Silica sol, slurry, catalyst and preparation method and application thereof and catalytic cracking method

Abstract

The present invention relates to the field of catalytic cracking, and discloses a silica sol, a slurry, a catalyst, a preparation method thereof, an application thereof, and a catalytic cracking method, wherein the silica sol comprises SiO2 and an organic acid radical of a first organic acid; wherein, in the silica sol, the content of SiO2 is 1-15% by weight, and the content of the organic acid radical of the first organic acid is 1-15% by weight; wherein, the pH of the silica sol is 0.5-4. The silica sol contains an organic acid, and has good stability at a higher temperature and a higher pH value. The slurry of the present invention, because a binder containing an organic acid is used, can reduce the amount of the binder, and the binder does not contain chlorine, so that the catalyst dechlorination process is simple, and the problem of the chlorine-containing sol binder is overcome; in addition, the catalyst also has good catalytic activity and wear resistance.

Description

Technical Field

[0001] The present invention relates to the field of catalytic cracking, and in particular to a silica sol, a preparation method of the silica sol, a slurry, a catalyst and a preparation method and application thereof, and a catalytic cracking method. Background Art

[0002] FCC has always been an important process technology for secondary processing of crude oil, and catalyst is one of its core technologies. Semi-synthetic FCC catalyst is to first synthesize molecular sieve catalytic materials, then use kaolin as filler, molecular sieve as active component, various silicon / aluminum gels as binders, mix them, and spray dry them to prepare the catalyst. The semi-synthetic method has a simple preparation process, low preparation cost, and strong flexibility in formula adjustment. At present, it occupies a dominant position in the FCC catalyst preparation process.

[0003] The main function of the binder in the semi-synthetic process is to enable the catalyst to obtain the strength and particle size distribution required for industrial applications. As the catalytic cracking process processes heavier and inferior crude oil, it becomes increasingly important for the binder to be compatible with the filler and active components to provide the ability to crack heavy oil while providing good reaction selectivity.

[0004] The binders used in semi-synthetic catalysts mainly include aluminum binders (aluminum sol or peptized pseudo-boehmite), silicon-aluminum binders, double aluminum binders (aluminum sol + peptized pseudo-boehmite) and silicon binders (silica sol or silica gel).

[0005] As early as the 1980s, China began to develop cracking catalysts containing silicon binder matrix. Changling Refinery and Chemical Plant and Beijing Petrochemical Research Institute cooperated to successfully develop a heavy oil cracking catalyst CHZ-1 containing silicon binder matrix. The results of small and medium-sized tests and industrial applications showed that the agent has excellent coke selectivity, heavy oil conversion ability and strong metal resistance. However, due to the easy gelation of silica sol, the catalyst slurry containing silica sol has poor stability and a short storage time. The current conventional catalyst production process cannot meet the production requirements, that is, the process of preparing silica sol and catalyst by intermittent method has problems such as unstable quality, harsh preparation conditions, long production cycle, and limited production capacity. Summary of the invention

[0006] The purpose of the present invention is to solve the problem of low stability of silica sol in the prior art and to provide a new silica sol and a preparation method thereof. The silica sol can stably exist at a higher temperature and a higher pH. When the silica sol is used to prepare a catalytic cracking catalyst, it can improve the coke selectivity, enhance the cracking ability of heavy oil macromolecules, and increase the gasoline yield.

[0007] In order to achieve the above-mentioned object, the first aspect of the present invention provides a silica sol, wherein the silica sol comprises SiO2 and an organic acid radical of a first organic acid;

[0008] Wherein, in the silica sol, the content of SiO2 is 1-15% by weight, and the content of the organic acid radical of the first organic acid is 1-15% by weight;

[0009] Wherein, the pH of the silica sol is 0.5-4.

[0010] Preferably, the silica sol also contains alcohol.

[0011] The second aspect of the present invention provides a method for preparing the silica sol as described above, the method comprising: mixing and reacting a silicate with an inorganic acid and a first organic acid to obtain a silica sol;

[0012] Preferably, the temperature during the reaction is controlled not to exceed 45°C.

[0013] The third aspect of the present invention provides a slurry, which comprises, on a dry basis, 10-40 wt % of a molecular sieve, 20-45 wt % of a clay, and 15-40 wt % of a binder comprising an organic acid;

[0014] Wherein, the content of organic acid in the slurry is 1-10 wt % based on organic acid radical;

[0015] Wherein, the binder contains silica sol;

[0016] Wherein, the pH of the slurry is 1.5-3.5.

[0017] Preferably, the molecular sieve is selected from at least one of Y-type zeolite, Beta zeolite and zeolite with MFI structure. Further preferably, based on the dry weight of the molecular sieve, the molecular sieve comprises 75-100 wt % of Y-type molecular sieve and 0-25 wt % of other molecular sieves selected from at least one of Beta zeolite and zeolite with MFI structure.

[0018] Preferably, the silica sol is the silica sol described above.

[0019] Preferably, the binder further comprises aluminum phosphate sol; on a dry basis, the content of silica sol in the slurry is 2-30 wt %; and the content of aluminum phosphate sol is 2-20 wt %.

[0020] Preferably, the aluminum phosphate sol contains an organic acid radical of a second organic acid.

[0021] A fourth aspect of the present invention provides a catalytic cracking catalyst, wherein the catalytic cracking catalyst is prepared from the slurry as described above.

[0022] A fifth aspect of the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising molding and calcining the slurry as described above to obtain a catalytic cracking catalyst.

[0023] A sixth aspect of the present invention provides a catalytic cracking catalyst prepared by the method described above.

[0024] A seventh aspect of the present invention provides use of the catalytic cracking catalyst as described above in the field of catalytic cracking.

[0025] An eighth aspect of the present invention provides a catalytic cracking method, which comprises: contacting hydrocarbon oil with a catalyst for reaction under catalytic cracking conditions; the catalyst is the catalytic cracking catalyst as described above.

[0026] The silica sol of the present invention contains organic acid and can be stably present for a long time at a higher temperature and a higher pH. In the case of preferably containing alcohol or a preferred preparation method, the stable existence time of the silica sol can be further extended. When it is used to prepare a catalytic cracking catalyst, it can improve the coke selectivity, enhance the cracking ability of heavy oil macromolecules, and improve the gasoline yield.

[0027] In the present invention, the use of a binder containing an organic acid can greatly reduce the viscosity of the binder and the slurry, improve the fluidity of the material, thereby appropriately reducing the amount of binder used, reducing the catalyst manufacturing cost, and can increase the solid content of the slurry, thereby reducing the energy consumption of spray drying.

