after acid treatment are shown in Figures 1 and 2, respectively. It can be seen that the natural mineral after acid treatment (i.e. the solid phase) contains more pores, has a rich specific surface area and pore volume, and can fully adsorb and accommodate alcohol and continuously provide metal ions to combine with alcohol, thereby playing a slow-release role and having strong stability.

[0110] (2) 30.24 grams of a 30% mass concentration propyl alcohol aqueous solution was slowly added to the acid-treated natural mineral system, and reacted for 30 minutes at 50°C under stirring to obtain a composite system;

[0111] (3) 0.87 grams of ferric chloride was mixed with 6.08 grams of a 80% mass concentration phytic acid solution at 50°C and reacted for 2 hours to obtain a system containing a phytic acid-metal ion chelate;

[0112] (4) The composite system obtained in step (2) and the system containing the phytic acid-metal ion chelate obtained in step (3) were mixed in a mass ratio of 6:4 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0113] The performance of the catalyst was evaluated using a rock pyrolysis instrument: 2.1 grams of the catalyst was mixed with 3 grams of an oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture was placed in a rock pyrolysis instrument for pyrolysis, the specific temperature rising process is as described above, the pyrolysis products were analyzed using a gas chromatograph, and the kerogen pyrolysis temperature was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0114] Example 5

[0115] The present embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and a preparation method thereof, which comprises the following steps:

[0116] (1) 80 grams of montmorillonite was mixed with a 7 mol / L citric acid solution at a mass ratio of 1:7 at 40°C, and reacted for 45 minutes at 40°C to obtain an acid-treated natural mineral system; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0117] The total mass (in terms of the mass of the element) of magnesium and calcium in the liquid phase of the acid-treated natural mineral system accounts for 20% of the mass of the metals in the montmorillonite;

[0118] (2) 11.81 grams of a 45% mass concentration methanol aqueous solution was slowly added to the acid-treated natural mineral system, and reacted for 35 minutes at 55°C under stirring to obtain a composite system;

[0119] (3) mixing 1.85 g of cobalt chloride with 5.54 g of a phytic acid solution with a mass concentration of 63% at 40°C and reacting for 3 hours to obtain a system containing a phytic acid-metal ion chelate;

[0120] (4) mixing the composite system obtained in step (2) and the system containing the phytic acid-metal ion chelate obtained in step (3) according to a mass ratio of 5:5 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0121] The performance of the catalyst was evaluated by using a rock pyrolysis instrument: 1.8 g of the catalyst was mixed with 3 g of an oil shale sample (80-120 mesh) to obtain a mixture, 0.8 g of the mixture was weighed and placed in a rock pyrolysis instrument for pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, the kerogen pyrolysis temperature was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0122] Example 6

[0123] The embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and a preparation method thereof.

[0124] (1) mixing 100 g of dolomite and a citric acid solution with a concentration of 9 mol / L according to a mass ratio of 1:9 at 80°C, and obtaining an acid-treated natural mineral system after reacting at 80°C for 50 minutes; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0125] The total mass (in terms of the mass of the element) of magnesium and calcium in the liquid phase of the acid-treated natural mineral system accounts for 95% of the mass of the metal in the dolomite;

[0126] (2) slowly adding 104.27 g of an ethanol aqueous solution with a mass concentration of 55% to the acid-treated natural mineral system, and obtaining a composite system after reacting at 35°C for 25 minutes under stirring;

[0127] (3) mixing 1.66 g of nickel chloride with 13.25 g of a phytic acid solution with a mass concentration of 47% at 90°C and reacting for 3.5 hours to obtain a system containing a phytic acid-metal ion chelate;

[0128] (4) mixing the composite system obtained in step (2) and the system containing the phytic acid-metal ion chelate obtained in step (3) according to a mass ratio of 4:6 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0129] The performance of the catalyst is evaluated by using a rock pyrolysis instrument: 1.5 grams of the catalyst is mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture is weighed and placed in a rock pyrolysis instrument to perform pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis products are analyzed by using a gas chromatograph, the kerogen pyrolysis temperature is obtained according to the analysis results, and the activation energy is calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0130] Example 7

[0131] The embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and a preparation method of the catalyst.

