Hydrocracking catalyst and method for its preparation

Abstract

The present application relates to the field of hydrocracking catalyst preparation, in particular to a kind of hydrocracking catalyst and preparation method thereof.The method comprises the following steps: 1) first mixing nickel nitrate with acidic aqueous solution to obtain mixed solution;2) the mixed solution obtained in step 1) is mixed with base material, molecular sieve, additive and second active ingredient or its precursor to obtain mixed material;3) the mixed material obtained in step 3) is sequentially formed, dried and calcined;Wherein, relative to 1kg of nickel nitrate, the amount of the acidic aqueous solution is 1-8kg.Using the method provided in the present application to prepare hydrocracking catalyst can realize the continuousness of preparation process, and the metal component uniformity between the prepared catalyst particles is higher, which is beneficial to the uniformity of intrinsic activity of catalyst.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hydrocracking catalyst preparation, in particular to a hydrocracking catalyst and a preparation method thereof. BACKGROUND

[0002] At present, the method for preparing the hydrocracking catalyst by the co-extrusion method generally comprises the following steps: firstly, mixing a certain proportion of molybdenum trioxide (solid), nickel nitrate (solid), alumina, molecular sieve and additives by manual feeding; secondly, adding a dilute nitric acid solution with a certain concentration to continue kneading and rolling; thirdly, supplementing clean water during the rolling process according to the situation; fourthly, forming a small block of material suitable for extrusion after sufficient and appropriate rolling; fifthly, extruding the material in the extruder to form a material with a required size and shape by installing a suitable module; and finally, drying and calcining the material at a suitable temperature to obtain the hydrocracking catalyst. Due to the scale effect, the uniformity of the catalyst material is poor during the production process, and the quality of the catalyst product is prone to fluctuation. The whole production process is intermittent production, which results in high labor intensity and low production efficiency. In addition, since the current feeding method of nickel nitrate is manual feeding, the metal distribution between the catalyst particles is uneven, and a small amount of nickel-containing solid is also scattered, which pollutes the surrounding environment. The collection and cleaning will produce hazardous waste and are extremely harmful to the occupational health of the operators.

[0003] CN102451708A discloses a preparation method of a hydrocracking catalyst. The method adopts a co-precipitation method to generate a mixture of NixWyOz composite oxides and alumina precursors, and then mixes, filters, shapes, dries and calcines the mixture with MoO3 to obtain the final catalyst. The method for generating the mixture of NixWyOz composite oxides and Al2O3 by the co-precipitation method comprises the following steps: preparing a mixed acid solution A containing Ni, W and aluminum salts, preparing an alkaline solution B containing aluminum, and forming a gel by parallel flow of the B solution and the A solution. In the method, there are two parts of aluminum sources, one of which is the acid mixed solution A, and the other of which is the alkaline solution B containing aluminum. In this way, the crystal grain growth can be effectively controlled during the formation of the precipitate, the reduction of the specific surface area and the deterioration of the adhesion of the catalyst can be inhibited, and thus the pore structure and the mechanical strength of the catalyst product are improved. The method is mainly used for preparing a bulk catalyst with a high metal content. The catalyst has higher activity for the deep impurity removal process of hydrocarbons, and can process heavier raw materials.

[0004] CN109622028A discloses a high stability catalytic cracking diesel hydrocracking catalyst, which is composed of a cracking component and a hydrogenation component. The cracking component is a modified molecular sieve, SAPO molecular sieve / amorphous silicon aluminum composite material, and the hydrogenation component is a VIB group and VIII group metal oxide. The hydrocracking catalyst introduces elemental phosphorus in the molding preparation process, and the hydrogenation component is loaded onto the above-mentioned by vacuum impregnation method after hydrothermal treatment. The hydrocracking catalyst effectively reduces the number of strong acid centers and increases the number of medium-strong acid centers, reduces the distance between the hydrogenation active centers and the acid centers of the catalyst, and improves the stability of the catalyst on the basis of ensuring the activity of the catalyst.

