Heavy oil hydrogenation catalyst and preparation method thereof

Abstract

The invention discloses a heavy oil hydrogenation catalyst and a preparation method thereof, and the preparation method of the heavy oil hydrogenation catalyst comprises the following steps: (1) carrying out deoiling treatment on a waste heavy oil hydrogenation catalyst to obtain a material A; (2) uniformly mixing an organic auxiliary agent, a silicon source and water, and heating to obtain a material B; (3) mixing the material A and the material B to obtain a material C; (4) adding an active metal precursor and an organic high-molecular polymer into an aqueous solution of a weakly alkaline compound, and treating to obtain a material D; and (5) putting the material C into a ball rolling machine, introducing the material D, pseudo-boehmite and a heated organic high-molecular polymer aqueous solution while rolling, and drying and roasting a material E obtained after treatment to obtain the catalyst. The invention also provides the heavy oil hydrogenation catalyst prepared by the preparation method. The problem of pollution caused by the waste hydrogenation catalyst is solved, and meanwhile, a high-added-value utilization means is provided for the waste hydrogenation catalyst.

Description

Technical Field

[0001] This invention belongs to the field of petroleum processing technology, and relates to a catalytic material and its preparation method, particularly to a heavy oil hydrogenation catalyst and its preparation method. Background Technology

[0002] Currently, a large amount of non-regenerable spent catalysts are generated globally each year, with various types of hydrotreating catalysts accounting for a significant proportion. The hydrotreating of low-quality crude oil primarily employs fixed-bed residue hydrotreating and fluidized-bed residue hydrotreating technologies. Fixed-bed residue hydrotreating catalysts have a basic lifespan of approximately 8000 hours, and each residue hydrotreating unit generates several hundred tons of spent catalyst annually. China currently has dozens of residue hydrotreating units, generating tens of thousands of tons of spent catalyst annually. Although the number of fluidized-bed residue hydrotreating units in China is relatively small, the daily discharge of catalyst results in the annual discharge of thousands of tons of spent catalyst. The content of active metals molybdenum and nickel in residue hydrotreating catalysts is relatively low compared to other catalysts, therefore, even when sold to catalyst recycling companies, refineries still incur substantial costs. How to effectively utilize spent catalysts has become a widespread concern for refineries, catalyst manufacturers, and research institutions.

[0003] The use of spent catalysts as raw materials to prepare new catalysts has garnered widespread attention. USP6030915 discloses a process for preparing a macroporous hydrotreating catalyst. This process involves removing some carbon and sulfur from the spent hydrotreating catalyst through heat treatment, grinding the heat-treated catalyst, mixing the ground catalyst with at least one additive, and molding the mixture to form a new hydrotreating catalyst. Alumina is used as a binder in the catalyst, and the additives include bauxite, diatomaceous earth, kaolin, and sepiolite. This process is particularly suitable for preparing fluidized bed catalysts. However, this patent only addresses the alteration of the catalyst's pore structure and acid properties; it does not restore the active metal to improve its hydrotreating activity.

[0004] CN108067273A discloses a method for preparing a hydrogenation catalyst, comprising the following steps: (1) microwave treatment and pulverization of a molybdenum-nickel-based waste catalyst; (2) mixing a portion of the pulverized catalyst with an alkali to obtain filtrate 1 and solid 1; reacting the other portion with an acid under a water vapor atmosphere containing hydrogen sulfide to obtain an aluminum salt solution and solid 2; preparing basic nickel carbonate; (3) reacting filtrate 1 and the aluminum salt solution in step (2) to obtain boehmite and filtrate 2; adding Na2S solution to filtrate 2 to generate MoS3 precipitate, filtering and preparing MoO3; (4) adding acid to solid 1 in step (2) and adding Na2Co3 to prepare basic nickel carbonate; (5) preparing the required support from the boehmite; and preparing the obtained molybdenum oxide and basic nickel carbonate into the required molybdenum-nickel-phosphorus solution to obtain the catalyst. Although this method effectively utilizes the active metal and alumina support of the waste catalyst, the preparation process is relatively cumbersome, and other hazardous wastes such as waste liquid will be generated during the waste catalyst treatment process. Summary of the Invention

[0005] The core objective of this invention is to provide a heavy oil hydrogenation catalyst and its preparation method, particularly a heavy oil hydrogenation catalyst prepared from waste heavy oil hydrogenation catalyst and its preparation method. The preparation method of this invention can optimize the pore structure of the outer alumina layer while enhancing the interaction forces between alumina supports, improving the wear resistance of the supports, and solving the problem of poor wear resistance of spherical supports prepared by the rolling ball method. Simultaneously, it can improve the catalyst's metal-carrying capacity and activity stability. The technical solution provided by this invention fully utilizes the portion of the support with less deposited metal and its active metal components in the waste heavy oil hydrogenation catalyst, solving the pollution problem of waste hydrogenation catalysts, and providing a high-value-added utilization method for waste hydrogenation catalysts.

