Process for the preparation of a hydrodemetallization catalyst

Abstract

The application discloses a method for preparing a hydrogen demetallization catalyst. The method comprises the following steps: (1) mixing catalyst powder, an alkaline additive and water to obtain a slurry, grinding, hydrothermal treatment, filtering, drying, and obtaining powder A; (2) mixing alumina, an alkaline additive and water to obtain a slurry, grinding, hydrothermal treatment, drying, and obtaining powder B; (3) mixing modified activated carbon X loaded with a first active metal M1 and powder A, and grinding to obtain powder AXM1; (4) preparing a binder mixed solution C; (5) mixing powder AXM1, powder B and the binder mixed solution C to obtain a spherical forming body D; (6) impregnating D with an impregnation solution containing a carbon source and a second active metal M2, standing, drying, and obtaining an intermediate E; and (7) calcining E in an inert atmosphere first, and then in an oxygen-containing atmosphere, and thus the catalyst is prepared. According to the method, not only the industrial dust generated in the catalyst production process is recovered, but also the activity and stability of the catalyst are improved.

Description

Technical Field

[0001] This invention relates to a method for preparing a hydrodemetallization catalyst, particularly a method for preparing a hydrodemetallization catalyst for the hydrotreating of residual oil. Background Technology

[0002] Currently, the number of large-scale oil refining and chemical plants in China continues to increase, and the number of residue hydrotreating units is also growing rapidly, reaching more than 30 sets. With the increasing deterioration and heavier nature of crude oil, the properties of feedstock for residue hydrotreating units are also deteriorating overall. Processing residue feedstocks with high metal content, high sulfur content, and high carbon residue is often required. The impurity removal and tolerance capabilities of the entire residue hydrotreating catalyst system directly affect the long-term stable operation of the unit. Residue hydrotreating catalysts generate catalyst dust during production. This dust often accumulates in dust removal systems and becomes solid waste for recycling. However, the recycling process often causes significant environmental pollution and hinders cost reduction in catalyst production.

[0003] CN103041868A discloses a method for preparing a spherical catalyst support. This method improves the physical properties of the alumina support surface by adding anionic and cationic surfactants to the alumina precursor, adjusting the adhesion and rheological properties of the material during support forming, reducing the plasticity of the support after forming, and significantly increasing the yield of spherical supports. However, the alumina support prepared by this method has a small pore size, making it unsuitable for the hydrogenation reaction of heavy residue oil.

[0004] CN101492612A discloses a hydrogenation catalyst and its preparation method. A suitable microporous alumina and macroporous alumina are mixed and kneaded to form an alumina support, which is then loaded with a hydrogenation active component and an alkali metal component to prepare the catalyst. However, the catalyst's performance still needs further improvement.

[0005] Currently, most residue hydrotreating catalysts are metal components that are loaded once. Due to the different adsorption capacities of each active component on the support, components with strong adsorption capacity tend to accumulate at the pore openings, while components with weak adsorption capacity are distributed inside the pores, resulting in uneven distribution of active metals. Therefore, the catalyst's ability to demetalize and accommodate metals is limited. Summary of the Invention

[0006] To overcome the shortcomings of existing technologies, this invention provides a method for preparing a hydrodemetallization catalyst, particularly a method for preparing a hydrodemetallization catalyst for residue oil. The catalyst preparation method provided by this invention not only fully utilizes the catalyst powder generated during catalyst production to prepare hydrodemetallization catalysts, especially for residue oil hydrodemetallization catalysts, but also recovers industrial dust generated during catalyst production, while simultaneously improving the activity and stability of the catalyst, avoiding the generation of solid waste, and reducing the cost of catalyst production.

[0007] The first aspect of this invention provides a method for preparing a hydrogenation demetallization catalyst, comprising:

[0008] (1) The catalyst powder, alkaline additive and water are mixed to obtain a slurry, which is then ground, hydrothermally reacted, filtered and dried to obtain powder A;

[0009] (2) Alumina, alkaline additives and water are mixed to obtain a slurry, which is then ground, subjected to hydrothermal reaction and dried to obtain powder B;

[0010] (3) Oxidize activated carbon powder X to obtain modified activated carbon X, load the first active metal M1 onto modified activated carbon X to obtain M1 / modified activated carbon X, mix M1 / modified activated carbon X with powder A and grind to obtain powder AXM1.

[0011] (4) Prepare adhesive mixture C;

[0012] (5) Powder AXM1, powder B and binder mixture C are formed by ball rolling to obtain spherical body D;

[0013] (6) The sphere-shaped body D was impregnated with an impregnation solution containing a carbon source and a second active metal M2, then allowed to stand and dried to obtain catalyst intermediate E;

[0014] (7) The catalyst intermediate E is calcined in steps, first under an inert atmosphere and then under an oxygen-containing atmosphere to obtain the hydrogenation demetallization catalyst.

[0015] In step (1), the catalyst powder refers to the catalyst powder produced during the catalyst production process, which can be one or more of the following: residue oil hydrodemetallization catalyst powder, residue oil hydrodesulfurization catalyst powder, and residue oil hydrodecarbonization catalyst powder. The particle size of the catalyst powder is between 0.01 and 1.00 mm. The catalyst powder refers to waste catalyst that does not meet the requirements for catalyst use in at least one aspect such as particle size and bulk density.