[0005] CN109759124A provides a nitrogen-resistant hydrocracking catalyst and a preparation method thereof. The hydrocracking catalyst is composed of a silicon-aluminum molecular sieve / amorphous silicon-aluminum composite material, a large-pore alumina, and SB powder. The silicon-aluminum molecular sieve / amorphous silicon-aluminum composite material is a composite material synthesized by taking a silicon-aluminum molecular sieve as a core and wrapping the modified molecular sieve with amorphous silicon-aluminum. The composite material presents a gradient distribution of acid strength and pore structure. The VIB group and VIII group metal oxides are loaded thereon to prepare a hydrocracking catalyst suitable for high-nitrogen distillate hydrocracking reaction.

[0006] CN108714433A discloses a hydrocracking catalyst, a preparation method thereof, and an application thereof. The hydrocracking catalyst includes an active component and an additive, wherein the active component includes Y molecular sieve, beta molecular sieve, large-pore alumina, and modified clay. The Y molecular sieve accounts for 2-30% by weight, the beta molecular sieve accounts for 2-30% by weight, the large-pore alumina accounts for 50-70% by weight, and the modified clay accounts for 1-12% by weight. The hydrocracking catalyst has high selectivity, high activity, and high stability, and has the advantages of high light oil yield, high diesel yield, and good diesel properties when applied to high-temperature coal tar hydrogenation to prepare diesel components.

[0007] However, the above-mentioned inventions mainly improve the catalyst formula, and do not involve the preparation process.

[0008] In view of the deficiencies of the prior art, how to improve the preparation process of the hydrocracking catalyst according to the characteristics of the production process, so as to improve the uniformity of the active metal components in the prepared catalyst and ensure the catalytic performance of the catalyst, is an important topic in the field. SUMMARY

[0009] The purpose of the present application is to overcome the problems of uneven content of active metal components in the catalyst, inability to continuous production and the like in the prior art, and to provide a brand new preparation method of hydrocracking catalyst by co-extrusion. The method changes the feeding mode of the solid nickel salt in the original process from manual intermittent feeding to feeding as a uniform solution, which can realize the continuous process of preparation, and the prepared catalyst particles not only have high uniformity of metal components, which is beneficial to the uniformity of intrinsic activity of the catalyst, but also have simple preparation method, low production cost, no generation of hazardous waste, and no harm to the health of the operators.

[0010] In order to achieve the above-mentioned purpose, one aspect of the present application provides a preparation method of hydrocracking catalyst, characterized in that the method comprises the following steps:

[0011] 1) mixing nickel nitrate with an acidic aqueous solution to obtain a mixed solution;

[0012] 2) secondly mixing the mixed solution obtained in step 1) with a base material, a molecular sieve, an additive and a second active component or a precursor thereof to obtain a mixture;

[0013] 3) sequentially performing shaping, drying and calcination on the mixture obtained in step 3),

[0014] wherein the amount of the acidic aqueous solution is 1-8 kg relative to 1 kg of nickel nitrate.

[0015] Preferably, the amount of the acidic aqueous solution is 2-6 kg relative to 1 kg of nickel nitrate.

[0016] More preferably, the amount of the acidic aqueous solution is 3.5-5 kg relative to 1 kg of nickel nitrate.

[0017] Preferably, the second active component is one or more of oxides of tungsten, oxides of molybdenum, oxides of cobalt and oxides of phosphorus.

[0018] Preferably, the second active component precursor is a salt containing one or more elements selected from tungsten, molybdenum, cobalt and phosphorus.

[0019] More preferably, the second active component is molybdenum trioxide.

[0020] Preferably, in step 1), the acidic aqueous solution is selected from one or more of aqueous nitric acid, aqueous acetic acid and aqueous oxalic acid.

[0021] More preferably, the acidic aqueous solution is aqueous nitric acid.

[0022] Preferably, the concentration of the acidic aqueous solution is 1-5 wt%.

[0023] More preferably, the concentration of the acidic aqueous solution is 2-4% by weight.

[0024] Preferably, the base is selected from one or more of alumina, silica-containing alumina and pseudoboehmite.

[0025] More preferably, the base is alumina.