[0006] The technical solution provided by this invention includes the following aspects:

[0007] I. This invention first provides a method for preparing a heavy oil hydrogenation catalyst, the preparation method comprising the following steps:

[0008] (1) The waste heavy oil hydrogenation catalyst was deoiled to obtain material A;

[0009] (2) Under mixed conditions, organic additives, silicon source and water are mixed and heated to obtain material B;

[0010] (3) Mix material A obtained in step (1) and material B obtained in step (2) to obtain material C;

[0011] (4) The active metal precursor and organic polymer are added to a nitrogen-containing weak alkaline compound aqueous solution and treated to obtain material D;

[0012] (5) Under the rolling ball-forming condition, the material C obtained in step (3) is placed in the ball rolling machine, and the material D obtained in step (4), boehmite and the organic polymer aqueous solution after heat treatment are uniformly introduced while rolling. After treatment, material E is obtained, and then the catalyst is obtained by drying and calcining.

[0013] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the waste heavy oil hydrogenation catalyst mentioned in step (1) refers to a hydrogenation catalyst that no longer meets the original reaction requirements or has not been completely deactivated due to gradation reasons. It can be a fluidized bed hydrogenation catalyst discharged from a fluidized bed hydrogenation process, or a heavy oil hydrogenation catalyst that has not been completely deactivated discharged from a fixed bed hydrogenation process. Specifically, it can be one or more of the following: hydrogenation demetallization catalyst, hydrogenation desulfurization catalyst, and hydrogenation denitrification catalyst. The active metal in the waste heavy oil hydrogenation catalyst is generally a Group VIB metal and / or a Group VIII metal, and the support is generally at least one of alumina, silica-containing alumina, or alumina containing molecular sieves. In addition to sulfides containing active metals, the waste heavy oil hydrogenation catalyst also includes carbon deposits and heavy metal impurities. The metal content on the waste heavy oil hydrogenation catalyst generally accounts for 1.0 wt% to 30.0 wt% of the catalyst weight.

[0014] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the waste heavy oil hydrogenation catalyst in step (1) is spherical in shape, and in a further preferred case, the diameter of the waste heavy oil hydrogenation catalyst is greater than 1.0 mm.

[0015] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the deoiling treatment in step (1) can be any of the existing technologies that can achieve deoiling of waste heavy oil hydrogenation catalysts. Specifically, it can be one or more of the following: gas stripping, solvent extraction, supercritical extraction, and vacuum drying. Solvent extraction is preferred. The solvent used is petroleum ether, toluene, or a mixed solution of petroleum ether and alcohol solvent. The alcohol solvent can be a C1-C4 small molecule alcohol, specifically selected from one or more of methanol, ethanol, propanol, ethylene glycol, glycerol, isopropanol, and butanol, with ethanol being preferred. The volume ratio of petroleum ether to alcohol solvent is 0.5 to 2:1. The extraction treatment can be carried out in a Soxhlet extractor, and the extraction time is generally controlled to be 30 to 50 hours. The purpose of extraction is to remove the soluble oil adsorbed on the sample. Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, step (1) of deoiling the waste heavy oil hydrogenation catalyst further includes drying and calcination steps. The drying temperature is 80-120℃, the drying time is 5-12h, the calcination temperature is 500-700℃, and the calcination time is 2-6h. The calcination is carried out in the presence of an oxygen-containing atmosphere, which can be air, oxygen, or a mixture of oxygen and an inert atmosphere, with an oxygen volume content of 20-90%. Even further, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, grinding and sieving are also included after calcination. The main purpose is to remove the portion of the waste heavy oil hydrogenation catalyst with a large amount of deposited metal on its outer layer. The grinding process removes the portion of the waste heavy oil hydrogenation catalyst with a large amount of deposited metal on its outer layer after deoiling, retaining the portion with less deposited metal inside. Grinding can be achieved using a granulator, which can be any equipment commonly used in the field. During operation, the granulator generally requires compressed air to prevent solid materials from entering the rotating disc shaft and to reduce particle adhesion. The compressed air can be any of air, high-temperature air, or steam. Specifically, in this invention, the material after degreasing, drying, and calcination rotates at high speed on the rotating disc within the granulator. Under the influence of centrifugal force, friction, gravity, and air, the portion of the waste hydrogenation catalyst with the most deposited metal is ground off. The processing time in the granulator is generally controlled to be 5–60 minutes, with the rotating disc speed at 1000–3000 rpm and the compressed air volume at 20–120 m³ / min. 3 / min, wherein the compressed air is water-containing compressed air, and the water inlet is 5-30 mL / min.

[0016] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the particle size of material A in step (1) is 0.1 to 1.2 mm, preferably 0.2 to 1.0 mm.

[0017] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the organic additive mentioned in step (2) is gelatin, which can be selected from one or more of industrial gelatin, edible gelatin and pharmaceutical gelatin; wherein industrial gelatin is one or more of hide glue, bone glue and hot melt adhesive powder.

[0018] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the heating temperature in step (2) is 40-60℃.