[0016] In step (1), the catalyst powder comprises an alumina support and an active metal component, wherein the active metal is at least one of a Group VIII metal and / or at least one of a Group VIB metal. Preferably, the Group VIII metal is Co and / or Ni, and the Group VIB metal is preferably Mo and / or W. Based on the mass of the catalyst powder, the alumina content is 50.0%–90.0%, the Group VIII metal content (based on oxides) is 0.5%–10.0%, and the Group VIB metal content (based on oxides) is 4.0%–30.0%. The catalyst powder may also contain conventional auxiliary components, such as at least one of silicon, phosphorus, and boron, accounting for less than 15.0% of the catalyst powder mass.

[0017] In step (1), the catalyst powder is calcined catalyst powder.

[0018] In step (1), the slurry contains 2-50 g of catalyst powder per 100 ml and 0.01-0.5 g of alkaline additive per 100 ml.

[0019] In step (1), the alkaline auxiliary is one or more of the following non-ammonium alkaline compounds: sodium hydroxide, potassium hydroxide, sodium carboxylate (such as sodium acetate, sodium formate, etc.).

[0020] In step (1), the powder grinding can be carried out by ball milling, sand milling or other processing methods, and the ground sample with an average particle size of 1 to 10 μm is obtained after grinding.

[0021] In step (1), the hydrothermal reaction conditions are: temperature of 120-200℃, pH of 7.0-9.0, and reaction time of 4-20h.

[0022] In step (1), the drying conditions are as follows: the drying temperature is 90-180℃ and the drying time is 1-24h.

[0023] In step (2), the alkaline auxiliary agent is one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, and sodium carboxylate (e.g., sodium acetate, sodium formate).

[0024] In step (2), the alumina is p-type alumina or x-type alumina.

[0025] In step (2), the slurry contains 3 to 20 g of alumina per 100 ml and 0.05 to 2.0 g of alkaline additives per 100 ml.

[0026] In step (2), the powder grinding can be carried out by ball milling, sand milling or other processing methods, and the ground sample with an average particle size of 0.1 to 5 μm is obtained after grinding.

[0027] In step (2), the hydrothermal reaction conditions are: temperature of 180-320℃, pH of 9.0-13.0, and reaction time of 6-48h.

[0028] In step (2), the drying conditions are as follows: the drying temperature is 120℃~180℃, and the drying time is 2~6h.

[0029] In step (3), the first active metal is at least one of Group VIII metals. Preferably, the Group VIII metal is Co and / or Ni.

[0030] In step (3), the specific surface area of ​​the activated carbon X is 800-1500 m². 2 / g, can be burned off in an air roasting atmosphere at 500-700℃.

[0031] In step (3), the conditions for the oxidation treatment are as follows: the solution is a nitric acid solution with a concentration of 5-12 mol / L, the volume-to-mass ratio of the oxidizing liquid to activated carbon X is 0.9-1.8 ml / g, the temperature is 80-100℃, and the treatment time is 6-12 h.

[0032] In step (3), the first active metal source is selected from at least one of nickel salts (or cobalt salts), such as nickel acetate, nickel chloride, nickel nitrate and nickel sulfate (or the corresponding cobalt salts).

[0033] In step (3), the content of the first active metal, calculated as first active metal nitrate, accounts for 20.0% to 70.0% of the mass of the modified activated carbon.

[0034] In step (3), the ratio of M1 / modified activated carbon X to powder A is 1.0:2.0~5.0.

[0035] In step (3), the powder grinding can be carried out by ball milling, sand milling, or other methods to obtain a ground sample with an average particle size of 1-10 μm. The average particle size after grinding in step (2) is smaller than the average particle size after grinding in step (3), by at least 0.5 μm, and preferably at least 2.0 μm smaller.

[0036] In step (4), the adhesive mixture C includes an acid, water and a colloid. The acid is one or more of nitric acid, citric acid, acetic acid, sulfuric acid, oxalic acid, acetic acid, etc., and the colloid is at least one of methylcellulose, guar gum, polyethylene glycol, etc.

[0037] In step (4), the mass concentration of acid in the adhesive mixture C is 0.5%-4.5%.

[0038] In step (4), the mass concentration of the colloid in the adhesive mixture C is 0.5%-2.5%.

[0039] In step (4), the adhesive mixture C may also contain an additive, which is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus.

[0040] In step (5), the preferred method for ball forming is as follows: Powder AXM1 and powder B are divided into N parts (N is 2 or more), i.e., from the first part to the Nth part. Each time, one part of powder AXM1 and powder B is added, reducing the amount of powder AXM1 added in the current part while increasing the amount of powder B added in the current part. The process includes:

[0041] (5-1) Place the first batch of powder AXM1 and the first batch of powder B into the turntable of the ball rolling machine, and simultaneously spray the binder mixture C onto the turntable. Rotate the ball rolling machine to form spherical particles.