[0026] Preferably, the molecular sieve is selected from one or more of Y-type molecular sieve, beta-type molecular sieve and A-type molecular sieve, more preferably Y-type molecular sieve.

[0027] Preferably, the Y-type molecular sieve is selected from one or more of sodium Y-type molecular sieve, hydrogen Y-type molecular sieve, ammonia Y-type molecular sieve and rare earth Y-type molecular sieve.

[0028] More preferably, the molecular sieve is hydrogen Y-type molecular sieve.

[0029] Preferably, the adjuvant is selected from one or more of sesbania powder, methyl cellulose, citric acid and carbon black.

[0030] More preferably, the adjuvant is sesbania powder.

[0031] Preferably, in step 2), the mixture of the base, the molecular sieve, the adjuvant and the second active ingredient or its precursor is contacted with the mixed solution of step 1) to obtain the mixture.

[0032] Preferably, in step 2), the weight ratio of the base, the molecular sieve, the adjuvant and the second active ingredient is (40-70):(10-40):(1-5):(10-20); more preferably, the weight ratio of the base, the molecular sieve, the adjuvant and the second active ingredient is (52-55):(23-27):(2-4):(15-19).

[0033] Preferably, in step 2), the weight ratio of the base, the molecular sieve, the adjuvant and the second active ingredient precursor calculated as active ingredient oxide is (40-70):(10-40):(1-5):(10-20); more preferably, the weight ratio of the base, the molecular sieve, the adjuvant and the second active ingredient precursor calculated as active ingredient oxide is (52-55):(23-27):(2-4):(15-19).

[0034] Preferably, the amount of the mixed solution of step 1) is 0.5-2 kg relative to 1 kg of the mixture of the base, the molecular sieve, the adjuvant and the second active ingredient or its precursor of step 2).

[0035] More preferably, the amount of the mixed solution of step 1) is 0.6-1.2 kg relative to 1 kg of the mixture of the base, the molecular sieve, the adjuvant and the second active ingredient or its precursor of step 2).

[0036] Further preferably, the amount of the mixed solution of step 1) is 0.6-0.8 kg relative to 1 kg of the mixture of the base, the molecular sieve, the adjuvant and the second active ingredient or its precursor of step 2).

[0037] Preferably, the drying condition comprises a drying temperature of 80-150 ℃ and a drying time of 1-10 h.

[0038] More preferably, the drying condition comprises a drying temperature of 90-130 ℃ and a drying time of 2-4 h.

[0039] Preferably, the calcination condition comprises a calcination temperature of 500-1000 ℃ and a calcination time of 1-8 h.

[0040] More preferably, the calcination condition comprises a calcination temperature of 450-550 ℃ and a calcination time of 2-4 h.

[0041] The second aspect of the present application provides a hydrocracking catalyst prepared by the preparation method of the first aspect of the present application.

[0042] By the above technical solution, the nickel nitrate is mixed with the acidic aqueous solution, and then the obtained mixed solution is mixed with other solid components, so that the dispersion uniformity of the nickel nitrate in the final product catalyst can be ensured, thereby improving the quality and catalytic performance of the catalyst.

[0043] Secondly, by separately feeding the nickel nitrate and other solid materials, the other solid materials can be continuously dosed and mixed, so that the preparation process is continuous, and the production efficiency is improved and the production cost is reduced.

[0044] In addition, in addition to the activity component of the prepared catalytic cracking catalyst being more uniformly distributed, compared with the catalyst prepared by the traditional batch production method, the specific surface area, pore volume, bulk density, pressure strength, length distribution, particle size and other properties of the catalytic cracking catalyst prepared by the method of the present application completely meet the quality requirements. DETAILED DESCRIPTION

[0045] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the purposes of the application. The endpoints of the ranges and any values are provided as approximations only and are understood to be open-ended. Thus, the endpoints can be combined with one another to form ranges that are not expressly delineated herein. The ranges and individual points within the ranges can be combined with one another to form new ranges.

