Heavy oil hydrogenation catalyst and preparation method thereof

Abstract

The invention provides a heavy oil hydrogenation catalyst and a preparation method thereof. The preparation method of the catalyst comprises the following steps: (1) pretreating a waste hydrogenation catalyst to obtain a first material; (2) uniformly mixing an organic auxiliary agent with water, and carrying out heating treatment to obtain a second material; (3) mixing an active metal precursor, an organic high-molecular polymer, organic acid and water, and treating to obtain a third material; (4) uniformly mixing the first material, the second material and pseudo-boehmite to obtain a fourth material; and (5) mixing the third material, the fourth material and the heated organic high-molecular polymer aqueous solution, molding, drying and roasting to obtain the heavy oil hydrogenation catalyst. According to the preparation method provided by the invention, the strength and wear resistance of the catalyst can be improved, the activity and stability of the catalyst are optimized, and the pollution problem of the waste hydrogenation catalyst is solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of oil refining, and relates to a catalyst and a preparation method thereof, in particular to a heavy oil hydrogenation catalyst and a preparation method thereof. BACKGROUND

[0002] At present, a large amount of waste catalysts which cannot be regenerated are produced in the world every year, and the hydrogenation catalysts of various types account for a considerable proportion. At present, the hydrogenation treatment of poor crude oil mainly adopts fixed bed residual oil hydrogenation technology and ebullated bed residual oil hydrogenation technology. Among them, the basic service life of the fixed bed residual oil hydrogenation catalyst is about 8000 hours, and hundreds of tons of waste catalysts are produced by each residual oil hydrogenation device every year. Although the ebullated bed residual oil hydrogenation device is relatively less in China at present, thousands of tons of waste catalysts are still accumulated every year due to the daily discharge of catalysts. The content of active metals molybdenum and nickel on the residual oil hydrogenation catalyst is relatively low compared with other catalysts, so even if sold to a catalyst recovery enterprise, the refinery still needs to pay a large fee.

[0003] The waste catalyst treatment process mainly includes: ① incineration, ② grinding, ③ oxidation roasting, ④ alkaline leaching to recover molybdenum and vanadium, ⑤ acid leaching to recover cobalt and nickel, ⑥ waste residue discharge, etc. Recovering metals in waste catalysts is a good choice, which not only saves resources, but also reduces environmental pollution. However, the existing waste catalyst metal recovery technology generally has some problems: valuable metals such as vanadium, molybdenum, cobalt and nickel cannot be recovered all at once, and only one or two of them can be recovered, and the recovery rate is low, usually only 70% to 80%. Metal recovery is a good choice for catalysts that have no use value, but the benefit is not obvious. How to effectively utilize this part of waste catalysts has become a problem focused by the field.

[0004] Using waste hydrogenation catalyst as raw material to prepare new hydrogenation catalyst has become the focus of research in the field, but at present, it is mainly for distillate waste hydrogenation catalyst. The waste residual oil hydrogenation catalyst has a large amount of metal impurities deposited therein, which covers the surface of the catalyst, reduces the number of active centers, causes the catalyst pore to be blocked, hinders the utilization of the inner surface of the catalyst, and causes the waste of active metals. Moreover, it is difficult to recover the activity by regeneration, that is, even if used to prepare new hydrogenation catalyst, it will also have a great impact on the performance of the catalyst, leading to rapid deactivation. However, using waste catalyst to directly prepare new catalyst is still the direction of everyone's efforts.

[0005] CN03133558.6 discloses a method for preparing a hydrorefining catalyst from waste catalyst. The method involves grinding the waste hydrorefining catalyst, adding hydrorefining active metal oxides or active metal salts, and then adding a binder to knead and shape the mixture. The shaped material is then regenerated to obtain a new hydrorefining catalyst. In this patent, the catalyst regeneration process involves four stages and requires the replenishment of active metals, while causing minimal alteration to the catalyst's pore structure. Summary of the Invention

[0006] To address the problem of inefficient utilization of waste heavy oil hydrogenation catalysts in existing technologies, this invention aims to provide a heavy oil hydrogenation catalyst prepared from waste heavy oil hydrogenation catalysts and its preparation method. The preparation method provided by this invention optimizes the catalyst's pore structure and enhances the interaction forces between alumina supports, improving the catalyst's strength and wear resistance, thereby optimizing the overall activity and stability of the catalyst. It fully utilizes the support portion of the waste hydrogenation catalyst with less deposited metal and its active metal components, while simultaneously solving the pollution problem of waste hydrogenation catalysts.