[0042] (5-2) Add the second part of powder AXM1 and the second part of powder B, while continuing to spray the binder mixture C. The ball continues to increase in size.

[0043] (5-3) Using the current portion of powder AXM1 and the current portion of powder B, continuously increase the size of the ball in the manner of step (5-2) until the Nth portion of powder AXM1 and the Nth portion of powder B are all formed into balls;

[0044] (5-4) After drying and calcination, spherical shape D is obtained.

[0045] In step (5), powder AXM1 and powder B are divided into N parts, where N is 2 or more, preferably 3-20, and more preferably 3-10.

[0046] In step (5), the total mass of each corresponding portion of powder AXM1 and powder B is 0.90 to 1.10 times (the total mass of the first portion of powder AXM1 and the first portion of powder B). For example, when powder AXM1 and powder B are added for the xth time, the total mass of the xth portion of powder AXM1 and the xth portion of powder B is 0.90 to 1.10 times (the total mass of the first portion of powder AXM1 and the first portion of powder B), where x is 1 to N.

[0047] In step (5), the mass ratio of the first powder AXM1 to the first powder B is 90-98:2-10, and the amount of the current powder AXM1 added is 77% to 95% of the amount of the previous powder AXM1 added.

[0048] In step (5), the mass ratio of the Nth powder AXM1 to the Nth powder B is 50-70:30-50.

[0049] In step (5), the total amount of the binder mixture C added accounts for 80.0% to 150.0% of the total mass of powder AXM1 and powder B added.

[0050] In step (5), during the spheroidizing process of each corresponding part of powder AXM1 and powder B, the amount of binder mixture C added accounts for 80% to 150% of the mass of each corresponding part of powder AXM1 and powder B.

[0051] In step (5), the spheroidization time of each corresponding part of powder AXM1 and powder B is controlled at 0.5-1.5h.

[0052] In step (5), there is no strict limit to the spraying rate of the adhesive mixture C, as long as it is to ensure uniform ball formation.

[0053] In step (5), the diameter of the spherical shape D is 2 to 5 mm.

[0054] In step (5-4), the drying conditions are as follows: drying temperature is 100℃-180℃, and drying time is 2-6 hours. The calcination conditions are as follows: calcination temperature is 400℃-650℃, and calcination time is 2-6 hours. The calcination atmosphere is one or more of air, nitrogen, and water vapor, preferably an air atmosphere.

[0055] In step (6), the carbon source includes a polymer compound and water-soluble cellulose.

[0056] In step (6), the polymer compound is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc.

[0057] In step (6), the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, etc.

[0058] In step (6), the impregnation solution contains 5% to 15% by mass of polymeric compounds and 0.5% to 3.0% by mass of water-soluble cellulose.

[0059] In step (6), the impregnation method can be any impregnation method used in industry, such as saturated impregnation, vacuum impregnation, etc.

[0060] In step (6), the volume-to-mass ratio of the impregnation solution (in ml) to the spherical shape D (in g) is 0.8 to 1.5 ml / g.

[0061] In step (6), the second active metal M2 is at least one of the group VIB metals. Preferably, the group VIB metal is Mo and / or W.

[0062] In step (6), the content of Group VIB metals (calculated as oxides) in the impregnation solution is 8.0 to 48.0 g / 100 ml.

[0063] In step (6), the source of the second active metal M2 in the impregnation solution containing the second active metal M2 can be one or two of ammonium tetramolybdate, ammonium heptamolybdate, etc.

[0064] In step (6), the standing conditions are: temperature of 20℃-40℃ and time of 2-12h.

[0065] In step (6), the drying conditions are as follows: the drying temperature is 100℃-180℃, and the drying time is 2-6h.

[0066] In step (7), the first calcination conditions are: calcination at a temperature of 500–700°C for 2–8 hours. The inert atmosphere is one or more of nitrogen and argon.

[0067] In step (7), the second calcination conditions are: calcination temperature of 600℃-750℃ and calcination time of 2-6h. The calcination atmosphere is an oxygen-containing gas, preferably air.

[0068] In step (7), the hydrogenation demetallization catalyst, based on the weight of the catalyst, contains 0.5% to 8.0% of Group VIII metals as oxides and 4.0% to 18.0% of Group VIB metals as oxides.

[0069] The second aspect of the present invention provides a residue oil hydrodemetallization catalyst prepared by the above method.

[0070] In this invention, the catalyst has a specific surface area of ​​150–180 m². 2 / g, with a pore volume of 0.45~0.85mL / g.

[0071] In this invention, the mechanical strength of the catalyst is 10.0 to 22.0 N / mm.

[0072] In this invention, the pore distribution of the catalyst is as follows: pores with a diameter <10nm account for 10% to 18% of the total pore volume, pores with a diameter of 10-30nm account for 50% to 60% of the total pore volume, and pores with a diameter >30nm account for less than 30% of the total pore volume.

[0073] In this invention, the catalyst further includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus. Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxides, is 0.5% to 8.0%. The auxiliary component can be derived from catalyst powder, introduced during the preparation of the support, or introduced after the preparation of the support.