[0046] The first aspect of the present application provides a method for preparing a hydrocracking catalyst, wherein the method comprises the following steps:

[0047] 1) mixing nickel nitrate with an acidic aqueous solution to obtain a mixed solution;

[0048] 2) mixing the mixed solution obtained in step 1) with a base material, a molecular sieve, an additive and a second active component or a precursor thereof to obtain a mixed material;

[0049] 3) sequentially performing shaping, drying and calcination on the mixed material obtained in step 3),

[0050] wherein the amount of the acidic aqueous solution is 1-8 kg relative to 1 kg of nickel nitrate.

[0051] Nickel nitrate has strong hygroscopicity and is extremely deliquescent in air, so when it is used as a raw material for preparing a hydrocracking catalyst, it cannot be weighed and fed by a continuous metering device like other solid raw materials, and it is also difficult to mix uniformly in the mixing process. Therefore, not only does this make the hydrocracking catalyst only capable of being produced in a batch mode, but it also leads to uneven dispersion of the active metal components in the prepared hydrocracking catalyst, which affects the product quality.

[0052] To this end, the inventors of the present application have found through a large amount of practice and research that nickel nitrate can be mixed with an acidic aqueous solution and then mixed with other solid raw materials other than nickel nitrate. This not only allows other solid raw materials to be weighed and fed automatically by an automatic metering device, greatly reducing manual operations, but also ensures that nickel nitrate is uniformly dispersed in the mixed solution, thereby achieving uniform distribution of nickel nitrate in subsequent processes and ensuring the performance uniformity of the prepared hydrocracking catalyst. Thus, the present application is completed.

[0053] According to the present application, the type of the acidic aqueous solution is not particularly limited and can be any of the various acidic aqueous solutions commonly used in the art for preparing a hydrocracking catalyst. For example, the acidic aqueous solution can be one or more of an aqueous nitric acid solution, an aqueous acetic acid solution and an aqueous oxalic acid solution; preferably, the acidic aqueous solution is an aqueous nitric acid solution.

[0054] In the present application, the concentration of the acidic aqueous solution is not particularly limited, for example, the concentration of the acidic aqueous solution can be 1-5 wt%, preferably 2-4 wt%.

[0055] In addition, the source of the nickel nitrate is not particularly limited, for example, nickel nitrate or a hydrate of nickel nitrate can be selected. In the present application, it is preferred to use a hydrate of nickel nitrate, and more preferably, a nickel nitrate hexahydrate. When a hydrate of nickel nitrate is used, the actual amount used is calculated based on the amount of nickel nitrate.

[0056] According to the present application, when the nickel nitrate is first mixed with the acidic aqueous solution, the amount of the acidic aqueous solution used is 2-6 kg for 1 kg of nickel nitrate; preferably, the amount of the acidic aqueous solution used is 3.5-5 kg for 1 kg of nickel nitrate. By controlling the content of the nickel nitrate and the acidic aqueous solution within the above range, the uniform distribution of the nickel nitrate can be further achieved, and the performance uniformity of the prepared hydrocracking catalyst can be ensured.

[0057] According to the present application, the mixture obtained in step 1) is second mixed with other solid raw materials other than nickel nitrate, which are various conventional solid raw materials used in the preparation of hydrocracking catalysts in the art, such as a base material, a molecular sieve, an additive, and other active ingredients or precursors thereof capable of improving the activity of the hydrocracking catalyst, etc., other than nickel nitrate.

[0058] The base material can be various base materials commonly used in the art, for example, the base material can be selected from one or more of alumina, silica-containing alumina, and pseudo-boehmite; preferably, the base material is alumina.

[0059] The molecular sieve can be selected from various molecular sieves commonly used in the art that can further improve the catalytic performance of the hydrocracking catalyst, for example, can be selected from one or more of Y-type molecular sieve, β-type molecular sieve, and A-type molecular sieve, preferably Y-type molecular sieve.

[0060] As the Y-type molecular sieve, it can be one or more of sodium Y-type molecular sieve, hydrogen Y-type molecular sieve, ammonia Y-type molecular sieve, and rare earth Y-type molecular sieve, and more preferably, hydrogen Y-type molecular sieve.