[0028] The preferred aluminum phosphate sol of the present invention has very good stability and can be stored for a long time without affecting its bonding performance.

[0029] In the preferred embodiment of the present invention, a composite binder combining aluminum phosphate sol and silica sol is used, which can combine the characteristics of aluminum phosphate sol with good bonding properties, good catalyst strength, and certain cracking activity, and the advantage of silica sol in producing less coke in the catalyst reaction product, thereby further improving the catalyst's wear resistance, activity and selectivity for coke.

[0030] The mixed binder of aluminum phosphate sol and silica sol does not contain chlorine. When using it to prepare the catalyst, the slurry before spray molding and the catalyst after spray molding will not contain chlorine, thus avoiding equipment corrosion and environmental pollution. The binder has a low curing temperature and can be cured below 200°C (the curing temperature of chlorine-containing aluminum sol is generally greater than 300°C), so it can greatly reduce the temperature of the spray molding tail gas, thereby greatly reducing energy consumption and reducing the catalyst manufacturing cost.

[0031] In the present invention, when the preferred molecular sieve is used, more gasoline or more liquid products can be produced in catalytic cracking, and the coke selectivity of the catalyst can also be improved. DETAILED DESCRIPTION

[0032] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0033] A first aspect of the present invention provides a silica sol, wherein the silica sol comprises SiO2 and an organic acid radical of a first organic acid;

[0034] Wherein, in the silica sol, the content of SiO2 is 1-15% by weight, and the content of the organic acid radical of the first organic acid is 1-15% by weight;

[0035] Wherein, the pH of the silica sol is 0.5-4.

[0036] In the present invention, the content of SiO2 in the silica sol is 1-15% by weight, such as 1, 3, 6, 9, 12, 15% by weight and any range between any two values, preferably 5-11% by weight.

[0037] In the present invention, the content of the organic acid radical of the first organic acid in the silica sol is 1-15 wt %, such as 1, 3, 6, 9, 12, 15 wt % and any range between any two values, preferably 4-12 wt %.

[0038] Preferably, the first organic acid is at least one selected from oxalic acid, acetic acid, sulfosalicylic acid, citric acid and formic acid, more preferably oxalic acid and / or sulfosalicylic acid.

[0039] Preferably, the silica sol further contains alcohol. In the preferred case, the stability of the silica sol can be further improved.

[0040] Preferably, the alcohol is selected from at least one of ethanol, propanol, ethylene glycol and glycerol;

[0041] Preferably, in the silica sol, the content of the alcohol is 1-20 wt % (for example, 1, 5, 10, 15, 20 wt % and any range between any two values), more preferably 4-13 wt %.

[0042] Preferably, the silica sol also contains acid radicals of inorganic acids.

[0043] Preferably, the inorganic acid is selected from at least one of HCl, HNO3 and H2SO4, more preferably H2SO4.

[0044] Preferably, by weight, the content ratio of the acid radical of the inorganic acid to the organic acid radical of the first organic acid is 0.02-1:1 (for example, it can be 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1:1 and any range between any two values).

[0045] In the present invention, the pH of the silica sol is 0.5-4 (for example, it can be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 5 and any range between any two values); more preferably, it is 1-3.

[0046] Preferably, the viscosity of the silica sol is 0.2-50 mPa·s. The viscosity can be measured at 25° C. using a NDJ21 type rotary viscometer.

[0047] It should be understood that the silica sol also contains water.

[0048] The silica sol can be prepared in a conventional manner. Preferably, the preparation method of the silica sol is as shown in the second aspect.

[0049] The second aspect of the present invention provides a method for preparing the silica sol as described above, the method comprising: mixing and reacting a silicate with an inorganic acid and a first organic acid to obtain the silica sol.

[0050] It should be understood that the amount of each component should be such that the content of each component in the obtained silica sol is within the range described in the first aspect. The types of the inorganic acid, the first organic acid and the alcohol are as described in the first aspect and will not be repeated here.

[0051] The silicate may be a conventional silicate in the art, such as sodium silicate, including but not limited to sodium water glass, etc.

[0052] Preferably, the inorganic acid is in the form of an inorganic acid solution, and the content of the inorganic acid in the inorganic acid solution is 5-40 wt % (for example, 5, 10, 15, 20, 25, 30, 35, 40 wt % and any range between any two values).

[0053] Preferably, the first organic acid is present in the form of an alcohol solution of the first organic acid, and the content of the first organic acid in the alcohol solution of the first organic acid is 30-80 weight % (for example, it can be 30, 40, 50, 60, 70, 80 weight % and any range between any two values).

[0054] Preferably, the temperature during the reaction is controlled not to exceed 45°C, more preferably not to exceed 35°C.

[0055] In the present invention, unless otherwise specified, the solvent used is water, which is preferably decationized water.

[0056] The third aspect of the present invention provides a slurry, which comprises, on a dry basis, 10-40 wt % of a molecular sieve, 20-45 wt % of a clay, and 15-40 wt % of a binder comprising an organic acid;

[0057] Wherein, the content of organic acid in the slurry is 1-10 wt % based on organic acid radical;

[0058] Wherein, the binder contains silica sol;

[0059] Wherein, the pH of the slurry is 1.5-3.5.

[0060] In the present invention, on a dry basis, the slurry comprises 10-40 wt% of molecular sieve (for example, 10, 15, 20, 25, 30, 35, 40 wt% and any range between any two values), 20-45 wt% of clay (for example, 20, 25, 30, 35, 40, 45 wt% and any range between any two values), and 15-40 wt% of a binder comprising an organic acid (for example, 15, 20, 25, 30, 35, 40 wt% and any range between any two values). Preferably, on a dry basis, the slurry comprises 30-40 wt% of molecular sieve, 30-45 wt% of clay and 20-35 wt% of a binder comprising an organic acid.

[0061] In the present invention, the dry basis is processed according to the NB / SH / T 0953-2017 catalytic cracking catalyst ignition loss determination method. It should be understood that the dry basis means that the moisture and burnable components (such as organic matter) in the slurry are not included.

[0062] In the present invention, the binder contains an organic acid, but the organic acid may not only come from the binder, but may also enter the slurry through exogenous addition or the like.

[0063] In the present invention, calculated as organic acid radicals, the content of organic acid in the slurry is 1-10 wt % (for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 wt % and any range between any two values). Preferably, calculated as organic acid radicals, the content of organic acid in the slurry is 4-8 wt %.

[0064] In the present invention, the organic acid radical is based on the total weight of the slurry and is calculated based on the theoretical value of various forms of organic acids present in the slurry.

