Catalytic cracking catalyst composition, process for its preparation and use

Abstract

The present application relates to the technical field of catalytic cracking, and discloses a catalytic cracking catalyst composition and a preparation method and application thereof. The catalyst composition comprises the following components based on the dry basis weight of the catalyst composition: 9.5-40 wt% of high colloidal solubility macroporous pseudoboehmite calculated based on alumina, 2-20 wt% of a binder, 20-50 wt% of a molecular sieve and 15-50 wt% of clay; the content of alumina in the high colloidal solubility macroporous pseudoboehmite is 98-100 wt%; the total pore volume of the catalyst composition is not less than 0.2 mL / g; and the mesopore volume of 4-10 nm in the catalyst composition accounts for more than 60% of the total pore volume. The catalyst has a high abrasion resistance index, a strong heavy oil conversion capacity and a high total yield of gasoline and diesel.

Description

Technical Field

[0001] This invention relates to the field of catalytic cracking technology, specifically to a catalytic cracking catalyst composition, its preparation method, and its application. Background Technology

[0002] The pores in FCC catalysts mainly include micropores (0-2 nm), mesopores (2-0 nm), and macropores (>50 nm). Micropores primarily originate from molecular sieves, while mesopores and macropores are closely related to the matrix components. Commonly used matrices include clay and binders. Common binders include alumina sol, acidified boehmite, and silica sol. Acidified boehmite, formed by acid-solubilized boehmite, possesses excellent binding properties. Heat treatment can produce γ-Al₂O₃ with a rich porous structure; therefore, acidified boehmite is one of the most commonly used binders in FCC catalysts.

[0003] The colloidal index of boehmite reflects its binding properties; a high colloidal index generally indicates high strength in cracking catalysts prepared from it. Common preparation methods for boehmite include the carbonization method (NaAlO2-CO2), the aluminum sulfate method (NaAlO2-Al2(SO4)3), and the aluminum alkoxide method. Some boehmite prepared by these methods can achieve a colloidal index exceeding 95%. However, boehmite with high colloidal properties generally has a small pore volume. For example, while the colloidal index of boehmite prepared by the carbonization method for catalytic cracking binders can reach around 95%, its pore volume is generally below 0.40 mL / g. In contrast, SB powder boehmite produced by the aluminum alkoxide method, exemplified by Sasol in Germany, can reach a colloidal index of 99%, with a pore volume typically around 0.5 mL / g.

[0004] Patent application CN106629794A discloses a method for preparing highly colloidal boehmite using the aluminum alkoxide method. The raw material, aluminum alkoxide, undergoes filtration, hydrolysis, aging and evaporation, and spray drying to produce boehmite with good colloidal properties, concentrated pore distribution, and a single crystal phase. The colloidal index of this invention is 98.2-99.7%. However, the invention does not provide the pore volume of the product or the pore volume after colloidal treatment followed by drying and calcination. Furthermore, it requires the use of metallic aluminum as a raw material, making the process relatively complex. While the product has low impurity content, it is costly. For boehmite with a high colloidal index, it generally needs to be first colloidalized with acid before it can be used as a binder or molded into a catalyst support. During the process of adding acid to form a colloidal solution, the agglomerated crystals are dispersed by the acid colloidal solution. After drying, the pore volume generally decreases significantly. Therefore, for high colloidal index boehmite, the pore volume after colloidal treatment and subsequent drying is crucial for the product's performance. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor crude oil conversion capacity and low total yield of gasoline and diesel in the production of paraffin-based catalytic feedstocks in the prior art, and to provide a catalytic cracking catalyst, its preparation method and application. This catalyst has a good anti-wear index, strong heavy oil conversion capacity and high total yield of gasoline and diesel.

[0006] To achieve the above objectives, the first aspect of the present invention provides a catalytic cracking catalyst composition, characterized in that, based on the dry weight of the catalyst composition, the catalyst composition comprises the following components: 9.5-40 wt% highly colloidal macroporous boehmite (calculated as alumina), 2-20 wt% binder, 20-50 wt% molecular sieve, and 15-50 wt% clay; wherein the alumina content in the highly colloidal macroporous boehmite is 98-100 wt%; the pore volume V1 of the highly colloidal macroporous boehmite is 0.45-0.7 mL / g, and the colloidal index DI is 95-100%; the pore volume V2 of the highly colloidal macroporous boehmite after colloidal dissolution is 0.4-0.55 mL / g; the total pore volume of the catalyst composition is not less than 0.2 mL / g; and the mesopore volume of 4-10 nm in the catalyst composition accounts for more than 60% of the total pore volume.

[0007] Preferably, the total pore volume of the catalyst composition is 0.2-0.3 mL / g.

[0008] Preferably, the pore volume of 4-10 nm in the catalyst composition accounts for 65-80% of the total pore volume.

[0009] A second aspect of the present invention provides a method for preparing a catalytic cracking catalyst composition, wherein the method comprises the following steps:

[0010] (1) A highly soluble macroporous boehmite is mixed with deionized water and pulped, and then acidified in the presence of acid A to obtain an acidified slurry; wherein the alumina content in the highly soluble macroporous boehmite is 98-100% by weight; the pore volume V1 of the highly soluble macroporous boehmite is 0.45-0.7 mL / g, and the gel solubility index DI is 95-100%; the pore volume V2 of the highly soluble macroporous boehmite after gelation is 0.4-0.55 mL / g;

[0011] (2) Mix molecular sieve, clay and deionized water, then add acidified slurry and mix, then add binder to obtain catalyst slurry;

[0012] (3) The catalyst slurry is spray-dried, shaped, and calcined to obtain a catalytic cracking catalyst;

[0013] The total amount of highly colloidal macroporous pseudoboehmite, molecular sieve, clay, and binder is 100 parts by weight. The amount of highly colloidal macroporous pseudoboehmite (calculated as alumina) is 9.5-40 parts by weight, the amount of binder is 2-20 parts by weight, the amount of molecular sieve is 20-50 parts by weight, and the amount of clay is 15-50 parts by weight.

[0014] The third aspect of this invention provides the application of the catalytic cracking catalyst composition described in the first aspect in the production of paraffin-based catalytic feedstock oil.

[0015] The inventors of this invention discovered in their research that introducing highly colloidal macroporous pseudoboehmite into the catalytic cracking catalyst composition can accumulate abundant 4-10nm mesoporous structures while ensuring adhesion, thereby improving the strength and pore structure distribution of the catalytic cracking catalyst.