[0061] In the present application, the solid raw material can also contain various additives, for example, can contain various additives commonly used in the art such as extrusion aids, binders, etc.

[0062] Preferably, the additive contains an extrusion aid, which can be selected from one or more of sesbania gum, methyl cellulose, citric acid, and carbon black; preferably, the extrusion aid is sesbania gum.

[0063] In addition, according to the present application, a second active ingredient or a precursor thereof can be added to the hydrocracking catalyst during preparation in addition to the nickel nitrate.

[0064] The second active ingredient or the precursor thereof can be various active ingredients or precursors thereof used in the art to improve the performance of a hydrocracking catalyst. As the second active ingredient, for example, one or more selected from the group consisting of an oxide of tungsten, an oxide of molybdenum, an oxide of cobalt, and an oxide of phosphorus can be used; as the second active ingredient precursor, for example, a salt containing one or more elements selected from the group consisting of tungsten, molybdenum, cobalt, and phosphorus can be used.

[0065] In the present application, preferably, the second active ingredient is molybdenum trioxide. When molybdenum trioxide is selected as the second active ingredient, it can greatly improve the catalytic performance of the prepared catalytic oxidation catalyst in cooperation with the nickel oxide converted from the nickel nitrate by calcination.

[0066] According to the present application, the weight ratio of the base, the molecular sieve, the promoter, and the second active ingredient can be (40-70):(10-40):(1-5):(10-20); preferably, the weight ratio of the base, the molecular sieve, the promoter, and the second active ingredient is (50-60):(20-30):(2-5):(12-19), and more preferably, the weight ratio of the base, the molecular sieve, the promoter, and the second active ingredient is (52-55):(23-27):(2-4):(15-19). Thereby, the catalytic performance of the prepared catalytic oxidation catalyst can be improved.

[0067] According to the present application, the weight ratio of the base, the molecular sieve, the promoter, and the second active ingredient precursor in terms of active ingredient oxide can be (40-70):(10-40):(1-5):(10-20); preferably, the weight ratio of the base, the molecular sieve, the promoter, and the second active ingredient precursor in terms of active ingredient oxide is (50-60):(20-30):(2-5):(12-19), and more preferably, the weight ratio of the base, the molecular sieve, the promoter, and the second active ingredient precursor in terms of active ingredient oxide is (52-55):(23-27):(2-4):(15-19). Thereby, the catalytic performance of the prepared catalytic oxidation catalyst can be improved.

[0068] In the present application, when the mixture of the nickel nitrate obtained in step 1) and the acid aqueous solution is mixed with the base, the molecular sieve, the additive and the second active ingredient or its precursor, the base, the molecular sieve, the additive and the second active ingredient or its precursor can be added into the mixture in any order; two or more of the base, the molecular sieve, the additive and the second active ingredient or its precursor can be mixed and then added into the mixture, and the rest of the materials can be added into the mixture; or the base, the molecular sieve, the additive and the second active ingredient or its precursor can be mixed thoroughly, and then the obtained solid mixture is mixed with the mixture.

[0069] In the present application, preferably, the mixture obtained by mixing the base, the molecular sieve, the additive and the second active ingredient or its precursor is contacted with the mixture, so as to obtain the mixture. In this way, the base, the molecular sieve, the additive and the second active ingredient or its precursor can be mixed by automatic and continuous metering of the equipment, so as to greatly reduce manual operation, simplify the preparation process and reduce production cost.

[0070] In the present application, when the second mixing is performed, the amount of the mixture of step 1) used is 0.5-2 kg relative to 1 kg of the mixture of the base, the molecular sieve, the additive and the second active ingredient or its precursor of step 2); preferably, the amount of the mixture of step 1) used is 0.6-1.2 kg relative to 1 kg of the mixture of the base, the molecular sieve, the additive and the second active ingredient or its precursor of step 2); preferably, the amount of the mixture of step 1) used is 0.6-0.8 kg relative to 1 kg of the mixture of the base, the molecular sieve, the additive and the second active ingredient or its precursor of step 2). In this way, the strength of the prepared hydrocracking catalyst can be ensured, and the catalytic performance and service life are improved.