[0065] In the present invention, the pH of the slurry is 1.5-3.5 (for example, it can be 1.5, 2, 2.5, 3, 3.5 and any range between any two values). Preferably, the pH of the slurry is 2-3.5.

[0066] Preferably, the viscosity of the slurry is 10000-200000 mPa·s.

[0067] The viscosity can be measured at 25° C. using a NDJ21 type rotational viscometer.

[0068] Preferably, the solid content of the slurry is 15-50% by weight, for example, it can be 15, 20, 25, 30, 35, 40, 45, 50% by weight and any range between any two values.

[0069] In the present invention, solid content refers to the percentage of the weight of the remaining part of the slurry after drying to the total weight of the slurry. The drying method may be, for example, placing the slurry in an oven at 60-90° C. and drying to constant weight.

[0070] In the present invention, the molecular sieve is preferably a molecular sieve capable of catalytic cracking reaction, more preferably a zeolite molecular sieve and / or a non-zeolite molecular sieve.

[0071] The zeolite molecular sieve is preferably large-pore zeolite and / or medium-pore zeolite.

[0072] The large-pore zeolite is a zeolite with a pore structure of at least 0.7 nanometer ring openings, such as one or more of Y-type zeolite, faujasite, L zeolite, Beta zeolite, Ω zeolite, mordenite, and ZSM-18 zeolite, preferably Y-type zeolite and / or Beta zeolite.

[0073] The Y-type zeolite may be one or more of NaY-type zeolite, Y-type zeolite containing phosphorus and / or rare earth (such as REY molecular sieve), and ultrastable Y zeolite.

[0074] Among them, the ultrastable Y zeolite may be, for example, hydrogen-type ultrastable Y zeolite, phosphorus-containing ultrastable Y zeolite and transition metal-containing ultrastable Y zeolite. The hydrogen-type ultrastable Y zeolite includes but is not limited to HSY series molecular sieves, SOY series molecular sieves and DASY series molecular sieves; the phosphorus-containing ultrastable Y zeolite may be, for example, PSRY and PREHY molecular sieves; the transition metal-containing ultrastable Y zeolite may be, for example, REY molecular sieve.

[0075] The medium-pore zeolite is a zeolite with a pore structure having a ring opening greater than 0.56 nanometers and less than 0.7 nanometers, such as one or more of zeolite with an MFI structure, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, and MCM-56 zeolite; preferably, zeolite with an MFI structure.

[0076] A typical representative of the molecular sieve with MFI structure is ZSM-5 zeolite developed by Mobil Corporation of the United States, which has a ten-membered ring structure. Preferably, the molecular sieve with MFI structure is ZSM-5 molecular sieve and / or ZSM-5 molecular sieve modified with phosphorus or transition metal; preferably, the molecular sieve with MFI structure is at least one of ZSM-5, ZRP-1, ZRP-5, ZSP-2, ZSP-3 and ZSP-4.

[0077] The molar ratio of SiO2:Al2O3 of the molecular sieve with MFI structure is 15-100:1; preferably, the molar ratio of SiO2:Al2O3 of the molecular sieve with MFI structure is 20-60:1.

[0078] The non-zeolite molecular sieve refers to a molecular sieve in which the aluminum and / or silicon in the zeolite are partially or completely replaced by one or more of other elements such as phosphorus, titanium, gallium, and germanium, including one or more of silicates with different silicon-to-aluminum ratios (such as metal silicates, titanosilicates), metal aluminates, metal phosphates, aluminum phosphates, metal aluminum phosphates, and silicoaluminophosphates (such as SAPO molecular sieves).

[0079] Preferably, the molecular sieve is selected from at least one of Y-type zeolite, Beta zeolite and zeolite with MFI structure. Further preferably, based on the dry weight of the molecular sieve, the molecular sieve comprises 75-100 wt % of Y-type molecular sieve and 0-25 wt % of other molecular sieves selected from at least one of Beta zeolite and zeolite with MFI structure.

[0080] Preferably, the molecular sieve is Y-type zeolite.

[0081] In a preferred embodiment of the present invention, the molecular sieve comprises a hydrogen-type ultrastable Y zeolite molecular sieve.

[0082] In a preferred embodiment of the present invention, the molecular sieve comprises a hydrogen-type ultrastable Y zeolite molecular sieve and an ultrastable Y zeolite molecular sieve containing a transition metal.

[0083] Preferably, the weight ratio of the hydrogen-type ultrastable Y zeolite molecular sieve to the transition metal-containing ultrastable Y zeolite molecular sieve is 1:0.1-4 (for example, it can be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4 and any range between any two values).

[0084] In a specific embodiment of the present invention, the molecular sieve comprises REY molecular sieve and HSY-12 molecular sieve; based on dry matter, their weight ratio is 1:0.1-4 (for example, it can be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4 and any range between any two values).

[0085] Preferably, the clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite; more preferably kaolin and / or halloysite.

[0086] In the present invention, the silica sol is preferably the silica sol described in the first aspect of the present invention.

[0087] In a preferred embodiment of the present invention, the binder further comprises aluminum phosphate sol.

[0088] Preferably, on a dry basis, the content of silica sol in the slurry is 2-30 wt % (for example, 2, 5, 10, 15, 20, 25, 30 wt % and any range between any two values), more preferably 5-20 wt %; the content of aluminum phosphate sol is 2-20 wt % (for example, 2, 5, 10, 15, 20 wt % and any range between any two values), preferably 5-18 wt %.

[0089] In the present invention, the aluminum phosphate sol may be conventional aluminum phosphate sol in the art.

[0090] Preferably, the pH of the aluminum phosphate sol is 0.5-3.5 (for example, it can be 0.5, 1, 1.5, 2, 2.5, 3, 3.5 and any range between any two values), preferably 1-3.

[0091] Preferably, the viscosity of the aluminum phosphate sol is 5-80 mPa·s; more preferably 20-60 mPa·s.

[0092] In the present invention, the Al content in the aluminum phosphate sol is 3-10 wt % (for example, it can be 3, 4, 5, 6, 7, 8, 9, 10 wt % and any range between any two values), preferably 4-9 wt %.

[0093] In the present invention, compared with 1 part by weight of Al, the content of P element is 0.5-1.5 parts by weight, for example, it can be 0.5, 0.7, 0.9, 1.1, 1.3, 1.5 parts by weight and any range between any two values, more preferably 0.8-1.2 parts by weight.

[0094] Preferably, the aluminum phosphate sol contains an organic acid radical of a second organic acid.

