Process for the preparation of a hydrodemetallation catalyst

Abstract

The application discloses a preparation method of a hydrodemetallization catalyst. The method comprises the following steps: (1) mixing catalyst powder, an alkaline additive and water to obtain a slurry, grinding, hydrothermal treatment, filtration, 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) loading a first active metal M1 on activated carbon X to obtain M1 / activated carbon X, mixing M1 / activated carbon X and powder A, and grinding to obtain powder AXM1; (4) preparing a binder mixed solution C; (5) rolling the powder AXM1, the powder B and the binder mixed solution C into a spherical shape according to a specific mode to obtain a spherical molding body D; and (6) impregnating the spherical molding body D with an impregnation solution containing a second active metal to obtain the hydrodemetallization catalyst. According to the method, industrial dust generated in the production process of the catalyst is recovered, and the activity and stability of the catalyst are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to a preparation method of a hydrodemetallization catalyst, in particular a preparation method of a hydrodemetallization catalyst for residual oil hydroprocessing. BACKGROUND

[0002] With the increasing of the quality of crude oil, the quality of the feedstock of the residual oil hydroprocessing unit is also deteriorating, and the feedstock often contains high metal, high sulfur and high carbon residue. The ability of the catalyst system to remove and accommodate impurities directly affects whether the unit can operate stably for a long period. Catalyst dust is generated during the production of the residual oil hydroprocessing catalyst, and the catalyst dust is accumulated in the dust removal system and then becomes solid waste for recycling. The recycling process often causes environmental pollution and is not conducive to reducing the cost of catalyst production.

[0003] CN103041868A discloses a preparation method of a spherical catalyst carrier. The method improves the physical properties of the surface of the alumina carrier, adjusts the adhesion and rheological properties of the material during the molding of the carrier, reduces the plastic deformation of the molded carrier, and greatly improves the yield of the spherical carrier by adding anionic and cationic surfactants to the alumina precursor. However, the alumina carrier prepared by the method has a small pore size and is not suitable for the hydrogenation reaction of heavy residual oil.

[0004] CN101492612A discloses a hydroprocessing catalyst and a preparation method thereof. The catalyst is prepared by kneading suitable small-pore alumina and large-pore alumina to form an alumina carrier, and then loading hydrogenation active components and alkaline metal components. However, the capacity of the catalyst still needs to be further improved.

[0005] Currently, the residual oil hydroprocessing catalyst is loaded with metal components once. Due to the different adsorption capacities of the active components on the carrier, the components with strong adsorption capacity are easily enriched at the pore openings, and the components with weak adsorption capacity are distributed in the pores, resulting in uneven distribution of the active metal. Therefore, the capacity of the catalyst for removing and accommodating metal is limited. SUMMARY

[0006] In order to overcome the deficiencies in the prior art, the present application provides a preparation method of a hydrodemetallization catalyst, in particular a preparation method of a residual oil hydrodemetallization catalyst. The catalyst preparation method provided by the present application can not only utilize the catalyst dust generated during the production of the catalyst to prepare a hydrodemetallization catalyst, in particular a residual oil hydrodemetallization catalyst, but also recycle the industrial dust generated during the production of the catalyst, improve the activity and stability of the catalyst, avoid the generation of solid waste, and reduce the cost of catalyst production.

[0007] The first aspect of the present application provides a preparation method of a hydrodemetallization catalyst, comprising:

[0008] (1) mixing catalyst powder, alkaline additive and water to obtain a slurry, grinding, hydrothermal reaction, filtering, drying, and preparing powder A;

[0009] (2) mixing alumina, alkaline additive and water to obtain a slurry, grinding, hydrothermal reaction, drying, and preparing powder B;

[0010] (3) loading a first active metal M1 on activated carbon X to obtain M1 / activated carbon X, and mixing M1 / activated carbon X and powder A, and grinding to obtain powder AXM1;