[0071] According to the present application, the mixture obtained by performing the second mixing is sequentially subjected to shaping, drying and calcination.

[0072] In the present application, the shaping method is not particularly limited, and various conventional shaping methods in the art can be used. For example, the shaping can be achieved by extrusion molding, which is a conventional method in the art, and will not be described here.

[0073] In the present application, the drying can be performed by using various conventional methods for drying hydrocracking catalysts in the art, for example, the drying conditions can include a drying temperature of 80-150 ℃ and a drying time of 1-10 h; preferably, the drying conditions include a drying temperature of 90-130 ℃ and a drying time of 2-4 h. By performing the drying under the above conditions, the drying effect can be achieved while the strength of the prepared catalyst is ensured.

[0074] In the present application, the calcination can also be performed by various conventional methods for calcining hydrocracking catalysts in the art. For example, the calcination conditions can include a calcination temperature of 500-1000℃ and a calcination time of 1-8h; preferably, the calcination conditions include a calcination temperature of 450-550℃ and a calcination time of 2-4h. By performing the calcination under the above conditions, the conversion rate of the active substance can be ensured, thereby improving the catalytic performance of the prepared hydrocracking catalyst.

[0075] The present application provides a hydrocracking catalyst prepared by the preparation method of the first aspect of the present application.

[0076] According to the second aspect of the present application, the uniformity of the distribution of the active metal components in the prepared catalyst is high, and the performance of the catalyst is more uniform, thereby ensuring the stable and smooth progress of the catalytic reaction process.

[0077] According to a particularly preferred embodiment of the present application, nickel nitrate is first mixed with 2-4wt% nitric acid aqueous solution at a weight ratio of 1:2.5-3 to obtain a mixed solution; base alumina, hydrogen Y-type molecular sieve, auxiliary component Eudragit and second active component molybdenum trioxide are second mixed at a weight ratio of (52-55):(23-27):(2-4):(15-19) to obtain a mixture; then the mixed solution obtained by the first mixing and the mixture obtained by the second mixing are mixed at a weight ratio of 0.6-0.8:1 to obtain a mixed material; finally, the mixed material is extruded, dried and calcined to obtain a hydrocracking catalyst.

[0078] The present application will be described in detail by way of examples below.

[0079] In the following examples, the pore volume parameters are measured by the method described in Q / SH 361 913;

[0080] The specific surface area is measured by the method described in GB / T 5816;

[0081] The bulk density is measured by the method described in Q / SH 361 928;

[0082] The lateral pressure strength is measured by the method described in Q / SH 361 926;

[0083] The MoO3 and NiO contents are measured by the method described in Q / SH 361 925.

[0084] The raw material nickel nitrate hexahydrate is purchased from Liaoning Jinyi Company, and the remaining raw materials are all conventional commercially available products unless otherwise specified.

[0085] Example 1

[0086] 1) 16.34 kg of nickel nitrate hexahydrate is mixed with 44.64 kg of nitric acid aqueous solution with a concentration of 2.5% by weight, to obtain a mixed solution, wherein the weight ratio of the nickel nitrate hexahydrate to the nitric acid aqueous solution is 1:4.35, calculated based on the nickel nitrate;

[0087] 2) After the alumina powder, the molybdenum trioxide powder, the hydrogen Y type molecular sieve and the sesbania powder are continuously metered by the loss-on- drying balance according to a weight ratio of 53:16.5:25:3, the plow kneader is used for mixing, to obtain 91.94 kg of a mixture;

[0088] 3) The mixed solution obtained in step 1) and the mixture obtained in step 2) are sent into the plow kneader for sufficient kneading, and after the kneading is uniform, the mixture is rolled, wherein the weight ratio of the mixed solution obtained in step 1) to the mixture obtained in step 2) is 0.66:1;

[0089] 4) The rolled material is sent into a molding device for extrusion molding, and the obtained molded material is in a cylindrical shape with a length of 3-8 mm;

[0090] 5) The product obtained in step 4) is dried at 110°C for 2 h, and then calcined at 550°C for 2 h, to obtain the hydrocracking catalyst S1.