[0132] (1) 70 grams of magnesite and a phosphoric acid solution with a concentration of 13 mol / L are mixed at a mass ratio of 1:11 at 100°C, and after 10 minutes of reaction at 100°C, an acid-treated natural mineral system is obtained; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0133] The total mass (in terms of the mass of the element) of magnesium and calcium in the liquid phase of the acid-treated natural mineral system accounts for 40% of the mass of the metal in the magnesite;

[0134] (2) 55.10 grams of an ethanol aqueous solution with a mass concentration of 65% is slowly added to the acid-treated natural mineral system, and the mixture is reacted at 25°C for 45 minutes under stirring to obtain a composite system;

[0135] (3) 0.4 grams of a mixture of copper chloride and yttrium chloride (the mass ratio of copper chloride to yttrium chloride is 1:1) and 0.8 grams of a phytic acid solution with a mass concentration of 32% are mixed and reacted at 70°C for 5 hours to obtain a system containing a phytic acid-metal ion chelate;

[0136] (4) the composite system obtained in step (2) and the system containing the phytic acid-metal ion chelate obtained in step (3) are mixed at a mass ratio of 3:7 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0137] The performance of the catalyst is evaluated by using a rock pyrolysis instrument: 0.6 grams of the catalyst is mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture is weighed and placed in a rock pyrolysis instrument to perform pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis products are analyzed by using a gas chromatograph, the kerogen pyrolysis temperature is obtained according to the analysis results, and the activation energy is calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0138] Example 8

[0139] The embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and a preparation method of the catalyst.

[0140] (1) 65 grams of calcite and oxalic acid solution with a concentration of 17 mol / L were mixed at a mass ratio of 1:13 at 30°C, and after 55 minutes of reaction at 30°C, an acid-treated natural mineral system was obtained; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0141] The total mass of magnesium and calcium (in terms of the mass of the element) in the liquid phase of the acid-treated natural mineral system accounts for 50% of the metal mass in the calcite;

[0142] (2) 26 grams of a 70% mass concentration methanol aqueous solution were slowly added to the acid-treated natural mineral system, and the mixture was reacted at 30°C under stirring conditions for 40 minutes to obtain a composite system;

[0143] (3) 0.19 grams of a mixture of zinc chloride and barium chloride (mass ratio of zinc chloride to barium chloride is 1:1) and 1.33 grams of a 22% mass concentration phytic acid solution were mixed at 80°C and reacted for 4 hours to obtain a system containing a phytic acid-metal ion chelate;

[0144] (4) The composite system obtained in step (2) and the system containing a phytic acid-metal ion chelate obtained in step (3) were mixed at a mass ratio of 2:8 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0145] The performance of the catalyst was evaluated using a rock pyrolysis instrument: 0.9 grams of the catalyst was thoroughly mixed with 3 grams of oil shale sample (80-120 mesh), 0.8 grams of the mixture was weighed and placed into a rock pyrolysis instrument for pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis products were analyzed by a gas chromatograph, and then the kerogen pyrolysis temperature was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0146] Example 9

[0147] The present embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and the preparation method thereof comprises the following steps:

[0148] (1) 40 grams of dolomite and acetic acid solution with a concentration of 4 mol / L were mixed at a mass ratio of 1:15 at 60°C, and after 15 minutes of reaction at 60°C, an acid-treated natural mineral system was obtained; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0149] The total mass of magnesium and calcium (in terms of the mass of the element) in the liquid phase of the acid-treated natural mineral system accounts for 60% of the metal mass in the dolomite;

[0150] (2) slowly adding 3.76 grams of 80% mass concentration of propanol aqueous solution into the acid-treated natural mineral system, and reacting for 50 minutes at 20°C under stirring to obtain a composite system;

[0151] (3) mixing 0.14 grams of a mixture of zirconium chloride and silver chloride (mass ratio of zirconium chloride to silver chloride is 1:1) with 0.56 grams of 13% mass concentration of phytic acid solution at 55°C and reacting for 1.5 hours to obtain a system containing phytic acid-metal ion chelate;

[0152] (4) mixing the composite system obtained in step (2) with the system containing phytic acid-metal ion chelate obtained in step (3) according to a mass ratio of 1:9 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0153] The performance of the catalyst is evaluated by using a rock pyrolysis instrument: 1.2 grams of catalyst is mixed with 3 grams of oil shale sample (80-120 mesh) uniformly, 0.8 grams of the mixture is weighed and put into a rock pyrolysis instrument for pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis products are analyzed by using a gas chromatograph, and then the kerogen pyrolysis temperature is obtained according to the analysis results, and the activation energy is calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0154] Example 10

[0155] The embodiment provides a catalyst for reducing the activation energy of kerogen in-situ conversion, and a preparation method thereof.