[0007] The first aspect of this invention provides a method for preparing a heavy oil hydrogenation catalyst, comprising the following steps:

[0008] (1) The waste hydrogenation catalyst is pretreated to obtain the first material;

[0009] (2) After mixing the organic additive with water, heat treatment is performed to obtain the second material;

[0010] (3) The active metal precursor, organic polymer, organic acid and water are mixed and treated to obtain a third material;

[0011] (4) The first material obtained in step (1), the second material obtained in step (2), and the pseudoboehmite are mixed evenly to obtain the fourth material;

[0012] (5) The third material obtained in step (3), the fourth material obtained in step (4), and the organic polymer aqueous solution after heat treatment are mixed and kneaded to obtain the catalyst precursor, and then dried and calcined to obtain the heavy oil hydrogenation catalyst.

[0013] In a further preferred embodiment, as some specific implementations, the spent hydrotreating catalyst mentioned in step (1) refers to a hydrotreating 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 hydrotreating catalyst discharged from a fluidized bed hydrotreating process, or a heavy oil hydrotreating catalyst that has not been completely deactivated from a fixed bed hydrotreating process. Specifically, it can be one or more of the following: hydrodemetallization catalyst, hydrodesulfurization catalyst, and hydrodenitrogenation catalyst. The active metal in the spent hydrotreating 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 spent hydrotreating catalyst also includes carbon deposits and heavy metal impurities. The metal content on the spent hydrotreating catalyst generally accounts for 1.0 wt% to 30.0 wt% of the catalyst weight.

[0014] In a further preferred embodiment, the waste hydrogenation catalyst in step (1) is strip-shaped, specifically cylindrical, clover-shaped, or four-leaf clover-shaped, and the diameter of the waste hydrogenation catalyst is greater than 1.0 mm.

[0015] In a further preferred embodiment, as some specific implementations, the pretreatment of the waste hydrogenation catalyst in step (1) includes the following:

[0016] (1.1) The waste hydrogenation catalyst is deoiled, then dried and calcined;

[0017] (1.2) The material after step (1.1) is cut into strips, ground and screened to remove the part with more metal deposited on the outer layer of the waste hydrogenation catalyst;

[0018] (1.3) The material obtained after screening in step (1.2) is crushed.

[0019] In a further preferred embodiment, as some specific implementations, the oil removal process described in step (1.1) can employ any of the existing oil removal methods, specifically one or more of the following: gas stripping, solvent extraction, supercritical extraction, and vacuum drying. Solvent extraction is preferred, using petroleum ether, toluene, or a mixed solution of petroleum ether and an 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 process 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.

[0020] In a further preferred embodiment, as some specific implementations, the drying temperature in step (1.1) is 80-120°C, the drying time is 5-12h, the calcination temperature is 400-700°C, and the calcination time is 2-6h.

[0021] In a further preferred embodiment, as some specific implementations, the strip-breaking operation in step (1.2) involves crushing the strip-shaped waste hydrogenation catalyst into small particles; the grinding operation involves grinding away the portion of the waste hydrogenation catalyst with more deposited metal on the outer layer after strip breaking, retaining the portion with less deposited metal inside. Strip breaking and grinding can be achieved using a granulator, which can be a commonly used device in the art. During operation, the granulator generally requires compressed air to prevent solid material from entering the rotating disc shaft and to reduce particle adhesion. Compressed air can be replaced by air, high-temperature air, or steam. Specifically, in this invention, the material processed in step (1.1) is first subjected to short-term, ultra-high-speed strip breaking on the rotating disc in the granulator. Then, the rotation speed of the rotating disc in the granulator is reduced, and the strip-breaking material is further ground. Under the influence of centrifugal force, friction, gravity, and air, the portion of the waste hydrogenation catalyst with more deposited metal on the outer layer is ground away. The material processed in step (1.1) undergoes a breaking process of 2–8 minutes in the pellet mill, with a turntable speed of 3500–5000 rpm during breaking. The grinding process takes 5–60 minutes, with a turntable speed of 1000–3000 rpm during grinding. Throughout the breaking and grinding processes, the compressed air volume is 20–120 m³ / min. 3 / min, wherein the compressed air is water-containing compressed air, and the water inlet is 5-30 mL / min.

