A hydrogenation catalyst, its preparation method and application

Abstract

This invention provides a hydrotreating catalyst, its preparation method, and its application. The preparation method includes the following steps: pretreating the hydrotreating catalyst to be regenerated to obtain a pretreated hydrotreating catalyst; the pretreatment includes at least an oil removal process; mixing the pretreated hydrotreating catalyst, a first pseudoboehmite, a first binder, and water, and then performing a first kneading molding to obtain a molded body A; mixing a second pseudoboehmite, a second binder, and water, and then performing a second kneading molding to obtain a molded body B; mixing molded bodies A and B to obtain a mixture; subjecting the mixture to a first drying and a first calcination; and after sieving, obtaining catalyst supports A1 and B1 respectively; and subjecting catalyst supports A1 and B1 to metal impregnation treatment, a second drying, and a second calcination to obtain hydrotreating catalysts A2 and B2 respectively. This invention can avoid temperature runaway, achieve catalyst recovery and reuse, and also co-produce fresh catalyst.

Description

Technical Field

[0001] This invention belongs to the field of catalysts, specifically relating to a hydrogenation catalyst, its preparation method, and its application. Background Technology

[0002] During the hydrogenation reaction, the activity of the hydrogenation catalyst gradually decreases with prolonged operation, rendering it unusable. Since these unusable spent catalysts still contain active metals such as vanadium, molybdenum, cobalt, and nickel, directly discarding them not only wastes resources and increases production costs but also pollutes the environment. Regenerating and reusing spent catalysts is a breakthrough in improving catalyst utilization, reducing production costs, and solving pollution problems.

[0003] The primary cause of catalyst deactivation in spent catalysts is the formation of carbon deposits. Currently, catalyst deactivation due to carbon deposits can be restored by carbon removal, such as high-temperature treatment in an oxygen-containing regeneration atmosphere to remove carbon deposits. However, because spent catalysts contain a large amount of carbon, high-temperature treatment in an oxygen-containing atmosphere releases a significant amount of heat, making temperature control uncontrollable and prone to runaway. This further reduces the catalyst's catalytic activity, potentially rendering it inactive, ultimately resulting in poor impurity removal performance of the regenerated catalyst. Therefore, how to fully utilize spent catalysts to obtain hydrogenation catalysts with high impurity removal rates has been a long-standing research topic in this field. Summary of the Invention

[0004] This invention provides a method for preparing a hydrotreating catalyst. By introducing a molded body B to dilute the distribution density of the hydrotreating catalyst to be regenerated during the first calcination, temperature runaway is avoided. Furthermore, metal impregnation treatment provides new active metal sites for the hydrotreating catalyst. After a second calcination, the impurity removal and stability performance of the hydrotreating catalyst are further improved. Simultaneously, the preparation method provided by this invention can also be used to co-produce fresh catalyst.

[0005] The present invention also provides a hydrotreating catalyst, which has high catalytic activity and is particularly effective in removing impurities such as nitrogen, sulfur, and metals from feedstock oil.

[0006] This invention provides a hydrotreating method that uses the above-mentioned hydrotreating catalyst to hydrotreat the feedstock oil, which has advantages such as good hydrotreating effect.

[0007] One aspect of the present invention provides a method for preparing a hydrotreating catalyst, comprising the following steps: pretreating the hydrotreating catalyst to be regenerated to obtain a pretreated hydrotreating catalyst; the pretreatment includes at least an oil removal treatment; mixing the pretreated hydrotreating catalyst, a first pseudoboehmite, a first binder, and water, and then performing a first kneading molding to obtain a molded body A; mixing a second pseudoboehmite, a second binder, and water, and then performing a second kneading molding to obtain a molded body B, wherein the particle size of the molded body B is larger than the particle size of the molded body A; mixing the molded body A and the molded body B to obtain a mixture; subjecting the mixture to a first drying and a first calcination, and then sieving to obtain catalyst support A1 and support B1 respectively; subjecting catalyst support A1 and support B1 to a metal impregnation treatment, a second drying, and a second calcination to obtain hydrotreating catalyst A2 and hydrotreating catalyst B2 respectively.

[0008] In the preparation method described above, the molded body A is 35%-85% of the mass content of the mixture.

[0009] In the preparation method described above, the mass ratio of the first pseudoboehmite to the pretreated hydrogenation catalyst is (0.5-1.5):1.

[0010] In the preparation method described above, the hydrogenation catalyst to be regenerated is 5-30% of the mass content of the hydrogenation treatment catalyst A2.

[0011] In the preparation method described above, the particle size of the molded body A is 0.8 to 2.5 mm, and the particle size of the molded body B is more than 0.5 mm larger than the particle size of the molded body A.

[0012] The preparation method described above includes the following pretreatment steps: sequentially screening and deoiling the hydrogenation catalyst to be regenerated, and then pulverizing the material obtained after deoiling.

[0013] As described above, the deoiling process involves sequentially eluting the sieved catalyst with an organic solvent and then drying it. The organic solvent is selected from at least one of ethanol, petroleum ether, and gasoline. The elution temperature is 20–80°C, and the drying temperature is 80–180°C.

[0014] Alternatively, the deoiling process may involve dry distillation or stripping of the sieved catalyst using an inert gas, with the dry distillation or stripping temperature being 200–450°C.

[0015] In the preparation method described above, the first drying temperature is 80–150°C and the time is 1–8 h; and / or, the second drying temperature is 80–150°C and the time is 1–8 h.