[0016] The catalytic cracking catalyst composition provided by this invention has abundant 4-10nm mesoporous structures compared with existing catalytic cracking catalysts, and is particularly suitable for processing paraffin-based feedstock oils. The 4-10nm pore structure of the catalyst is more matched with the molecular size of paraffin-based feedstock oils, which can significantly increase the gasoline and diesel fractions and has a high heavy oil conversion capacity. Attached Figure Description

[0017] Figure 1 This is a pore size distribution diagram of the catalyst composition in Example 1 of the present invention;

[0018] Figure 2 This is a pore size distribution diagram of the catalyst composition of Comparative Example 1 of the present invention. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] The first aspect of this invention provides a catalytic cracking catalyst composition, wherein, based on the dry weight of the catalyst composition, the catalyst composition comprises the following components: 9.5-40 wt% highly colloidal macroporous boehmite (calculated as alumina), 2-20 wt% binder, 20-50 wt% molecular sieve, and 15-50 wt% clay; wherein the alumina content of the highly colloidal macroporous boehmite is 98-100 wt%; the pore volume V1 of the highly colloidal macroporous boehmite is 0.45-0.7 mL / g, and the colloidal index DI is 95-100%; the pore volume V2 of the highly colloidal macroporous boehmite after colloidal dissolution is 0.4-0.55 mL / g; the total pore volume of the catalyst composition is not less than 0.2 mL / g; and the mesopore volume of 4-10 nm in the catalyst composition accounts for more than 60% of the total pore volume.

[0021] In this invention, it is understood that the highly soluble macroporous boehmite contained in the catalyst composition can be either highly soluble macroporous boehmite before acidification or highly soluble macroporous boehmite after acidification.

[0022] In this invention, it is understood that the contents of the binder, molecular sieve and clay are all on a dry basis.

[0023] In this invention, it is understood that the pore volume V1 of the highly soluble macroporous pseudoboehmite refers to the pore volume of the product obtained after calcining the highly soluble macroporous pseudoboehmite at 600°C for 3 hours, measured by N2 adsorption. The pore volume V2 of the highly soluble macroporous pseudoboehmite after gelation refers to the pore volume of the product obtained after drying the colloidal solution obtained by gelation with acid and then calcining it at 600°C for 3 hours during gelation index testing, measured by N2 adsorption. In this invention, it is understood that the decrease in pore volume V2 of the highly soluble macroporous pseudoboehmite after gelation is relatively small, indicating that the highly soluble macroporous pseudoboehmite still retains a high pore volume during acid gelation.

[0024] In this invention, the method for measuring the gel solubility index is as follows: 10 grams of boehmite is weighed, calcined at 600℃ for 3 hours, cooled in a desiccator, and weighed to obtain W0 grams. The dry basis weight a0 = W0 / 10 is obtained. The weight of the boehmite is weighed m1 = 6 / a0 grams. The m1 grams of boehmite is placed in a 100 mL polytetrafluoroethylene cup, and deionized water is added to a final volume of 40 grams. The mixture is stirred evenly using a magnetic rotor, and then 20 mL of 0.19 N dilute nitric acid solution is added. The mixture is stirred magnetically for 20 minutes. The entire solution is poured into a centrifuge tube and centrifuged at 1900 rpm for 20 minutes. The upper colloidal solution is poured out, placed in a weighed crucible, dried at 80℃, calcined at 600℃ for 3 hours, cooled in a desiccator, and weighed to obtain m2 grams. The gel solubility index DI = (m2 / 6) * 100%.

[0025] In this invention, the content of each substance in the catalyst composition refers to the mass percentage of the dry basis content of each substance relative to the dry basis content of the catalyst composition; the dry basis amount of each substance refers to the amount remaining after calcining each substance at 800°C for 1 hour.

[0026] In this invention, preferably, the high-solubility macroporous boehmite has a relative crystallinity of 70-99% and a grain size of 4-15 nm. Compared to boehmite in the prior art, the high-solubility macroporous boehmite of this invention has the advantages of a larger grain size, good solubility, and pore structure.

[0027] In this invention, the relative crystallinity is measured by the Q / SH 361 744 method, that is, by using the external standard method, the relative crystallinity of the sample is calculated by measuring the integrated area of ​​the diffraction peak at 2θ = 38.3° of the sample and the standard. The standard used is S87-16b, which was prepared by the Petroleum and Chemical Research Institute and calibrated to have a crystallinity of 98.0%.

[0028] In this invention, the grain size is determined by measuring the integral width β1 of the diffraction peak at 2θ = 38.3° using an X-ray diffractometer. The grain size L is calculated according to β1 = K × λ / (L × cosθ), where K = 1.075, and λ is the wavelength of the Ka1 spectral line of the anodic radiation, taken as λ = 1.5406 × 10⁻⁶. -10 rice.

[0029] In this invention, the highly colloidal macroporous pseudoboehmite is used as one of the raw materials of the catalyst composition. It has a large pore volume and strength, which makes the catalyst composition have excellent strength and pore size distribution.

[0030] In a preferred embodiment, the catalyst composition comprises, on a dry basis, 10-35 wt% highly colloidal macroporous pseudoboehmite (calculated as alumina), 5-20 wt% binder, 25-45 wt% molecular sieve, and 20-45 wt% clay.

[0031] In this invention, preferably, the total pore volume of the catalyst composition is 0.2-0.3 mL / g. For example, it can be 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3 mL / g, or any range between any two sets of data.

[0032] In this invention, the catalyst composition has a rich mesoporous structure, making it particularly suitable for the processing and production of paraffin-based catalytic feedstocks. Preferably, the mesopore volume of 4-10 nm in the catalyst composition accounts for 65-80% of the total pore volume, for example, it can be 65%, 70%, 75%, 80%, or any range between two sets of data.

[0033] In this invention, preferably, the specific surface area of ​​the catalyst composition is 260-320 m². 2 / g, further preferably 270-300m 2 / g.

[0034] In this invention, the total pore volume and specific surface area of ​​the catalyst composition are determined by the low-nitrogen adsorption method, and the proportion of mesopore volume in the 4-10 nm range is determined by the peak fitting method.

[0035] In this invention, the catalyst composition exhibits excellent wear resistance by introducing highly soluble macroporous pseudoboehmite with a high colloidal index and large pore volume. Preferably, the wear index of the catalyst composition is 0.5-3% / h, for example, it can be 0.5, 1, 1.5, 2, 2.5, 3% / h or any range between two sets of data, and more preferably 1-2.5% / h.

[0036] In this invention, the wear index of the catalyst composition was measured by the method NB / SH / T 0964-2017.

[0037] In this invention, there is no particular limitation on the type of binder; binders conventionally defined in the art are all applicable to this invention. Preferably, the binder is selected from at least one of aluminum sol, silica sol, acidified boehmite, aluminosilicate gel, and aluminum phosphate sol; more preferably, it is selected from at least one of aluminum sol, silica sol, and acidified boehmite.

[0038] In this invention, there is no particular limitation on the type of clay; all clays conventionally defined in the art are applicable to this invention. Preferably, the clay is selected from at least one of kaolin, bentonite, montmorillonite, sepiolite, and diatomaceous earth.