[0019] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the amount of organic additive added in step (2) is 2wt% to 10wt% of the mass of material A in step (1).

[0020] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the silicon source mentioned in step (2) is one or more of tetraethyl orthosilicate and silica sol.

[0021] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the amount of silicon source added in step (2) is 2wt% to 10wt% of the mass of material A in step (1), based on the mass of silicon oxide.

[0022] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the active metal mentioned in step (4) is at least one of Group VIB metals and at least one of Group VIII metals, and the active metal precursor is a salt containing the active metal. Among them, the Group VIB metal can be W and / or Mo, preferably Mo; the Group VIII metal is Ni and / or Co, preferably Ni; the molybdenum precursor can be ammonium heptamolybdate and / or ammonium tetramolybdate; and the nickel precursor can be basic nickel carbonate.

[0023] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the organic polymer mentioned in steps (4) and (5) is one or more of starch, cellulose ether, and flour, preferably starch. More specifically, the starch is one or more of mung bean starch, cassava starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether can be at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethyl cellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethyl cellulose, and phenylcellulose, preferably methylcellulose.

[0024] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the nitrogen-containing weak base compound mentioned in step (4) is ammonia water, and even further, the concentration of ammonia water is 15wt% to 25wt%.

[0025] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the amount of organic polymer added in step (4) (by mass) is 5 wt% to 30 wt% of the dry basis of boehmite, preferably 10 wt% to 25 wt%.

[0026] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the pseudoboehmite described in step (5) after calcination at 600°C has the following properties: specific surface area greater than 270 m². 2 / g, preferably 280-310m 2 / g, with a pore volume of 0.9–1.1 mL / g, preferably 0.95–1.10 mL / g. The pseudoboehmite can be freely selected from commercially available pseudoboehmite products that meet the specified requirements, or it can be prepared in-house by those skilled in the art according to the preparation methods disclosed in the prior art.

[0027] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the raw materials of the pseudoboehmite in step (5) and the alumina support in the waste heavy oil hydrogenation catalyst are the same or different, preferably the same.

[0028] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, when uniformly introducing material D, boehmite, and the heated organic polymer aqueous solution obtained in step (4) into step (5), it is preferable to first mix material D and boehmite, and then uniformly add them to the heated organic polymer aqueous solution.

[0029] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the concentration of the aqueous solution of the heat-treated organic polymer in step (5) is 0.5wt% to 5wt%, preferably 1wt% to 3wt%. The preparation method is as follows: add the organic polymer to water, heat and mix at 60 to 100°C for 10 to 40 minutes, and obtain the aqueous solution of the heat-treated organic polymer after the organic polymer has completely dissolved.

[0030] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the amount of the aqueous solution of the heated organic polymer in step (5) added is 0.3 to 1.0 times the mass ratio of the pseudoboehmite in step (5).

[0031] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the mass ratio of material C (based on the mass of material A contained therein) to the dry basis of pseudoboehmite in step (5) is 1:4 to 4:1.

[0032] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the drying temperature in step (6) is 80-120℃ and the drying time is 4-12h.

[0033] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the calcination temperature in step (6) is 400-600℃ and the calcination time is 1-5h.

[0034] Furthermore, in the above-mentioned method for preparing heavy oil hydrogenation catalyst, the catalyst particle size in step (6) is 0.3 to 2.0 mm, preferably 0.4 to 1.5 mm.

[0035] II. A second aspect of the present invention provides a heavy oil hydrogenation catalyst prepared by the above-described method.

[0036] Furthermore, as a specific embodiment, the above-mentioned heavy oil hydrogenation catalyst includes an active metal component and a support. The active metal is one or more group VIB metals and / or group VIII metals, wherein the active metal exists on the support in the form of an oxide, and the support is silica-containing alumina. Based on the weight of the catalyst and calculated as oxides, the content of the group VIB metal component is 4 wt% to 12 wt%; the content of the group VIII metal component is 1 wt% to 3 wt%.

[0037] Furthermore, as a specific implementation method, the silicon oxide content is 0.4wt% to 8wt% based on the weight of the carrier.

[0038] Furthermore, as a specific implementation method, the heavy oil hydrogenation catalyst described above has the following properties: a specific surface area of ​​160–240 m². 2 / g, with a pore volume of 0.55~0.80mL / g.

[0039] Thirdly, the present invention provides an application of the above-mentioned heavy oil hydrogenation catalyst in the heavy oil hydrogenation process.

[0040] Furthermore, in the above applications, the heavy oil is at least one of atmospheric residue and vacuum residue.

[0041] Furthermore, in the above applications, the hydrogenation process conditions are as follows: reaction pressure 15–20 MPa, temperature 350–450 °C, and liquid hourly space velocity 0.1–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–1000.