[0074] The third aspect of this invention provides the application of the residue hydrodemetallization catalyst prepared by the above method in residue hydrotreating.

[0075] Compared with existing technologies, the hydrogenation demetallization catalyst prepared by the method of this invention has the following advantages:

[0076] The method of this invention has two main aspects: First, by using spheroidizing to control the particle size of two powders, a carrier with a continuously distributed pore structure from the inside out is prepared, solving the problem of the inability to continuously transition between the inner and outer pore structures when using different pore structures. Therefore, the catalyst prepared using this carrier has higher reactivity and metal-containing capacity. Second, a non-ammonium alkaline compound is used to treat the catalyst dust, and hydrothermal treatment is used to efficiently separate the alumina support from the active metal (the separated active metal can be used to prepare hydrogenation catalysts as needed). This fully utilizes the support component in the catalyst dust. Simultaneously, the non-ammonium alkaline compound treatment of the catalyst dust or alumina can form a pore structure on the alumina surface. The process involves several steps. First, the carbon powder is partially oxidized to generate more alkaline sites for loading the active metal, thus improving its dispersion during subsequent impregnation. Second, a membrane coating process is performed on a matrix support containing the first active metal. This is followed by inert gas calcination, which gradually evaporates moisture and compresses the latex particles to form a thin film containing crosslinkable groups. This crosslinking process creates a three-dimensional network film. Simultaneously, a second active metal is introduced during the coating process, allowing the crosslinking groups to directly disperse the second active metal during the formation of the three-dimensional network film. Through the second calcination in the stepwise calcination, the carbon film is burned off, allowing the metal to be directly and uniformly dispersed onto the support and work in conjunction with the first active metal, thereby improving the hydrogenation demetallization activity and stability. Third, to further control the distribution of the active components, the activated carbon powder is oxidized to generate a large number of hydrophilic groups, which anchor the first active metal, improving its dispersion and further preventing the interaction between nickel and the alumina support. The nickel is first loaded onto the activated carbon support, then ground into powder and granulated. This method effectively disperses the nickel first, reducing the formation of inactive nickel-aluminum spinel.

[0077] In summary, the catalyst prepared by this invention not only has good activity but also good stability, which is beneficial for extending the operating cycle of the device. Detailed Implementation

[0078] In this invention, the pore structure was tested using a cryogenic liquid nitrogen adsorption-desorption method, with the specific surface area obtained according to the BET equation and the pore size distribution according to the BJH model; crushability was tested using an intelligent particle strength testing machine; and the metal component content was analyzed using spectrophotometry. The catalyst powder used in the examples was powder generated during actual catalyst production and collected by a collector.

[0079] The present invention and its effects are further described below with reference to embodiments, but are not limited to the following embodiments.

[0080] Example 1

[0081] (1) Add 150g of catalyst powder (residue oil hydrodemetallization catalyst powder, particle size 0.01~1.00mm, based on the mass of the catalyst, the alumina content is 89.2%, the molybdenum oxide content is 8.6%, and the nickel oxide content is 2.2%) and 2g of sodium hydroxide to 2L of purified water, grind it with a ball mill to obtain a slurry with an average particle size of 6.0μm, adjust the pH of the slurry to 8.0, and then transfer it to a 5L high-pressure reactor for hydrothermal reaction at a reaction temperature of 180℃ for 10h. After the reaction, the product obtained is filtered by conventional means, and the filtered product is dried at 150℃ for 6h to obtain powder A.

[0082] (2) Add 84g of p-type alumina and 2g of sodium hydroxide to 2L of clean water, grind them with a ball mill to obtain a slurry with an average particle size of 3.5μm, and hydrothermally react at 260℃ for 8h. After the reaction is completed, the product is filtered by conventional means, and the filtered product is dried at 170℃ for 4h to obtain powder B.

[0083] (3) Prepare activated carbon powder X (specific surface area of ​​1000 m²) 2 / g), and subjected to oxidation treatment under the following conditions: nitric acid solution with a concentration of 8.0 mol / L, temperature of 90℃, and treatment time of 8 h. The first active metal M1 was loaded onto activated carbon X (M1 is Ni, Ni source is nickel nitrate, and the amount is 66.05% of the mass of activated carbon X), and M1 / modified activated carbon and powder A were mixed at a mass ratio of 1:5 and ground evenly to an average particle size of 4.5 μm to obtain powder AXM1;

[0084] (4) Add 20g of nitric acid and 18g of guar gum powder to 1L of aqueous solution, and then add 48g of phosphoric acid to prepare adhesive mixture C;

[0085] (5) Divide powder AXM1 and powder B into four portions, namely the first to the fourth portion. The total mass of powder AXM1 and powder B in each corresponding portion is 100g. Each time one portion of powder AXM1 and powder B is added, the amount of powder AXM1 added in the current portion is reduced, while the amount of powder B added in the current portion is increased. The mass ratio of powder AXM1 to powder B in the first portion is 90:10. The amount of powder AXM1 added in the current portion is 87% of the amount of powder AXM1 added in the previous portion. When each portion of powder AXM1 and powder B forms balls, the amount of binder mixture C added is 110% of the total mass of powder AXM1 and powder B in the current portion. The process includes:

[0086] (5-1) Place the first batch of powder AXM1 and the first batch of powder B into the turntable of the ball rolling machine, and simultaneously spray the binder mixture C onto the turntable. Rotate the ball rolling machine to form spherical particles. The forming time is 0.5 hours.