[0039] In this invention, there is no particular limitation on the type of molecular sieve; any molecular sieve conventionally defined in the art is applicable to this invention. Preferably, the molecular sieve is selected from at least one of Y-type molecular sieves, MFI-type zeolites, and Beta zeolites.

[0040] In this invention, there is no particular limitation on the type of Y-type molecular sieve; for example, it can be a modified or unmodified Y-type molecular sieve. Preferably, the Y-type molecular sieve is selected from at least one of NaY, HY, REY, REHY, USY, and REUSY.

[0041] A second aspect of the present invention provides a method for preparing a catalytic cracking catalyst composition, wherein the method comprises the following steps:

[0042] (1) A highly soluble macroporous boehmite is mixed with deionized water and pulped, and then acidified in the presence of acid A to obtain an acidified slurry; wherein the alumina content in the highly soluble macroporous boehmite is 98-100% by weight; the pore volume V1 of the highly soluble macroporous boehmite is 0.45-0.7 mL / g, and the gel solubility index DI is 95-100%; the pore volume V2 of the highly soluble macroporous boehmite after gelation is 0.4-0.55 mL / g;

[0043] (2) Mix molecular sieve, clay and deionized water, then add acidified slurry and mix, then add binder to obtain catalyst slurry;

[0044] (3) The catalyst slurry is spray-dried, shaped, and calcined to obtain a catalytic cracking catalyst composition;

[0045] The total amount of highly colloidal macroporous pseudoboehmite, molecular sieve, clay, and binder is 100 parts by weight. The amount of highly colloidal macroporous pseudoboehmite (calculated as alumina) is 9.5-40 parts by weight, the amount of binder is 2-20 parts by weight, the amount of molecular sieve is 20-50 parts by weight, and the amount of clay is 15-50 parts by weight.

[0046] In this invention, preferably, the total amount of highly colloidal macroporous pseudoboehmite, molecular sieve, clay, and binder is 100 parts by weight, the amount of highly colloidal macroporous pseudoboehmite (calculated as alumina) is 10-35 parts by weight, the amount of binder is 5-20 parts by weight, the amount of molecular sieve is 25-45 parts by weight, and the amount of clay is 20-45 parts by weight.

[0047] The method provided by this invention uses highly soluble macroporous pseudoboehmite with a high colloidal index and large pore volume as a raw material. This highly soluble macroporous pseudoboehmite retains a large pore volume after colloidal dissolution, with a relatively small decrease in pore volume. Therefore, using it as one of the raw materials for preparing a catalyst results in a catalyst composition with excellent performance. This preparation method is simple and easy to operate, and has excellent industrial prospects.

[0048] In this invention, the mixing and pulping in step (1) can be carried out under stirring conditions. Preferably, in step (1), the stirring time is 0.5-5 hours.

[0049] In this invention, the type of acid A is not particularly limited; it can be an inorganic acid or an organic acid. Preferably, in step (1), acid A is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, and phosphoric acid.

[0050] In this invention, there is no particular limitation on the amount of acid A used. Preferably, in step (1), the amount of acid A used is such that the molar ratio of hydrogen ions in the acid solution to the highly colloidal macroporous pseudoboehmite (calculated as alumina) is 0.05-0.5:1, preferably 0.1-0.35:1.

[0051] In this invention, the range of conditions for acid treatment is relatively wide. Preferably, in step (1), the acid treatment conditions include an acidification time of 0.5-2 hours, more preferably 0.5-1.5 hours.

[0052] In a preferred embodiment, in step (1), the solid content of the acidified slurry is 10-30 wt%.

[0053] In a preferred embodiment, in step (1), the highly soluble macroporous pseudoboehmite is prepared by the following method:

[0054] Hydrated alumina and / or amorphous alumina, deionized water and acid B are mixed to obtain a mixed slurry. The mixed slurry is subjected to a hydrothermal reaction, and the product is dried to obtain the highly colloidal macroporous pseudoboehmite.

[0055] In a preferred embodiment, the alumina concentration in the mixed slurry is 5-50% by weight, preferably 6-40% by weight, and more preferably 8-20% by weight.

[0056] In this invention, there is no particular limitation on the amount of acid B used. Preferably, the molar ratio of acid B to alumina in the mixed slurry is 0.02-0.8, more preferably 0.08-0.6.

[0057] In this invention, the range of types of acid B is relatively wide, and acids conventionally defined in the art are all applicable to this invention. Preferably, acid B is an inorganic acid and / or an organic acid.

[0058] In this invention, there is no particular limitation on the types of inorganic and organic acids. Preferably, the inorganic acid is selected from at least one of hydrochloric acid, nitric acid, and sulfuric acid, and the organic acid is selected from at least one of formic acid, acetic acid, and oxalic acid.

[0059] In this invention, the selection range of hydrothermal reaction conditions is relatively wide. Preferably, the hydrothermal reaction conditions include: a temperature of 90-220℃, a time of 6-48h, and a stirring speed of 10-100r / min; more preferably, the hydrothermal reaction conditions include: a temperature of 100-200℃, a time of 6-42h, and a stirring speed of 10-90r / min.

[0060] In this invention, the range of drying conditions is relatively wide. Preferably, the drying temperature is 60-120℃, and more preferably 80-110℃.

[0061] Typically, the colloidal index and pore volume of boehmite are inversely proportional, and the pore volume decreases significantly after colloidal treatment, indicating poor colloidal properties. However, this invention employs a hydrothermal reaction to prepare highly colloidal boehmite. By controlling the type and amount of alumina raw material (molar ratio of acid B to alumina) and the hydrothermal reaction conditions (temperature, time, stirring rate, etc.), the resulting boehmite exhibits a high colloidal index and pore volume. After colloidal treatment, the pore volume of the boehmite decreases only slightly, maintaining a relatively large pore volume and demonstrating excellent colloidal properties.

[0062] In this invention, the types of binders, clays and molecular sieves used in step (2) are the same as in the first aspect, and their specific contents have been described in the first aspect, so they will not be repeated here.

[0063] In this invention, to ensure sufficient contact between the raw materials, step (2) is carried out under mixing conditions. Preferably, the mixing conditions include: mixing temperature 20-90℃ and mixing time 0.5-12h.

[0064] In a preferred embodiment, the solid content of the catalyst slurry is 20-50 wt%.

[0065] In this invention, the range of selection for the roasting conditions in step (3) is relatively wide. Preferably, the roasting conditions in step (3) include: a temperature of 300-600℃ and a time of 0.5-5h; more preferably, the roasting conditions include: a temperature of 350-550℃ and a time of 0.5-3.5h.

[0066] In this invention, step (3) also includes washing and drying after roasting, which can be carried out according to existing methods in the field. This invention does not have any special requirements for this.

[0067] The third aspect of this invention provides the application of the catalytic cracking catalyst composition described in the first aspect in the production of paraffin-based catalytic feedstock oil.