[0022] In a further preferred embodiment, as some specific implementations, the particle diameter of the material obtained after sieving in step (1.2) is 1 / 8 to 9 / 10 of the diameter of the original waste hydrogenation catalyst.

[0023] In a further preferred embodiment, as some specific implementations, the material obtained after screening in step (1.2) is crushed to 120 mesh or more, preferably 200 mesh or more, as described in step (1.3).

[0024] In a further preferred embodiment, 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.

[0025] In a further preferred embodiment, the heating temperature in step (2) is 40 to 60°C.

[0026] In a further preferred embodiment, as some specific implementations, the amount of organic additive added in step (2) is 2wt% to 10wt% of the mass of the first material in step (1).

[0027] In a further preferred embodiment, the active metal in step (3) 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. 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.

[0028] In further preferred embodiments, the organic polymer mentioned in step (3) is one or more of starch, cellulose ether, and flour, preferably starch. More specifically, 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 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.

[0029] In a further preferred embodiment, as some specific implementations, the mass ratio of the organic polymer to water in step (3) is 0.1 to 0.5.

[0030] In a further preferred embodiment, the organic acid mentioned in step (3) is one or more of citric acid, acetic acid, lactic acid, malic acid, and tartaric acid, preferably citric acid.

[0031] In a further preferred embodiment, as some specific implementations, the mass ratio of the organic polymer and the organic acid in step (3) is 1:1 to 1:4.

[0032] In a further preferred embodiment, as some specific implementations, the heating treatment temperature in step (3) is 30-50°C and the treatment time is 2-6 hours.

[0033] In a further preferred embodiment, as some specific implementations, the amount of organic polymer added in step (3) (by mass) is 5 wt% to 25 wt% of the dry basis mass of boehmite in step (4), preferably 10 wt% to 20 wt%.

[0034] In a further preferred embodiment, the raw materials of the pseudoboehmite in step (4) and the alumina support in the waste hydrogenation catalyst are the same or different, preferably the same.

[0035] In a further preferred embodiment, as some specific implementations, the pseudoboehmite described in step (4) after calcination at 600°C has the following properties: specific surface area greater than 280 m². 2 / g, preferably 290-320m 2 / g, with a pore volume of 0.95–1.2 mL / g, preferably 1.00–1.15 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.

[0036] In a further preferred embodiment, in step (4), the first material obtained in step (1) is preferably premixed with the second material obtained in step (2), and then mixed with boehmite to obtain the fourth material.

[0037] In a further preferred embodiment, as some specific implementations, the mass ratio of the first material to the pseudoboehmite dry basis in step (4) is 1:4 to 4:1.

[0038] In a further preferred embodiment, the concentration of the heat-treated organic polymer aqueous solution in step (5) is 0.5wt% to 8wt%, preferably 1wt% to 5wt%. The preparation method is as follows: the organic polymer is added to water and heated and mixed at 60 to 100°C for 10 to 40 minutes until the organic polymer is completely dissolved to obtain the heat-treated organic polymer aqueous solution.

[0039] In a further preferred embodiment, as some specific implementations, the mass ratio of the amount of the heated organic polymer aqueous solution added in step (5) to the mass ratio of the fourth material in step (4) is 0.2 to 1.0.

[0040] In a further preferred embodiment, as some specific implementations, the molding technology described in step (5) is prior art known to those skilled in the art. The specific molding operation can be selected by those skilled in the art according to actual needs, and can be any shape such as cylindrical strip, clover shape, four-leaf clover shape, or sphere. The perforated plate used in the extrusion molding process has a hole diameter of 1.0 mm or more.