[0016] In the preparation method described above, the first calcination is carried out in an oxygen-containing atmosphere at a temperature of 400–1300°C for 0.5–6 h; and / or, the second calcination is carried out in an oxygen-containing atmosphere at a temperature of 300–1050°C for 0.5–6 h.

[0017] In a second aspect, the present invention provides a hydrogenation catalyst obtained by the preparation method described above.

[0018] The hydrotreating catalyst described above has a specific surface area of ​​20–400 m². 2 / g, with a total pore volume of 0.2 to 3 mL / g, and the proportion of pores larger than 50 nm in the hydrogenation catalyst to the total pore volume reaches more than 10%.

[0019] A third aspect of the present invention provides a hydrotreating method, wherein the above-mentioned catalyst is used to hydrotreat the feedstock oil.

[0020] The implementation of this invention has at least the following beneficial effects:

[0021] The method for preparing a hydrotreating catalyst provided by this invention first pretreats the hydrotreating catalyst to be regenerated, making it part of the catalyst and improving the utilization rate of the support and active metal in the catalyst. Then, by introducing a shaped body B into the pre-shaped catalyst, the distribution density of the catalyst during the first calcination is diluted, preventing runaway temperature and subsequent reduction in catalytic activity. Furthermore, metal impregnation treatment provides new active metal sites for the hydrotreating catalyst. After a second calcination, the catalytic activity and impurity removal rate of the hydrotreating catalyst are further improved, ensuring that the activity of the hydrotreating catalyst meets the application requirements. This hydrotreating catalyst can effectively remove metal and other impurities from feedstock oil. The preparation method provided by this invention not only enables catalyst recycling but also allows for the combined production of fresh catalyst.

[0022] The method for preparing hydrotreating catalyst provided by this invention is particularly suitable for recycling heavy and residual oil hydrotreating catalysts whose activity has been reduced due to carbon buildup. Detailed Implementation

[0023] The specific embodiments listed below are merely descriptions of the principles and features of the present invention. The examples given are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] This invention provides a method for preparing a hydrotreating catalyst, comprising the following steps: pretreating the hydrotreating catalyst to be regenerated to obtain a pretreated hydrotreating catalyst; the pretreatment includes at least an oil removal process; mixing the pretreated hydrotreating catalyst, a first pseudoboehmite, a first binder, and water, and then performing a first kneading molding to obtain a molded body A; mixing a second pseudoboehmite, a second binder, and water, and then performing a second kneading molding to obtain a molded body B, wherein the particle size of molded body B is larger than that of molded body A; mixing molded body A and molded body B to obtain a mixture; subjecting the mixture to a first drying and a first calcination, and then sieving to obtain catalyst support A1 and support B1 respectively; subjecting catalyst support A1 and support B1 to a metal impregnation treatment, and then performing a second drying and a second calcination to obtain hydrotreating catalyst A2 and hydrotreating catalyst B2.

[0025] In this invention, the hydrogenation catalyst to be regenerated refers to a hydrogenation catalyst whose activity decreases during the hydrogenation process due to carbon deposition. The preparation method of this invention is particularly suitable for recycling hydrogenation catalysts with a carbon deposition content greater than 10%.

[0026] This invention does not limit the specific type of hydrogenation catalyst to be regenerated. Depending on the hydrogenation feedstock, the hydrogenation catalyst to be regenerated includes distillate oil hydrogenation catalysts and heavy / residue oil hydrogenation catalysts. The preparation method of this invention is particularly suitable for recycling heavy / residue oil hydrogenation catalysts.

[0027] The present invention does not limit the process used for the regenerated hydrogenation catalyst, and can be applied to processes such as hydrodesulfurization, hydrodenitrification, hydrodemetallization, and hydrodeasphalting.

[0028] In this invention, the hydrogenation catalyst to be regenerated comprises at least a hydrogenation active metal component and a support. The content of the hydrogenation active metal is generally 3–26 wt% of the total weight of the hydrogenation catalyst to be regenerated, and the mass of the hydrogenation active metal is based on metal oxides. The hydrogenation active metal component includes, but is not limited to, at least one metal from Group VIB and Group VIII of the periodic table, such as vanadium, molybdenum, cobalt, nickel, and iron. The support includes, but is not limited to, at least one from alumina, silica, titanium dioxide, silicon carbide, boron oxide, zirconium oxide, and molecular sieves.

[0029] In this invention, the first and second pseudoboehmite are pseudoboehmite containing only alumina, or pseudoboehmite containing silicon dioxide, titanium dioxide, zirconium oxide, etc. It should be noted that the support material in the hydrogenation catalyst to be regenerated can be the same as or different from the first and second pseudoboehmite materials selected in this invention, but preferably the same.

[0030] This invention does not limit the pretreatment process, as long as it can remove impurities from the surface of the hydrogenation catalyst to be regenerated. Since the surface of the hydrogenation catalyst to be regenerated contains impurities such as feedstock oil, targeted degreasing treatment can effectively remove these surface impurities. In this invention, kneading is used to achieve uniform mixing of the materials, resulting in a homogeneous and plastic mixture. A molding process is then used to form a molded body with a specific shape and size.

[0031] The shape and size of the molded body mainly depend on the molding method. Those skilled in the art can select a specific molding method according to actual needs. Molding methods include, but are not limited to, drop ball molding, rolling ball granulation, extrusion molding, and sheet molding. Correspondingly, the shape of the molded body can be spherical, strip-shaped, sheet-shaped, etc. When the shape of the molded body is strip-shaped, it specifically includes cylindrical, clover-shaped, and four-leaf clover-shaped forms.