[0156] (1) mixing 90 grams of montmorillonite with 12 mol / L sulfuric acid solution according to a mass ratio of 1:19 at 75°C, and reacting for 25 minutes at 75°C to obtain an acid-treated natural mineral system; the acid-treated natural mineral system comprises a solid phase and a liquid phase;

[0157] The total mass (in terms of the mass of the element) of magnesium and calcium in the liquid phase of the acid-treated natural mineral system accounts for 70% of the mass of the metal in the montmorillonite;

[0158] (2) slowly adding 18.99 grams of 90% mass concentration of methanol aqueous solution into the acid-treated natural mineral system, and reacting for 15 minutes at 45°C under stirring to obtain a composite system;

[0159] (3) mixing 0.04 grams of a mixture of magnesium chloride and calcium chloride (mass ratio of magnesium chloride to calcium chloride is 1:1) with 0.08 grams of 8% mass concentration of phytic acid solution at 45°C and reacting for 5.5 hours to obtain a system containing phytic acid-metal ion chelate;

[0160] (4) mixing the complex system obtained in step (2) and the system containing phytic acid-metal ion chelate obtained in step (3) according to a mass ratio of 5.5:4.5 to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

[0161] The performance of the catalyst was evaluated by using a rock pyrolysis instrument: 0.45 g of the catalyst was mixed with 3 g of the oil shale sample (80-120 mesh) to obtain a mixture, 0.8 g of the mixture was weighed and placed in a rock pyrolysis instrument for pyrolysis, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, the kerogen pyrolysis temperature was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0162] Comparative Example 1

[0163] In this comparative example, no catalyst was added: 0.8 g of the oil shale sample (80-120 mesh) was weighed and placed in a rock pyrolysis instrument for pyrolysis, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, the kerogen pyrolysis temperature was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0164] Comparative Example 2

[0165] In this comparative example, only cobalt chloride was used as the catalyst: 1.85 g of cobalt chloride was mixed with 3 g of the oil shale sample (80-120 mesh) to obtain a mixture, 0.8 g of the mixture was weighed and placed in a rock pyrolysis instrument for pyrolysis, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, the kerogen pyrolysis temperature was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0166] Comparative Example 3

[0167] In this comparative example, only the methanol aqueous solution with a mass concentration of 90% was used as the catalyst: 18.99 g of the methanol aqueous solution with a mass concentration of 90% was mixed with 3 g of the oil shale sample (80-120 mesh) to obtain a mixture, 0.8 g of the mixture was weighed and placed in a rock pyrolysis instrument for pyrolysis, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, the kerogen pyrolysis temperature was obtained according to the analysis results, and the activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 1.

[0168] Comparative Example 4

[0169] The comparative example is compared with example 3, and the comparative example only uses the solid phase in the acid-treated natural mineral system prepared in step (1) of example 3 as a catalyst. 2.4 grams of catalyst is mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture is weighed and placed in a rock pyrolysis instrument to perform a pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis product is analyzed by using a gas chromatograph, the kerogen pyrolysis temperature is obtained according to the analysis result, and the activation energy is calculated according to the Arrhenius formula, and the result is shown in Table 1.

[0170] Comparative example 5

[0171] The comparative example is compared with example 3, and the comparative example only uses the composite system prepared in step (2) of example 3 as a catalyst. 2.4 grams of the composite system is mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture is weighed and placed in a rock pyrolysis instrument to perform a pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis product is analyzed by using a gas chromatograph, the kerogen pyrolysis temperature is obtained according to the analysis result, and the activation energy is calculated according to the Arrhenius formula, and the result is shown in Table 1.

[0172] Comparative example 6

[0173] The comparative example is compared with example 3, and the comparative example only uses the system containing phytic acid-metal ion chelate prepared in step (3) of example 3 as a catalyst. 2.4 grams of the system containing phytic acid-metal ion chelate is mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture is weighed and placed in a rock pyrolysis instrument to perform a pyrolysis reaction, the specific temperature rising process is as described above, the pyrolysis product is analyzed by using a gas chromatograph, the kerogen pyrolysis temperature is obtained according to the analysis result, and the activation energy is calculated according to the Arrhenius formula, and the result is shown in Table 1.