[0041] In a further preferred embodiment, the drying conditions in step (5) are as follows: the drying temperature is 80-120°C and the drying time is 4-12 hours.

[0042] In a further preferred embodiment, the calcination conditions in step (5) are as follows: the calcination temperature is 400-600°C and the calcination time is 1-5 hours.

[0043] In a further preferred embodiment, the hydrogenation catalyst obtained in step (5) has a particle size of 0.6 to 2.0 mm, preferably 0.8 to 1.5 mm.

[0044] A second aspect of the present invention provides a heavy oil hydrogenation catalyst obtained by the above preparation method.

[0045] In a further preferred embodiment, as some specific implementations, the above-mentioned heavy oil hydrogenation catalyst includes an active metal component and a support. The active metal is at least one Group VIB metal and at least one Group VIII metal, wherein the active metal exists in the form of an oxide on the support, and the support is alumina. Based on the weight of the catalyst, the content of the Group VIB metal component, calculated as oxide, is 6 wt% to 15 wt%; the content of the Group VIII metal component is 1.5 wt% to 4 wt%.

[0046] In further preferred embodiments, as some specific implementations, the heavy oil hydrogenation catalyst described above has the following properties: a specific surface area of ​​150–230 m². 2 / g, with a pore volume of 0.60~0.75mL / g.

[0047] A third aspect of the present invention provides an application of the above-mentioned heavy oil hydrogenation catalyst in the heavy oil hydrogenation process.

[0048] In a further preferred embodiment, as some specific implementations, in the above applications, the heavy oil is at least one of atmospheric residue and vacuum residue.

[0049] In further preferred embodiments, as specific implementations, the hydrogenation process conditions in the above applications are as follows: reaction pressure of 15–20 MPa, temperature of 350–450 °C, and liquid hourly space velocity of 0.1–1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–1000.

[0050] Compared with the prior art, the heavy oil hydrotreating catalyst and its preparation method of the present invention have the following advantages:

[0051] 1. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, the waste hydrogenation catalyst is first pretreated by a combination of high-speed and low-speed treatment in a granulator. The high-speed treatment breaks the strip-shaped waste hydrogenation catalyst into small particles, while the low-speed treatment grinds away the outer layer of the small particles, which has a large amount of deposited metal and significant activity loss. The inner layer of the waste hydrogenation catalyst, which has relatively less metal deposit and higher activity, is retained and fully utilized. After pulverization, it is used as part of the support for the new catalyst, which improves the utilization effect of the support and active metal in the waste hydrogenation catalyst. At the same time, it can also ensure that the activity and stability of the new catalyst meet the requirements for use. This realizes the comprehensive utilization of metals and support in the waste hydrogenation catalyst, improves the resource utilization rate, provides a new treatment and utilization method for waste hydrogenation catalyst, and reduces the preparation cost of the new catalyst.

[0052] 2. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, the material obtained by dissolving the organic auxiliary gelatin in water after heating has high adhesiveness. After premixing with the first material, it can enhance the interaction between the particles of the first material, and also enhance the interaction with the subsequently mixed boehmite. Furthermore, as the temperature decreases, the gelatin will gradually gel, changing from a sol to a gel, which can cover the surface and pores of the first material, preventing the subsequently introduced active metal solution from entering the first material. This fully utilizes the active metal inherent in the waste catalyst, avoids repeated loading of active metal, and saves the amount of active metal used.

[0053] 3. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, the organic polymer is heated and decomposed into small molecules in water, giving the aqueous solution high adhesion. During the molding process, this enhances the interaction between the recycled waste and the boehmite, overcoming the poor adhesion of the recycled waste, making the support easier to mold, and improving the strength of the catalyst. Furthermore, the organic polymer is modified with organic acids, making its molecules smaller and its viscosity lower. When mixed with the mixture, this increases the proportion of mesopores in the alumina support and optimizes the pore structure of the support.