[0032] The shapes of molded body A and molded body B can be the same or different, but at least the size of molded body B must be larger than the size of molded body A.

[0033] This invention mixes molded body A and molded body B before performing a first drying and a first calcination. This not only avoids the release of a large amount of combustion heat during the first calcination of molded body A, which could cause a temperature runaway phenomenon, but also effectively combines with the conventional carrier preparation process, making full use of the heat generated during the first calcination process and effectively improving production efficiency.

[0034] Since the size of the molded body B is larger than that of the molded body A, after the first calcination, the catalyst support A1 and the fresh support B1 are obtained by sieving.

[0035] In this invention, the metal impregnation treatment is used to load active metal components onto catalyst supports A1 and B1. Specifically, metal impregnation treatment of catalyst support A1 provides new active metal sites for hydrogenation catalyst A2, and after a second drying and second calcination, the catalytic activity of hydrogenation catalyst A2 is further enhanced. Simultaneously, this invention also performs metal impregnation treatment on fresh support B1, enabling the co-production of fresh catalyst B2.

[0036] The metal immersion treatment employs conventional immersion methods in the art, such as spray immersion, saturated immersion, or supersaturated immersion.

[0037] When the metal impregnation treatment is performed by impregnation, a salt solution containing a hydrogenating active metal is impregnated onto catalyst support A1 or support B1, followed by a second drying and a second calcination. The hydrogenating active metal component includes at least one metal from Group VIB or Group VIII of the periodic table.

[0038] Based on fresh catalyst B2, and with active metals calculated as oxides, the concentration of salts containing hydrogenated active metals in the solution and the amount of solution used resulted in the final catalyst containing 3 wt% to 26 wt% of active metal components.

[0039] According to the technical solution of the present invention, the hydrogenation catalyst to be regenerated is first pretreated to make it part of the hydrogenation catalyst A2, thereby improving the utilization rate of the support and active metal in the hydrogenation catalyst to be regenerated. Then, by introducing a shaped body B into the shaped catalyst, the density of the catalyst during the first calcination is diluted to avoid temperature runaway and subsequent reduction in catalytic activity. In addition, metal impregnation treatment provides new active metal sites for the catalyst. After a second calcination, the impurity removal performance of the catalyst is further improved. Furthermore, the preparation method provided by the present invention can also be used to produce fresh catalysts.

[0040] In the mixture, the distribution density of molded body A during the first calcination can be adjusted by controlling the amount of molded body A and molded body B added. In one embodiment of the present invention, molded body A is 35%-85% of the mass content of the mixture, for example, a range of 35%, 40%, 50%, 60%, 70%, 80%, 85%, or any combination thereof. By controlling the mass percentage of molded body A within the above range, not only can the heat generated during the first calcination process be utilized to the maximum extent, effectively improving production efficiency, but also the temperature runaway phenomenon that leads to a decrease in catalytic activity can be avoided, which is beneficial to improving the activity of the catalyst.

[0041] In this invention, by introducing a first pseudoboehmite into the pretreated hydrogenation catalyst and performing a molding process, followed by a first drying and a first calcination process, the proportion of macropores (especially pores larger than 50 nm) in the catalyst support can be increased, the pore structure of the catalyst can be improved, the aggregation of active metals can be avoided, and thus the performance of the catalyst can be enhanced.

[0042] By controlling the amount of first pseudoboehmite added to the pretreated hydrogenation catalyst, the pore structure of the catalyst can be improved. In one embodiment of the present invention, the mass ratio of the first pseudoboehmite to the pretreated hydrogenation catalyst is (0.5 to 1.5):1, for example, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, or any combination thereof. The inventors have found that when the mass ratio of the first pseudoboehmite to the pretreated hydrogenation catalyst is within the above range, not only can the support and active metal in the hydrogenation catalyst to be regenerated be utilized to the maximum extent, but the pore structure and strength of the catalyst can also be improved, which is beneficial to enhancing the activity of the catalyst.

[0043] In this invention, the boehmite used is in powder form, and the powder has a colloidal solubility greater than 10%. The first binder and the second adhesive are each independently an inorganic acid and / or an organic acid, specifically including at least one of nitric acid, acetic acid, formic acid, and hydrochloric acid.

[0044] To ensure the smooth progress of the above kneading and molding, an auxiliary agent is added to the mixture before the first kneading or the second kneading and molding. The auxiliary agent includes at least one of guar gum powder, methylcellulose, starch, polyvinyl alcohol, and polyacrylamide. The amount of the auxiliary agent added is 0.5% to 20% of the mass of the mixture.

[0045] The pore structure of the carrier can be adjusted by using a pore expander. In this invention, the pore expander can be added to the mixture before the first or second kneading process, as needed. The pore expander can be at least one of starch, synthetic cellulose, polyol, and surfactant. Specifically, the synthetic cellulose includes at least one of hydroxymethyl cellulose, methyl cellulose, and ethyl cellulose; the polyol includes at least one of polyethylene glycol, polypropylene alcohol, and polyvinyl alcohol; and the surfactant includes at least one of fatty alcohol polyvinyl ether, fatty alcohol amides and their derivatives, propylene alcohol copolymers with a molecular weight of 200-10000, and maleic acid copolymers.

[0046] During the preparation process, by controlling the amount of pretreated hydrogenation catalyst added to the molded body A, the mass ratio of the hydrogenation catalyst to be regenerated in the hydrogenation catalyst A2 can be controlled.