[0174] Table 1: Catalyst performance evaluation results of examples 1-10 and comparative examples 1-6

[0175] As shown in Table 1, compared with the comparative example 1 without adding catalyst, the pyrolysis temperature of the inventive examples 1-10 is reduced by 4.3-12.5%, and the activation energy is reduced by 23.25-38.66%. The comparative example 2 uses direct addition of transition metal compound as catalyst without phytic acid chelation treatment, and the pyrolysis temperature and activation energy of the comparative example 2 are not reduced compared with the inventive examples 1-10. The pyrolysis temperature and activation energy of the comparative example 3 using alcohol as catalyst are not reduced compared with the comparative example 1. The pyrolysis temperature and activation energy of the comparative example 4 using solid phase in acid treated natural mineral system as catalyst are not reduced compared with the comparative example 1. The pyrolysis temperature and activation energy of the comparative example 5 using alcohol compound and acid treated natural mineral composite system as catalyst are not obviously reduced. The pyrolysis temperature of the comparative example 6 using the system containing phytic acid-metal ion chelate as catalyst is reduced by 3℃, and the activation energy reduction effect is not obvious.

[0176] In summary, the catalyst of the present application combines the composite system of alcohol compound and acid treated natural mineral and the system containing phytic acid-metal ion chelate. The crystalline alcohol compound slowly undergoes chemical reaction under formation conditions to form magnesium and / or calcium-alcohol complex, while continuously releasing water molecules in supercritical state, which can efficiently dissolve hydrocarbons and salts in the rock formation to achieve the effect of energy enhancement and oil displacement. Moreover, the metal ions introduced into the oil shale by two ways in the present application have significant Lewis acid characteristics, which can fully exert the catalytic effect of the metal to promote the cracking of long-chain aliphatic hydrocarbons into short-chain aliphatic hydrocarbons, thereby playing a catalytic cracking role to rapidly convert kerogen into short-chain flowable hydrocarbons. Under this catalytic mechanism, the alkaline earth metal ions and / or transition metal ions and the water molecules released by the alcohol compound in the composite system jointly play a role to reduce the pyrolysis temperature and the activation energy of kerogen in situ conversion. Therefore, the catalyst of the present application strengthens the catalytic pyrolysis reaction effect, significantly reduces the activation energy of kerogen in situ conversion and the pyrolysis temperature, and has good application prospect.

Claims

1. A catalyst for reducing the activation energy for kerogen in situ conversion comprising: The first component and the second component; The first component comprises a composite system of an acid-treated natural mineral and an alcohol or alcohol solution, the natural mineral is a natural mineral containing magnesium and / or calcium, the acid-treated natural mineral comprises a solid phase and a liquid phase; the second component comprises a system containing phytic acid-metal ion chelate, the metal ion comprises alkaline earth metal ion and / or transition metal ion.

2. The catalyst for reducing the activation energy of kerogen in situ conversion according to claim 1, wherein, The mass ratio of the first component to the second component is 9-1:1-9.

3. The catalyst for reducing the activation energy of kerogen in situ conversion according to claim 1, wherein, The acid-treated natural mineral is prepared by mixing and reacting the natural mineral containing magnesium and / or calcium with an acid solution.

4. The catalyst for reducing the activation energy for kerogen in situ conversion according to claim 3, wherein, The mixing mass ratio of the natural mineral containing magnesium and / or calcium to the acid solution is 1:2-20.

5. The catalyst for reducing the activation energy of kerogen in situ conversion according to claim 1, wherein, The total mass of magnesium and / or calcium in the liquid phase of the acid-treated natural mineral accounts for 20-95% of the total mass of metal in the natural mineral containing magnesium and / or calcium.

6. The catalyst for reducing the activation energy for kerogen in situ conversion of claim 1, wherein, The composite system is prepared by mixing and reacting the acid-treated natural mineral with an alcohol or alcohol solution.

7. The catalyst for reducing the activation energy of kerogen in situ conversion according to claim 1, wherein, The mass ratio of magnesium and / or calcium in the liquid phase of the acid-treated natural mineral to the mass of the alcohol or alcohol solution is 8-2:2-8.

8. The catalyst for reducing the activation energy of kerogen in situ conversion according to claim 1, wherein, The alkaline earth metal ion and / or transition metal ion comprises one or a combination of vanadium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, zinc ion, yttrium ion, zirconium ion, silver ion, magnesium ion, calcium ion and barium ion.

9. The catalyst for reducing the activation energy of kerogen in situ conversion according to claim 1, wherein, The system containing phytic acid-metal ion chelate is prepared by mixing and reacting an alkaline earth metal compound and / or a transition metal compound with a phytic acid solution.

