Solid organic matter in-situ conversion catalyst, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a solid organic matter in-situ conversion catalyst, and a preparation method therefor and a use thereof. The catalyst comprises a first component and a second component; the first component comprises a carrier and a Y-type molecular sieve grown on the carrier, and the carrier comprises an alkali-treated mineral; the second component comprises a metal-phytic acid complex. The preparation method for the catalyst comprises: treating a mineral containing silicon dioxide by means of an alkaline solution, then mixing same with a silicon source, an aluminum source, a seed crystal and an inorganic salt, and crystallizing the mixture to obtain the first component; mixing a metal compound with a phytic acid solution for reaction to obtain the second component; and mixing the first component with the second component to obtain the catalyst. The catalyst of the present invention can efficiently convert solid organic matter in oil shale in situ into oil and gas, and exhibits high in-situ conversion activity.

Description

Solid organic matter in-situ conversion catalyst, its preparation method and application TECHNICAL FIELD

[0001] The present application relates to a solid organic matter in-situ conversion catalyst, its preparation method and application, and belongs 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 type of efficient and environmentally friendly technology for developing deep underground oil shale. Its principle is to realize in-situ upgrading and conversion of oil shale by in-situ heating and / or injection of catalyst, and then collect the produced shale oil and hydrocarbon gas through soaking well.

[0003] In the in-situ conversion technology, oil shale pyrolysis catalyst can accelerate the breaking of long-chain molecular bonds in organic matter, converting solid or heavy organic matter into flowable light petroleum hydrocarbon. 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 underground. However, due to the complexity and diversity of formation conditions, the in-situ conversion of oil shale faces the problem of low catalyst activity.

[0004] CN112892394A discloses a sulfonic acid-based anionic gemini surfactant. The sulfonic acid-based anionic gemini surfactant is used as a shale oil reservoir imbibition oil displacement agent to change the surface wettability of the shale oil reservoir, treat the oil-wet core into hydrophilic, and improve the shale oil imbibition recovery rate.

[0005] CN116716092A discloses a modifier for converting shale oil reservoir into stable strong hydrophilic. The preparation method of the modifier includes the following steps: drying treatment of nano materials to remove water; mixing a certain proportion of deionized water, nano materials, surfactants and coupling agents to obtain the modifier. The modifier can convert shale oil reservoir rocks into stable strong hydrophilic, improve the crude oil migration capacity, and thus improve the shale oil reservoir recovery rate.

[0006] CN112694885A uses a high-activity drag-reducing agent to improve the recovery rate of shale oil. The high-activity drag-reducing agent can imbibed into the shale matrix to drive the crude oil into the cracks or large pores, while the fracturing fluid is not backflowed, and is retained in the shale matrix to increase the formation energy and improve the recovery rate of shale oil.

[0007] CN113563861A discloses a nanoemulsion, which comprises the following components: a nonionic surfactant, an anionic surfactant, a small molecule alcohol, a light oil and water. The nanoemulsion can change the oil-water interfacial tension, change the rock wettability, and at the same time reduce the adsorption amount of surfactant, can improve the imbibition oil production during the soaking period after fracturing of the tight / shale reservoir, and achieve the effect of increasing production.

[0008] CN110982505A discloses a tight oil reservoir permeability increasing oil displacement system, which is composed of a surfactant, an oil-soluble substance and water, and the system is in the form of oil-in-water droplets. The system can improve the recovery rate of tight oil reservoirs by using multiple surfactants.

[0009] CN115703076A discloses a catalyst applied in processing fossil energy materials. The catalyst comprises 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 materials. However, the catalyst contains various organic substances, adding these organic substances into the formation will pollute the formation, and the activity of the catalyst is not high.

[0010] CN114477317A discloses a needle-shaped nano iron-based double metal hydroxide, which comprises a divalent metal cation selected from Fe 3+ , Ni 2+ , Mn 2+ and Co 2+ in the layer plate, and OH-, CO3 2- and OCN - comprise the interlayer region anions. The needle-shaped nano iron-based double metal hydroxide has the characteristics of rich active sites, high temperature resistance and stable structure. When used for catalyzing oil shale pyrolysis, it can reduce the pyrolysis temperature and realize the controllable distribution of oil shale pyrolysis products, and convert oil shale pyrolysis products into medium and low carbon hydrocarbon organic matter. Although the needle-shaped nano iron-based double metal hydroxide as a catalyst can reduce the pyrolysis temperature and activation energy in the process of oil shale kerogen conversion, it is prepared by mutual precipitation, which has the problems of complex preparation process, poor catalyst stability, etc., and the activity of the catalyst has not been effectively improved.

[0011] CN114522722A discloses a molecular sieve-containing catalyst for catalytic cracking of oil shale, which comprises rare earth mesoporous molecular sieve, quaternary ammonium base, supported metal nano alumina, cyclohexane ethyl acetate and surfactant, and the pore size of the rare earth mesoporous molecular sieve is 3-7 nm. The catalyst accelerates the process of oil mother matter to oil and gas conversion by using the rare earth mesoporous molecular sieve, and reduces the oil shale cracking conversion temperature. However, the components of the catalyst are too complex, the preparation process is complex, and the compatibility of each component is poor, which limits the practical application of the catalyst.

[0012] CN116063622A discloses a fracturing fluid thickening agent and oil displacement fracturing fluid, which is applied to shale oil and gas exploitation, can meet the requirements of sand carrying and fracture forming and oil displacement at the same time, and can significantly improve the oil recovery rate.

[0013] CN115895630A discloses a imbibition oil displacement agent and coupled imbibition fracturing fluid, which has the advantages of high imbibition recovery degree and good stimulation effect, and is suitable for shale oil, low permeability, ultra-low permeability reservoir stimulation operation.

[0014] CN103878031A discloses a catalyst for oil shale pyrolysis, which is made of raw materials with the following mass percentage: molecular sieve 2%-8%, activated clay 1%-5%, organic cobalt salt 10%-60%, metal sulfide 5%-20%, glycerol ester 8%-30%, and paraffin 15%-35%. The catalyst can improve the pyrolysis efficiency of oil shale.

[0015] CN115785942A discloses a conductive proppant, which has a core-shell structure composed of an aggregate core treated with a surface modifier and a conductive composite layer coated on the surface of the aggregate core. The conductive composite layer comprises a high molecular material, a conductive agent and a curing agent. The conductive proppant can be used in in-situ exploitation technology of shale oil, and can improve the heat conduction efficiency of shale oil reservoir through electric heating, effectively improve the in-situ exploitation effect of shale oil, and improve the in-situ conversion efficiency of shale oil.