[0087] (5-2) Add the second part of powder AXM1 and the second part of powder B, while continuing to spray the binder mixture C. The ball continues to increase in size, and the molding time is 0.5 hours.

[0088] (5-3) Using the current portion of powder AXM1 and the current portion of powder B, continuously increase the size of the ball in the manner of step (5-2) until the Nth portion of powder AXM1 and the Nth portion of powder B are all formed into balls;

[0089] (5-4) Dry at 160℃ for 5 hours, and then calcine at 600℃ for 3 hours to obtain spherical shape D, wherein the diameter of spherical shape D is 2.5-4.5 mm.

[0090] (6) The spheres were impregnated with an impregnation solution containing polyimide, hydroxymethyl cellulose and the second active metal Mo at a volume-to-mass ratio of 1.2 ml / g to form a morph D. The mass content of polyimide in the impregnation solution was 6.0%, the mass content of hydroxymethyl cellulose was 0.6%, the molybdenum source was ammonium heptamolybdate, and the content of Mo in the impregnation solution (calculated as oxide) was 9.83 g / 100 ml. After standing at 30°C for 6 h and drying at 120°C for 4 h, catalyst intermediate E was obtained.

[0091] (7) Catalyst intermediate E was subjected to stepwise calcination. First, it underwent a first calcination (inert gas nitrogen) at 650°C for 4 hours to form a carbon film and disperse the metal. Then, it underwent a second calcination (air atmosphere) at 650°C for 4 hours, during which the carbon film was burned off, and the metal formed oxides, ultimately yielding the hydrodemetallization catalyst. Hydrodemetallization catalyst CAT-1 was obtained. Other physicochemical properties of catalyst CAT-1 are shown in Table 1.

[0092] Example 2

[0093] Compared with Example 1, the difference is that in step (1), a slurry with an average particle size of 5.5 μm was obtained by grinding with a ball mill, and the pH value of the slurry was adjusted to 9.0. The hydrothermal reaction temperature was 180℃, the reaction time was 18h, and after the reaction was completed, the product was filtered by conventional methods, and the filtered product was dried at 150℃ for 5h to obtain powder A; in step (3), powder AXM1 with an average particle size of 5.0 μm was obtained by grinding with a ball mill. Finally, the hydrogenation demetallization catalyst CAT-2 was prepared. Other physicochemical properties of catalyst CAT-2 are shown in Table 1.

[0094] Example 3

[0095] Compared with Example 1, the difference is that in step (1), a slurry with an average particle size of 4.5 μm was obtained by grinding with a ball mill, and the pH value of the slurry was adjusted to 8.5. The hydrothermal reaction temperature was 200℃, the reaction time was 16h, and after the reaction was completed, the product was filtered by conventional methods, and the filtered product was dried at 180℃ for 5h to obtain powder A; in step (3), powder AXM1 with an average particle size of 4.0 μm was obtained by grinding with a ball mill. Finally, the hydrogenation demetallization catalyst CAT-3 was prepared. Other physicochemical properties of catalyst CAT-3 are shown in Table 1.

[0096] Example 4

[0097] Compared with Example 1, the difference lies in the mass ratio of the first powder AXM1 to the first powder B in step (5) being 95:5, and the amount of the first powder AXM1 added being 81% of the amount of the previous powder AXM1 added. The obtained product was dried at 160°C for 4 hours and then calcined at 600°C for 4 hours to obtain spherical D. Finally, the hydrogenation demetallization catalyst CAT-4 was obtained. Other physicochemical properties of catalyst CAT-4 are shown in Table 1.

[0098] Example 5

[0099] Same as Example 1, except that in step (3), activated carbon powder X (with a specific surface area of ​​1000 m²) is prepared. 2 / g), and carried out oxidation treatment under the following conditions: the solution is nitric acid solution with a concentration of 6.0 mol / L, the temperature is 95℃, and the treatment time is 10h; in step (6), the impregnation solution used has a polyimide mass content of 12.0% and a hydroxymethyl cellulose mass content of 1.2%. And finally, the hydrogenation demetallization catalyst CAT-5 was obtained. Other physicochemical properties of catalyst CAT-5 are shown in Table 1.

[0100] Example 6

[0101] Compared with Example 1, the difference is that in step (2), p-type alumina is replaced with x-type alumina; in step (3), activated carbon powder X (with a specific surface area of ​​1000 m²) is prepared. 2 / g), and carried out oxidation treatment under the following conditions: the solution is nitric acid solution with a concentration of 6.0 mol / L, the temperature is 100℃, and the treatment time is 10h; in step (4), 30g of nitric acid and 20g of guar gum powder are added to 1L of aqueous solution, and then 48g of phosphoric acid is added to prepare binder mixture C. And finally, the hydrogenation demetallization catalyst CAT-6 is obtained. Other physicochemical properties of catalyst CAT-6 are shown in Table 1.