10. The catalyst for reducing the activation energy for kerogen in situ conversion according to claim 9, wherein, The mixing mass ratio of the alkaline earth metal compound and / or transition metal compound to the phytic acid solution is 1:1-10.

11. A method for preparing the catalyst for reducing the activation energy of kerogen in-situ conversion according to any one of claims 1-10, comprising the following steps: (1) mixing and reacting a natural mineral containing magnesium and / or calcium with an acid solution for a period of time to obtain an acid-treated natural mineral system, the acid-treated natural mineral system comprising a solid phase and a liquid phase; (2) mixing and reacting the acid-treated natural mineral system obtained in step (1) with an alcohol or alcohol solution for a period of time to obtain a composite system; (3) mixing and reacting an alkaline earth metal compound and / or a transition metal compound with a phytic acid solution for a period of time to obtain a system containing phytic acid-metal ion chelate; (4) mixing the composite system obtained in step (2) with the system containing phytic acid-metal ion chelate obtained in step (3) to obtain the catalyst for reducing the activation energy of kerogen in-situ conversion.

12. The method of making according to claim 11, wherein, In step (1), the natural mineral containing magnesium and / or calcium comprises one or a combination of magnesite, calcite, dolomite and montmorillonite.

13. The method of making according to claim 11, wherein, In step (1), the acid solution comprises an inorganic acid solution and / or an organic acid solution, the inorganic acid solution comprises one or a combination of sulfuric acid solution, hydrochloric acid solution, nitric acid solution and phosphoric acid solution, the organic acid solution comprises one or a combination of formic acid solution, citric acid solution, oxalic acid solution and acetic acid solution; the concentration of the acid solution is 0.1-20 mol / L.

14. The method of making according to claim 11, wherein, In step (1), the mixing mass ratio of the natural mineral containing magnesium and / or calcium to the acid solution is 1:2-20.

15. The method of making according to claim 11, wherein, In step (1), the reaction temperature of the natural mineral containing magnesium and / or calcium to the acid solution is 20-100℃, and the reaction time is 10-60 minutes.

16. The method of making according to claim 11, wherein, In step (1), the total mass of magnesium and / or calcium in the liquid phase of the natural mineral system after acid treatment accounts for 20-95% of the total mass of metals in the natural mineral containing magnesium and / or calcium.

17. The method of making according to claim 11, wherein, In step (2), the mixing ratio of the natural mineral system after acid treatment to the alcohol or alcohol solution is that the mass ratio of magnesium and / or calcium in the liquid phase of the natural mineral system after acid treatment to the mass of the alcohol or alcohol solution is 8-2:2-8.

18. The method of making according to claim 11, wherein, In step (2), the alcohol includes one or a combination of several of methanol, ethanol and propanol, and the alcohol solution includes one or a combination of several of methanol aqueous solution, ethanol aqueous solution and propanol aqueous solution, and the mass concentration of the alcohol solution is 10-90%.

19. The method of making according to claim 11, wherein, In step (2), the reaction temperature of the natural mineral system after acid treatment to the alcohol or alcohol solution is 20-60℃, and the reaction time is 10-60 minutes.

20. The method of manufacturing according to claim 11, wherein, In step (3), the alkaline earth metal compound and / or transition metal compound includes one or a salt compound of several of vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, silver, magnesium, calcium and barium.

21. The method of manufacturing according to claim 11, wherein, In step (3), the mass concentration of the phytic acid solution is 5-80%.

22. The method of manufacturing according to claim 11, wherein, In step (3), the mixing mass ratio of the alkaline earth metal compound and / or transition metal compound to the phytic acid solution is 1:1-10.

23. The method of manufacturing according to claim 11, wherein, In step (3), the reaction temperature of the alkaline earth metal compound and / or transition metal compound to the phytic acid solution is 30-100℃, and the reaction time is 0.5-6 hours.

24. The method of manufacturing according to claim 11, wherein, In step (4), the mixing mass ratio of the composite system to the system containing phytic acid-metal ion chelate is 9-1:1-9.

25. A method of oil shale pyrolysis comprising the steps of: The catalyst for reducing the activation energy of kerogen in-situ conversion according to any one of claims 1-10 is contacted with oil shale and pyrolysis reaction is carried out to reduce the activation energy of kerogen in-situ conversion of oil shale, to obtain pyrolysis products.

26. The oil shale pyrolysis process as set forth in claim 25 wherein, The amount of the catalyst for reducing the activation energy of kerogen in-situ conversion is 10-90% of the total mass of the oil shale.

Images