[0016] CN117345241A discloses a method for extracting shale oil and gas from low-mature oil shale by supercritical CO2-double U-shaped well fracturing-in-situ catalysis. The method uses supercritical carbon dioxide fluid to perform staged fracturing on horizontal wells to form a complex fracture network. Then, proppants and catalysts are injected into the fractured cracks, and hot gas is injected to increase the temperature of the oil shale formation. Shale oil and gas and hot gas are produced through production wells and recovered on the ground separation device. The separated hot gas can be recycled. The technology uses a double U-shaped well mode, uses supercritical carbon dioxide fracturing technology to form a complex fracture network connected to each other in the oil shale formation, to provide a seepage channel for the migration of hot gas and shale oil and gas. Moreover, the extraction of supercritical carbon dioxide can extract organic matter in the pores of oil shale, which is beneficial to the efficient cracking of the catalyst to organic matter. At the same time, the catalyst can effectively reduce the heating temperature required for the pyrolysis of organic matter in oil shale, thereby strengthening the oil shale mining effect, and realizing efficient and economical in-situ conversion of oil shale.

[0017] CN116425505A discloses a strength stabilizer for ultra-high temperature working condition well cementing of in-situ conversion of shale oil, which can guarantee the well cementing quality and integrity of in-situ thermal recovery well of shale oil, and improve the efficiency of shale oil resource exploitation.

[0018] CN102965302A and CN107532198A report a technology for improving the in-situ conversion efficiency of oil shale by microbial preparation.

[0019] At present, most of the catalysts for in-situ conversion of oil shale are prepared by simply mixing various surfactants or functional components, which has many problems such as low catalyst activity, unfriendly environmental protection of organic components to the formation, and complex catalyst preparation process.

[0020] Therefore, it is still one of the problems to be solved in the art to develop a new catalyst for in-situ conversion of solid organic matter in oil shale. SUMMARY

[0021] To solve at least one of the above technical problems, the purpose of the present application is to provide a solid organic matter in-situ conversion catalyst and a preparation method and application thereof. The catalyst of the present application can efficiently convert the solid organic matter in oil shale into oil and gas in-situ, and has high in-situ conversion activity.

[0022] To achieve the above purpose, the first aspect of the present application provides a solid organic matter in-situ conversion catalyst, which comprises: a first component and a second component; the first component comprises a carrier and a Y-type molecular sieve grown on the carrier, and the carrier comprises a mineral after alkali treatment; the second component comprises a metal-phytic acid complex.

[0023] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the mass ratio of the first component to the second component is 9-1:1-9.

[0024] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the alkali-treated mineral is obtained by treating a mineral containing silicon dioxide with an alkaline solution.

[0025] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the mineral containing silicon dioxide is obtained by calcining a natural mineral containing silicate.

[0026] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the natural mineral containing silicate includes one or a combination of kaolin, rectorite, halloysite, montmorillonite, diatomite, illite and coal gangue.

[0027] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the Y-type molecular sieve in the first component accounts for 1%-90% of the mass of the carrier.

[0028] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the specific surface area of the carrier in the first component is 120-200 m 2 / g, and the pore volume is 0.15-0.25 mL / g.

[0029] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the crystallinity of the Y-type molecular sieve in the first component is above 80%, and the average crystal grain size is 100-600 nm.

[0030] In the above-mentioned in-situ conversion catalyst for solid organic matter, preferably, the metal in the metal-phytate complex includes lanthanide metals.

[0031] The second aspect of the present application provides a preparation method of the above-mentioned in-situ conversion catalyst for solid organic matter, which includes the following steps:

[0032] (1) treating a mineral containing silicon dioxide with an alkaline solution to obtain an alkali-treated mineral system, the alkali-treated mineral system including a solid phase and a liquid phase;

[0033] (2) mixing the alkali-treated mineral system obtained in step (1) with a silicon source, an aluminum source, a crystal seed and an inorganic salt to obtain a mixture; and subjecting the mixture to at least crystallization to obtain a first component;

[0034] (3) mixing and reacting a metal compound with a phytic acid solution to obtain a second component;

[0035] (4) mixing the first component obtained in step (2) with the second component obtained in step (3) to obtain the solid organic matter in-situ conversion catalyst.

[0036] In the above preparation method, preferably, in step (1), the mineral containing silica is obtained by calcining a natural mineral containing silicate. More preferably, the calcining temperature is 400-1000°C, and the calcining time is 1-5 hours.

[0037] In the above preparation method, preferably, in step (1), the natural mineral containing silicate includes one or a combination of kaolin, rectorite, halloysite, montmorillonite, diatomite, illite and coal gangue.

[0038] In the above preparation method, preferably, in step (1), the alkaline solution includes one or a combination of sodium hydroxide, sodium carbonate, ammonia and sodium bicarbonate, and the mass concentration of the alkaline solution is 1-25%.

[0039] In the above preparation method, preferably, in step (1), the mixing mass ratio of the alkaline solution to the mineral containing silica is (1-5):1, the temperature for treating the mineral containing silica with the alkaline solution is 40-100°C, and the time is 1-4 hours.

[0040] In the above preparation method, preferably, in step (1), the silica in the liquid phase of the mineral system after alkaline treatment is 1-30% of the total mass of silica in the mineral containing silica. Those skilled in the art can understand that the content of silica in the mineral containing silica is the same as that in the natural mineral containing silicate.

[0041] In the above preparation method, preferably, in step (2), the silicon source includes one or a combination of tetraethyl orthosilicate, silica sol, white carbon black and water glass.

[0042] In the above preparation method, preferably, in step (2), the aluminum source includes one or a combination of pseudo-boehmite, aluminum hydroxide, aluminum sulfate and sodium aluminate.

[0043] In the above preparation method, preferably, in step (2), the inorganic salt includes one or a combination of halogen compounds, borides, aluminate, phosphate, borate and silicate.

[0044] In the above preparation method, preferably, in step (2), the halogen compound comprises one or a combination of several of sodium chloride, sodium fluoride, magnesium chloride, calcium chloride, barium chloride, chromium chloride, iron chloride, copper chloride, aluminum chloride, sodium bromide, calcium bromide, and magnesium bromide; the boride comprises one or a combination of several of boron fluoride, magnesium boride, titanium boride, chromium boride, and calcium boride; the aluminate comprises one or a combination of several of sodium aluminate, calcium aluminate, magnesium aluminate, and ammonium aluminate; the phosphate comprises one or a combination of several of sodium phosphate, calcium phosphate, magnesium phosphate, and ammonium phosphate; the borate comprises one or a combination of several of sodium borate, calcium borate, magnesium borate, and ammonium borate; and the silicate comprises one or a combination of several of sodium silicate, calcium silicate, magnesium silicate, and ammonium silicate.