[0102] Example 7

[0103] Compared with Example 1, the difference is that in step (6), the impregnation solution used has a polyimide content of 14.0% and a hydroxymethyl cellulose content of 2.0%; in step (7), the catalyst intermediate E is calcined in steps. First, it undergoes a first calcination (inert gas nitrogen) at 550°C for 3 hours to form a carbon film and disperse the metal. Then, it undergoes a second calcination (air atmosphere) at 600°C for 5 hours. Finally, the hydrogenation demetallization catalyst CAT-7 is obtained. Other physicochemical properties of catalyst CAT-7 are shown in Table 1.

[0104] Comparative Example 1

[0105] Compared with Example 1, the difference is that in step (1), a ball mill was not used for grinding to obtain a slurry with an average particle size of 15.6 μm, while in step (3), a ball mill was used to grind the particles to obtain powder AXM1 with an average particle size of 15.6 μm. Finally, the hydrodemetallization catalyst DAT-1 was obtained. Other physicochemical properties of catalyst DAT-1 are shown in Table 1.

[0106] Comparative Example 2

[0107] Compared with Example 1, the difference is that powder A obtained in step (1) is removed. In step (3), powder A is replaced by an equal amount of powder B, and the powder is ground using a ball mill to obtain powder AXM1 with an average particle size of 2.2 μm. Finally, the hydrodemetallization catalyst DAT-2 is obtained. Other physicochemical properties of catalyst DAT-2 are shown in Table 1.

[0108] Comparative Example 3

[0109] Compared with Example 1, the difference is that all materials in step (5) are directly mixed, extruded, and shaped. The hydrogenation demetallization catalyst DAT-3 is finally obtained. Other physicochemical properties of catalyst DAT-3 are shown in Table 1.

[0110] Comparative Example 4

[0111] Compared to Example 1, the difference lies in the exchange of powder A and powder B, resulting in a catalyst with a continuous distribution of smaller pores at the inside and larger pores at the outside. The final hydrogenation demetallization catalyst DAT-4 was thus obtained. Other physicochemical properties of catalyst DAT-4 are shown in Table 1.

[0112] Comparative Example 5

[0113] Compared to Example 1, the difference lies in that no alkaline additives were introduced during the processing of powders A and B. The final hydrogenation demetallization catalyst DAT-5 was obtained. Other physicochemical properties of catalyst DAT-5 are shown in Table 1. Comparative Example 6

[0114] Compared to Example 1, the difference lies in that powder AXM1 and powder B were added to a ball rolling machine at a mass ratio of 1:1 for molding. The resulting hydrogenation demetallization catalyst DAT-6 was thus prepared. Other physicochemical properties of catalyst DAT-6 are shown in Table 1.

[0115] Table 1. Physicochemical properties of the hydrogenation demetallization catalysts in each example.

[0116] Serial Number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Catalyst number CAT-1 CAT-2 CAT-3 CAT-4 CAT-5 CAT-6 CAT-7 <![CDATA[Specific surface area, m 2 / g]]> 165 162 167 159 161 167 158 <![CDATA[Pore volume, cm 3 / g]]> 0.75 0.77 0.78 0.76 0.74 0.75 0.72 Mechanical strength, N / mm 13.8 13.5 13.4 13.1 13.3 13.6 13.5 Active ingredient content <![CDATA[MoO3,wt%]]> 14.3 14.4 14.2 14.5 14.3 14.4 14.2 NiO, wt% 2.5 2.4 2.5 2.6 2.4 2.5 2.3 Additive content <![CDATA[P2O5,wt%]]> 2.3 2.2 2.4 2.5 2.2 2.4 2.2 Pore ​​distribution <10nm,% 13.5 13.1 13.6 13.3 13.9 13.5 13.3 10-30nm, % 58.6 56.4 57.6 58.5 58.1 58.3 57.8 >30nm, % 27.9 30.5 28.8 28.2 28.0 28.2 28.9

[0117] Table 2 Physicochemical properties of the comparative hydrogenation demetallization catalysts

[0118]

[0119]

[0120] Evaluation test

[0121] The catalysts obtained in Examples 1-7 and Comparative Examples 1-6 were subjected to activity and stability tests on a 200ml fixed-bed hydrogenation test apparatus. The feedstock was residual oil with a density of 993.4 kg / m³. 3 The sample was prepared at 20°C, with an S content of 3.14 wt%, and metallic Ni and V contents of 33.7 μg / g and 68.8 μg / g, respectively. The CCR content was 12.5 wt%. The demetallization rate of Comparative Example 6 after 1200 h of operation was 100%. The demetallization rates for other examples and comparative examples were the relative demetallization rates after 1200 h of operation. Specific experimental conditions are shown in Table 3, and experimental results are shown in Tables 4 and 5.

[0122] Table 3 Experimental conditions

[0123] Reaction temperature, °C 375 Reaction pressure, MPa 15.7 <![CDATA[Liquid hourly space velocity, h -1 > 1.0 Hydrogen-to-oil ratio, V / V 700

[0124] Table 4. Test results of the hydrogenation demetallization catalysts in each example.