[0095] Preferably, in the aluminum phosphate sol, compared with 1 weight part of Al, the content of the organic acid radical of the second organic acid is 0.3-4 weight parts (for example, it can be 0.3, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4 weight parts and any range between any two values), more preferably 1-3 weight parts.

[0096] Preferably, the second organic acid is selected from at least one of oxalic acid, acetic acid, sulfosalicylic acid, citric acid and formic acid, more preferably oxalic acid and / or sulfosalicylic acid.

[0097] It should be understood that the aluminum phosphate sol also contains water.

[0098] The aluminum phosphate sol can be prepared in a conventional manner. Preferably, the preparation method of the aluminum phosphate sol comprises: mixing an acid-soluble aluminum precursor with water to obtain a slurry with a solid content of 10-38 weight % (for example, it can be 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38 weight % and any range between any two values); adding phosphoric acid and a second organic acid to the slurry for reaction to obtain the aluminum phosphate sol.

[0099] Preferably, the acid-soluble aluminum precursor is selected from at least one of pseudo-boehmite, hydrated alumina with a diaspore structure, hydrated alumina with a gibbsite structure, hydrated alumina with a Bayerite structure, γ-alumina, η-alumina, θ-alumina and x-alumina; more preferably, pseudo-boehmite.

[0100] Preferably, the phosphoric acid is in the form of a phosphoric acid solution; preferably, the phosphoric acid content in the phosphoric acid solution is 60-98% by weight, more preferably 80-90% by weight.

[0101] Preferably, the first organic acid is present in the form of a first organic acid solution, and the content of the first organic acid in the first organic acid solution is 40-98% by weight, more preferably 40-70% by weight.

[0102] Preferably, the acid-soluble aluminum precursor is used in an amount such that the Al content in the aluminum phosphate sol is 3-10 wt %, more preferably 4-8 wt %.

[0103] Preferably, the phosphoric acid is used in an amount such that the weight ratio of P to Al is 0.5-1.5, more preferably 0.8-1.2.

[0104] Preferably, the second organic acid is used in an amount such that the weight ratio of the organic acid to Al is 0.3-4 parts by weight, more preferably 1-3 parts by weight.

[0105] During the preparation of aluminum phosphate sol, preferably, the temperature is controlled not to exceed 80°C during the reaction, for example, it may not exceed 50, 55, 60, 65, 70, 75, 80°C and any range between any two values, more preferably not exceeding 65°C.

[0106] It should be understood that the organic acid includes the first organic acid as described above and the second organic acid as described above.

[0107] The organic acid preferably includes at least one of oxalic acid, sulfosalicylic acid, citric acid and formic acid, and more preferably includes oxalic acid.

[0108] In the present invention, unless otherwise specified, the solvent used is water, which is preferably decationized water.

[0109] A fourth aspect of the present invention provides a catalyst, wherein the cracking catalyst is prepared from the slurry as described above.

[0110] Preferably, the catalyst has an apparent bulk density of 0.60-0.80 g / mL.

[0111] Preferably, the pore volume of the catalyst is 0.32-0.41 cm 3 / g.

[0112] Preferably, the catalyst has an attrition index of 0.5-3 wt% / h.

[0113] The above parameters can be evaluated by conventional methods in the art.

[0114] A fifth aspect of the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising molding and calcining the slurry as described above to obtain a catalytic cracking catalyst.

[0115] Preferably, the forming method is spray drying, and the tail gas temperature is 170-190°C.

[0116] Preferably, the calcination conditions include: temperature of 400-600° C.; time of 1-10 h.

[0117] In a preferred embodiment of the present invention, the preparation method of the catalyst comprises sequentially adding clay, aluminum phosphate sol and molecular sieve into silica sol, mixing evenly to obtain a slurry; spray drying the slurry to obtain a microsphere catalyst; and drying and calcining the microsphere catalyst to obtain a catalyst product.

[0118] Preferably, the method further comprises, before drying the microsphere catalyst, aging the microsphere catalyst in water at a temperature of 60-70°C and a pH of 4-6, filtering, washing with a 2-5 wt% ammonium sulfate solution at 60-70°C, filtering again, washing with water at 60-70°C, and adjusting the pH to 8-9 with aqueous ammonia after filtering.

[0119] In the present invention, clay and molecular sieve are preferably added in the form of clay powder and molecular sieve slurry, respectively, wherein the solid content of the molecular sieve slurry is preferably 30-40% by weight.

[0120] It should be understood that in order to obtain a product with good catalytic performance, the materials should be mixed as evenly as possible during the preparation process.

[0121] The mixing, washing and drying operations are conventional in the art and will not be described in detail here.

[0122] A sixth aspect of the present invention provides a catalytic cracking catalyst prepared by the method described above.

[0123] The performance of the catalyst is as described in the fourth aspect and will not be repeated here.

[0124] A seventh aspect of the present invention provides use of the catalytic cracking catalyst as described above in the field of catalytic cracking.

[0125] An eighth aspect of the present invention provides a catalytic cracking method, which comprises: contacting hydrocarbon oil with a catalyst for reaction under catalytic cracking conditions; the catalyst is the catalytic cracking catalyst as described above.

[0126] In the present invention, the hydrocarbon oil has a wide selection range and can be a conventional choice in the art, and the present invention will not be described in detail here.

[0127] The present invention has a wide range of reaction conditions for the catalytic cracking. Specifically, for example, the reaction conditions may include: a temperature of 400-550°C; a catalyst-oil ratio (weight) of 3-10; a feed oil space velocity of 5-20h -1 .

[0128] In the present invention, preferably, the catalytic cracking method further comprises: hydrothermal aging the catalyst before the reaction. The present invention has a wide range of conditions for the hydrothermal aging. Preferably, the hydrothermal aging is carried out using 90%-100% water vapor. Further preferably, the hydrothermal aging conditions also include: a temperature of 700-900°C, preferably 750-850°C, and a time of 5-24h, preferably 10-16h.

[0129] The present invention will be described in detail below through examples.

[0130] In each embodiment and comparative example, the raw materials used to prepare the catalyst are as follows:

[0131] Pseudo-boehmite: produced by Shanxi Aluminum Plant, Al2O3 content 61% by weight, of which β trihydrate Al2O3 <4% by weight;

[0132] Concentrated phosphoric acid: chemically pure, 85% by weight, produced by Beijing Chemical Plant;

[0133] REY molecular sieve: produced by Qilu Branch of Catalyst, unit cell constant is 2.469nm, RE2O317.57w%, Na2O1.45w%.