[0068] In this invention, the composition of the paraffinic feedstock oil is selected over a wide range. Preferably, the characteristic factor K value of the paraffinic catalytic feedstock oil is not less than 12.1, and more preferably 12.1-12.8. The advantage of this preferred embodiment is that the molecular size of the feedstock oil matches the pore size of the catalyst, reducing the diffusion resistance of the feedstock oil molecules.

[0069] In this invention, to further investigate the catalyst's resistance to heavy metal contamination, a pre-impregnation treatment with contaminated metals can be performed before processing paraffin-based catalytic feedstock oil using the catalytic cracking catalyst composition, simulating an industrial balancing agent. Preferably, the pre-impregnation is carried out in a kerosene solution.

[0070] In this invention, preferably, the catalytic cracking composition may undergo an aging treatment before use, which is carried out in a solid bed reactor. Preferably, the aging treatment conditions include: a temperature of 760-800°C and a time of 4-17 hours.

[0071] In this invention, the range of application conditions is relatively wide. Preferably, the application includes: a reaction temperature of 450-550℃ and an agent-to-oil weight ratio of 3-10:1.

[0072] The catalytic cracking catalyst composition provided by this invention is particularly suitable for the processing and production of paraffin-based catalytic feedstock oils. The abundant 4-10 nm pore structure in the catalyst composition has a good matching relationship with the size of paraffin-based crude oil, which can significantly increase the gasoline and diesel fractions and has a high heavy oil conversion capacity.

[0073] The present invention will be described in detail below through embodiments. Unless otherwise specified, all raw materials used in the following embodiments are commercially available.

[0074] The raw materials used in the preparation of the catalyst are described as follows: kaolin with a solid content of 79 wt%; alumina content in the alumina sol of 22 wt%; SiO2 content in the silica sol of 27.0 wt%; properties of conventional boehmite and mesoporous boehmite are shown in Table 1; acidified boehmite with a solid content of 12.0 wt%, acidified with hydrochloric acid, and the molar ratio of acid (HCl) to alumina during acidification was 0.20; the rare earth ultrastable Y zeolite REUSY used had a solid content of 78 wt% and a cell constant of [missing information]. The content of Na2O is 1.6% by weight, and the content of RE2O3 is 12.0%.

[0075] The analysis and evaluation methods are explained below:

[0076] Method for measuring the gel solubility index: Weigh 10 grams of boehmite, calcine at 600℃ for 3 hours, cool in a desiccator until room temperature, and weigh to obtain W0 grams. Calculate the dry basis weight a0 = W0 / 10. Weigh the boehmite weight m1 = 6 / a0 grams. Place m1 grams of boehmite in a 100 mL PTFE cup, add deionized water to 40 grams, stir evenly with a magnetic rotor, then add 20 mL of 0.19 N dilute nitric acid solution and stir magnetically for 20 minutes. Pour the entire solution into a centrifuge tube and centrifuge at 1900 rpm for 20 minutes. Pour off the upper colloidal solution, place it in a weighed crucible, dry at 80℃, calcine at 600℃ for 3 hours, cool in a desiccator until room temperature, and weigh to obtain m2 grams. The gel solubility index DI = (m2 / 6) * 100%.

[0077] Specific surface area and pore volume analysis: A Micromeritics ASAP 2405NV1.01 automated adsorption analyzer was used, employing the low-temperature static nitrogen adsorption capacity method. The sample surface area was 1.33 × 10⁻⁶. -2 The sample was degassed under vacuum at 300℃ for 4 hours using N2 as the adsorption medium, and the adsorption-desorption isotherm was measured at 77.4K. The specific surface area of ​​the sample was calculated using the BET formula, and the volume of N2 adsorbed by the sample at a relative pressure p / p0 = 0.98 was measured and converted to liquid nitrogen volume, i.e., total pore volume. The micropore volume was calculated using the t-plot method, and the difference between the two was the volume of macropores in the 2-100 nm range. The pore volumes of mesopores in the 4-10 nm range were obtained using peak fitting.

[0078] Catalyst strength: A certain amount of catalyst is placed in a fixed device and milled under a constant airflow for 5 hours. The average percentage of wear in the last four hours (excluding the first hour) is called the catalyst wear index, expressed as % per hour. The method and standard are: airlift method Q / SYLS0518-2002.

[0079] Catalytic cracking catalyst evaluation: The catalytic cracking catalyst was evaluated on the ACE unit.

[0080] Example 1

[0081] 12g of concentrated HCl (36 wt%) was added to 700g of deionized water. While stirring, 108g of amorphous alumina rapid desorption powder (86.4 wt% on a dry basis) and 37g of pseudoboehmite USA (85 wt% on a dry basis) were added sequentially. The alumina concentration was 14.6 wt%, and the acid / alumina molar ratio was 0.098. After thorough stirring, the mixture was transferred to a 1000mL self-pressurized reactor and placed in a homogeneous reactor. The stirring speed was 10 rpm, and the temperature was maintained at 150℃ for 24 hours. After cooling, the reaction slurry was removed and dried in an oven at 80℃ for 24 hours to obtain hydrated alumina P1. XRD characterization showed that P1 had a pseudoboehmite structure. The relative crystallinity and grain size are listed in Table 1. P1 was calcined at 600℃ for 3 hours to obtain alumina Z1. The colloidal index DI of P1 was measured and listed in Table 1. The alumina obtained by drying and calcining the upper colloidal solution during the measurement of the colloidal index is denoted as J1. The composition of Z1 was characterized by XRF, and the results are listed in Table 2. The pore volumes V1 of Z1 and V2 of J1 were measured by N2 adsorption, and the results are also listed in Table 2.

[0082] Take 28.6g of highly colloidal macroporous pseudoboehmite P1 with a solid content of 70% by weight, add 138g of deionized water, and stir for 30min. Add 4.0g of 36% by weight hydrochloric acid and acidify for 60min to obtain an acidified sample of highly colloidal macroporous pseudoboehmite.

[0083] 51g of kaolin with a solid content of 79 wt% was added to 192g of deionized water and stirred for 20 min. Then, 41g of REUSY molecular sieve with a solid content of 78 wt% was added, and stirring continued for 20 min. Next, a highly colloidal macroporous pseudoboehmite acidification sample was added and stirred for 20 min. Finally, 28g of alumina sol with a solid content of 22 wt% was added, and stirring was carried out for 30 min to obtain a catalyst slurry. This slurry was spray-dried, calcined at 550℃ for 2 h, and then washed and dried to obtain the catalytic cracking catalyst CAT-1. The CAT-1 catalyst, on a dry basis, contains 35 wt% REUSY molecular sieve, 39 wt% kaolin, 20 wt% highly colloidal macroporous pseudoboehmite, and 6 wt% alumina sol, with the following pore size distribution: Figure 1 As shown, from Figure 1 It can be seen that, in addition to the pore structure at a pore size of 3.8 nm, the obtained catalyst has obvious pore structures in the 4-10 nm range, indicating that the catalyst contains abundant mesoporous structures.