[0125]

[0126]

[0127] Table 5. Experimental results of hydrogenation demetallization catalysts in each comparative example.

[0128]

[0129] As can be seen from Tables 1-5, compared with the comparative catalyst, the hydrodemetallization catalyst prepared according to the method of the present invention has higher reactivity and stability, and can well meet the requirements of the hydrodemetallization process of heavy and residual oils.

Claims

1. A method for preparing a hydrodemetallization catalyst, comprising: (1) mixing a catalyst powder, an alkaline additive and water to obtain a slurry, grinding, hydrothermal reaction, filtering, drying, and preparing a powder A; (2) mixing alumina, an alkaline additive and water to obtain a slurry, grinding, hydrothermal reaction, drying, and preparing a powder B; (3) oxidizing an activated carbon powder X to obtain a modified activated carbon X, loading a first active metal M1 on the modified activated carbon X to obtain M1 / modified activated carbon X, mixing the M1 / modified activated carbon X and the powder A, and grinding to obtain a powder AXM1; (4) preparing a binder mixture C; (5) using a rolling ball forming method to form the powder AXM1, the powder B and the binder mixture C to obtain a spherical formed body D, specifically: dividing the powder AXM1 and the powder B into N portions, N being 2 or more, i.e. a first portion to an Nth portion, adding one portion of the powder AXM1 and the powder B each time, reducing the amount of the powder AXM1 in the current portion, and increasing the amount of the powder B in the current portion, the process comprising: (5-1) placing the first portion of the powder AXM1 and the first portion of the powder B on a rotating disc of a rolling ball machine, spraying the binder mixture C on the rotating disc, and rotating the rolling ball machine to form the material into spherical particles, (5-2) adding the second portion of the powder AXM1 and the second portion of the powder B, and continuing to spray the binder mixture C to continue to increase the size of the ball, (5-3) using the powder AXM1 in the current portion and the powder B in the current portion, and increasing the size of the ball in the manner of step (5-2) until the Nth portion of the powder AXM1 and the Nth portion of the powder B are all formed into balls; (5-4) drying and calcining to obtain the spherical formed body D; (6) immersing the spherical formed body D in an impregnation solution containing a carbon source and a second active metal M2, standing, drying, and obtaining a catalyst intermediate E; (7) performing step-by-step calcination on the catalyst intermediate E, first performing first calcination in an inert atmosphere, and then performing second calcination in an oxygen-containing atmosphere, and obtaining a hydrodemetallization catalyst. The average particle size of the alumina after grinding in step (2) is smaller than the average particle size of the powder after grinding in step (3); and the powder after grinding in step (3) has an average particle size of 1-10 μm.

2. The method of claim 1, wherein, In step (1), the catalyst powder refers to a calcined catalyst powder produced in a catalyst production process; and the particle size of the catalyst powder is 0.01-1.00 mm.

3. The method of claim 2, wherein, In step (1), the catalyst powder is one or more of a residue hydrodemetallization catalyst powder, a residue hydrodesulfurization catalyst powder, and a residue hydrodecarbon catalyst powder.

4. The method of claim 1, wherein, In step (1), the catalyst powder comprises an alumina carrier and an active metal component, the active metal being at least one of a Group VIII metal and a Group VIB metal; wherein the Group VIII metal is Co and / or Ni, and the Group VIB metal is Mo and / or W.

5. The method of claim 4, wherein, In step (1), in the catalyst powder, the active metal is a Group VIII metal and a Group VIB metal, the mass content of alumina is 50.0%-90.0% based on the mass of the catalyst powder, the mass content of the Group VIII metal in the form of an oxide is 0.5%-10.0%, and the mass content of the Group VIB metal in the form of an oxide is 4.0%-30.0%.

6. The method of claim 1 or 2, wherein, In step (1), in the slurry, the content of the catalyst powder is 2-50 g / 100 mL, and the content of the basic additive is 0.01-0.5 g / 100 mL. And / or, in step (1), the basic additive is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate. And / or, in step (1), the average particle size of the ground catalyst powder is 1-10 μm. And / or, in step (1), the hydrothermal reaction conditions are as follows: the temperature is 120-200 ℃, the pH value is 7.0-9.0, and the reaction time is 4-20 h. And / or, in step (1), the drying conditions are as follows: the drying temperature is 90-180 ℃, and the drying time is 1-24 h.

7. The method of claim 1, wherein, In step (2), the basic additive is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate. And / or, in step (2), the alumina is p-type alumina or χ-type alumina. And / or, in step (2), in the slurry, the content of the alumina is 3-20 g / 100 mL, and the content of the basic additive is 0.05-2.0 g / 100 mL. In step (2), the average particle size of the ground alumina is 0.1-5 μm. And / or, in step (2), the hydrothermal reaction conditions are as follows: the temperature is 180-320 ℃, the pH value is 9.0-13.0, and the reaction time is 6-48 h. And / or, in step (2), the drying conditions are as follows: the drying temperature is 120-180 ℃, and the drying time is 2-6 h.