[0045] In the above preparation method, preferably, in step (2), the amount of the inorganic salt is 1-30% of the mass of Al2O3 in the aluminum source.

[0046] In the above preparation method, preferably, in step (2), the seed crystal comprises one or a combination of several of NaY molecular sieve, REY molecular sieve, and USY molecular sieve, and the amount of the seed crystal is 1-30% of the mass of Al2O3 in the aluminum source.

[0047] In the above preparation method, preferably, in step (2), the molar ratio of Na2O, Al2O3, and SiO2 in the mixture is (1.0-3.5):1:(7-15).

[0048] In the above preparation method, preferably, in step (2), the temperature of the crystallization is 92-100°C, and the time is 16-40h.

[0049] In step (2) of the above preparation method, after the crystallization is completed, the conventional steps of solid-liquid separation, washing, and / or drying, etc. can be optionally performed, and then the first component is obtained.

[0050] In the above preparation method, preferably, in step (3), the metal compound comprises a lanthanide metal compound. More preferably, the lanthanide metal compound comprises one or a combination of several of a nitrate of a lanthanide metal, a chloride of a lanthanide metal, a carbonate of a lanthanide metal, and a sulfate of a lanthanide metal.

[0051] In the above preparation method, preferably, in step (3), the mass concentration of the phytic acid solution is 5-80%.

[0052] In the above preparation method, preferably, in step (3), the mass ratio of the metal compound to the phytic acid solution is 1:1.5-10.

[0053] In the preparation method, preferably, in step (3), the reaction temperature of the metal compound and the phytic acid solution is 80-180°C, more preferably 90-160°C, and the reaction time is 0.5-6 hours, more preferably 1-4 hours.

[0054] In step (3) of the preparation method, after the reaction is completed, the pH value can be adjusted, solid-liquid separation, washing, and / or drying, and other conventional steps can be optionally performed, thereby obtaining the second component.

[0055] In the preparation method, preferably, in step (4), the mixing mass ratio of the first component and the second component is 9-1:1-9.

[0056] The third aspect of the present application provides an oil shale in-situ conversion method, comprising the following steps: contacting the solid organic matter in-situ conversion catalyst with oil shale, thereby catalyzing the in-situ conversion of the solid organic matter in the oil shale, and obtaining oil and gas products.

[0057] In the oil shale in-situ conversion method, preferably, the amount of the solid organic matter in-situ conversion catalyst is 10-90% of the mass of the oil shale.

[0058] The present application has at least the following beneficial effects:

[0059] 1. The present application treats the calcined natural mineral with an alkaline solution, which not only increases the specific surface area and pore volume of the natural mineral, but more importantly, provides a part of the silicon source required for synthesizing the molecular sieve and abundant crystal growth points for the synthesis of Y-type molecular sieve, forms an environment more conducive to the growth of molecular sieve, and lays a solid foundation for the uniform distribution and growth of the subsequent nano Y-type molecular sieve on the mineral after alkaline treatment.

[0060] 2. The present application mixes and reacts the mineral system after alkaline treatment with a silicon source, an aluminum source, a seed crystal, and an inorganic salt to synthesize Y-type molecular sieve. The addition of inorganic salt changes the rate and state of silicon-aluminum combination in the synthesis system, divides the precursor of Y-type molecular sieve into smaller particles, and the crystal begins to grow and crystallize around the smaller particles. The addition of inorganic salt changes the synthesis conditions and environment, and promotes the formation of nano Y-type molecular sieve. The present application successfully synthesizes nano Y-type molecular sieve with smaller average grain size on the mineral after alkaline treatment without using organic template agents. The nano Y-type molecular sieve in the catalyst increases the contact area with organic matter during the in-situ modification of the solid organic matter of oil shale, and the Y-type molecular sieve has strong B acid and L acid acidity, so the cracking effect is more obvious during the modification and conversion.

[0061] 3.The present application utilizes phytic acid solution to complex lanthanide metal ions, and phytic acid can have a very strong complexation reaction with lanthanide metal ions to form lanthanide metal-phytic acid complexes. Since the radius of lanthanide metal ions is large, the coordination number is usually 6-12, and most of them have 4f electrons, which belong to hard acid, so the lanthanide metal-phytic acid complexes can change the water and oil properties of the surface of kerogen in the rock formation on the one hand, and on the other hand, due to the characteristics of the chemical activity of lanthanide metal, the lanthanide metal-phytic acid complexes can efficiently dissolve the kerogen in the rock formation, that is, the combination of hydrocarbons and lanthanide metal ions can change the properties of kerogen, strengthen the flowability of hydrocarbons, and achieve the effect of in-situ upgrading.

[0062] 4.The present application mixes the alkali-treated minerals and the nanometer Y-type molecular sieves and lanthanide metal-phytic acid complexes grown thereon together to form the final catalyst composite system, and the lanthanide metal ions will enter the pore channels of the Y-type molecular sieves under underground conversion conditions to form a more stable structure, continuously play the role of improving the activity of the catalyst, and thus realize the improvement of the in-situ conversion efficiency of solid organic matter in oil shale. BRIEF DESCRIPTION OF DRAWINGS

[0063] Fig. 1 is an electron microscope photo of the Y-type molecular sieve grown on the carrier of calcined and alkali-treated kaolin in Example 1.

[0064] Fig. 2 is an XRD spectrum of the Y-type molecular sieve synthesized in Example 1. DETAILED DESCRIPTION

[0065] 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 will be described in detail below, but it cannot be understood as limiting the implementable scope of the present application.

[0066] The specific experimental steps or conditions not mentioned in the following examples and comparative examples can be operated according to the conventional experimental steps described in the existing technical literature or the conditions. The reagents or instruments used are not marked with the manufacturer, which are conventional products that can be obtained by market purchase.

[0067] The sources of raw materials in the following examples and comparative examples are as follows:

[0068] Diatomaceous earth, industrial product, Jinan Shuangying Chemical Co., Ltd.

[0069] Kaolin, industrial product, Suzhou Kaolin Co., Ltd.

[0070] Lepidocrocite, industrial product, Hubei Zhongxiang Minglu Lepidocrocite Development Co., Ltd.

[0071] Montmorillonite, industrial product, Shenzhen Chunwang Environmental Protection Technology Co., Ltd.