[0084] Example 2

[0085] 2.2 L of aluminum sulfate solution with an alumina concentration of 104 g / L, obtained from Zibo Qimao Catalyst Co., Ltd., was diluted with deionized water to a final volume of 4.0 L under stirring and placed in raw material reactor A. 1000 mL of a self-made sodium aluminate solution with an alumina concentration of 220 g / L and a caustic coefficient of 1.65 was placed in raw material reactor B. 2 L of deionized water was added to a 3 L neutralization reactor, and the temperature was adjusted to 50 °C. The stirring and feed pumps for raw materials A and B were started, and a continuous parallel-flow neutralization reaction was carried out. The neutralization pH was 8.5, the neutralization temperature was 50 °C, and the residence time was 20 min. The slurry was collected. After neutralization, the collected slurry was filtered and washed with 60 L of deionized water at 50 °C to obtain a filter cake. 20g of concentrated HCl (36 wt%) was added to 400g of deionized water, and 400g of the filter cake prepared above (28.8 wt% on a dry basis) was added under stirring. The alumina concentration was 11.3 wt%, and the acid / alumina molar ratio was 0.177. After stirring evenly, the mixture was transferred to a 1000mL autoclave reactor and placed in a homogeneous reactor. The stirring speed was 10 rpm, and the temperature was maintained at 150℃ for 12 hours. After cooling, the reaction slurry was removed and dried in an oven at 90℃ for 24 hours to obtain hydrated alumina P2. P2 was characterized by XRD and showed to have a pseudoboehmite structure. The relative crystallinity and grain size are listed in Table 1. P2 was calcined at 600℃ for 3 hours to obtain alumina Z2. The colloidal index DI of P2 was measured and listed in Table 1. Alumina obtained by drying and calcining the upper colloidal solution during the colloidal index measurement was denoted as J2. The composition of Z2 was characterized by XRF, and the results are listed in Table 2. The pore volumes V1 of Z2 and V2 of J2, measured by the N2 adsorption method, are listed in Table 2.

[0086] Take 35.7g of highly colloidal macroporous pseudoboehmite P2 with a solid content of 70% by weight, add 173g of deionized water, and stir for 30min. Add 5.5g of 36% by weight hydrochloric acid and acidify for 60min to obtain an acidified sample of highly colloidal macroporous pseudoboehmite.

[0087] 42g of kaolin with a solid content of 79 wt% was added to 158g of deionized water and stirred for 20 min. Then, 45g of REUSY molecular sieve with a solid content of 78 wt% was added, and stirring continued for 20 min. Next, a highly colloidal macroporous pseudoboehmite acidification sample was added and stirred for 20 min. Finally, 24g of alumina sol with a solid content of 22 wt% was added, and stirring was carried out for 30 min to obtain the final catalyst slurry. This slurry was spray-dried, calcined at 550℃ for 2 h, and then washed and dried to obtain the catalytic cracking catalyst CAT-2 of this invention. The CAT-2 catalyst, on a dry basis, contains 38 wt% REUSY molecular sieve, 32 wt% kaolin, 25 wt% highly colloidal macroporous pseudoboehmite, and 5 wt% alumina sol.

[0088] Example 3

[0089] 18.5 g of concentrated HNO3 (36 wt%) and 108 g of commercially available amorphous alumina rapid desorption powder (0.864 g dry basis) from Shandong Branch of Aluminum Corporation of China were added to 700 g of deionized water. The alumina concentration was 11.2 wt%, and the acid / alumina molar ratio was 0.202. After stirring evenly, the mixture was transferred to a 1000 mL autoclave reactor and placed in a homogeneous reactor. The stirring speed was 10 rpm, and the temperature was maintained at 150 °C for 48 hours. After cooling, the reaction slurry was removed and dried in an oven at 80 °C for 24 hours to obtain hydrated alumina P3. XRD characterization showed that P3 had a pseudoboehmite structure. The relative crystallinity and grain size are listed in Table 1. P3 was calcined at 600 °C for 3 hours to obtain alumina Z3. The colloidal index DI of P3 was measured and listed in Table 1. The alumina obtained by drying and calcining the upper colloidal solution during the colloidal index measurement was denoted as J3. The composition of Z3 was characterized by XRF, and the results are listed in Table 2. The pore volumes V1 of Z3 and V2 of J3 were measured by N2 adsorption, and the results are also listed in Table 2.

[0090] Take 14.0 g of highly colloidal macroporous pseudoboehmite P3 with a solid content of 70 wt% and add it to 52 g of deionized water, stir for 30 min. Add 1.8 g of 36 wt% hydrochloric acid and acidify for 90 min to obtain an acidified sample of highly colloidal macroporous pseudoboehmite.

[0091] 52g of kaolin with a solid content of 79 wt% was added to 170g of deionized water and stirred for 30 min. Then, 41g of REUSY molecular sieve with a solid content of 78 wt% was added, and stirring continued for 30 min. Next, a highly colloidal macroporous pseudoboehmite acidification sample was added and stirred for 20 min. Finally, 47g of alumina sol with a solid content of 22 wt% and 19g of silica sol with a solid content of 27 wt% were added, and stirring was carried out for 60 min to obtain a catalyst slurry. This slurry was spray-dried, calcined at 550℃ for 2 h, and then washed and dried to obtain the catalytic cracking catalyst CAT-3 of this invention. The CAT-3 catalyst, on a dry basis, contains 35 wt% REUSY molecular sieve, 40 wt% kaolin, 10 wt% highly colloidal macroporous pseudoboehmite, 10 wt% alumina sol, and 5 wt% silica sol.

[0092] Example 4

[0093] 75g of concentrated HNO3 (65% by weight), 450g of amorphous alumina rapid desorption powder (0.864% dry basis) commercially available from China Aluminum Shandong Branch, and 150g of pseudoboehmite USA (85% dry basis) commercially available from Shandong Yantai Heng Hui Chemical Co., Ltd. were added to 500g of deionized water. The alumina concentration was 40.0% by weight, and the acid / alumina molar ratio was 0.362. After stirring evenly, the mixture was transferred to a 1000mL self-pressurized reactor and placed in a homogeneous reactor. The stirring speed was 10 rpm, and the temperature was maintained at 150℃ for 24 hours. After cooling, the reaction slurry was removed, dried in an oven, and maintained at 80℃ for 24 hours to obtain hydrated alumina P4. XRD characterization showed that P4 had a pseudoboehmite structure. The relative crystallinity and grain size are listed in Table 1. P4 was calcined at 600℃ for 3 hours to obtain alumina Z4. The colloidal index DI of P4 was measured and listed in Table 1. The alumina obtained by drying and calcining the upper colloidal solution during the measurement of the colloidal index is denoted as J4. The composition of Z4 was characterized by XRF, and the results are listed in Table 2. The pore volumes V1 of Z4 and V2 of J4 were measured by N2 adsorption, and the results are also listed in Table 2.