[0042] Compared with the prior art, the heavy oil hydrogenation catalyst and its preparation method of the present invention have the following advantages:

[0043] 1. In the preparation method of the heavy oil hydrogenation catalyst provided by the present invention, the waste hydrogenation catalyst is first pretreated by deoiling. Then, the outer layer of the waste hydrogenation catalyst with more deposited metal and greater activity loss is removed by grinding. The inner layer of the waste hydrogenation catalyst with relatively less metal deposition and higher activity is retained and fully utilized, and is used as the inner layer of the new catalyst support. This improves the utilization effect of the support and active metal in the waste hydrogenation catalyst, and at the same time ensures that the activity and stability of the new catalyst meet the requirements for use. This realizes the comprehensive utilization of active metal and support in waste heavy oil hydrogenation catalyst, improves resource utilization, provides a new treatment and utilization method for waste hydrogenation catalyst, and reduces the preparation cost of the new catalyst.

[0044] 2. In the preparation method of the heavy oil hydrogenation catalyst provided by this invention, the organic additive gelatin, after being heated and dissolved in water, yields material B, which has high adhesiveness. When mixed with material A, it can enhance the interaction between particles of material A. As the temperature of material B decreases, the organic additive gelatin contained therein gradually gels, changing from a sol to a gel, which can cover the surface and pores of material A, preventing the subsequently introduced active metal solution from entering the core layer of the support. This fully utilizes the active metal inherent in the spent catalyst, avoids repeated loading of active metal, and saves on the amount of active metal used. Simultaneously, the introduction of the silicon source interacts with the alumina in material A, further improving its strength and compensating for the strength loss caused during the pretreatment of the spent catalyst.

[0045] 3. In the preparation method of the heavy oil hydrotreating catalyst provided by this invention, the organic polymer after heat treatment decomposes into small molecules in water, giving the aqueous solution high adhesion and enabling strong interaction between material B and material A. This enhances the interaction force between boehmite and also strengthens the interaction force between the reused waste hydrotreating catalyst and the outer alumina layer, improving the strength and wear resistance of the alumina support. The organic polymer reacts with ammonia water and then mixes with boehmite, resulting in poor adhesion; it only serves to expand pores, increasing the number of macropores in the outer alumina layer of the catalyst. This makes it less prone to clogging by metals and other impurities, solving the problem of mismatch between hydrodemetallization activity, hydrodesulfurization activity, and the ability to accommodate metals and other impurities in existing hydrotreating catalysts. This ensures the stability of the catalyst during long-term operation of the unit, making it particularly suitable for heavy oil and residue hydrotreating.

[0046] 4. In the preparation method of the heavy oil hydrogenation catalyst provided by the present invention, an active metal precursor and an organic polymer are added to an aqueous solution of a nitrogen-containing weakly alkaline compound, and the resulting material D is obtained after treatment. This process not only modifies the organic polymer, but also prepares an ammonia solution of the active metal. At the same time, the active metal and the polymer interact during the treatment process. During the mixing process with boehmite, the polymer weakens the interaction between the active metal and boehmite, and further weakens the interaction with the alumina support during the calcination process, thereby improving the utilization rate of the active metal.

[0047] 6. The preparation method of the heavy oil hydrogenation catalyst provided by the present invention has low requirements for the physical properties (specific surface area, pore volume and pore size) and mechanical properties of the waste heavy oil hydrogenation catalyst, and is particularly suitable for recycling heavy oil hydrogenation catalysts that can no longer meet the original reaction requirements or have not been completely deactivated due to gradation reasons. Detailed Implementation

[0048] The embodiments of the present invention will be described in further detail below with reference to examples. These examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0049] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated elements or components without excluding other elements or other components.

[0050] In this document, the terms "first," "second," etc., are used to distinguish two different elements or parts, and are not used to define specific positions or relative relationships. In other words, in some embodiments, the terms "first," "second," etc., can also be used interchangeably.

[0051] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0052] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0053] In the context of this invention, all numerical values ​​of parameters (e.g., quantity or condition) should be understood to be modified by the term “about” in all cases, regardless of whether “about” actually appears before the numerical value.

[0054] In the context of this invention, "substantially" means that deviations that are acceptable or considered reasonable to those skilled in the art are permitted, such as deviations within ±5%, ±2%, ±1%, ±0.5%, or ±0.1%.

[0055] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0056] In the context of this invention, any two or more embodiments or aspects of this invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of this invention.

[0057] In this invention, the specific surface area and pore volume were measured using a cryogenic liquid nitrogen physical adsorption method, specifically using a Micron ASAP2420 cryogenic nitrogen adsorption instrument. The procedure involved: a small sample was vacuum-treated at 300°C for 3–4 hours, and finally, the product was placed under cryogenic liquid nitrogen conditions (-200°C) for nitrogen adsorption-desorption testing. The surface area was obtained using the BET equation, and the pore size distribution was obtained using the BJH model.

[0058] In the context of this invention, the wear index of microsphere carriers with a particle size less than 0.8 mm is tested using the high-speed air jet method (see ASTM D5757-00), and the wear index of microsphere carriers with a particle size greater than 0.8 mm is measured using the drum method with a KM-ZV wear meter.