[0047] In this invention, the hydrogenation catalyst to be regenerated comprises 5-30% by mass of hydrogenation catalyst A2, for example, 5%, 10%, 15%, 18%, 20%, 25%, 30%, or any combination thereof. The inventors have discovered that when the hydrogenation catalyst to be regenerated comprises 5-30% by mass of hydrogenation catalyst A2, not only can the support and active metal in the hydrogenation catalyst to be regenerated be utilized to the maximum extent, but the reduction in catalyst activity caused by temperature runaway during the first calcination can also be avoided.

[0048] In this invention, the particle size of molded body A and molded body B directly affects the particle size of hydrogenation catalyst A2 and catalyst B2. This invention does not limit the particle size of molded body A and molded body B; they can be adjusted according to actual needs, as long as the difference in particle size between the two is greater than 0.5 mm. In one embodiment, the particle size of molded body A is 0.8–2.5 mm, and the particle size of molded body B is greater than 0.5 mm larger than that of molded body A.

[0049] In one embodiment of the present invention, the pretreatment includes: sequentially screening and deoiling the hydrogenation catalyst to be regenerated, and then pulverizing the material obtained after deoiling.

[0050] In the above pretreatment, the sieving process can employ conventional sieving methods in the art to remove excess impurities. The deoiling process can employ conventional deoiling methods in the art, specifically at least one of solvent elution, gas stripping, and dry distillation.

[0051] When the deoiling process is solvent elution, it specifically includes: using organic solvents to sequentially elute the sieved catalyst, followed by a third drying process.

[0052] The organic solvent is selected from at least one of ethanol, petroleum ether, and gasoline. The elution temperature is 20–80°C and the elution time is 1–4 h. The volume ratio of organic solvent to sieved catalyst is (1–4):1. The third drying can be carried out under a nitrogen atmosphere by purging and drying at a temperature of 80–180°C.

[0053] When the deoiling process is gas stripping or dry distillation, it specifically includes: using a flowing inert gas to deoil and dry the sieved catalyst.

[0054] The temperature for dry distillation or stripping is 200–450°C, and the inert gas includes at least one of nitrogen, argon, helium, and neon.

[0055] The material obtained after degreasing is then pulverized, specifically by grinding the material obtained after degreasing to 60-400 mesh.

[0056] In this invention, during the first drying and first calcination of the mixture, the first drying temperature is 80–150°C, and the time is 1–8 hours. The first calcination is carried out in an oxygen-containing atmosphere, with a calcination temperature of 400–1300°C and a calcination time of 0.5–6 hours. The calcination can be carried out in a calcination furnace. This invention does not limit the calcination method; static calcination or dynamic calcination can be used, and the oxygen-containing atmosphere can be air.

[0057] In this invention, during the second drying and second calcination of catalyst supports A1 and B1 after metal impregnation treatment, the second drying temperature is 80–150°C, and the time is 1–8 hours. The second calcination is carried out in an oxygen-containing atmosphere, with a calcination temperature of 300–1050°C and a calcination time of 0.5–6 hours. The second calcination can be carried out in a calcination furnace. This invention does not limit the calcination method; static calcination or dynamic calcination can be used, and the oxygen-containing atmosphere can be air.

[0058] This invention also provides a hydrotreating catalyst (also called a hydrogenation catalyst), obtained by the above-described preparation method. The properties of this hydrotreating catalyst are as follows: specific surface area of ​​20–400 m² / g. 2 / g, with a total pore volume of 0.2-3mL / g, and the pore volume of pores larger than 50nm accounts for more than 10% of the total pore volume.

[0059] The present invention also provides a hydrotreating method, which uses the above-mentioned hydrotreating catalyst to hydrotreat the feedstock oil, and has advantages such as good hydrotreating effect.

[0060] This invention provides a hydrotreating catalyst, its preparation method, and its applications. The preparation method first pretreats the hydrotreating catalyst to be regenerated, making it part of the catalyst itself, thus improving the utilization rate of the support and active metal in the catalyst. Then, by introducing a shaped body B into the pre-shaped catalyst, the distribution density of the catalyst during the first calcination is diluted, preventing runaway temperature that could reduce catalytic activity. This also allows for full utilization of the heat generated during the first calcination process, effectively improving production efficiency. Furthermore, metal impregnation treatment provides new active metal sites for the catalyst. After a second calcination, the catalytic activity and impurity removal rate of the hydrotreating catalyst are further enhanced, ensuring that the activity of the hydrotreating catalyst meets usage requirements. This hydrotreating catalyst can effectively remove nitrogen, metal, and other impurities from feedstock oil. Simultaneously, the preparation method provided by this invention not only enables catalyst recycling but also allows for the combined production of fresh catalyst.

[0061] The methods and effects provided by the embodiments of the present invention will be further explained below through examples and comparative examples, but this does not limit the present invention.

[0062] In the examples and comparative examples, the first pseudoboehmite dry adhesive powder was purchased from Shandong Xingdu Petrochemical Technology Co., Ltd.; the second pseudoboehmite dry adhesive powder was purchased from Yantai Heng Hui Chemical Co., Ltd., with a dry basis weight of 69%, a pore volume of 1.10 mL / g, and a specific surface area of ​​192 m². 2 / g.

[0063] Example 1

[0064] The deactivated catalyst from the hydrotreating of industrial wax oil was used as the hydrogenation catalyst to be regenerated. The catalyst was NiMo / Al2O3 with a carbon deposition of 16.8 wt% and an S content of 7.5 wt%.