[0094] Take 35.7g of highly colloidal macroporous pseudoboehmite P4 with a solid content of 70% by weight, add 214g of deionized water, and stir for 30min. Add 5.0g of 36% by weight hydrochloric acid and acidify for 60min to obtain an acidified sample of highly colloidal macroporous pseudoboehmite.

[0095] 52g of kaolin with a solid content of 79 wt% was added to 170g of deionized water and stirred for 40 min. Then, 35g of REUSY molecular sieve with a solid content of 78 wt% was added, and stirring continued for 30 min. Next, a highly colloidal macroporous pseudoboehmite acidification sample was added and stirred for 20 min. Finally, 18g of silica sol with a solid content of 27 wt% was added, and stirring continued for 30 min to obtain a catalyst slurry. This slurry was spray-dried, calcined at 500℃ for 2.5 h, and then washed and dried to obtain the catalytic cracking catalyst CAT-4. On a dry basis, the obtained CAT-4 catalyst contained 30 wt% REUSY molecular sieve, 40 wt% kaolin, 25 wt% highly colloidal macroporous pseudoboehmite, and 5 wt% silica sol.

[0096] Example 5

[0097] 188g of 36% acetic acid and 372g of commercially available amorphous alumina quick-release powder (dry basis 0.864) from Shandong Branch of Aluminum Corporation of China were added to 428g of deionized water. The alumina concentration was 35.0% wt%, and the acid / alumina molar ratio was 0.331. After stirring evenly, the mixture was transferred to a 1000mL self-pressurized reactor and placed in a homogeneous reactor. The stirring speed was 10 rpm, and the temperature was maintained at 125℃ for 48 hours. After cooling, the reaction slurry was removed and dried in an oven at 110℃ for 24 hours to obtain hydrated alumina P5. XRD characterization showed that P5 had a pseudoboehmite structure. The relative crystallinity and grain size are listed in Table 1. P5 was calcined at 600℃ for 3 hours to obtain alumina Z5. The colloidal index DI of P5 was measured and listed in Table 1. The alumina obtained by drying and calcining the upper colloidal solution during the colloidal index measurement was denoted as J5. The composition of Z5 was characterized by XRF, and the results are listed in Table 2. The pore volumes V1 of Z5 and V2 of J5 were measured by N2 adsorption, and are also listed in Table 2.

[0098] Take 42.9 g of highly colloidal macroporous pseudoboehmite P5 with a solid content of 70 wt% and add it to 257 g of deionized water, stir for 30 min. Add 6.0 g of 36 wt% hydrochloric acid and acidify for 60 min to obtain an acidified sample of highly colloidal macroporous pseudoboehmite.

[0099] 41g of kaolin with a solid content of 79 wt% was added to 165g of deionized water and stirred for 40 min. Then, 39g of REUSY molecular sieve with a solid content of 78 wt% was added, and stirring continued for 30 min. Next, a highly colloidal macroporous pseudoboehmite acidification sample was added and stirred for 20 min. Finally, 28g of alumina sol with a solid content of 22 wt% was added, and stirring was continued for 30 min to obtain a catalyst slurry. This slurry was spray-dried, calcined at 500℃ for 2.5 h, and then washed and dried to obtain the catalytic cracking catalyst CAT-5. On a dry basis, the obtained CAT-5 catalyst contained 33 wt% REUSY molecular sieve, 31 wt% kaolin, 30 wt% highly colloidal macroporous pseudoboehmite, and 6 wt% alumina sol.

[0100] Comparative Example 1

[0101] Using commercially available Sasol SB boehmite as a control sample CP1, XRD characterization was performed. CP1 exhibited a boehmite structure, and its relative crystallinity and grain size are listed in Table 1. CP1 was calcined at 600℃ for 3 hours to obtain alumina CZ1; the colloidal index DI of CP1 was measured and listed in Table 1. Alumina obtained by drying and calcining the upper colloidal solution during colloidal index measurement was designated CJ1. The composition of CZ1 was characterized using XRF, and the results are listed in Table 2. The pore volumes V1 of CZ1 and V2 of CJ1 were measured using N2 adsorption and are listed in Table 2.

[0102] The catalytic cracking catalyst was prepared according to the method in Example 1. The resulting DCAT-1 catalyst contained 35 wt% REUSY molecular sieve, 39 wt% kaolin, 20 wt% CP1 boehmite, and 6 wt% alumina sol. Its pore size distribution is as follows: Figure 2 As shown, from Figure 2 As can be seen, the obtained comparative catalyst has a pore structure at a pore size of 3.8 nm, but no obvious pore structure was found in the 4-10 nm range.

[0103] Comparative Example 2

[0104] A pseudoboehmite (CP2) obtained from the Shandong branch of Aluminum Corporation of China Limited (Chalco) was used as a control sample. XRD characterization revealed that CP2 possessed a pseudoboehmite structure; its relative crystallinity and grain size are listed in Table 1. CP2 was calcined at 600℃ for 3 hours to obtain alumina CZ2; the colloidal index (DI) of CP2 was measured and is listed in Table 1. Alumina obtained by drying and calcining the upper colloidal solution during the colloidal index measurement was designated CJ2. The composition of CZ2 was characterized using XRF, and the results are listed in Table 2. The pore volumes V1 of CZ2 and V2 of CJ2 were measured using N2 adsorption and are listed in Table 2.

[0105] The catalytic cracking catalyst was prepared according to the method of Example 1. The resulting DCAT-2 catalyst contained 35 wt% REUSY molecular sieve, 39 wt% kaolin, 20 wt% CP2 boehmite, and 6 wt% alumina sol.

[0106] Comparative Example 3

[0107] 108g of commercially available amorphous alumina quick-release powder (dry basis 0.864) from Shandong Branch of Aluminum Corporation of China was added to 700g of deionized water, resulting in an alumina concentration of 11.5% by weight. After stirring evenly, the mixture was transferred to a 1000mL self-pressurized reactor and placed in a homogeneous reactor. The stirring speed was 10 rpm, and the temperature was maintained at 130℃ for 24 hours. After cooling, the reaction slurry was removed and poured into a vacuum filter funnel. 3L of 90℃ deionized water was added for washing. The filter cake was dried in an oven and maintained at 120℃ for 24 hours to obtain hydrated alumina CP3. XRD characterization showed that CP3 had a pseudoboehmite structure. The relative crystallinity and grain size are listed in Table 1. CP3 was calcined at 600℃ for 3 hours to obtain alumina CZ3. The colloidal index DI of CP3 was measured and listed in Table 1. The alumina obtained by drying and calcining the upper colloidal solution during the colloidal index measurement was denoted as CJ3. The composition of CZ3 was characterized by XRF, and the results are listed in Table 2. The pore volumes V1 of CZ3 and V2 of CJ3 were measured by N2 adsorption, and the results are also listed in Table 2.