[0054] 4. In the preparation method of the heavy oil hydrogenation catalyst of the present invention, an active metal precursor and an organic polymer are added to an aqueous solution of an organic acid, and a third material is obtained after treatment. This process not only modifies the organic polymer, but also allows the active metal precursor to interact with the organic acid to form a soluble metal complex. During the mixing process with boehmite, the organic acid 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.

[0055] 5. In the method for preparing heavy oil hydrogenation catalyst of the present invention, the requirements for the physical properties (specific surface area, pore volume and pore size) and mechanical properties of the waste hydrogenation catalyst are relatively low. It 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

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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%.

[0063] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0064] 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.

[0065] 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.

[0066] In the context of this invention, the sediment content in the generated oil was determined according to SHT0701-2001, the method for determining total sediment in residual fuel oil (thermal filtration method), using an FDR-1431 residual fuel oil total sediment analyzer.

[0067] In the context of this instruction manual, all chemical reagents used are available by purchasing commercially available products.

[0068] In the context of this invention, the side compressive strength of the strip catalyst is measured by a ZQJ-Ⅱ type intelligent particle strength testing machine.

[0069] Example 1

[0070] (1) Pretreatment of waste hydrogenation catalyst

[0071] Cylindrical strip-shaped hydrogenation catalyst (particle size 1.0–1.1 mm, containing 4.1 wt% Mo, 5.6 wt% Ni, and 11.8 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 at a rotary speed of 4000 rpm for 5 min, with a compressed air volume of 60 m³ / min. 3 The flow rate was 10 mL / min, with the water feed rate at 10 mL / min. The rotary table speed was then reduced to 2000 rpm, and the treatment lasted 20 minutes. The compressed air volume was 50 m³ / min. 3 The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain a material with a particle size of 0.6 mm. This material is then crushed to a mesh size of 200 or finer to obtain the first material.

[0072] (2) Catalyst preparation

[0073] The second material was obtained by mixing 30g of leather glue with 800g of water and heating to 50℃. The third material was obtained by mixing 205g of ammonium heptamolybdate, 82.3g of basic nickel carbonate, 200g of corn starch, 200g of citric acid, and 200g of water, heating to 30℃ for 4 hours, and obtaining 80g of corn starch in 2000g of water and heating at 70℃ for 30 minutes. The resulting organic polymer aqueous solution was obtained after heat treatment. The fourth material was obtained by mixing 1000g of the first material, the second material, and 2860g of boehmite. The third material, the fourth material, and 2000g of the heat-treated organic polymer aqueous solution were mixed, extruded into strips, and then dried at 110℃ for 8 hours and calcined at 490℃ for 3 hours to obtain cylindrical strip catalysts with a diameter of 0.9–1.1 mm, containing 8.0 wt% MoO3 and 2.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0074] (3) Catalyst Evaluation

[0075] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 425℃, 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.

[0076] Example 2

[0077] (1) Pretreatment of waste hydrogenation catalyst

[0078] Cylindrical strip-shaped hydrogenation catalyst (particle size 1.0–1.1 mm, containing 4.1 wt% Mo, 5.6 wt% Ni, and 11.8 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 at a rotary speed of 4000 rpm for 5 min, with a compressed air volume of 60 m³ / min. 3 The flow rate was 10 mL / min, with the water feed rate at 10 mL / min. The rotary table speed was then reduced to 1800 rpm, and the treatment lasted 15 minutes. The compressed air volume was 50 m³ / min. 3 The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain a material with a particle size of 0.7 mm. This material is then crushed to a mesh size of 200 or finer to obtain the first material.

[0079] (2) Catalyst preparation

[0080] The second material was obtained by mixing 50g of gelatin with 800g of water and heating to 50℃. The third material was obtained by mixing 103g of ammonium heptamolybdate, 41.2g of basic nickel carbonate, 150g of methylcellulose, 225g of acetic acid, and 400g of water, heating to 40℃ for 3 hours after homogenization. 60g of methylcellulose was added to 2000g of water and heated at 80℃ for 20 minutes to obtain a heat-treated organic polymer aqueous solution. The fourth material was obtained by mixing 1000g of the first material, the second material, and 1430g of boehmite. The fourth material was obtained by mixing the third material, the fourth material, and 1000g of the heat-treated organic polymer aqueous solution, extruding into strips, and then drying at 110℃ for 8 hours and calcining at 510℃ for 3 hours to obtain a cylindrical strip catalyst with a diameter of 0.9–1.1 mm, containing 8.0 wt% MoO3 and 2.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0081] (3) Catalyst Evaluation

[0082] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 425℃, 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.