8. The method of claim 1, wherein, The average particle size of the ground alumina in step (2) is at least 0.5 μm smaller than the average particle size of the ground powder in step (3).

9. The method of claim 1, wherein, The average particle size of the ground alumina in step (2) is at least 2.0 μm smaller than the average particle size of the ground powder in step (3).

10. The method of claim 1, wherein, In step (3), the oxidation treatment conditions are as follows: the solution is a nitric acid solution with a concentration of 5-12 mol / L, the volume-to-mass ratio of the oxidation solution to the activated carbon X is 0.9-1.8 mL / g, the temperature is 80-100 ℃, and the treatment time is 6-12 h. And / or, in step (3), the first active metal is at least one of the Group VIII metals, wherein the Group VIII metal is Co and / or Ni. And / or, in step (3), the content of the first active metal in the form of a first active metal nitrate is 20%-70% of the mass of the modified activated carbon X. In step (3), the ratio of M1 / modified activated carbon X to powder A is 1.0:2.0-5.

0.

11. The method of claim 1, wherein, In step (4), the binder mixture C comprises water, acid and colloid, the acid is one or more of nitric acid, citric acid, acetic acid, sulfuric acid, oxalic acid, and the colloid is at least one of methyl cellulose, sesbania powder and polyethylene glycol; In step (4), the mass concentration of the acid in the binder mixture C is 0.5%-4.5%; In step (4), the mass concentration of the colloid in the binder mixture C is 0.5%-2.5%.

12. The method of claim 1, wherein, In step (5), N is 3-20. In step (5), the total mass of the first portion of the powder AXM1 and the first portion of the powder B is 0.90-1.10 times the total mass of the first portion of the powder AXM1 and the first portion of the powder B. In step (5), the mass ratio of the first portion of the powder AXM1 to the first portion of the powder B is 90-98:2-10, and the addition amount of the current portion of the powder AXM1 is 77%-95% of the addition amount of the previous portion of the powder AXM1. In step (5), the mass ratio of the Nth portion of the powder AXM1 to the Nth portion of the powder B is 50-70:30-50. In step (5), the total addition amount of the binder mixture C accounts for 80.0%-150.0% of the total mass of the powder AXM1 and the powder B. In step (5), the ball formation time of each corresponding portion of the powder AXM1 and the powder B is controlled to be 0.5-1.5h. In step (5), the diameter of the ball-formed body D is 2-5mm.

13. The method of claim 12, wherein, In step (5), N is 3-10.

14. The method of claim 12, wherein, In step (5), the addition amount of the binder mixture C in the ball formation process of each corresponding portion of the powder AXM1 and the powder B accounts for 80%-150% of the mass of each corresponding portion of the powder AXM1 and the powder B.

15. The method of claim 1, wherein, In step (5-4), the drying conditions are as follows: the drying temperature is 100°C-180°C, and the drying time is 2-6h; the calcination conditions are as follows: the calcination temperature is 400°C-650°C, and the calcination time is 2-6h; and the calcination atmosphere is air.

16. The method of claim 1, wherein, In step (6), the carbon source comprises a high molecular compound and water-soluble cellulose; in the impregnation solution, the mass content of the high molecular compound is 5%-15%, and the mass content of the water-soluble cellulose is 0.5%-3.0%; and the volume-to-mass ratio of the impregnation solution to the ball-formed body D is 0.8-1.5mL / g. In step (6), the second active metal M2 is at least one of the Group VIB metals, wherein the Group VIB metal is Mo and / or W. In step (6), the content of the Group VIB metal in the impregnation solution is 8.0-48.0g / 100mL in terms of oxide. In step (6), the standing conditions are as follows: the temperature is 20°C-40°C, and the time is 2-12h. In step (6), the drying conditions are as follows: the drying temperature is 100°C-180°C, and the drying time is 2-6h.

17. The method of claim 16, wherein, The high molecular compound is one or more of polyimide, polyfurfuryl alcohol, and phenol-formaldehyde resin, and the water-soluble cellulose is one or more of methylol cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose.

18. The method of claim 1, wherein, In step (7), the first calcination condition is that the temperature is 500-700 ℃ and the calcination time is 2-8 h; and / or the second calcination condition is that the calcination temperature is 600-750 ℃ and the calcination time is 2-6 h.

19. The method of claim 1, wherein, In step (7), the hydrogen demetallization catalyst contains 0.5-8.0% of Group VIII metal and 4.0-18.0% of Group VIB metal, both in terms of oxides, based on the weight of the catalyst.

20. The hydrogen demetallization catalyst prepared by any of the methods of claims 1-19.

21. The catalyst of claim 20, wherein, The specific surface area of the hydrodemetallization catalyst is 150 to 180 m 2 / g, the pore volume is 0.45 to 0.85 mL / g, and / or the mechanical strength of the hydrodemetallization catalyst is 10.0 to 22.0 N / mm.

22. The use of the hydrogen demetallization catalyst prepared by any of the methods of claims 1-19 in residual oil hydroprocessing.

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