[0108] The catalytic cracking catalyst was prepared according to the method of Example 1. The resulting DCAT-3 catalyst contained 35 wt% REUSY molecular sieve, 39 wt% kaolin, 20 wt% CP3 boehmite, and 6 wt% alumina sol.

[0109] Comparative Example 4

[0110] 3.1 g of concentrated HNO3 (68 wt%) was added to 700 g of deionized water, along with 108 g of commercially available amorphous alumina rapid desorption powder (0.864 g dry basis) from Shandong Branch of Aluminum Corporation of China, resulting in an alumina concentration of 11.5 wt%. After thorough mixing, the slurry was transferred to a 1000 mL self-pressurized reactor and placed in a homogeneous reactor. The mixture was stirred at 10 rpm and kept at 150 °C for 12 hours. After cooling, the slurry was removed and poured into a vacuum filter funnel. 3 L of deionized water at 90 °C was added for washing. The filter cake was dried in an oven at 100 °C for 24 hours to obtain hydrated alumina CP4. XRD characterization showed that CP4 exhibited a pseudoboehmite structure. The relative crystallinity and grain size are listed in Table 1. CP4 was calcined at 600 °C for 3 hours to obtain alumina CZ4. The colloidal index (DI) of CP4 was measured and is listed in Table 1. The alumina obtained by drying and calcining the upper colloidal solution during the measurement of the colloidal index is denoted as CJ4. The composition of CJ4 was characterized by XRF, and the results are listed in Table 2. The pore volumes V1 of CJ4 and V2 of CJ4 were measured by N2 adsorption, and the results are also listed in Table 2.

[0111] The cracking catalyst was prepared according to the method of Example 1. The resulting DCAT-4 catalyst contained 35 wt% REUSY molecular sieve, 39 wt% kaolin, 20 wt% CP4 boehmite, and 6 wt% alumina sol.

[0112] Table 1

[0113] Relative crystallinity, % Grain size, nm Colloidal index (DI), % Example 1 P1 84.3 10.2 98.6 Example 2 P2 76.5 5.5 99.1 Example 3 P3 81.1 7.9 96.5 Example 4 P4 77.7 8.5 98.8 Example 5 P5 82.4 5.5 99.5 Comparative Example 1 CP1 83.7 4.9 99.2 Comparative Example 2 CP2 81.5 4.3 99.6 Comparative Example 3 CP3 113.1 12.3 65.1 Comparative Example 4 CP4 75.9 7.9 24.0

[0114] Table 2

[0115]

[0116]

[0117] Note: The content of each substance in Table 2 is expressed as a percentage by weight.

[0118] Table 3

[0119]

[0120]

[0121] Note: The content of each substance in Table 3 is expressed in weight % (%).

[0122] As shown in Tables 1 and 2, the colloidal indices of comparative samples CP1 and CP2 in Comparative Examples 1 and 2 are consistent with the properties of the highly colloidal macroporous pseudoboehmite prepared in the embodiments of the present invention. However, the pore volume V2 of CJ1 and CJ2 after colloidalization and subsequent drying and calcination is lower than the 0.40 mL / g index of the highly colloidal macroporous pseudoboehmite prepared in the embodiments of the present invention. In Comparative Examples 3 and 4, the pore volume V1 of the calcined comparative samples CP3 and CP4 is consistent with the properties of the highly colloidal macroporous pseudoboehmite prepared in the embodiments of the present invention. However, their colloidal properties are poor, and the pore volume V2 of CJ3 and CJ4 after colloidalization and subsequent drying and calcination is lower than the 0.40 mL / g index of the highly colloidal macroporous pseudoboehmite prepared in the embodiments of the present invention.

[0123] As can be seen from the data in Table 3, the catalyst composition of the present invention containing highly colloidal macroporous pseudoboehmite has a high water droplet pore volume under the condition of comparable wear performance. The pore volume of 4-10 nm can account for more than 75% of the total pore volume, indicating that the catalyst composition has a rich mesoporous structure.

[0124] Catalysts CAT-1-5 and DCAT-1-4 were pre-impregnated in a kerosene solution of nickel naphthenate and vanadium naphthenate to achieve nickel and vanadium concentrations of 1500 ppm and 3000 ppm, respectively. They were then aged at 800°C with 100% steam for 4 hours in a fixed-bed aging unit and evaluated in an ACE unit. Paraffin-based feedstock was used, and the properties of the feedstock are shown in Table 4. The reaction temperature was 500°C, and the catalyst-to-oil weight ratio was 8.02. The evaluation results are shown in Table 5.

[0125] Wherein, conversion rate % = gasoline yield % + liquefied gas yield % + dry gas yield % + coke yield.

[0126] Table 4

[0127]

[0128]

[0129] Table 5

[0130]

[0131]

[0132] Table 5 shows that, compared with the catalyst DCAT-1-4 prepared in the comparative example, the catalyst CAT-1-5 prepared according to the embodiments of the present invention has increased gasoline and diesel yields, but significantly reduced heavy oil yield. This indicates that the catalytic cracking catalyst prepared in this invention has excellent heavy oil cracking capability and good selectivity for gasoline and diesel.

[0133] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalytic cracking catalyst composition, characterized in that, Based on the dry weight of the catalyst composition, the catalyst composition comprises the following components: 9.5-40 wt% highly colloidal macroporous boehmite (calculated as alumina), 2-20 wt% binder, 20-50 wt% molecular sieve, and 15-50 wt% clay; wherein the alumina content of the highly colloidal macroporous boehmite is 98-100 wt%; the pore volume V1 of the highly colloidal macroporous boehmite is 0.45-0.7 mL / g, and the colloidal index DI is 95-100%; the pore volume V2 of the highly colloidal macroporous boehmite after colloidal dissolution is 0.4-0.55 mL / g; the total pore volume of the catalyst composition is not less than 0.2 mL / g; and the mesopore volume of 4-10 nm in the catalyst composition accounts for more than 60% of the total pore volume. Wherein, the pore volume V1 of the highly colloidal macroporous pseudoboehmite refers to the pore volume of the product obtained by calcining the highly colloidal macroporous pseudoboehmite at 600℃ for 3h, as measured by the N2 adsorption method. The pore volume V2 of the highly soluble macroporous pseudoboehmite after solubilization refers to the pore volume of the product obtained by N2 adsorption method after drying the colloidal solution obtained by solubilization of the highly soluble macroporous pseudoboehmite with acid and then calcining it at 600℃ for 3 hours during the solubilization index test.