[0083] Example 3

[0084] (1) Pretreatment of waste hydrogenation catalyst

[0085] Cylindrical strip-shaped hydrogenation catalyst (particle size 1.0–1.1 mm, containing 6.8 wt% Mo, 6.3 wt% Ni, and 10.5 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 at a rotor speed of 3500 rpm for 5 min, followed by a reduction in rotor speed to 1500 rpm for 10 min, with a compressed air volume of 50 m³ / min. 3 The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain a material with a particle size of 0.8 mm. This material is then crushed to a mesh size of 200 or finer to obtain the first material.

[0086] (2) Catalyst preparation

[0087] The second material was obtained by mixing 80g of leather glue with 800g of water and heating to 50℃. The third material was obtained by mixing 81.5g of ammonium heptamolybdate, 32.7g of basic nickel carbonate, 100g of corn starch, 200g of citric acid, and 300g of water, heating to 50℃ for 2 hours, and obtaining 40g of corn starch in 2000g of water and heating at 90℃ for 15 minutes. The resulting organic polymer aqueous solution was obtained after heat treatment. The fourth material was obtained by mixing 1000g of the first material, the second material, and 715g of boehmite. The third and fourth materials were mixed with 500g of the heat-treated organic polymer aqueous solution, extruded into strips, and then dried at 110℃ for 8 hours and calcined at 540℃ for 3 hours to obtain a cylindrical strip catalyst with a diameter of 0.9–1.1 mm, containing 12.0 wt% MoO3 and 3.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0088] (3) Catalyst Evaluation

[0089] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 425℃, 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.

[0090] Example 4

[0091] The method was essentially the same as in Example 3, except that 80g of hide glue was replaced with 100g of bone glue, 100g of corn starch was replaced with 90g of flour, and 40g of corn starch was replaced with 50g of flour, resulting in cylindrical strip catalysts with a diameter of 0.9–1.1 mm, containing 12.0 wt% MoO3 and 3.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0092] 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.

[0093] Example 5

[0094] 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 425°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.

[0095] Comparative Example 1

[0096] (1) Pretreatment of waste hydrogenation catalyst

[0097] Cylindrical strip-shaped hydrogenation catalyst (particle size 1.0–1.1 mm, containing 6.8 wt% Mo, 6.3 wt% Ni, and 10.5 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 at a rotor speed of 3500 rpm for 5 min, followed by a reduction in rotor speed to 1500 rpm for 10 min, with a compressed air volume of 50 m³ / min. 3 The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain a material with a particle size of 0.8 mm. This material is then crushed to a mesh size of 200 or finer to obtain the first material.

[0098] (2) Catalyst preparation

[0099] 81.5g ammonium heptamolybdate, 32.7g basic nickel carbonate, 100g citric acid, and 300g water were mixed and heated to 50℃ for 2 hours to obtain the third material. 40g corn starch was added to 2000g water and heated at 90℃ for 15 minutes to obtain a heat-treated organic polymer aqueous solution. 1000g of the first material and 715g boehmite were mixed to obtain the fourth material. The third and fourth materials were mixed with 500g of the heat-treated organic polymer aqueous solution, extruded into strips, and the resulting catalyst precursor was dried at 110℃ for 8 hours and calcined at 540℃ for 3 hours to obtain a cylindrical strip catalyst with a diameter of 0.9–1.1 mm, containing 12.0 wt% MoO3 and 3.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0100] (3) Catalyst Evaluation

[0101] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 425℃, 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.