[0072] Halloysite, industrial product, Suzhou Kaolin Co., Ltd.

[0073] Illite, industrial product, Suzhou Kaolin Co., Ltd.

[0074] Coal gangue, industrial product, Shandong Tai'an Huafeng Co., Ltd.

[0075] Sodium hydroxide, aluminum hydroxide, sodium aluminate, aluminum sulfate, chemically pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0076] Pseudo-boehmite (ignition loss: 33.03%, Al2O3 mass fraction 65.9%), industrial product, Lanzhou Petrochemical Company.

[0077] Ammonia, chemically pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0078] Silica sol (SiO2 mass content 30%), chemically pure, Shanghai Test Group.

[0079] White carbon black (SiO2 mass content 90%), Beijing Jindaxin New Material Co., Ltd.

[0080] Tetraethyl orthosilicate (SiO2 mass content 28%), water glass (SiO2 mass content 28.5%), National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0081] Seed crystal: NaY molecular sieve, REY molecular sieve, USY molecular sieve, industrial product, Lanzhou Petrochemical Company.

[0082] Phytic acid: chemically pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0083] Magnesium chloride, chromium boride, calcium silicate, ammonium silicate, magnesium aluminate, calcium phosphate, copper chloride, calcium bromide, ammonium phosphate, magnesium boride, chemically pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0084] Lanthanum chloride, cerium chloride, lanthanum nitrate, cerium nitrate, ytterbium chloride, cerium carbonate, lanthanum carbonate, ytterbium carbonate, lanthanum sulfate, cerium sulfate: chemically pure, National Pharmaceutical Group Chemical Reagent Co., Ltd.

[0085] Oil shale: 80-120 mesh, China Petroleum and Natural Gas Co., Ltd. Changqing Oilfield Branch.

[0086] Characterization method of the first component in the catalyst of the following examples:

[0087] Specific surface area and pore volume of the carrier in the first component: the specific surface area and pore volume of the sample were analyzed by using a Micromeritics ASAP-3000 type automatic physical adsorption instrument.

[0088] Crystallinity of Y zeolite in the first component: tested by X-ray diffractometer (D / max-2000PC). Test conditions: X-ray Cu K α , tube voltage 40 kV, tube current 20 mA, filter Ni scanning rate 10 (°) / min, scanning range 2θ = 4°-70°.

[0089] Average crystal grain size of Y zeolite in the first component: tested by scanning electron microscope (Ultra Plus scanning electron microscope of German Carl Zeiss Company).

[0090] The performance evaluation method of the catalysts of the following examples and comparative examples includes:

[0091] Rock-eval 6 rock pyrolysis instrument produced by French VINCI Company is used to evaluate the pyrolysis catalytic performance of the catalyst. The standard for performing pyrolysis reaction is GB / T 18602-2012. The test process includes: heating the mixture of the catalyst and the oil shale sample to 300℃ at a heating rate of 10℃ / min and keeping constant for 3 minutes, analyzing S1 by gas chromatograph, performing programmed temperature rising in the temperature range of 300℃-800℃ at a heating rate of 10℃ / min, and analyzing S2 by gas chromatograph. S1 refers to the free hydrocarbon content (mg / g) generated by pyrolysis of unit mass of oil shale sample below 300℃, and S2 refers to the hydrocarbon content (mg / g) generated by pyrolysis of unit mass of oil shale sample at 300-800℃. 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:

[0092] The thermal decomposition of a substance is described by formula (4.1):

[0093] Wherein, f(α) is a function, the type of which depends on the reaction mechanism;

[0094] α is the conversion degree, which is a normalized form of the weight loss data of the oil shale sample, and it can be defined as formula (4.2)

[0095] Wherein, 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;

[0096] k is the reaction rate constant related to temperature, which is usually defined by the Arrhenius formula:

[0097] wherein 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;

[0098] Substituting equation (4.3) into equation (4.1), we get:

[0099] According to the homogeneous kinetics of the reaction, f(a) can be defined as:

[0100] f(a) = (1 - a) n (4.5), wherein n is the order of the reaction;

[0101] Substituting equation (4.5) into equation (4.4), the expression of the reaction rate is:

[0102] For non-isothermal measurement of the linear heating rate program, equation (4.4) can be rewritten in the final form:

[0103] Finally, the graph is plotted, and the values of the activation energy E and the pre-exponential factor A can be obtained from the slope and intercept of the linear fitting line, respectively.

[0104] Example 1

[0105] The present embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof, which comprises the following steps:

[0106] (1) After 20 grams of kaolin is calcined at 400°C for 5h, and mixed with an ammonia solution with a mass concentration of 10% at a liquid-solid ratio of 5:1, the mixture is treated at 100°C for 4h to obtain an alkali-treated mineral system; the alkali-treated mineral system comprises a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 2% of the total mass of silicon dioxide in the kaolin;

[0107] (2) The alkali-treated mineral system obtained in step (1) is mixed with 13.49 grams of tetraethyl orthosilicate, 2 grams of pseudoboehmite, 0.28 grams of NaY molecular sieve, and 0.01 grams of magnesium chloride to obtain a mixture, and the molar ratio of Na2O, Al2O3 and SiO2 in the mixture is 1:1:7, then the mixture is crystallized at 100°C for 40h, and then filtered and washed to obtain a first component; the first component comprises an alkali-treated mineral (i.e. the solid phase described above) as a carrier, and a Y-type molecular sieve grown on the carrier; the electron microscope photograph of the first component is shown in Figure 1; the XRD spectrum of the Y-type molecular sieve is shown in Figure 2, wherein Y1-Y8 represent eight characteristic peaks of the Y-type molecular sieve.

[0108] (3) 0.90 g of lanthanum chloride was mixed with 1.35 g of a phytic acid solution with a mass concentration of 5% at 80°C and reacted for 6 hours to obtain a second component;

[0109] (4) The first component obtained in step (2) and the second component obtained in step (3) were mixed in a mass ratio of 9:1 and uniformly dispersed to obtain the solid organic matter in-situ conversion catalyst.

[0110] The specific surface area and pore volume of the solid phase (i.e., the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0111] The performance of the catalyst was evaluated using a rock pyrolysis instrument: 0.3 g of the catalyst was uniformly mixed with 3 g of an oil shale sample (80-120 mesh), 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 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 2.