[0134] HSY-12 molecular sieve: produced by Qilu Catalyst Company, unit cell constant is 2.458nm, RE2O3 content is 12.18w%, Na2O content is 1.03w%;

[0135] Halloysite: produced by China Kaolin Co., Ltd., quartz sand <1.5% by weight, Al2O3 37.1% by weight, Fe2O3 0.50% by weight, Na2O 0.04% by weight, solid content 74% by weight;

[0136] Chlorine-containing aluminum sol: produced by the Qilu Branch of Catalyst Company, made of metallic aluminum and hydrochloric acid, containing Al2O3: 22.10% by weight, Cl: 9.36% by weight, Al / Cl weight ratio 1.25:1, pH value 2.90;

[0137] Sulfuric acid: chemically pure, concentration 98% by weight, produced by Beijing Chemical Plant;

[0138] Oxalic acid: chemically pure, colorless crystals or white powder, produced by Beijing Chemical Plant;

[0139] Citric acid: chemically pure, colorless crystals or white powder, produced by Beijing Chemical Plant;

[0140] Acetic acid: chemically pure, colorless crystalline hygroscopic solid, produced by Beijing Chemical Plant;

[0141] Ethanol: chemically pure, concentration 95% by weight, produced by Beijing Chemical Plant;

[0142] Sodium water glass: contains SiO2 concentration of 26.3% by weight, modulus 3.2, produced by Catalyst Qilu Branch.

[0143] The properties of the crude oil are shown in Table 1.

[0144] Table 1

[0145] Crude oil 70w% vacuum wax oil + 30w% atmospheric residue oil Density (20℃), g·cm-3 0.9011 Carbon residue, weight % 3.15 Viscosity, mm2·S-1 42 100℃ 14.0 80℃ 19.05 Elemental composition, weight % C 85.6 H 12.9 S 0.74 N 0.36 Hydrocarbon composition, weight % Saturated hydrocarbons 56.9 Aromatics 24.2 Gel 17.3 Asphaltene 1.6 Metal content, ppm Fe 5.1 Ni 4.8 Cu 0.07 V 1.1 Na 1.0 Vacuum distillation range, ℃ Initial distillation point - 5％ 215 10％ 274 30％ 365 50％ 418 70％ 459 90％ 540 Characteristic factor 12.1

[0146] Chemical analysis and evaluation methods are as follows:

[0147] 1. Organic acid content is the theoretical value of organic acid weight content in slurry;

[0148] 2. For the determination of apparent bulk density and pore volume, refer to the RIPP test method;

[0149] 3. Determination of catalyst wear index: A certain amount of catalyst is placed in a wear index determination device and blown for 5 hours under a constant airflow. Except for the first hour, the weight percentage of fine powder less than 15 microns produced in the last four hours to the weight percentage of catalyst larger than 15 microns in the sample is called the catalyst wear rate, also known as the wear index, and the unit is weight %·h -1 .

[0150] The above analysis methods can be found in "Petrochemical Analysis Methods (RIPP Test Methods)" (edited by Yang Cuiding et al., Science Press, 1990).

[0151] The conversion rate refers to [(dry gas + liquefied gas + gasoline + coke) / fresh raw material] × 100%; the liquid product yield refers to the sum of the yields of (liquefied gas + gasoline + diesel); and the coke selectivity refers to (coke / conversion rate) × 100%.

[0152] The data given in the examples are all based on the weight percentage of each component in the solution.

[0153] Preparation Example 1

[0154] This preparation example is used to illustrate the preparation method of aluminum phosphate sol binder.

[0155] At room temperature (25°C), 4.92 kg of pseudo-boehmite (containing 3 kg of Al2O3) and 9.0 kg of decationized water were slurried for 30 minutes, and 6 kg of concentrated phosphoric acid was added to the slurry under stirring, and then 8 kg of oxalic acid solution (4 kg of oxalic acid + 4 kg of decationized water) was added, and the addition rate of concentrated phosphoric acid and oxalic acid was controlled so that the reaction temperature did not exceed 60°C. The reaction was continued with stirring for 40 minutes to obtain a colorless and transparent aluminum phosphate sol with a pH of 1.5.

[0156] The aluminum phosphate sol P-1 was analyzed to contain 6.21% by weight of P, 6.11% by weight of Al, P / Al (weight)=1.02, and 15.40% by weight of oxalic acid.

[0157] Preparation Example 2

[0158] This preparation example is used to illustrate the preparation method of aluminum phosphate sol binder.

[0159] At room temperature (25°C), 4.92 kg of pseudo-boehmite (containing 3 kg of Al2O3) and 9.0 kg of decationized water were slurried for 30 minutes, and 6 kg of concentrated phosphoric acid was added to the slurry under stirring, followed by 8 kg of acetic acid solution (6.5 kg of acetic acid + 1.5 kg of decationized water). The addition rate of concentrated phosphoric acid and acetic acid was controlled so that the reaction temperature did not exceed 60°C. The reaction was continued with stirring for 40 minutes to obtain a colorless and transparent aluminum phosphate sol with a pH of 1.6.

[0160] The aluminum phosphate sol P-2 was analyzed to contain 6.21% by weight of P, 6.11% by weight of Al, P / Al (weight)=1.02, and 25.03% by weight of acetic acid.

[0161] Preparation Example 3

[0162] This preparation example is used to illustrate the preparation method of aluminum phosphate sol binder.

[0163] The operation was carried out according to the method described in Preparation Example 1, except that the reaction temperature was controlled not to exceed 65°C, and the pH of the obtained aluminum phosphate sol was 1.5.

[0164] The aluminum phosphate sol P-1 was analyzed to contain 6.21% by weight of P, 6.11% by weight of Al, P / Al (weight)=1.02, and 15.40% by weight of oxalic acid.

[0165] Preparation Example 4

[0166] This preparation example is used to illustrate the preparation method of silica sol binder.

[0167] Take 0.86 kg of sulfuric acid, add 7.6 kg of decationized water to dilute, and after cooling, add 2.5 kg of oxalic acid solution (1.2 kg of oxalic acid + 1.3 kg of ethanol). Take 5.85 kg of sodium water glass, add 8.0 kg of decationized water to dilute, and slowly add the diluted sodium water glass to the above sulfuric acid-oxalic acid dilute solution under stirring, and control the addition speed of sodium water glass so that the temperature of the reaction system does not exceed 35°C to obtain silica sol S-1 with a SiO2 concentration of 6.2% by weight and a pH value of 2.1.

[0168] Preparation Example 5

[0169] This preparation example is used to illustrate the preparation method of silica sol binder.