[0102] Comparative Example 2

[0103] (1) Pretreatment of waste hydrogenation catalyst

[0104] Cylindrical strip-shaped hydrogenation catalyst (particle size 1.0–1.1 mm, containing 6.8 wt% Mo, 6.3 wt% Ni, and 10.5 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 at a rotor speed of 3500 rpm for 5 min, followed by a reduction in rotor speed to 1500 rpm for 10 min, with a compressed air volume of 50 m³ / min. 3 The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain a material with a particle size of 0.8 mm. This material is then crushed to a mesh size of 200 or finer to obtain the first material.

[0105] (2) Catalyst preparation

[0106] The second material was obtained by mixing 80g of leather glue with 800g of water and heating to 50℃. The third material was obtained by mixing 81.5g of ammonium heptamolybdate, 32.7g of basic nickel carbonate, 100g of corn starch, 200g of citric acid, and 300g of water, heating to 50℃ for 2 hours. The fourth material was obtained by mixing 1000g of the first material, the second material, and 715g of boehmite. The fifth material was obtained by mixing the third material, the fourth material, and 500g of water, extruding into strips, and obtaining the catalyst precursor. This precursor was then dried at 110℃ for 8 hours and calcined at 540℃ for 3 hours to obtain cylindrical strip catalysts with a diameter of 0.9–1.1 mm, containing 12.0 wt% MoO3 and 3.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0107] (3) Catalyst Evaluation

[0108] The catalyst activity was evaluated using a batch autoclave. The evaluation conditions were: reaction temperature 425℃, 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.

[0109] Comparative Example 3

[0110] (1) Pretreatment of waste hydrogenation catalyst

[0111] Cylindrical strip-shaped hydrogenation catalyst (particle size 1.0–1.1 mm, containing 6.8 wt% Mo, 6.3 wt% Ni, and 10.5 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 at a rotor speed of 3500 rpm for 5 min, followed by a reduction in rotor speed to 1500 rpm for 10 min, with a compressed air volume of 50 m³ / min.3 The feed rate is 10 mL / min, with water flow rate of 10 mL / min, to obtain a material with a particle size of 0.8 mm. This material is then crushed to a mesh size of 200 or finer to obtain the first material.

[0112] (2) Catalyst preparation

[0113] The second material was obtained by mixing 80g of leather glue with 800g of water and heating to 50℃. The third material was obtained by mixing 81.5g of ammonium heptamolybdate, 32.7g of basic nickel carbonate, 200g of citric acid, and 300g of water, heating to 50℃ for 2 hours, and obtaining 40g of corn starch in 2000g of water and heating at 90℃ for 15 minutes. The resulting organic polymer aqueous solution was obtained after heat treatment. The fourth material was obtained by mixing 1000g of the first material, the second material, and 715g of boehmite. The third and fourth materials were mixed with 500g of the heat-treated organic polymer aqueous solution, extruded into strips, and then dried at 110℃ for 8 hours and calcined at 540℃ for 3 hours to obtain cylindrical strip catalysts with a diameter of 0.9–1.1 mm, containing 12.0 wt% MoO3 and 3.0 wt% NiO. The physicochemical properties, yield, and wear data of the catalyst are shown in Table 1.

[0114] (3) Catalyst Evaluation

[0115] 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 425℃, 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 resulting oil are shown in Table 4.

[0116] Table 1 Physicochemical properties of catalysts

[0117]

[0118] Table 2 Properties of Crude Oil

[0119] Crude properties Value Sulfur, % 5.3 Carbon residue, % 22.6 Nickel + Vanadium / pg-g -1 ]] 218 Asphaltene, % 6.5 Residue yield at >540°C, % 78.0

[0120] Table 3 Evaluation results of catalysts for autoclaves

[0121]

[0122]

[0123] 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.