[0112] Example 2

[0113] The present embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof includes the following steps:

[0114] (1) 30 g of a cumulonimbus soil was calcined at 1000°C for 1 h, and then mixed with an aqueous ammonia solution with a mass concentration of 20% at a liquid-solid ratio of 2:1, and treated at 40°C for 1 h to obtain an alkali-treated mineral system; the alkali-treated mineral system includes a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 30% of the total mass of silicon dioxide in the cumulonimbus soil;

[0115] (2) The alkali-treated mineral system obtained in step (1) was mixed with 86.76 g of water glass, 5 g of aluminum hydroxide, 0.03 g of REY molecular sieve, and 0.65 g of chromium boride to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 1.8:1:15, and then crystallized at 96°C for 36 h, and then filtered and washed to obtain a first component; the first component includes an alkali-treated mineral (i.e., the solid phase described above) as a carrier, and a Y-type molecular sieve grown on the carrier;

[0116] (3) 0.03 g of cerium chloride was mixed with 0.3 g of a phytic acid solution with a mass concentration of 56% at 180°C and reacted for 0.5 hours to obtain a second component;

[0117] (4) mixing the first component obtained in step (2) and the second component obtained in step (3) according to a mass ratio of 8:2 and dispersing uniformly to obtain the solid organic matter in-situ conversion catalyst.

[0118] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0119] The performance of the catalyst was evaluated by using a rock pyrolysis instrument: 2.7 grams of the catalyst was mixed with 3 grams of oil shale sample (80-120 mesh) uniformly, 0.8 grams of the mixture was weighed and put into the 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 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 2.

[0120] Example 3

[0121] The present embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof includes the following steps:

[0122] (1) 25 grams of erionite was calcined at 800℃ for 1.5h, and then mixed with an ammonia water solution with a mass concentration of 25% according to a mass ratio of 1:1 (liquid-solid ratio), and treated at 60℃ for 3h to obtain an alkali-treated mineral system; the alkali-treated mineral system includes a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 15% of the total mass of silicon dioxide in the erionite;

[0123] (2) the alkali-treated mineral system obtained in step (1) was mixed with 4.16 grams of white carbon black, 3 grams of aluminum sulfate, 0.18 grams of USY molecular sieve and 0.27 grams of calcium silicate to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 2.5:1:10, and then crystallized at 96℃ for 36h, and then filtered and washed to obtain a first component; the first component includes the alkali-treated mineral (i.e. the solid phase described above) as a carrier, and a Y-type molecular sieve grown on the carrier;

[0124] (3) 0.45 grams of lanthanum nitrate was mixed with 4.05 grams of a phytic acid solution with a mass concentration of 72% at 100℃ for 1h to obtain a second component;

[0125] (4) the first component obtained in step (2) and the second component obtained in step (3) were mixed according to a mass ratio of 7:3 and dispersed uniformly to obtain the solid organic matter in-situ conversion catalyst.

[0126] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average crystal size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0127] The performance of the catalyst was evaluated using a rock pyrolysis instrument. 0.8 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 temperature rising process was as described above, the pyrolysis products were analyzed using a gas chromatograph, and the kerogen pyrolysis temperature was obtained according to the analysis results. The activation energy was calculated according to the Arrhenius formula, and the results are shown in Table 2.

[0128] Example 4

[0129] The present embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof, which comprises the following steps:

[0130] (1) 35 g of montmorillonite was calcined at 600°C for 2.5 h, and then mixed with an ammonia water solution with a mass concentration of 18% at a liquid-solid ratio of 3:1. After being treated at 80°C for 4 h, an alkali-treated mineral system was obtained. The alkali-treated mineral system comprises a solid phase and a liquid phase. The mass of silicon dioxide in the liquid phase accounts for 12% of the total mass of silicon dioxide in the montmorillonite;

[0131] (2) The alkali-treated mineral system obtained in step (1) was mixed with 31.20 g of water glass, 6.5 g of sodium aluminate, 0.30 g of REY molecular sieve and 0.16 g of ammonium silicate to obtain a mixture. The molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 3.5:1:9.5. Then, the mixture was crystallized at 98°C for 32 h, and then filtered and washed to obtain a first component. The first component comprises an alkali-treated mineral (i.e. the solid phase described above) as a carrier, and a Y-type molecular sieve grown on the carrier;

[0132] (3) 0.6 g of cerium nitrate was mixed with 3.0 g of a phytic acid solution with a mass concentration of 80% at 120°C for 2 h to obtain a second component;

[0133] (4) The first component obtained in step (2) was mixed with the second component obtained in step (3) at a mass ratio of 6:4 and uniformly dispersed to obtain the solid organic matter in-situ conversion catalyst.

[0134] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average crystal size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0135] The performance of the catalyst was evaluated using a rock pyrolysis instrument: 2.1 grams of the catalyst was mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 grams of the mixture was weighed and placed in a rock pyrolysis instrument to perform pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, and then the dry 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 2.

[0136] Example 5

[0137] The embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof, which comprises the following steps:

[0138] (1) 40 grams of diatomite was calcined at 750 DEG C for 3.5 hours, and then mixed with an ammonia water solution with a mass concentration of 1% at a liquid-solid ratio of 4:1, and treated at 70 DEG C for 2 hours to obtain an alkali-treated mineral system; the alkali-treated mineral system comprises a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 5% of the total mass of silicon dioxide in the diatomite;

[0139] (2) the alkali-treated mineral system obtained in step (1) was mixed with 28.96 grams of silica sol, 3 grams of pseudoboehmite, 0.14 grams of USY molecular sieve and 0.07 grams of magnesium aluminate to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 3:1:12.3, and then crystallization was performed at 97 DEG C for 26 hours, and then filtration and washing were performed to obtain a first component; the first component comprises the alkali-treated mineral (i.e. the solid phase) as a carrier and a Y-type molecular sieve grown on the carrier;

[0140] (3) 0.30 grams of ytterbium chloride was mixed with 1.80 grams of a phytic acid solution with a mass concentration of 63% at 110 DEG C for 3 hours to obtain a second component;

[0141] (4) the first component obtained in step (2) was mixed with the second component obtained in step (3) according to a mass ratio of 5:5 and uniformly dispersed to obtain the solid organic matter in-situ conversion catalyst.

[0142] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0143] The performance of the catalyst was evaluated by using a rock pyrolysis instrument: 1.8 grams of the catalyst was mixed with 3 grams of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 gram of the mixture was put into a rock pyrolysis instrument to perform a pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, and then the dry 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 2.