[0059] In the context of this invention, the content of oil sediments was determined using the SHT0701-2001 method for determining total sediments in residual fuel oil (thermal filtration method) and an FDR-1431 instrument for determining total sediments in residual fuel oil.

[0060] In the context of this instruction manual, all chemical reagents used are available by purchasing commercially available products.

[0061] Example 1

[0062] (1) Pretreatment of waste hydrogenation catalyst

[0063] Waste spherical hydrogenation catalyst (particle size 1.2–1.5 mm, containing 3.1 wt% Mo, 5.8 wt% Ni, and 13.2 wt% V) was extracted and deoiled using a petroleum ether-ethanol mixed solvent (volume ratio 1:1) for 40 h, dried at 110 °C for 8 h, and then calcined at 600 °C for 3 h. The resulting material was then processed in a granulator for 20 min under the following conditions: rotary table speed 1500 rpm and compressed air volume 40 m³ / min. 3The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain material A with a particle size of 0.5–0.6 mm.

[0064] (2) Catalyst preparation

[0065] Material B is obtained by mixing 20g of leather glue, 100g of tetraethyl orthosilicate, and 800g of water and heating to 50℃. Material C is obtained by mixing 1000g of material A and material B. Material D is obtained by mixing 149.8g of ammonium heptamolybdate, 60.1g of basic nickel carbonate, 240g of corn starch, and 240g of 15wt% ammonia solution. 40g of corn starch is weighed and added to 2000g of water, and heated at 90℃ for 15min to obtain a heat-treated aqueous solution of organic polymer. Under rolling spherical forming conditions, material C was placed in a spherical rolling mill, and while rolling, material D, 2860g of pseudoboehmite, and 2000g of a heat-treated organic polymer aqueous solution were uniformly introduced. After treatment, material E was obtained, which was then dried at 110℃ for 8h and calcined at 480℃ for 3h to obtain a spherical catalyst with a particle size of 0.5-0.7mm, containing 6.0wt% MoO3 and 1.5wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0066] (3) Catalyst Evaluation

[0067] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 430℃, reaction pressure 15.0 MPa, oil-to-catalyst volume ratio 13:1, and reaction time 60 min. The properties of the feedstock oil are shown in Table 2, and the evaluation results and the content of sediment in the generated oil are shown in Table 3.

[0068] Example 2

[0069] (1) Pretreatment of waste hydrogenation catalyst

[0070] Waste spherical hydrogenation catalyst (particle size 1.2–1.5 mm, containing 3.1 wt% Mo, 5.8 wt% Ni, and 13.2 wt% V) was extracted and deoiled using a petroleum ether-ethanol mixed solvent (volume ratio 2:1) for 40 h, dried at 110 °C for 8 h, and then calcined at 600 °C for 3 h. The resulting material was then processed in a granulator for 25 min under the following conditions: rotary table speed 1800 rpm and compressed air volume 50 m³ / min. 3 The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain material A with a particle size of 0.4–0.5 mm.

[0071] (2) Catalyst preparation

[0072] Material B was obtained by mixing 60g of gelatin, 167g of tetraethyl orthosilicate, and 800g of water and heating to 50℃. Material C was obtained by mixing 1000g of material A and material B. Material D was obtained by mixing 74.9g of ammonium heptamolybdate, 30.1g of basic nickel carbonate, 180g of methylcellulose, and 200g of 20wt% ammonia solution. 60g of methylcellulose was weighed and added to 2000g of water, and heated at 80℃ for 20min to obtain a heat-treated organic polymer aqueous solution. Material C was placed in a ball-forming machine, and material D, 1430g of boehmite, and 1000g of the heat-treated organic polymer aqueous solution were uniformly introduced during the ball-forming process. Material E was obtained after treatment, and then dried at 110℃ for 8h and calcined at 500℃ for 3h to obtain a spherical catalyst with a particle size of 0.4–0.6mm, containing 6.0wt% MoO3 and 1.5wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0073] (3) Catalyst Evaluation

[0074] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 430℃, reaction pressure 15.0 MPa, oil-to-catalyst volume ratio 13:1, and reaction time 60 min. The properties of the feedstock oil are shown in Table 2, and the evaluation results and the content of sediment in the generated oil are shown in Table 3.

[0075] Example 3

[0076] (1) Pretreatment of waste hydrogenation catalyst

[0077] Waste spherical hydrogenation catalyst (particle size 1.2–1.4 mm, containing 5.2 wt% Mo, 6.0 wt% Ni, and 8.5 wt% V) was extracted and deoiled using a petroleum ether-ethanol mixed solvent (volume ratio 1:2) for 40 h, dried at 110 °C for 8 h, and then calcined at 600 °C for 3 h. The resulting material was then processed in a granulator for 10 min under the following conditions: rotary table speed 2000 rpm and compressed air volume 60 m³ / min. 3 The feed rate is 10 mL / min, and the resulting material A has a particle size of 0.8–0.9 mm.