[0170] Take 1.2 kg of sulfuric acid, add 5 kg of decationized water to dilute, cool to room temperature (25°C), and then add 5.4 kg of oxalic acid solution (2.63 kg of oxalic acid + 2.77 kg of ethanol). Take 12.65 kg of sodium water glass, add 9 kg of decationized water to dilute, and slowly add the diluted sodium water glass to the above sulfuric acid-oxalic acid dilute solution under stirring, and control the addition speed of the sodium water glass so that the temperature of the reaction system does not exceed 35°C to obtain silica sol S-2 with a SiO2 concentration of 10.0% by weight and a pH value of 2.2.

[0171] Preparation Example 6

[0172] This preparation example is used to illustrate the preparation method of silica sol binder.

[0173] Take 0.5 kg of sulfuric acid, add 2.1 kg of decationized water to dilute, cool to room temperature (25°C), and then add 2.1 kg of oxalic acid solution (1.02 kg of oxalic acid + 1.08 kg of ethanol). Take 5.9 kg of sodium water glass, add 3.5 kg of decationized water to dilute, and slowly add the diluted sodium water glass to the above sulfuric acid-oxalic acid dilute solution under stirring, and control the addition speed of the sodium water glass so that the temperature of the reaction system does not exceed 35°C to obtain silica sol S-3 with a SiO2 concentration of 11% by weight and a pH value of 2.5.

[0174] Preparation Example 7

[0175] This preparation example is used to illustrate the preparation method of silica sol binder.

[0176] Take 0.86 kg of sulfuric acid, add 7.1 kg of decationized water to dilute, and after cooling, add 3 kg of citric acid solution (1.46 kg of citric acid + 1.54 kg of ethanol). Take 5.85 kg of sodium water glass, add 8.0 kg of decationized water to dilute, and slowly add the diluted sodium water glass to the above sulfuric acid-citric acid dilute solution under stirring, and control the addition speed of sodium water glass so that the temperature of the reaction system does not exceed 35°C to obtain silica sol S-4 with a SiO2 concentration of 6.2% by weight and a pH value of 2.1.

[0177] Preparation Example 8

[0178] This preparation example is used to illustrate the preparation method of silica sol binder.

[0179] The preparation was carried out according to the method described in Preparation Example 4, except that the temperature was controlled not to exceed 40°C during the reaction, to obtain silica sol S-5 with a SiO2 concentration of 6.2% by weight and a pH value of 2.1.

[0180] Comparative Preparation Example 1

[0181] This comparative preparation example is used to illustrate the preparation method of the silica sol binder.

[0182] The silica sol prepared according to the method described in CN1332754C is specifically prepared as follows: 0.63L sulfuric acid is diluted with 8.0kg decationized water and cooled. 7.61kg sodium water glass is diluted with 8.0kg decationized water and the diluted sodium water glass is slowly added to the above sulfuric acid dilute solution under stirring to obtain silica sol DS-1 with SiO2 concentration of 8.08% by weight and pH value of 2.5.

[0183] Comparative Preparation Example 2

[0184] This comparative preparation example is used to illustrate the preparation method of aluminum phosphate sol binder.

[0185] The aluminum phosphate sol was prepared according to the method described in CN102847547A, specifically by slurrying 0.66 kg of pseudo-boehmite (containing 0.40 kg of Al2O3) and 1.75 kg of decationized water for 30 minutes, slowly adding 2.6 kg of concentrated phosphoric acid (mass concentration 85%) to the slurry under stirring, heating to 70°C, and then reacting at this temperature for 45 minutes to obtain a colorless and transparent phosphorus-containing aluminum sol DP-1 with P / Al (weight) = 3.3 and pH = 2.46. The dry basis content was determined to be 42.95% by weight.

[0186] Example 1

[0187] This example is used to illustrate the preparation method of the catalyst described in the present invention.

[0188] According to the dosage described in Table 2, the catalyst was prepared as follows:

[0189] Add halloysite to the silica sol and stir for 1 hour to fully disperse the kaolin. Add aluminum phosphate sol and stir for 0.5 hour to prepare silicon-aluminum phosphate sol-clay slurry, then add HSY-12 molecular sieve slurry (solid content of 35 wt%) and REY molecular sieve slurry (solid content of 34 wt%) and stir for 0.5 hour to prepare sol-state catalyst slurry. The slurry is transported to a high-temperature spray tower by a high-pressure pump, sprayed and formed, and the tail gas temperature of the spray tower is controlled to be 180°C to obtain microspherical catalyst particles.

[0190] The microspherical catalyst particles were aged in decationized water at 70°C and a pH value of 4-5 for 1 hour, filtered, washed with a 5 wt% ammonium sulfate solution at 70°C for 10 minutes, filtered, and washed with decationized water at 70°C for 10 minutes, and the pH value was adjusted to 8.0-9.0 with ammonia water. After filtering, drying at 150°C for 1 hour, and calcining at 450°C for 3 hours, catalyst AI was prepared respectively.

[0191] The only difference is that there is no REY molecular sieve slurry in Catalyst H. The other preparation methods are the same.

[0192] Example 2

[0193] This example is used to illustrate the preparation method of the catalyst described in the present invention.

[0194] According to the dosage described in Table 2, the catalyst was prepared as follows:

[0195] Halloysite was added to the silica sol and stirred for 1 hour to fully disperse the kaolin. Then HSY-12 molecular sieve slurry (solid content of 35 wt%) and REY molecular sieve slurry (solid content of 34 wt%) were added and stirred for 0.5 hour to prepare a sol-state catalyst slurry. The slurry was transported to a high-temperature spray tower by a high-pressure pump and sprayed to form. The tail gas temperature of the spray tower was controlled to be 180°C to obtain microspherical catalyst particles.

[0196] The microspherical catalyst particles were aged in decationized water at 70°C and a pH value of 4-5 for 1 hour, filtered, washed with a 5 wt% ammonium sulfate solution at 70°C for 10 minutes, filtered, and washed with decationized water at 70°C for 10 minutes, and the pH value was adjusted to 8.0-9.0 with ammonia water. Catalyst J was prepared by filtering, drying at 150°C for 1 hour, and calcining at 450°C for 3 hours.

[0197] Comparative Example 1

[0198] This comparative example is used to illustrate the preparation method of a reference catalyst.

[0199] The method of Example 1 was followed, except that the silica sol binder prepared in Comparative Preparation Example 1 was used instead of the binder in Example 1 in an amount shown in Table 2, to obtain catalyst DB-1.