[0065] (1) The hydrogenation catalyst to be regenerated was eluted with petroleum ether, continuously rinsed at 80°C for 2 hours, and then dried by nitrogen purging at 100°C for 1 hour. After pulverizing to 120 mesh, the pretreated hydrogenation catalyst A was obtained; the volume ratio of petroleum ether to the hydrogenation catalyst to be regenerated was 3:1.

[0066] Mix 500g (dry basis) of the first pseudoboehmite dry adhesive powder (colloidal solubility index of 21%) and 15g of guar gum powder evenly. Add 450g of acetic acid solution with a concentration of 2wt% and knead for 15 minutes. Then add 80g of pretreated hydrogenation catalyst A and knead for 30 minutes. Finally, extrude the mixture into clover-shaped particles with a particle size of Φ1.5mm on an extruder. This mixture is designated as A-1.

[0067] (2) Weigh 1000g of the second pseudoboehmite dry adhesive powder (dry basis 69% by weight, pore volume 1.10mL / g, specific surface area 192m²). 2 / g), 12g of starch and 1440ml of aqueous solution containing acetic acid (10ml of acetic acid, product of Tianjin Chemical Reagent Factory No. 3) were added successively, and the mixture was extruded into cylindrical strips with a particle size of Φ0.9mm on an extruder, which was denoted as B-1.

[0068] (3) Mix A-1 and B-1 at 70%:30% (by weight, on a dry basis), age at 70°C for 2 hours, dry at 110°C for 3 hours, and then place them in a calcination furnace. Raise the temperature to 780°C at a rate of 100-200°C / hour and calcin in air for 3 hours. After sieving, catalyst support A-1S and support B-1S are obtained respectively.

[0069] (4) Weigh 150g of catalyst support A-1S with a water absorption rate of 1.00mL / g, spray it with 150mL of aqueous solution containing ammonium molybdate (containing 81wt% MoO3) and nickel nitrate (containing 25.2wt% NiO) according to the saturated absorption solution volume, homogenize it in the spraying equipment for 5 minutes, take it out and dry it at 120℃ for 3 hours, and then calcine it in air atmosphere at 550℃ for 3 hours to obtain catalyst A-1C;

[0070] (5) Weigh 150g of carrier B-1S and spray it with a phosphoric acid solution containing molybdenum trioxide (containing 99wt% MoO3) and basic nickel carbonate (containing 51wt% NiO). Spray the solution dropwise while spraying, and complete the spraying in 15 minutes. After homogenizing in the spraying equipment for 10 minutes, dry it at 120℃ for 5 hours, and then calcine it in air at 480℃ for 4 hours to obtain catalyst B-1C.

[0071] Example 2

[0072] The heavy oil hydrotreating decarbonization catalyst after the industrial unit has been in operation was used as the hydrotreating catalyst to be regenerated. The catalyst is CoMo / Al2O3 with a carbon content of 19.8 wt% and an S content of 9.5 wt%.

[0073] (1) The hydrogenation catalyst to be regenerated was purged at 350°C under nitrogen atmosphere for 1 hour and then pulverized to 200 mesh to obtain pretreated hydrogenation catalyst A.

[0074] Mix 500g (dry basis) of the first pseudoboehmite dry adhesive powder (silicon-containing pseudoboehmite dry adhesive powder with SiO2 content of 10% and colloidal index of 11%), 15g of guar gum powder, and 100g of pretreated hydrogenation catalyst A evenly and knead for 15 minutes. Add 460g of acetic acid solution with a concentration of 3wt% and knead for 45 minutes. Then, extrude the mixture into clover-shaped particles with a particle size of Φ1.3mm on an extruder. This mixture is designated as A-2.

[0075] (2) Weigh 1000g of the second pseudoboehmite dry adhesive powder (dry basis 69% by weight, pore volume 1.10mL / g, specific surface area 192m²). 2 25g of polyacrylamide (molecular weight 5000) and 1220ml of aqueous solution containing nitric acid (volume of nitric acid is 10ml, product of Tianjin Chemical Reagent Factory No. 3) were added successively, and the mixture was extruded into cylindrical strips with a particle size of Φ2.0mm on an extruder, which was denoted as B-2.

[0076] (3) Mix A-2 and B-2 at 60%:40% (by weight, on a dry basis), dry at 120°C for 3 hours, then place in a calcining furnace and raise to 880°C at a rate of 100-200°C / hour, calcining in air atmosphere for 3 hours. After sieving, catalyst support A-2S and support B-2S are obtained respectively.

[0077] (4) Weigh 150g of catalyst support A-2S with a water absorption rate of 1.00mL / g, spray it with 158mL of an aqueous solution containing ammonium molybdate (containing 81wt% MoO3) and cobalt nitrate (containing 25.2m% CoO, Beijing Chemical Reagent Company) according to the saturated absorption solution volume, homogenize it in the spraying equipment for 10 minutes, take it out and dry it at 120℃ for 3 hours, and then calcine it in air atmosphere at 450℃ for 4 hours to obtain catalyst A-2C;

[0078] (5) Weigh 150g of carrier B-2S and prepare catalyst B-2C according to step (5) of Example 1.

[0079] Example 3

[0080] The heavy oil hydrodesulfurization catalyst after the industrial unit has been in operation was used as the hydrodesulfurization catalyst to be regenerated. The catalyst is NiMo / Al2O3 with 13.8 wt% carbon deposit and 6.5 wt% S content.