[0078] (2) Catalyst preparation

[0079] Material B is obtained by mixing 100g of leather glue, 267g of tetraethyl orthosilicate, and 800g of water and heating to 50℃. Material C is obtained by mixing 1000g of material A and material B. Material D is obtained by mixing 65.6g of ammonium heptamolybdate, 21.0g of basic nickel carbonate, 125g of corn starch, and 150g of ammonia solution with a concentration of 25wt%. 80g of corn starch is weighed and added to 2000g of water, and heated at 70℃ for 30min to obtain a heat-treated organic polymer aqueous solution. Under spherical rolling conditions, material C is placed in a spherical rolling machine, and material D, 715g of boehmite, and 500g of the heat-treated organic polymer aqueous solution are uniformly introduced while rolling. Material E is obtained after treatment, and then dried at 110℃ for 8h and calcined at 530℃ for 3h to obtain a spherical catalyst with a particle size of 0.8-1.0mm, wherein the content of MoO3 is 10.0wt% and the content of NiO is 2.0wt%. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0080] (3) Catalyst Evaluation

[0081] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 430℃, reaction pressure 15.0 MPa, oil-to-catalyst volume ratio 13:1, and reaction time 60 min. The properties of the feedstock oil are shown in Table 2, and the evaluation results and the content of sediment in the generated oil are shown in Table 3.

[0082] Example 4

[0083] The process was essentially the same as in Example 3, except that 100g of hide glue was replaced with 75g of bone glue, 125g of corn starch was replaced with 100g of flour, and 80g of corn starch was replaced with 60g of flour, resulting in a spherical catalyst with a particle size of 0.8–1.0 mm, containing 10.0 wt% MoO3 and 2.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0084] The catalyst evaluation was the same as in Example 3. The properties of the feedstock oil used are shown in Table 2, and the evaluation results and the content of the generated oil sediments are shown in Table 3.

[0085] Example 5

[0086] The catalyst from Example 3 underwent long-term activity evaluation using a CSTR hydrogenation evaluation system for 1500 hours. The evaluation conditions were: reaction temperature 430°C, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 2, and the evaluation results and the content of sediment in the generated oil are shown in Table 4.

[0087] Comparative Example 1

[0088] (1) Pretreatment of waste hydrogenation catalyst

[0089] Waste spherical hydrogenation catalyst (particle size 1.2–1.4 mm, containing 5.2 wt% Mo, 6.0 wt% Ni, and 8.5 wt% V) was extracted and deoiled using a petroleum ether-ethanol mixed solvent (volume ratio 1:2) for 40 h, dried at 110 °C for 8 h, and then calcined at 600 °C for 3 h. The resulting material was then processed in a granulator for 10 min under the following conditions: rotary table speed 2000 rpm and compressed air volume 60 m³ / min. 3 The feed rate is 10 mL / min, and the resulting material A has a particle size of 0.8–0.9 mm.

[0090] (2) Catalyst preparation

[0091] 65.6 g of ammonium heptamolybdate, 21.0 g of basic nickel carbonate, 125 g of corn starch, and 150 g of 25 wt% ammonia solution were mixed to obtain material D. 80 g of corn starch was weighed and added to 2000 g of water, and heated at 70 °C for 30 min to obtain a heat-treated organic polymer aqueous solution. Under spherical rolling conditions, 1000 g of material A was placed in a spherical rolling machine, and material D, 715 g of boehmite, and 500 g of the heat-treated organic polymer aqueous solution were uniformly introduced while rolling. After treatment, material E was obtained, which was then dried at 110 °C for 8 h and calcined at 530 °C for 3 h to obtain a spherical catalyst with a particle size of 0.8–1.0 mm, containing 10.0 wt% MoO3 and 2.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0092] (3) Catalyst Evaluation

[0093] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 430℃, reaction pressure 15.0 MPa, oil-to-catalyst volume ratio 13:1, and reaction time 60 min. The properties of the feedstock oil are shown in Table 2, and the evaluation results and the content of sediment in the generated oil are shown in Table 3.

[0094] Comparative Example 2

[0095] (1) Pretreatment of waste hydrogenation catalyst

[0096] Waste spherical hydrogenation catalyst (particle size 1.2–1.4 mm, containing 5.2 wt% Mo, 6.0 wt% Ni, and 8.5 wt% V) was extracted and deoiled using a petroleum ether-ethanol mixed solvent (volume ratio 1:2) for 40 h, dried at 110 °C for 8 h, and then calcined at 600 °C for 3 h. The resulting material was then processed in a granulator for 10 min under the following conditions: rotary table speed 2000 rpm and compressed air volume 60 m³ / min. 3The feed rate is 10 mL / min, and the resulting material A has a particle size of 0.8–0.9 mm.