[0144] Example 6

[0145] The embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof, which comprises the following steps:

[0146] (1) 24 grams of illite was calcined at 950℃ for 4.5h, and then mixed with an ammonia water solution with a mass concentration of 5% at a liquid-solid ratio of 5:1, and treated at 50℃ for 3.5h to obtain an alkali-treated mineral system; the alkali-treated mineral system comprises a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 28% of the total mass of silicon dioxide in the illite;

[0147] (2) the alkali-treated mineral system obtained in step (1) was mixed with 25.97 grams of white carbon black, 5 grams of aluminum hydroxide, 0.26 grams of USY molecular sieve and 0.56 grams of calcium phosphate to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 1.3:1:14.3, and then crystallization was performed at 95℃ for 16h, and then filtration and washing were performed to obtain a first component; the first component comprises the alkali-treated mineral (i.e. the solid phase) as a carrier, and a Y-type molecular sieve grown on the carrier;

[0148] (3) 0.69 grams of cerium carbonate was mixed with 5.52 grams of a phytic acid solution with a mass concentration of 47% at 130℃ for 3.5h to obtain a second component;

[0149] (4) the first component obtained in step (2) was mixed with the second component obtained in step (3) according to a mass ratio of 4:6 and uniformly dispersed to obtain the solid organic matter in-situ conversion catalyst.

[0150] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0151] The performance of the catalyst was evaluated by using a rock pyrolysis instrument: 1.5 g of the catalyst was mixed with 3 g of 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 to perform pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, and then the dry 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 2.

[0152] Example 7

[0153] The embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof, which comprises the following steps:

[0154] (1) 37 g of coal gangue was calcined at 900 ℃ for 1.5 h, and then mixed with an ammonia water solution with a mass concentration of 8% at a liquid-solid ratio of 3:1, and treated at 70 ℃ for 2 h to obtain an alkali-treated mineral system; the alkali-treated mineral system comprises a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 10% of the total mass of silicon dioxide in the coal gangue;

[0155] (2) the alkali-treated mineral system obtained in step (1) was mixed with 10.46 g of water glass, 2 g of aluminum sulfate, 0.03 g of REY molecular sieve and 0.08 g of copper chloride to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 2.4:1:13.2, and then the mixture was crystallized at 97 ℃ for 22 h, and then filtered and washed to obtain a first component; the first component comprises an alkali-treated mineral (i.e. the solid phase) as a carrier and a Y-type molecular sieve grown on the carrier;

[0156] (3) 0.8 g of lanthanum carbonate was mixed with 1.2 g of a phytic acid solution with a mass concentration of 32% at 90 ℃ for 5 h to obtain a second component;

[0157] (4) the first component obtained in step (2) and the second component obtained in step (3) were mixed and uniformly dispersed at a mass ratio of 3:7 to obtain the solid organic matter in-situ conversion catalyst.

[0158] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0159] The performance of the catalyst was evaluated by using a rock pyrolysis instrument: 0.6 g of the catalyst was mixed with 3 g of oil shale sample (80-120 mesh) to obtain a mixture, 0.8 g of the mixture was weighed and put into a rock pyrolysis instrument to perform pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, and then the dry 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 2.

[0160] Example 8

[0161] The embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof.

[0162] (1) 22 g of erionite was calcined at 900 ℃ for 1.5 h, and then mixed with an ammonia water solution with a mass concentration of 13% at a liquid-solid ratio of 4:1, and treated at 65 ℃ for 2.5 h to obtain an alkali-treated mineral system; the alkali-treated mineral system comprises a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 4% of the total mass of silicon dioxide in the erionite;

[0163] (2) the alkali-treated mineral system obtained in step (1) was mixed with 44.53 g of tetraethyl orthosilicate, 6 g of sodium aluminate, 0.34 g of NaY molecular sieve and 0.43 g of calcium bromide to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 2.7:1:11.4, and then the mixture was crystallized at 92 ℃ for 38 h, and then filtered and washed to obtain a first component; the first component comprises the alkali-treated mineral (i.e. the solid phase) as a carrier, and a Y-type molecular sieve grown on the carrier;

[0164] (3) 0.36 g of ytterbium carbonate was mixed with 0.76 g of a phytic acid solution with a mass concentration of 22% at 160 ℃ for 1.5 h to obtain a second component;

[0165] (4) the first component obtained in step (2) and the second component obtained in step (3) were mixed and uniformly dispersed according to a mass ratio of 2:8 to obtain the solid organic matter in-situ conversion catalyst.

[0166] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0167] The performance of the catalyst was evaluated using a rock pyrolysis instrument: 0.9 g of the catalyst was mixed with 3 g of 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 to perform pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed by a gas chromatograph, and then the dry 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 2.

[0168] Example 9

[0169] The embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof, which comprises the following steps:

[0170] (1) 38.2 g of diatomite was calcined at 500 DEG C for 2.5 h, and then mixed with an ammonia water solution with a mass concentration of 16% at a liquid-solid ratio of 2:1, and treated at 75 DEG C for 1 h to obtain an alkali-treated mineral system; the alkali-treated mineral system comprises a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 1% of the total mass of silicon dioxide in the diatomite;

[0171] (2) the alkali-treated mineral system obtained in step (1) was mixed with 20.76 g of water glass, 4 g of aluminum sulfate, 0.29 g of NaY molecular sieve and 0.32 g of ammonium phosphate to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 3:1:8.5, and then crystallization was performed at 100 DEG C for 20 h, and then filtration and washing were performed to obtain a first component; the first component comprises an alkali-treated mineral (i.e. the solid phase) as a carrier and a Y-type molecular sieve grown on the carrier;

[0172] (3) 0.21 g of lanthanum sulfate was mixed with 0.98 g of a phytic acid solution with a mass concentration of 13% at 145 DEG C and reacted for 2.5 h to obtain a second component;

[0173] (4) the first component obtained in step (2) was mixed with the second component obtained in step (3) at a mass ratio of 1:9 and uniformly dispersed to obtain the solid organic matter in-situ conversion catalyst.

[0174] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0175] The performance of the catalyst was evaluated using a rock pyrolysis instrument: 1.2 g of the catalyst was mixed with 3 g of 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 to perform pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed by using a gas chromatograph, and then the dry 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 2.