[0091] Example 2

[0092] 1) 16.34 kg of nickel nitrate hexahydrate is mixed with 40.85 kg of nitric acid aqueous solution with a concentration of 4% by weight, to obtain a mixed solution, wherein the weight ratio of the nickel nitrate hexahydrate to the nitric acid aqueous solution is 1:3.98, calculated based on the nickel nitrate;

[0093] 2) After the alumina powder, the molybdenum trioxide powder, the hydrogen Y type molecular sieve and the sesbania powder are continuously metered by the loss-on- drying balance according to a weight ratio of 52:15:23:2, the plow kneader is used for mixing, to obtain 91.62 kg of a mixture;

[0094] 3) The mixed solution obtained in step 1) and the mixture obtained in step 2) are sent into the plow kneader for sufficient kneading, and after the kneading is uniform, the mixture is rolled, wherein the weight ratio of the mixed solution obtained in step 1) to the mixture obtained in step 2) is 0.62:1;

[0095] 4) The rolled material is sent into a molding device for extrusion molding, and the obtained molded material is in a cylindrical shape with a length of 3-8 mm;

[0096] 5) The product obtained in step 4) is dried at 110°C for 2 h, and then calcined at 550°C for 2 h, to obtain the hydrocracking catalyst S2.

[0097] Example 3

[0098] 1) 16.34 kg of nickel nitrate hexahydrate was mixed with 49.02 kg of a 2 wt% nitric acid aqueous solution to obtain a mixed solution, wherein the weight ratio of the nickel nitrate hexahydrate to the nitric acid aqueous solution was 1:4.8, calculated based on the nickel nitrate;

[0099] 2) 92.23 kg of a mixture was obtained by continuously metering the alumina powder, the molybdenum trioxide powder, the hydrogen Y-type molecular sieve and the sesbania powder in a weight ratio of 55:19:27:4 using a loss-on-ignition balance, and then mixing using a plowshare kneader;

[0100] 3) The mixed solution obtained in step 1) and the mixture obtained in step 2) were thoroughly kneaded in a plowshare kneader, and then were rolled after being uniformly kneaded, wherein the weight ratio of the mixed solution obtained in step 1) to the mixture obtained in step 2) was 0.71:1;

[0101] 4) The rolled material was sent into a molding device to be extrusion-molded, and the obtained molded material was in a cylindrical shape and had a length of 3-8 mm;

[0102] 5) The product obtained in step 4) was dried at 110°C for 2 h, and then was calcined at 550°C for 2 h to obtain the hydrocracking catalyst S3.

[0103] Comparative Example 1

[0104] 1) 91.94 kg of a mixture was obtained by continuously metering the alumina powder, the molybdenum trioxide powder, the hydrogen Y-type molecular sieve and the sesbania powder in a weight ratio of 53:16.5:25:3 using a loss-on-ignition balance;

[0105] 2) 16.34 kg of nickel nitrate hexahydrate was manually weighed, and was put into a plowshare kneader and mixed with the mixture obtained in step 1);

[0106] 3) The mixture obtained in step 2) was thoroughly kneaded with 44.64 kg of a 2.5 wt% nitric acid aqueous solution in a plowshare kneader, and then was rolled after being uniformly kneaded;

[0107] 4) The rolled material of step 3) was sent into a molding device to be extrusion-molded, and the obtained molded material was in a cylindrical shape and had a length of 3-8 mm;

[0108] 5) The product obtained in step 4) was dried at 110°C for 2 h, and then was calcined at 550°C for 2 h to obtain the hydrocracking catalyst D1.

[0109] The pore volume, the specific surface area, the bulk density and the side pressure strength of the hydrocracking catalysts S1-S3 and D1 prepared in the above examples and comparative example were tested, respectively, and the results are shown in Table 1.