[0081] (1) The hydrogenation catalyst to be regenerated was purged at 400°C under a nitrogen atmosphere for 1 hour and then pulverized to 280 mesh to obtain pretreated hydrogenation catalyst A.

[0082] 500g (dry basis) of the first pseudoboehmite dry adhesive powder (titanium-containing pseudoboehmite dry adhesive powder, with TiO2 content of 10% and gel solubility index of 15%), 15g of guar gum powder, 20g of polyvinyl alcohol, and 460g of acetic acid solution with a concentration of 2.5wt% were mixed evenly and kneaded for 15 minutes. Then, 130g of pretreated hydrogenation catalyst A was added and kneaded for 72 minutes. The mixture was then extruded into clover-shaped particles with a particle size of Φ1.6mm on an extruder and labeled as A-3.

[0083] (2) Weigh 1000g of the second pseudoboehmite dry adhesive powder (dry basis 69% by weight, pore volume 1.10mL / g, specific surface area 192m²). 2 / g), 25g of methylcellulose and 1440ml of aqueous solution containing acetic acid (10ml of acetic acid, product of Tianjin Chemical Reagent Factory No. 3) were added successively, and the mixture was extruded into cylindrical strips with a particle size of Φ2.8mm on an extruder, which was designated as B-3.

[0084] (3) Mix A-3 and B-3 at 40%:60% (by weight, on a dry basis), dry at 120°C for 3 hours, then place in a calcining furnace and heat to 980°C at a rate of 100-200°C / hour, calcining in air for 3 hours. After sieving, catalyst support A-3S and support B-3S are obtained respectively.

[0085] (4) Weigh 150g of catalyst support A-3S, spray it with 165mL of aqueous solution containing ammonium metatungstate (containing 83wt% WO3) and nickel nitrate (containing 25.2wt% NiO) according to the water absorption rate, homogenize it in the spraying equipment for 10 minutes, age it at 60℃ for 2 hours, take it out and dry it at 120℃ for 3 hours, and then calcine it in air atmosphere at 500℃ for 3 hours to obtain catalyst A-3C;

[0086] (5) Weigh 150g of carrier B-2S and prepare catalyst B-3C according to step (5) of Example 1.

[0087] Example 4

[0088] The hydrogenation catalyst of wax oil after the industrial plant has been in operation was used as the hydrogenation catalyst to be regenerated. The catalyst is NiW / Al2O3 with 9.8 wt% carbon deposit and 6.5 wt% S content.

[0089] (1) The hydrogenation catalyst to be regenerated was purged at 350°C under nitrogen atmosphere for 1 hour and then pulverized to 250 mesh to obtain pretreated hydrogenation catalyst A.

[0090] Mix 500g (dry basis) of the first pseudoboehmite dry adhesive powder (colloidal solubility index of 21%), 15g of guar gum powder, and 170g of pretreated hydrogenation catalyst A for 15 minutes. Then add 510g of acetic acid solution with a concentration of 4.5wt% and mix evenly. Knead for 30 minutes and then extrude into four-leaf strips with a particle size of 2.0mm on a single screw extruder. This strip is designated as A-4.

[0091] (2) Weigh 1000g of the second pseudoboehmite dry adhesive powder (dry basis 69% by weight, pore volume 1.10mL / g, specific surface area 192m²). 2 / g), 25g of polyacrylamide (molecular weight 5000) and 1400ml of aqueous solution containing acetic acid (10ml of acetic acid, product of Tianjin Chemical Reagent Factory No. 3) were added successively, and the mixture was extruded into cylindrical strips with a particle size of Φ3.5mm on an extruder, which was designated as B-4.

[0092] (3) Mix A-4 and B-4 at 35%:65% (by weight, on a dry basis), dry at 120°C for 3 hours, then place in a calcination furnace and raise to 750°C at a rate of 100-200°C / hour, calcining in air atmosphere for 3 hours. After sieving, catalyst support A-4S and support B-4S are obtained respectively.

[0093] (4) Weigh 150g of catalyst support A-4S with a water absorption rate of 1.00mL / g, spray it with 158mL of aqueous solution containing ammonium metatungstate (containing 88wt% WO3) and nickel nitrate (containing 25.2m% NiO, Beijing Chemical Reagent Company), while dripping it in and spraying it. The spraying is completed in 15 minutes. After homogenization in the spraying equipment for 10 minutes, dry it at 120℃ for 5 hours, and then calcine it in air atmosphere at 550℃ for 4 hours to obtain regenerated catalyst A-4C.

[0094] (5) Weigh 150g of carrier B-2S and prepare catalyst B-4C according to step (5) of Example 1.

[0095] Comparative Example 1

[0096] (1) Take the hydrogenation catalyst to be regenerated in Example 2 and perform carbonization treatment in an air atmosphere at 550°C for 2 hours to obtain pretreated hydrogenation catalyst E;

[0097] (2) Mix 500g (dry basis) of the first pseudoboehmite dry adhesive powder (with SiO2 content of 10% and colloidal index of 11%) and 15g of guar gum powder evenly. Add 450g of acetic acid solution with a concentration of 4.0wt% to the above materials and knead for 15 minutes. Then add 100g of pretreated hydrogenation catalyst E and knead for 45 minutes. After kneading, extrude it into 1.3mm clover strips on a single screw extruder. Dry it at 120℃ for 3 hours and then place it in a calcining furnace. Raise the temperature to 880℃ at a rate of 100-200℃ / hour and calcin for 3 hours to obtain catalyst support D-1.