[0176] Example 10

[0177] The embodiment provides a solid organic matter in-situ conversion catalyst, and a preparation method thereof, which comprises the following steps:

[0178] (1) 26.4 g of kaolin was calcined at 650 DEG C for 5 h, and then mixed with an ammonia water solution with a mass concentration of 8% at a liquid-solid ratio of 1:1, and treated at 85 DEG C for 3 h to obtain an alkali-treated mineral system; the alkali-treated mineral system comprises a solid phase and a liquid phase; the mass of silicon dioxide in the liquid phase accounts for 4% of the total mass of silicon dioxide in the kaolin;

[0179] (2) the alkali-treated mineral system obtained in step (1) was mixed with 6.30 g of white carbon black, 3 g of pseudo-boehmite, 0.16 g of USY molecular sieve and 0.35 g of magnesium boride to obtain a mixture, the molar ratio of Na2O, Al2O3 and SiO2 in the mixture was 3.2:1:7.3, and then the mixture was crystallized at 94 DEG C for 30 h, and then filtered and washed to obtain a first component; the first component comprises the alkali-treated mineral (i.e. the solid phase) as a carrier and a Y-type molecular sieve grown on the carrier;

[0180] (3) 0.09 g of cerium sulfate was mixed with 0.18 g of a phytic acid solution with a mass concentration of 8% at 105 DEG C for 5.5 h to obtain a second component;

[0181] (4) the first component obtained in step (2) was mixed with the second component obtained in step (3) at a mass ratio of 5.5:4.5 and uniformly dispersed to obtain the solid organic matter in-situ conversion catalyst.

[0182] The specific surface area and pore volume of the solid phase (i.e. the carrier) in the alkali-treated mineral system obtained in step (1) were tested, and the results are shown in Table 1. The crystallinity and average grain size of the Y-type molecular sieve in the first component obtained in step (2) were tested, and the results are shown in Table 1.

[0183] The performance of the catalysts was evaluated 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 to perform a pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed using a gas chromatograph, and then the dry 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 2.

[0184] Comparative Example 1

[0185] 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 to perform a pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed using a gas chromatograph, and then the dry 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 2.

[0186] Comparative Example 2

[0187] In this comparative example, only YbCl3 was used as the catalyst: 0.3 g of YbCl3 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 to perform a pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed using a gas chromatograph, and then the dry 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 2.

[0188] Comparative Example 3

[0189] In this comparative example, only USY molecular sieve was used as the catalyst: 0.45 g of USY molecular sieve 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 to perform a pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed using a gas chromatograph, and then the dry 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 2.

[0190] Comparative Example 4

[0191] In this comparative example, only the solid phase in the alkali-treated mineral system prepared in step (1) of Example 3 was used as the catalyst: 0.8 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 to perform a pyrolysis reaction, the specific temperature rising process was as described above, the pyrolysis products were analyzed using a gas chromatograph, and then the dry 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 2.

[0192] Comparative Example 5

[0193] This comparative example is compared with Example 3, and the first component prepared in step (2) of Example 3 is used as catalyst only. 0.8 g of the first component is mixed with 3 g of oil shale sample (80-120 mesh) to prepare a mixture, and 0.8 g of the mixture is put into a rock pyrolysis instrument to perform a pyrolysis reaction. The temperature rising process is as described above, and 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. The results are shown in Table 2.

[0194] Comparative Example 6

[0195] This comparative example is compared with Example 3, and the second component prepared in step (3) of Example 3 is used as catalyst only. 0.8 g of the second component is mixed with 3 g of oil shale sample (80-120 mesh) to prepare a mixture, and 0.8 g of the mixture is put into a rock pyrolysis instrument to perform a pyrolysis reaction. The temperature rising process is as described above, and 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. The results are shown in Table 2.

[0196] Table 1 Parameters of the carrier and molecular sieve in the first component of Examples 1-10

[0197] Table 2 Evaluation results of the catalyst performance of Examples 1-10 and Comparative Examples 1-6

[0198] As shown in Table 1, the specific surface area of the carrier in the first component of the catalyst of the present application is 120-200 m 2 / g, and the pore volume is 0.15-0.25 mL / g, which has a high specific surface area and pore volume. The present application successfully synthesizes the nano Y-type molecular sieve with a crystallinity of more than 80% and an average grain size of 100-600 nm on the alkali-treated mineral (i.e. the carrier) without using an organic template agent.

[0199] As can be seen from Table 2, compared with the comparative example 1 without adding catalyst, the pyrolysis temperature of the inventive examples 1-10 is reduced by 4.56-24.37%, and the activation energy is reduced by 23.34-37.56%. The pyrolysis temperature and activation energy of the comparative example 2 using a lanthanide metal compound as a catalyst are not reduced compared with the comparative example 1. The pyrolysis temperature of the comparative example 3 using a USY molecular sieve as a catalyst is slightly reduced compared with the comparative example 1. The alkali-treated mineral in the mineral system is not used as a catalyst in the comparative example 4, and the alkali-treated mineral does not have the effect of reducing the pyrolysis temperature and activation energy. The alkali-treated mineral growing Y-type molecular sieve is used as a catalyst in the comparative example 5, and the system containing lanthanide metal-phytic acid complex is used as a catalyst in the comparative example 6, and the effect is not obvious.

[0200] In summary, the catalyst of the present application includes the alkali-treated mineral growing nano Y-type molecular sieve and the lanthanide metal-phytic acid complex. Among them, the alkali-treated mineral growing nano Y-type molecular sieve has abundant specific surface area, pore volume and strong acidity, which can fully play the role of nano Y-type molecular sieve under the conditions of underground conversion, continuously play the role of improving the activity of the catalyst, thereby realizing the improvement of the in-situ conversion efficiency of oil shale. At the same time, the lanthanide metal ions are complexed by phytic acid to stabilize the lanthanide metal ions to form a lanthanide metal-phytic acid complex. On the one hand, the lanthanide metal-phytic acid complex changes the surface of the kerogen in the rock layer to hydrophilic and oleophobic properties, and on the other hand, due to the active chemical properties of the lanthanide metal, the lanthanide metal-phytic acid complex can efficiently dissolve the kerogen in the rock layer, i.e. the combination of hydrocarbons and lanthanide metal ions can change the properties of kerogen and strengthen the flowability of hydrocarbons to achieve the purpose of in-situ upgrading. In addition, the lanthanide metal-phytic acid complex can also have a coupling and synergistic effect with the alkali-treated mineral growing nano Y-type molecular sieve, and the lanthanide metal ions can enter the pore channel of the nano Y-type molecular sieve to further stabilize the molecular sieve structure, and together realize the improvement of the in-situ conversion efficiency of oil shale. Therefore, the catalyst of the present application has significantly improved activity when used for catalyzing the in-situ conversion of solid organic matter in oil shale, reduces the activation energy and pyrolysis temperature of kerogen in-situ conversion. The catalyst has good sustained effectiveness and stability, and is environmentally friendly, and the preparation process is relatively simple. The catalyst of the present application can improve the oil and gas recovery rate and has good application prospect.