[0110] Table 1

[0111]

[0112] As can be seen from the results in Table 1, the pore volume, specific surface area, bulk density and side pressure strength of the hydrocracking catalyst prepared by the method of the present application are at the same level as those of the hydrocracking catalyst prepared by the traditional batch method (comparative example 1), and can meet the requirements of quality control indexes.

[0113] Test example 1

[0114] Five samples were randomly sampled from the hydrocracking catalysts S1 and D1 prepared in example 1 and comparative example 1, each with a weight of 100 g, the contents of MoO3 and NiO in each sample were determined, and the average value and standard deviation (mean ± SD) of the contents of MoO3 and NiO in S1 and D1 were calculated, respectively, and the results are shown in Table 2.

[0115] Table 2

[0116] Item MoO3 content (wt. %) NiO content (wt. %) S1 16.46±0.2 5.45±0.1 D1 16.55±0.2 5.58±0.7 Mass index 1 0.1 1.0 2 0.2 1.0 15-19 4.8-6.4

[0117] As can be seen from the results in Table 2, the distribution of the active metal component NiO in the hydrocracking catalyst prepared by the method provided by the present application is significantly more uniform compared with the hydrocracking catalyst prepared by the traditional batch method.

[0118] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application, and all fall within the protection scope of the present application.

Claims

1. A method for preparing a hydrocracking catalyst, characterized in that, The method includes the following steps: 1) Nickel nitrate is first mixed with an acidic aqueous solution to obtain a mixed solution; 2) The mixture obtained by second mixing of the base material, molecular sieve, additives, and second active ingredient or its precursor is contacted with the mixture in step 1) to obtain a mixture material; 3) The mixture obtained in step 2) is sequentially shaped, dried, and calcined; In this embodiment, the amount of the acidic aqueous solution used is 2-6 kg relative to 1 kg of nickel nitrate, the acidic aqueous solution is a nitric acid aqueous solution, and the concentration of the acidic aqueous solution is 2-4% by weight. The second active ingredient is one or more of tungsten oxide, molybdenum oxide, cobalt oxide, and phosphorus oxide. In step 2), the weight ratio of the base material, the molecular sieve, the auxiliary agent, and the second active ingredient or the second active ingredient precursor calculated as active ingredient oxide is (52-55):(23-27):(2-4):(15-19). The amount of the mixture in step 1) is 0.5-2 kg relative to the 1 kg mixture of the base material, molecular sieve, additives, and second active ingredient or its precursor in step 2).

2. The preparation method according to claim 1, wherein, The second active ingredient precursor is a salt containing one or more elements selected from tungsten, molybdenum, cobalt, and phosphorus.

3. The preparation method according to claim 1, wherein, The second active ingredient is molybdenum trioxide.

4. The preparation method according to claim 1, wherein, The amount of the acidic aqueous solution used is 3.5-5 kg ​​relative to 1 kg of nickel nitrate.

5. The preparation method according to any one of claims 1-3, wherein, The base material is selected from one or more of alumina, silica-containing alumina, and pseudoboehmite; The molecular sieve is selected from one or more of Y-type molecular sieves, β-type molecular sieves, and A-type molecular sieves. The additives are selected from one or more of guar gum powder, methylcellulose, citric acid, and carbon black.

6. The preparation method according to claim 5, wherein, The base material is aluminum oxide; The molecular sieve is a hydrogen Y-type molecular sieve; The adjuvant is guar gum powder.

7. The preparation method according to any one of claims 1-3, wherein, The amount of the mixture in step 1) is 0.6-1.2 kg relative to 1 kg of the mixture of base material, molecular sieve, additives and second active ingredient or its precursor in step 2).

8. The preparation method according to claim 7, wherein, The amount of the mixture in step 1) is 0.6-0.8 kg relative to the 1 kg mixture of the base material, molecular sieve, additives, and second active ingredient or its precursor in step 2).

9. The preparation method according to any one of claims 1-3, wherein, The drying conditions include: a drying temperature of 80-150℃ and a drying time of 1-10 hours; The calcination conditions include: a calcination temperature of 500-1000℃ and a calcination time of 1-8 hours.

10. The hydrocracking catalyst prepared by the preparation method according to any one of claims 1-9.

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