2. The catalyst composition according to claim 1, wherein, Based on the dry weight of the catalyst composition, the catalyst composition comprises the following components: 10-35 wt% highly colloidal macroporous pseudoboehmite based on alumina, 5-20 wt% binder, 25-45 wt% molecular sieve and 20-45 wt% clay. And / or, the total pore volume of the catalyst composition is 0.2-0.3 mL / g; And / or, in the catalyst composition, the pore volume of 4-10 nm accounts for 65-80% of the total pore volume; And / or, the specific surface area of ​​the catalyst composition is 260-320 m². 2 / g.

3. The catalyst composition according to claim 2, wherein, The specific surface area of ​​the catalyst composition is 270-300 m². 2 / g.

4. The catalyst composition according to any one of claims 1-3, wherein, The wear index of the catalyst composition is 0.5-3% / h.

5. The catalyst composition according to claim 4, wherein, The wear index of the catalyst composition is 1-2.5% / h.

6. The catalyst composition according to any one of claims 1-3, wherein, The binder is selected from at least one of aluminum sol, silica sol, acidified boehmite, aluminosilicate gel, and aluminum phosphate sol. And / or, the clay is selected from at least one of kaolin, bentonite, montmorillonite, sepiolite and diatomite; And / or, the molecular sieve is selected from at least one of Y-type molecular sieves, MFI-type zeolites, and Beta zeolites.

7. The catalyst composition according to claim 6, wherein, The binder is selected from at least one of alumina sol, silica sol, and acidified pseudoboehmite.

8. The catalyst composition according to claim 6, wherein, The Y-type molecule is selected from at least one of NaY, HY, REY, REHY, USY, and REUSY.

9. A method for preparing a catalytic cracking catalyst composition, wherein, The method includes the following steps: (1) A highly soluble macroporous pseudoboehmite is mixed with deionized water and pulped, and then acidified in the presence of acid A to obtain an acidified slurry; wherein the alumina content in the highly soluble macroporous pseudoboehmite is 98-100% by weight; the pore volume V1 of the highly soluble macroporous pseudoboehmite is 0.45-0.7 mL / g, and the gel solubility index DI is 95-100%; the pore volume V2 of the highly soluble macroporous pseudoboehmite after gelation is 0.4-0.55 mL / g; (2) Mix molecular sieve, clay and deionized water, then add acidified slurry and mix, then add binder to obtain catalyst slurry; (3) The catalyst slurry is spray-dried, shaped, and calcined to obtain a catalytic cracking catalyst composition; The total amount of highly colloidal macroporous pseudoboehmite, molecular sieve, clay, and binder is 100 parts by weight. The amount of highly colloidal macroporous pseudoboehmite (calculated as alumina) is 9.5-40 parts by weight, the amount of binder is 2-20 parts by weight, the amount of molecular sieve is 20-50 parts by weight, and the amount of clay is 15-50 parts by weight.

10. The preparation method according to claim 9, wherein, In step (1), acid A is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, and phosphoric acid; And / or, in step (1), the amount of acid A used is such that the molar ratio of hydrogen ions in the acid solution to the molar ratio of the highly colloidal macroporous pseudoboehmite (based on alumina) is 0.05-0.5:

1.

11. The preparation method according to claim 10, wherein, In step (1), the amount of acid A used is such that the molar ratio of hydrogen ions in the acid solution to the dry basis of the highly colloidal macroporous pseudoboehmite, calculated as alumina, is 0.1-0.35:

1.

12. The preparation method according to claim 9, wherein, In step (1), the acid treatment conditions include an acidification time of 0.5-2 hours.

13. The preparation method according to claim 12, wherein, In step (1), the acid treatment conditions include an acidification time of 0.5-1.5 h.

14. The preparation method according to claim 9, wherein, In step (1), the solid content of the acidified slurry is 10-30 wt%.

15. The preparation method according to any one of claims 9-14, wherein, In step (1), the highly soluble macroporous pseudoboehmite is prepared by the following method: Hydrated alumina and / or amorphous alumina, deionized water and acid B are mixed to obtain a mixed slurry. The mixed slurry is subjected to a hydrothermal reaction, and the product is dried to obtain the highly colloidal macroporous pseudoboehmite. And / or, acid B is an inorganic acid and / or an organic acid; And / or, the inorganic acid is selected from at least one of hydrochloric acid, nitric acid and sulfuric acid, and the organic acid is selected from at least one of formic acid, acetic acid and oxalic acid.

16. The preparation method according to claim 15, wherein, In step (1), the alumina concentration in the mixed slurry is 5-50% by weight.

17. The preparation method according to claim 16, wherein, In step (1), the alumina concentration in the mixed slurry is 6-40% by weight.

18. The preparation method according to claim 17, wherein, In step (1), the alumina concentration in the mixed slurry is 8-20% by weight.

19. The preparation method according to claim 15, wherein, In step (1), the molar ratio of acid B to alumina in the mixed slurry is 0.02-0.

8.

20. The preparation method according to claim 19, wherein, In step (1), the molar ratio of acid B to alumina in the mixed slurry is 0.08-0.

6.

21. The preparation method according to claim 15, wherein, In step (1), the conditions for the hydrothermal reaction include: a temperature of 90-220℃, a time of 6-48h, and a stirring speed of 10-100r / min.

22. The preparation method according to claim 21, wherein, In step (1), the conditions for the hydrothermal reaction include: a temperature of 100-200℃, a time of 6-42h, and a stirring speed of 10-90r / min.

23. The preparation method according to claim 15, wherein, In step (1), the drying temperature is 60-120℃.

24. The preparation method according to claim 23, wherein, In step (1), the drying temperature is 80-110℃.

25. The preparation method according to any one of claims 9-14, wherein, In step (2), the binder is selected from at least one of aluminum sol, silica sol, acidified boehmite, aluminosilicate gel and aluminum phosphate sol; And / or, in step (2), the clay is selected from at least one of kaolin, bentonite, montmorillonite, sepiolite and diatomite; And / or, in step (2), the molecular sieve is selected from at least one of Y-type molecular sieve, MFI-type zeolite and Beta zeolite; And / or, in step (2), the solid content of the catalyst slurry is 20-50 wt%.

26. The preparation method according to claim 25, wherein, In step (2), the binder is selected from at least one of aluminum sol, silica sol and acidified boehmite.

27. The preparation method according to claim 25, wherein, In step (2), the Y-type molecule is screened from at least one of NaY, HY, REY, REHY, USY and REUSY.

28. The preparation method according to any one of claims 9-14, wherein, In step (3), the calcination conditions include a temperature of 300-600℃ and a time of 0.5-5.0h.

29. The preparation method according to claim 28, wherein, In step (3), the roasting conditions include a temperature of 350-550℃ and a time of 0.5-3.5h.

30. The use of a catalytic cracking catalyst composition according to any one of claims 1-8 in the production of paraffinic catalytic feedstock oil.

31. The application according to claim 30, wherein, The characteristic factor K value of the paraffin-based catalytic feedstock is not less than 12.1; And / or, application conditions include: reaction temperature of 450-550℃, and agent-to-oil weight ratio of 3-10:1.

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