[0098] (3) Weigh 150g of the above catalyst support D with a water absorption rate of 0.92mL / g, and spray it with 138mL of an aqueous solution containing ammonium molybdate (containing 81wt% MoO3) and cobalt nitrate (containing 25.2m% CoO, Beijing Chemical Reagent Company). The spraying is done dropwise and completed in 15 minutes. After homogenization in the spraying equipment for 10 minutes, it is dried at 120℃ for 5 hours and then calcined in air at 650℃ for 4 hours to obtain catalyst D-1C.

[0099] Comparative Example 2

[0100] (1) Mix 500g (dry basis) of first pseudoboehmite dry adhesive powder (colloidal index of 21%) (produced by Shandong Xingdu Petrochemical Technology Co., Ltd.) and 15g of guar gum powder evenly. Add 450g of acetic acid solution with a concentration of 4.0wt% to the above materials and knead for 30 minutes. After kneading, extrude it into clover strips with a particle size of Φ1.0mm on an extruder. Age at 70℃ for 2 hours, dry at 110℃ for 3 hours, and then place it in a calcining furnace. Raise the temperature to 780℃ at a rate of 100~200℃ / hour and calcin in air atmosphere for 3 hours to obtain carrier D-2.

[0101] (2) Weigh 150g of the above-mentioned carrier with a water absorption rate of 1.10mL / g, spray it with 165mL of an aqueous solution containing ammonium molybdate (containing 82wt% MoO3) and nickel nitrate (containing 25.2wt% NiO) according to the saturated absorption solution volume, homogenize it in the spraying equipment for 5 minutes, dry it at 60℃ for 2 hours, take it out and dry it at 120℃ for 3 hours, and then calcine it in air at 550℃ for 3 hours to obtain catalyst D-2C.

[0102] Comparative Example 3

[0103] (1) 1000g of second pseudo-boehmite dry adhesive powder, 12g of starch and 1440ml of aqueous solution containing acetic acid (acetic acid volume is 10ml, product of Tianjin Chemical Reagent Factory No. 3) were extruded into cylindrical strips with a particle size of Φ1.8mm on an extruder, aged at 70℃ for 2 hours, dried at 110℃ for 3 hours, and then placed in a calcining furnace, heated to 780℃ at a rate of 100~200℃ / hour, and calcined in air atmosphere for 3 hours to obtain carrier D-3;

[0104] (2) Weigh 150g of the above-mentioned carrier and prepare catalyst D-3C according to the method of step (5) in Example 1.

[0105] The properties of the A-series hydrogenation catalysts prepared in the above examples and comparative examples are shown in Table 1, and the properties of the B-series hydrogenation catalysts are shown in Table 2.

[0106] Table 1 Properties of Series A hydrogenation catalysts

[0107]

[0108] In the table, " / " indicates no test results.

[0109] According to Table 1:

[0110] 1. Compared with Comparative Example 1, the A-series catalysts in Examples 2 and 3 have larger pore volumes and a higher proportion of pores larger than 50 nm, indicating that the preparation methods of the examples are beneficial to improving pore volume and pore structure.

[0111] 2. Compared with Comparative Example 2, the A-series hydrogenation catalyst in the examples has a higher proportion of pores larger than 50 nm, indicating that the pore structure of the A-series hydrogenation catalyst in the examples is superior to that of fresh catalysts prepared by conventional methods.

[0112] 3. When the catalysts to be regenerated used in Comparative Example 1 and Example 2 are exactly the same, the A-series catalyst in Example 2 has a larger pore volume and a higher proportion of pores larger than 50 nm, indicating that the preparation method of Example 2 is more conducive to improving the pore volume and macropore ratio of the hydrogenation catalyst.

[0113] Table 2. Properties of Series B catalysts and contrast agents

[0114]

[0115] According to Table 2:

[0116] Compared to Comparative Example 3, the physicochemical properties of the B-series catalysts co-produced in this example are comparable to those of catalysts prepared using conventional methods. This demonstrates that the preparation method provided by this invention can co-produce fresh catalysts with physical properties substantially equivalent to those obtained by conventional methods.

[0117] Experimental Example 1

[0118] In a 100mL three-stage fixed-bed hydrogenation unit, catalysts A-1C, A-2C, D-1C, and D-2C were loaded into the three reactors, and activity and stability tests were conducted on catalysts A-1C, A-2C, D-1C, and D-2C. For ease of comparison, the first and second reactors were loaded with the same pre-catalysts. The feedstock was a mixed residue oil, the properties of which are shown in Table 3. The evaluation process conditions are shown in Table 4, and the evaluation results are shown in Table 5.

[0119] Table 3 Main Properties of Crude Oil

[0120]

[0121] Table 4 Process Conditions

[0122]

[0123]

[0124] Table 5 Comparison of Activity and Stability of Series A Catalysts

[0125]

[0126] In the table, the deasphalting rate, desulfurization rate, and demetallization rate represent the relative deasphalting rate, relative desulfurization rate, and relative demetallization rate. Specifically, they are obtained by comparing the desulfurization rate, demetallization rate, and denitrification rate of A-1C catalyst after 500 hours of operation with a benchmark of 1.00.

[0127] According to Table 5:

[0128] 1. The relative demetallization rates of catalysts A-1C and A-2C are both higher than those of D-1C and D-2C, indicating that the hydrogenation catalysts in the examples exhibit good catalytic activity. The inventors speculate that the high catalytic activity of the hydrogenation catalysts in the examples is due to their high macroporous ratio, which is beneficial for the diffusion of large molecules in the feedstock and the removal of impurities.