[0200] The specific method of preparing the slurry is as follows: add halloysite to the silica sol, stir for 1 hour to fully disperse the kaolin. Prepare silica sol-clay slurry, then add HSY-12 molecular sieve and REY molecular sieve, stir for 0.5 hour, and prepare sol-state catalyst slurry. The slurry is transported to a high-temperature spray tower by a high-pressure pump, sprayed and formed, and the tail gas temperature of the spray tower is controlled to be 180°C to obtain microspherical catalyst particles.

[0201] The microspherical catalyst particles were aged in decationized water at 70°C and a pH of 4-5 for 1 hour, filtered, washed with a 5 wt% ammonium sulfate solution at 70°C for 10 minutes, filtered, and washed with decationized water at 70°C for 10 minutes. The pH was adjusted to 8.0-9.0 with ammonia water, filtered, dried at 150°C for 1 hour, and calcined at 450°C for 3 hours to prepare catalyst DB-1.

[0202] Comparative Example 2

[0203] This comparative example is used to illustrate the preparation method of a reference catalyst.

[0204] The method of Example 1 was followed, except that aluminum sol and acidified pseudo-boehmite were used as binders to replace the binder in Example 1. The amounts used were shown in Table 2, and catalyst DB-2 was obtained.

[0205] The specific method of preparing the slurry is as follows: add halloysite to decationized water, stir for 5 minutes, add aluminum sol, stir for 1 hour to fully disperse the kaolin. Add pseudo-boehmite, stir for 30 minutes, adjust the pH value to 2.6 with dilute hydrochloric acid, prepare aluminum sol-clay slurry, then add HSY-12 molecular sieve and REY molecular sieve, stir for 0.5 hour, and prepare sol-state catalyst slurry. The slurry is transported to a high-temperature spray tower by a high-pressure pump, sprayed and formed, and the tail gas temperature of the spray tower is controlled to be 180°C to obtain microspherical catalyst particles.

[0206] The microspherical catalyst particles were calcined at 450°C for 3 hours, washed with a 3 wt% ammonium sulfate solution at 70°C for 10 minutes, filtered, and washed a second time with an ammonium sulfate solution of the same temperature and concentration. Then, they were washed a third time with decationized water at 70°C for 10 minutes, and the pH value was adjusted to 8.0-9.0 with ammonia water. After filtering and drying at 150°C for 1 hour, catalyst DB-2 was prepared.

[0207] Comparative Example 3

[0208] This comparative example is used to illustrate the preparation method of a reference catalyst.

[0209] The method of Example 1 was followed, except that the silica sol prepared in Comparative Preparation Example 1 and the aluminum phosphate sol prepared in Comparative Preparation Example 2 were used as binders to replace the binder in Example 1, and decationized water was added before adding kaolin. The amount used is shown in Table 2.

[0210] Catalyst DB-3 was prepared according to the method described in Example 1.

[0211] Test Case

[0212] 30 grams of the catalysts prepared in the above examples and comparative examples were taken and aged for 12 hours at 760°C and 100% steam. The aged catalysts were then loaded into a reactor of a small fixed fluidized bed device and subjected to catalytic cracking reaction on the crude oil shown in Table 1. The reaction conditions included: a reaction temperature of 480°C, a reaction space velocity of 16h -1 , the agent-oil weight ratio is 5.92.

[0213] The evaluation of the reaction products is shown in Table 3.

[0214]

[0215]

[0216] It can be seen from the results in Table 2 that catalysts A, B and C have the same silica sol content and different phosphate aluminum gel preparation methods, and catalyst A has the best wear resistance, indicating that under the preferred conditions of the present invention, the phosphate aluminum gel prepared under the preferred preparation conditions using phosphoric acid-oxalic acid acidifying agent has the best bonding performance.

[0217] Catalysts A, D, E, F and G have the same phosphate aluminum gel and are silica sols prepared by different methods. Catalyst A also has the best wear resistance, indicating that under the preferred conditions of the present invention, the silica sol prepared by sulfuric acid-oxalic acid ethanol solution has better bonding properties. Catalysts D and E have high silica contents and slightly larger pore volumes.

[0218] Catalysts H and A have the same type and content of binder, but different types of molecular sieves. The wear resistance of the catalysts is basically the same.

[0219] Catalysts I and J have better wear resistance than the comparative agent DB-1, indicating that the bonding performance of the silica sol binder prepared by the present invention is better than the silica sol provided in comparative example 1.

[0220] Catalyst AI has better wear resistance than comparison agents DB-2 and DB-3, indicating that the combined binder of phosphate aluminum gel and silica sol prepared in the present invention has better bonding performance.

[0221] It can be seen from the results in Table 3 that, compared with DB-1 to DB-3 prepared in comparative examples, the catalyst AJ prepared using the technical solution of the present invention has stronger heavy oil conversion ability, higher gasoline yield and better coke selectivity when used for catalytic cracking.

[0222] By using the preferred catalyst of the present invention, the matrix carrier provides a certain macroporous structure, which can provide space for the heavy oil macromolecules to undergo cracking reactions, and the catalyst surface is rich in silicon matrix, which reduces the condensation of the reaction products and coke. Adding the aluminum phosphate sol prepared by the present invention can also improve the strength of the catalyst. Therefore, by using the preferred catalyst of the present invention, it has stronger heavy oil cracking performance, better coke selectivity, and better catalyst wear resistance.

[0223] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An application of silica sol in the preparation of catalytic cracking catalyst, characterized in that: The silica sol comprises SiO2 and an organic acid radical of a first organic acid; Wherein, in the silica sol, the content of SiO2 is 1-15% by weight, and the content of the organic acid radical of the first organic acid is 1-15% by weight; Wherein, the pH of the silica sol is 0.5-4; The silica sol also contains acid radicals of inorganic acids; The content ratio of the acid radical of the inorganic acid to the organic acid radical of the first organic acid is 0.02-1:1 by weight; The silica sol also contains alcohol; The preparation method of the silica sol comprises: mixing and reacting a silicate with an inorganic acid and a first organic acid to obtain a silica sol; The first organic acid is present in the form of an alcohol solution of the first organic acid, and the content of the first organic acid in the alcohol solution of the first organic acid is 30-80% by weight.

2. The use according to claim 1, wherein: The content of SiO2 in the silica sol is 5-11% by weight, and the content of the organic acid radical of the first organic acid is 4-12% by weight; and / or Wherein, the pH of the silica sol is 1-3.

3. The use according to claim 1, wherein: The first organic acid is selected from at least one of oxalic acid, acetic acid, sulfosalicylic acid, citric acid and formic acid.