[0124] Table 4. Evaluation Results of CSTR Catalysts

[0125]

[0126] 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, comprising the following steps: (1) Pretreatment of the spent hydrogenation catalyst to obtain the first material; wherein the pretreatment of the spent hydrogenation catalyst includes the following: (1.1) The waste hydrogenation catalyst is deoiled, then dried and calcined; (1.2) The material processed in step (1.1) is subjected to cutting, grinding and screening; (1.3) The material obtained after screening in step (1.2) is crushed; (2) After mixing the organic additive with water, heat treatment is performed to obtain the second material; the organic additive is gelatin. (3) The active metal precursor, organic polymer, organic acid and water are mixed and treated to obtain the third material; (4) After mixing the first material obtained in step (1), the second material obtained in step (2), and the pseudoboehmite evenly, a fourth material is obtained; (5) The third material obtained in step (3), the fourth material obtained in step (4), and the organic polymer aqueous solution after heat treatment are mixed and kneaded to obtain the catalyst precursor, and then dried and calcined to obtain the heavy oil hydrogenation catalyst.

2. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The waste hydrogenation catalyst in step (1) refers to the fluidized bed hydrogenation catalyst discharged from the fluidized bed hydrogenation process, or the heavy oil hydrogenation catalyst that has not been completely deactivated from the fixed bed hydrogenation process. The waste hydrogenation catalyst is in the shape of a strip.

3. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The oil removal process in step (1.1) 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 small molecule alcohol of C1-C4.

4. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The drying temperature in step (1.1) is 80-120℃, the drying time is 5-12h, the calcination temperature is 400-700℃, and the calcination time is 2-6h.

5. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, Step (1.2) involves breaking the strips and grinding, which is achieved through a pellet mill. The material processed in step (1.1) is first broken into strips on the turntable inside the pellet mill, and then the rotation speed of the turntable inside the pellet mill is reduced. The material after the strip breaking is then ground. The strip breaking time of the material processed in step (1.1) in the pellet mill is 2 to 8 minutes, and the rotation speed of the turntable during the strip breaking process is 3500 to 5000 rpm. The grinding time is 5–60 minutes, and the turntable speed during grinding is 1000–3000 rpm; the compressed air volume is 20–120 m³ / min throughout the entire strip breaking and grinding process. 3 / min, wherein the compressed air is water-containing compressed air, and the water inlet is 5-30 mL / min.

6. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The particle diameter of the material obtained after screening in step (1.2) is 1 / 8 to 9 / 10 of the diameter of the original waste hydrogenation catalyst.

7. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, In step (1.3), the material obtained after screening in step (1.2) is crushed to a fineness of 120 mesh or higher, preferably 200 mesh or higher.

8. The method for preparing the heavy oil hydrogenation catalyst according to claim 1, wherein, The gelatin mentioned in step (2) is 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 the first material in step (1).

9. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The heating temperature in step (2) is 40 to 60°C.

10. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The active metal mentioned in step (3) 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. 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.

11. The method for preparing the heavy oil hydrotreating 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.

12. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The mass ratio of the organic polymer to water in step (3) is 0.1 to 0.

5.

13. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The organic acid mentioned in step (3) is one or more of citric acid, acetic acid, lactic acid, malic acid and tartaric acid, preferably citric acid; the mass ratio of the organic polymer and organic acid mentioned in step (3) is 1:1 to 1:

4.

14. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The organic polymer added in step (3) is 5 wt% to 25 wt% of the dry basis mass of the boehmite in step (4), preferably 10 wt% to 20 wt%.

15. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The heating treatment temperature in step (3) is 30-50℃, and the treatment time is 2-6h.

16. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The mass ratio of the first material to the dry basis of pseudoboehmite in step (4) is 1:4 to 4:

1.

17. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The drying conditions in step (5) are as follows: the drying temperature is 80-120℃ and the drying time is 4-12h; the calcination conditions in step (5) are as follows: the calcination temperature is 400-600℃ and the calcination time is 1-5h.

18. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The concentration of the organic polymer aqueous solution after heat treatment in step (5) is 0.5wt% to 8wt%, preferably 1wt% to 5wt%; 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 organic polymer aqueous solution after heat treatment after the organic polymer is completely dissolved.

19. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The amount of the organic polymer aqueous solution after heat treatment in step (5) is added in a mass ratio of 0.2 to 1.0 with the fourth material in step (4).

20. The method for preparing the heavy oil hydrotreating catalyst according to claim 1, wherein, The catalyst particle size obtained in step (5) is 0.6 to 2.0 mm, preferably 0.8 to 1.5 mm.

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

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

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