Claims

1. A solid organic matter in situ conversion catalyst comprising: A first component and a second component; the first component comprises a carrier and a Y-type molecular sieve grown on the carrier, the carrier comprises an alkali-treated mineral; The second component comprises a metal-phytic acid complex.

2. The solid organic matter in situ conversion catalyst of claim 1, wherein, The mass ratio of the first component to the second component is 9-1:1-9.

3. The solid organic matter in situ conversion catalyst of claim 1, wherein, The alkali-treated mineral is obtained by treating a mineral containing silicon dioxide with an alkaline solution.

4. The solid organic matter in situ conversion catalyst of claim 3, wherein, The mineral containing silicon dioxide is obtained by calcining a natural mineral containing silicate.

5. The solid organic matter in situ conversion catalyst of claim 4, wherein, The natural mineral containing silicate comprises one or a combination of kaolin, allophane, halloysite, montmorillonite, diatomite, illite and coal gangue.

6. The solid organic matter in situ conversion catalyst of claim 1, wherein, The specific surface area of the support in the first component is between 120 and 200 m 2 / g, and the pore volume is between 0.15 and 0.25 mL / g.

7. The solid organic matter in situ conversion catalyst of claim 1, wherein, The Y-type molecular sieve in the first component has a crystallinity of 80% or more and an average crystal size of 100-600 nm.

8. The solid organic matter in situ conversion catalyst of claim 1, wherein, The metal in the metal-phytic acid complex comprises a lanthanide metal.

9. A method for preparing the solid organic matter in-situ conversion catalyst according to any one of claims 1-8, comprising the following steps: (1) treating a mineral containing silicon dioxide with an alkaline solution to obtain an alkali-treated mineral system, the alkali-treated mineral system comprising a solid phase and a liquid phase; (2) mixing the alkali-treated mineral system obtained in step (1) with a silicon source, an aluminum source, a seed crystal and an inorganic salt to obtain a mixture; subjecting the mixture to at least crystallization to obtain a first component; (3) mixing and reacting a metal compound with a phytic acid solution to obtain a second component; (4) mixing the first component obtained in step (2) with the second component obtained in step (3) to obtain the solid organic matter in-situ conversion catalyst.

10. The production method according to claim 9, wherein In step (1), the mineral containing silicon dioxide is obtained by calcining a natural mineral containing silicate.

11. The production method according to claim 10, wherein In step (1), the natural mineral containing silicate comprises one or a combination of kaolin, allophane, halloysite, montmorillonite, diatomite, illite and coal gangue.

12. The production method according to claim 9, wherein In step (1), the alkaline solution comprises one or a combination of solutions of sodium hydroxide, sodium carbonate, ammonia and sodium bicarbonate, and the mass concentration of the alkaline solution is 1-25%.

13. The production method according to claim 9, wherein In step (1), the mixing mass ratio of the alkaline solution to the mineral containing silicon dioxide is (1-5):1, the temperature for treating the mineral containing silicon dioxide with the alkaline solution is 40-100°C, and the time is 1-4 h.

14. The production method according to claim 9, wherein In step (1), the silicon dioxide in the liquid phase of the alkali-treated mineral system is 1-30% of the total mass of the silicon dioxide in the mineral containing silicon dioxide.

15. The production method according to claim 9, wherein In step (2), the silicon source comprises one or a combination of tetraethyl orthosilicate, silica sol, white carbon black and water glass.

16. The method of manufacturing according to claim 9, wherein, In step (2), the aluminum source comprises one or a combination of pseudo-boehmite, aluminum hydroxide, aluminum sulfate and sodium aluminate.

17. The method of making according to claim 9, wherein, In step (2), the inorganic salt comprises one or a combination of halogen compounds, borides, aluminate, phosphate, borate and silicate.

18. The method of making according to claim 17, wherein, In step (2), the halogen compound comprises one or a combination of several of sodium chloride, sodium fluoride, magnesium chloride, calcium chloride, barium chloride, chromium chloride, iron chloride, copper chloride, aluminum chloride, sodium bromide, calcium bromide, and magnesium bromide; the boride comprises one or a combination of several of boron fluoride, magnesium boride, titanium boride, chromium boride, and calcium boride; the aluminate comprises one or a combination of several of sodium aluminate, calcium aluminate, magnesium aluminate, and ammonium aluminate; the phosphate comprises one or a combination of several of sodium phosphate, calcium phosphate, magnesium phosphate, and ammonium phosphate; the borate comprises one or a combination of several of sodium borate, calcium borate, magnesium borate, and ammonium borate; and the silicate comprises one or a combination of several of sodium silicate, calcium silicate, magnesium silicate, and ammonium silicate.

19. The production method according to claim 9, wherein In step (2), the inorganic salt is used in an amount of 1-30% of the mass of Al2O3 in the aluminum source.

20. The method of manufacturing according to claim 9, wherein, In step (2), the seed crystal comprises one or a combination of several of NaY molecular sieve, REY molecular sieve, and USY molecular sieve, and the seed crystal is used in an amount of 1-30% of the mass of Al2O3 in the aluminum source.

21. The method of manufacturing according to claim 9, wherein, In step (2), the mixture has a molar ratio of Na2O:Al2O3:SiO2 of (1.0-3.5):1:(7-15).

22. The method of manufacturing according to claim 9, wherein, In step (2), the crystallization is performed at a temperature of 92-100°C for 16-40 hours.

23. The method of manufacturing according to claim 9, wherein, In step (3), the metal compound comprises a lanthanide metal compound.

24. The method of manufacturing according to claim 23, wherein, In step (3), the lanthanide metal compound comprises one or a combination of several of a lanthanide metal nitrate, a lanthanide metal chloride, a lanthanide metal carbonate, and a lanthanide metal sulfate.

25. The method of manufacturing according to claim 9, wherein, In step (3), the phytic acid solution has a mass concentration of 5-80%.

26. The method of manufacturing according to claim 9, wherein, In step (3), the metal compound and the phytic acid solution are mixed in a mass ratio of 1:1.5-10.

27. The method of manufacturing according to claim 9, wherein, In step (3), the metal compound and the phytic acid solution are reacted at a temperature of 80-180°C for 0.5-6 hours.

28. A method for in situ conversion of oil shale comprising the steps of: The solid organic matter in-situ conversion catalyst of any one of claims 1-8 is contacted with oil shale to catalyze the in-situ conversion of solid organic matter in the oil shale, thereby obtaining oil and gas products.

29. The in situ conversion of oil shale according to claim 28, wherein, The solid organic matter in-situ conversion catalyst is used in an amount of 10-90% of the mass of the oil shale.

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