4. The use according to claim 3, wherein: The first organic acid is oxalic acid and / or sulfosalicylic acid.

5. The use according to any one of claims 1 to 4, wherein: The alcohol is selected from at least one of ethanol, propanol, ethylene glycol and glycerol.

6. The use according to any one of claims 1 to 4, wherein: The inorganic acid is selected from at least one of HCl, HNO3 and H2SO4.

7. The use according to claim 6, wherein: The inorganic acid is H2SO4.

8. The use according to any one of claims 1 to 4, wherein: The temperature is controlled not to exceed 45°C during the reaction.

9. The use according to any one of claims 1 to 4, wherein: The silicate is sodium water glass.

10. The use according to any one of claims 1 to 4, wherein: The inorganic acid exists in the form of an inorganic acid solution, and the content of the inorganic acid in the inorganic acid solution is 5-40 weight %.

11. A slurry, characterized in that: On a dry basis, the slurry comprises 10-40 wt % of a molecular sieve, 20-45 wt % of a clay, and 15-40 wt % of a binder comprising an organic acid; Wherein, the content of organic acid in the slurry is 1-10% by weight, calculated as organic acid radical; Wherein, the binder contains silica sol; the silica sol is the silica sol according to any one of claims 1 to 10; Wherein, the pH of the slurry is 1.5-3.

5.

12. The slurry according to claim 11, wherein The slurry comprises, on a dry basis, 30-40 wt % of molecular sieve, 30-45 wt % of clay, and 20-35 wt % of a binder comprising an organic acid.

13. The slurry according to claim 11, wherein Calculated as organic acid radical, the content of organic acid in the slurry is 3-9% by weight.

14. The slurry according to claim 11, wherein The pH of the slurry is 2-3.

5.

15. The slurry according to claim 11, wherein The solid content of the slurry is 15-50% by weight.

16. The slurry according to any one of claims 11 to 15, wherein: The molecular sieve is a molecular sieve capable of catalytic cracking reaction.

17. The slurry according to claim 16, wherein The molecular sieve is a zeolite molecular sieve and / or a non-zeolite molecular sieve.

18. The slurry according to claim 17, wherein The molecular sieve is at least one selected from Y-type zeolite, Beta zeolite and zeolite with MFI structure.

19. The slurry according to claim 18, wherein The molecular sieve comprises 75-100 wt % of Y-type molecular sieve and 0-25 wt % of other molecular sieves selected from at least one of Beta zeolite and molecular sieves with MFI structure, based on dry weight.

20. The slurry according to any one of claims 11 to 15, wherein: The clay is selected from at least one of kaolin, halloysite, montmorillonite, diatomaceous earth, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.

21. The slurry according to claim 20, wherein The clay is kaolin and / or halloysite.

22. The slurry according to any one of claims 11 to 15, wherein: The binder further comprises aluminum phosphate sol; on a dry basis, the content of silica sol in the slurry is 2-30% by weight, and the content of aluminum phosphate sol is 2-20% by weight.

23. The slurry according to claim 22, wherein On a dry basis, the content of the silica sol in the slurry is 5-20% by weight, and the content of the aluminum phosphate sol is 5-18% by weight.

24. The slurry according to claim 22, wherein The pH of the aluminum phosphate sol is 0.5-3.5; and / or In the aluminum phosphate sol, the content of Al is 3-10% by weight; and / or Compared to 1 part by weight of Al, the content of P element is 0.5-1.5 parts by weight; and / or The aluminum phosphate sol contains an organic acid radical of a second organic acid.

25. The slurry according to claim 24, wherein The pH of the aluminum phosphate sol is 1-3; and / or In the aluminum phosphate sol, the content of Al is 4-9% by weight; and / or The content of P element is 0.8-1.2 parts by weight relative to 1 part by weight of Al.

26. The slurry according to claim 24, wherein In the aluminum phosphate sol, the content of the organic acid radical of the second organic acid is 0.3-4 parts by weight compared to 1 part by weight of Al.

27. The slurry according to claim 26, wherein In the aluminum phosphate sol, the content of the organic acid radical of the second organic acid is 1-3 parts by weight compared to 1 part by weight of Al.

28. The slurry according to claim 24, wherein The second organic acid is selected from at least one of oxalic acid, acetic acid, sulfosalicylic acid, citric acid and formic acid.

29. The slurry according to claim 28, wherein The second organic acid is oxalic acid and / or sulfosalicylic acid.

30. The slurry according to claim 24, wherein The preparation method of the aluminum phosphate sol comprises: mixing an acid-soluble aluminum precursor with water to obtain a slurry with a solid content of 10-38% by weight; adding phosphoric acid and a second organic acid to the slurry for reaction to obtain the aluminum phosphate sol.

31. The slurry according to claim 30, wherein The temperature is controlled not to exceed 80° C. during the reaction.

32. The slurry according to claim 30, wherein The acid-soluble aluminum precursor is selected from at least one of pseudo-boehmite, hydrated alumina with a diaspore structure, hydrated alumina with a gibbsite structure, hydrated alumina with a bayerite structure, γ-alumina, η-alumina, θ-alumina and x-alumina.

33. The slurry according to claim 32, wherein The acid-soluble aluminum precursor is pseudo-boehmite.

34. The slurry according to claim 30, wherein The phosphoric acid exists in the form of a phosphoric acid solution, and the phosphoric acid content in the phosphoric acid solution is 60-98% by weight.

35. The slurry according to claim 30, wherein The second organic acid exists in the form of a second organic acid solution, and the content of the second organic acid in the second organic acid solution is 40-98% by weight.

36. The slurry of claim 24, wherein: The organic acid includes a first organic acid and a second organic acid.

37. A catalytic cracking catalyst, characterized in that The catalytic cracking catalyst is prepared from the slurry described in any one of claims 11-36.

38. A method for preparing a catalytic cracking catalyst, characterized in that: The method comprises molding and calcining the slurry described in any one of claims 11 to 36 to obtain a catalytic cracking catalyst.

39. The method of claim 38, wherein: The molding method is spray drying, and the tail gas temperature is 130-200°C.

40. The method of claim 39, wherein: The exhaust gas temperature is 170-190℃.

41. The method of claim 38, wherein: The calcination conditions include: temperature of 400-600° C.; time of 1-10 h.

42. A catalytic cracking catalyst prepared by the method according to any one of claims 38 to 41.

43. Use of the catalytic cracking catalyst according to claim 37 or 42 in the field of catalytic cracking.

44. A catalytic cracking method, characterized in that: The method comprises: contacting hydrocarbon oil with a catalyst for reaction under catalytic cracking conditions; the catalyst is the catalytic cracking catalyst according to claim 37 or 42.

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