[0129] 2. As the operation continued, the relative demetallization rate of catalysts A-1C and A-2C decreased by no more than 10%, while the decrease rate of D-1C and D-2C even reached more than 13%, indicating that the hydrogenation catalyst in the example exhibited good stability, could maintain long-term operation, and had a long service life.

[0130] 3. As the operation continued, the desulfurization rates of catalysts A-1C and A-2C were higher than those of D-1C and D-2C, showing good catalytic activity and stability. This is attributed to the high macroporous ratio of the hydrogenation catalyst in the example, which is beneficial to the diffusion of feedstock macromolecules and the removal of impurities.

[0131] 4. As the operating time increases, the relative denitrification rates of catalysts A-1C and A-2C decrease at a lower rate than those of D-1C and D-2C. By 3000 hours, the denitrification rates of both catalysts exceeded those of the control catalyst, indicating that the hydrotreating catalysts in the examples exhibit good stability, can maintain long-term operation, have a long service life, and well meet the needs of long-term operation.

[0132] Experimental Example 2

[0133] In a 200mL three-stage fixed-bed hydrogenation unit, catalysts B-1C, B-2C, and D-3C were loaded into the three reactors for activity and stability tests. For ease of comparison, the first and second reactors were loaded with the same pre-formaldehyde. The feedstock for evaluation was a mixture of deasphalted oil and coking wax oil (weight ratio 1:1), the properties of which are shown in Table 6. The evaluation process conditions are shown in Table 7, and the evaluation results are shown in Table 8.

[0134] Table 6 Main Properties of Crude Oil

[0135]

[0136] Table 7 Process Conditions

[0137] <![CDATA[Liquid hourly space velocity, h -1 > 0.30 Hydrogen-to-oil ratio (by volume) 800 Reaction temperature, °C 368

[0138] Table 8 Comparison of B-series catalyst performance experiments

[0139] B-1C 87 71 75 B-2C 86 73 77 D-3C 86 70 75

[0140] In the table, the desulfurization rate, denitrification rate, and residual carbon removal rate represent the results of evaluating the hydrogenation reaction after 200 hours of operation.

[0141] According to Table 8:

[0142] 1. Compared with the comparative example, the B series catalysts of the examples exhibited excellent desulfurization rate and residual carbon removal activity, comparable to the comparative agent prepared alone.

[0143] The preferred embodiments and experimental verifications of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A method for preparing a hydrogenation catalyst, characterized in that, Includes the following steps: The hydrogenation catalyst to be regenerated is pretreated to obtain a pretreated hydrogenation catalyst; the pretreatment includes at least an oil removal process; the carbon deposit content of the hydrogenation catalyst to be regenerated is greater than 10%. The pretreated hydrogenation catalyst, the first pseudoboehmite, the first binder, and water are mixed and then kneaded to obtain molded body A. The second pseudo-boehmite, the second adhesive, and water are mixed and then kneaded to obtain a molded body B, wherein the particle size of the molded body B is larger than that of the molded body A. Molded body A and molded body B are mixed to obtain a mixture. The mixture is then subjected to a first drying and a first calcination. After sieving, catalyst support A1 and support B1 are obtained respectively. Molded body A accounts for 35%-85% of the mass content of the mixture. Catalyst support A1 and support B1 were subjected to metal impregnation, second drying, and second calcination to obtain hydrogenation catalyst A2 and hydrogenation catalyst B2, respectively.

2. The preparation method according to claim 1, characterized in that, The mass ratio of the first pseudoboehmite to the pretreated hydrogenation catalyst is (0.5~1.5):

1.

3. The preparation method according to claim 1, characterized in that, The hydrogenation catalyst to be regenerated is 5-30% of the mass content of the hydrogenation treatment catalyst A2.

4. The preparation method according to claim 1, characterized in that, The particle size of the molded body A is 0.8 to 2.5 mm, and the particle size of the molded body B is more than 0.5 mm larger than that of the molded body A.

5. The preparation method according to claim 1, characterized in that, The pretreatment includes: sequentially screening and deoiling the hydrogenation catalyst to be regenerated, and then crushing the material obtained after deoiling. The deoiling process involves sequentially eluting the sieved catalyst with an organic solvent and then drying it. The organic solvent is selected from at least one of ethanol, petroleum ether, and gasoline. The elution temperature is 20-80°C, and the drying temperature is 80-180°C. Alternatively, the deoiling process may involve dry distillation or stripping of the sieved catalyst using an inert gas, with the dry distillation or stripping temperature being 200~450℃.

6. The preparation method according to any one of claims 1-5, characterized in that, The first drying temperature is 80–150°C, and the time is 1–8 hours; and / or, the second drying temperature is 80–150°C, and the time is 1–8 hours; and / or, The first calcination is carried out in an oxygen-containing atmosphere at a temperature of 400–1300°C for 0.5–6 hours; and / or, The second calcination is carried out in an oxygen-containing atmosphere at a temperature of 300–1050°C for 0.5–6 hours.

7. A hydrogenation catalyst, characterized in that, The hydrogenation catalyst is hydrogenation catalyst A2 obtained by the preparation method according to any one of claims 1-6; The specific surface area of ​​the hydrogenation catalyst is 20–400 m². 2 / g, with a total pore volume of 0.2 to 3 mL / g, and the proportion of pores larger than 50 nm in the hydrogenation catalyst to the total pore volume reaches more than 10%.

8. A hydrogenation treatment method, characterized in that, The feedstock oil is hydrotreated using the hydrotreating catalyst described in claim 7.

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