[0097] (2) Catalyst preparation

[0098] Material B was obtained by mixing 100g of leather glue, 267g of tetraethyl orthosilicate, and 800g of water and heating to 50℃. Material C was obtained by mixing 1000g of material A and material B. Material D was obtained by first mixing 65.6g of ammonium heptamolybdate, 21.0g of basic nickel carbonate, and 125g of corn starch with 150g of 25wt% ammonia water. Material C was then placed in a ball-forming machine under rolling conditions, and material D, 715g of boehmite, and 500g of water were uniformly introduced during rolling. After treatment, material E was obtained, which was then dried at 110℃ for 8h and calcined at 530℃ for 3h to obtain a spherical catalyst with a particle size of 0.8–1.0mm, containing 10.0wt% MoO3 and 2.0wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0099] (3) Catalyst Evaluation

[0100] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 430℃, reaction pressure 15.0 MPa, oil-to-catalyst volume ratio 13:1, and reaction time 60 min. The properties of the feedstock oil are shown in Table 2, and the evaluation results and the content of sediment in the generated oil are shown in Table 3.

[0101] Comparative Example 3

[0102] (1) Pretreatment of waste hydrogenation catalyst

[0103] Waste spherical hydrogenation catalyst (particle size 1.2–1.4 mm, containing 5.2 wt% Mo, 6.0 wt% Ni, and 8.5 wt% V) was extracted and deoiled using a petroleum ether-ethanol mixed solvent (volume ratio 1:2) for 40 h, dried at 110 °C for 8 h, and then calcined at 600 °C for 3 h. The resulting material was then processed in a granulator for 10 min under the following conditions: rotary table speed 2000 rpm and compressed air volume 60 m³ / min. 3 The feed rate is 10 mL / min, and the resulting material A has a particle size of 0.8–0.9 mm.

[0104] (2) Catalyst preparation

[0105] Material B is obtained by mixing 100g of leather glue, 267g of tetraethyl orthosilicate, and 800g of water and heating to 50℃. Material C is obtained by mixing 1000g of material A and material B. Material D is obtained by mixing 65.6g of ammonium heptamolybdate, 21.0g of basic nickel carbonate, and 150g of ammonia solution with a concentration of 25wt%. 80g of corn starch is weighed and added to 2000g of water, and heated at 70℃ for 30min to obtain a heat-treated organic polymer aqueous solution. Under spherical rolling conditions, material C is placed in a spherical rolling machine, and material D, 715g of boehmite, and 500g of the heat-treated organic polymer aqueous solution are uniformly introduced while rolling. Material E is obtained after treatment, and then dried at 110℃ for 8h and calcined at 530℃ for 3h to obtain a spherical catalyst with a particle size of 0.8-1.0mm, wherein the content of MoO3 is 10.0wt% and the content of NiO is 2.0wt%. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0106] (3) Catalyst Evaluation

[0107] The catalyst was evaluated over a long period using a CSTR hydrogenation evaluation system, with an operating time of 1500 hours. The evaluation conditions were: reaction temperature 430℃, reaction pressure 15.0 MPa, and volume hourly space velocity (VHSV) 0.3 h⁻¹. -1 The hydrogen-to-oil volume ratio was 600:1. The properties of the feedstock oil used are shown in Table 2, and the evaluation results and the content of sediment in the generated oil are shown in Table 4.

[0108] Table 1 Physicochemical properties of catalysts

[0109]

[0110]

[0111] The catalysts in Examples 1 and 2, having a particle size of less than 0.8 mm, had their wear measured using the high-speed air jet method (see ASTM D5757-00); the catalysts in Examples 3 and 4, and Comparative Examples 1-3, had a particle size of more than 0.8 mm, and therefore their wear was measured using the drum method.

[0112] Table 2 Properties of Crude Oil

[0113] Crude oil properties numerical values sulfur,% 6.1 Carbon residue,% 24.5 <![CDATA[Nickel + Vanadium / μg·g -1 > 265 Asphalt, % 7.9 >540℃ residue oil yield, % 83.0

[0114] Table 3 Evaluation results of catalysts for autoclaves

[0115]

[0116] The evaluation result of Comparative Example 1 was used as a benchmark and denoted as 100. The results of other embodiments and comparative examples were obtained by comparing them with the results of Comparative Example 1.

[0117] Table 4. Evaluation Results of CSTR Catalysts

[0118]

[0119] The results in Example 5 were obtained by comparing the results of Comparative Example 3 with the results of Comparative Example 3, with 100 as the baseline.

Claims

1. A method for preparing a heavy oil hydrotreating catalyst, the method comprising the following steps: (1) The waste heavy oil hydrogenation catalyst was deoiled to obtain material A; (2) Under mixed conditions, organic additives, silicon source and water are mixed and heated to obtain material B; (3) Mix material A obtained in step (1) and material B obtained in step (2) to obtain material C; (4) Add the active metal precursor and organic polymer to an aqueous solution of a nitrogen-containing weakly alkaline compound, and obtain material D after treatment; (5) Under the rolling ball-forming condition, the material C obtained in step (3) is placed in the ball rolling machine, and the material D obtained in step (4), boehmite and the organic polymer aqueous solution after heat treatment are uniformly introduced while rolling. The material E obtained after treatment is dried and calcined to obtain the catalyst. in, The organic polymers in steps (4) and (5) are one or more of starch, cellulose ether, and flour.

2. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The waste heavy oil hydrogenation catalyst in step (1) comes from the fluidized bed hydrogenation catalyst discharged from the fluidized bed hydrogenation process, or from the heavy oil hydrogenation catalyst that has not been completely deactivated in the fixed bed hydrogenation process, and is selected from one or more of the hydrogenation demetallization catalyst, hydrogenation desulfurization catalyst, and hydrogenation denitrification catalyst.

3. The method for preparing the heavy oil hydrogenation catalyst according to claim 1 or 2, wherein, The waste heavy oil hydrogenation catalyst in step (1) is spherical in shape and has a diameter greater than 1.0 mm.

4. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The oil removal process in step (1) uses one or more of the following methods: air stripping, solvent extraction, supercritical extraction, and vacuum drying, with solvent extraction being the preferred method.

5. The method for preparing the heavy oil hydrogenation catalyst according to claim 4, wherein, The solvent used for solvent extraction is petroleum ether, toluene, or a mixed solution of petroleum ether and alcohol, wherein the alcohol is a C1-C4 alcohol, and the volume ratio of petroleum ether to alcohol is 0.5 to 2:

1.

6. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, Step (1) after the deoiling treatment of the waste heavy oil hydrogenation catalyst also includes drying and calcination steps. The drying temperature is 80-120℃ and the calcination temperature is 500-700℃. The calcination is carried out in the presence of an oxygen-containing atmosphere.

7. The method for preparing the heavy oil hydrogenation catalyst according to claim 6, wherein, After roasting, the process includes grinding and sieving. Grinding is achieved through a granulator, which is supplied with compressed air during operation.

8. The method for preparing the heavy oil hydrogenation catalyst according to claim 7, wherein, The material is processed in the pellet mill for 5–60 minutes, with the turntable speed at 1000–3000 rpm and the compressed air volume at 20–120 m³ / min. 3 / min, wherein the compressed air is water-containing compressed air, and the water inlet is 5-30 mL / min.

9. The method for preparing the heavy oil hydrogenation catalyst according to claim 1 or 7, wherein, In step (1), the particle size of material A is 0.1 to 1.2 mm, preferably 0.2 to 1.0 mm.

10. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The organic additive mentioned in step (2) is gelatin, selected from one or more of industrial gelatin, edible gelatin and pharmaceutical gelatin; wherein industrial gelatin is one or more of hide glue, bone glue and hot melt adhesive powder; the amount of organic additive added is 2wt% to 10wt% of the mass of material A mentioned in step (1).

11. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The heating temperature in step (2) is 40-60℃.

12. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The silicon source mentioned in step (2) is one or more of tetraethyl orthosilicate and silica sol. The amount of silicon source added is 2wt% to 10wt% of the mass of material A in step (1) based on the mass of silicon oxide.

13. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The active metal mentioned in step (4) is at least one of Group VIB metals and at least one of Group VIII metals. The active metal precursor is a salt containing the active metal, wherein the Group VIB metal is W and / or Mo, preferably Mo; the Group VIII metal is Ni and / or Co, preferably Ni; the molybdenum precursor is ammonium heptamolybdate and / or ammonium tetramolybdate; and the nickel precursor is basic nickel carbonate.

14. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The starch is one or more of mung bean starch, tapioca starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, lotus root starch, and corn starch, preferably corn starch and / or potato starch; the cellulose ether is at least one of methylcellulose, hydroxyethyl methylcellulose, carboxymethylcellulose, ethylcellulose, benzylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, cyanoethylcellulose, benzyl cyanoethylcellulose, carboxymethyl hydroxyethylcellulose, and phenylcellulose, preferably methylcellulose.

15. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The nitrogen-containing weak base compound mentioned in step (4) is ammonia water, and the concentration of ammonia water is 15wt% to 25wt%.

16. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The organic polymer added in step (4) is 5 wt% to 30 wt% of the dry basis of boehmite, preferably 10 wt% to 25 wt%.

17. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The concentration of the aqueous solution of the heat-treated organic polymer in step (5) is 0.5wt% to 5wt%, preferably 1wt% to 3wt%. The preparation method is to add the organic polymer to water, heat and mix at 60 to 100°C for 10 to 40 minutes, and obtain the aqueous solution of the heat-treated organic polymer after the organic polymer has completely dissolved.

18. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The amount of the aqueous solution of the heat-treated organic polymer added in step (5) is 0.3 to 1.0 in mass ratio with that of the boehmite in step (5).

19. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The drying temperature in step (6) is 80-120℃ and the drying time is 4-12h; the calcination temperature in step (6) is 400-600℃ and the calcination time is 1-5h.

20. A heavy oil hydrogenation catalyst obtained by the preparation method according to any one of claims 1-19.

21. The application of the heavy oil hydrogenation catalyst according to claim 20 in the heavy oil hydrogenation process.

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