[0011] (4) preparing binder mixed solution C;

[0012] (5) dividing powder AXM1 and powder B into N parts (N is 2 or more), i.e., first part to Nth part, adding one part of powder AXM1 and powder B each time, reducing the addition amount of powder AXM1 in the current part, and increasing the addition amount of powder B in the current part, and the process comprises:

[0013] (5-1) placing the first part of powder AXM1 and the first part of powder B on the turntable of a ball rolling machine, and spraying binder mixed solution C on the turntable at the same time, and rolling the ball to form spherical particles,

[0014] (5-2) adding the second part of powder AXM1 and the second part of powder B, and continuing to spray binder mixed solution C, and continuously increasing the ball,

[0015] (5-3) using the powder AXM1 of the current part and the powder B of the current part, and continuously increasing the ball in the manner of step (5-2) until the Nth part of powder AXM1 and the Nth part of powder B are all formed into balls;

[0016] (5-4) drying and calcining to obtain spherical forming body D;

[0017] (6) impregnating spherical forming body D with an impregnation solution containing a second active metal M2, standing, drying, and calcining to obtain a hydrodemetallization catalyst.

[0018] In step (1), the catalyst powder refers to catalyst powder generated in the production process of the catalyst, which can be one or more of residual oil hydrodemetallization catalyst powder, residual oil hydrodesulfurization catalyst powder, and residual oil hydrodecarbon catalyst powder. The particle size of the catalyst powder is 0.01-1.00 mm. The catalyst powder refers to waste catalyst that does not meet the requirements of catalyst use in at least one aspect of particle size and bulk specific gravity.

[0019] 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 / 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 Mo and / or W. The mass content of the alumina is 50.0% to 90.0%, the mass content of the Group VIII metal in terms of the oxide is 0.5% to 10.0%, and the mass content of the Group VIB metal in terms of the oxide is 4.0% to 30.0%, based on the mass of the catalyst powder. The catalyst powder can also contain a conventional auxiliary component, such as at least one of silicon, phosphorus, boron, etc., in an amount of 15.0% or less, based on the mass of the catalyst powder.

[0020] In step (1), the catalyst powder is a calcined catalyst powder.

[0021] In step (1), the content of the catalyst powder in the slurry is 2 to 50 g / 100 ml, and the content of the basic auxiliary agent is 0.01 to 0.5 g / 100 ml.

[0022] In step (1), the basic auxiliary agent is one or more of sodium hydroxide, potassium hydroxide, sodium carboxylate (such as sodium acetate, sodium formate, etc.), and other non-ammonium basic compounds.

[0023] In step (1), the powder grinding can be performed by ball milling, sand milling, etc., to obtain a ground sample having an average particle size of 1 to 10 μm.

[0024] In step (1), the hydrothermal reaction conditions are as follows: the temperature is 120 to 200°C, the pH value is 7.0 to 9.0, and the reaction time is 4 to 20 h.

[0025] In step (1), the drying conditions are as follows: the drying temperature is 90 to 180°C, and the drying time is 1 to 24 h.

[0026] In step (2), the basic auxiliary agent is one or more of sodium hydroxide, potassium hydroxide, sodium carboxylate (such as sodium acetate, sodium formate, etc.), and other basic compounds.

[0027] In step (2), the alumina is ρ-type alumina or χ-type alumina.

[0028] In step (2), the content of the alumina in the slurry is 3 to 20 g / 100 ml, and the content of the basic auxiliary agent is 0.05 to 2.0 g / 100 ml.

[0029] In step (2), the powder grinding can be performed by ball milling, sand milling, etc., to obtain a ground sample having an average particle size of 0.1 to 5 μm.

[0030] 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 6-48h.

[0031] In step (2), the drying conditions are as follows: the drying temperature is 120-180℃, and the drying time is 2-6h.

[0032] In step (3), the first active metal is at least one of the Group VIII metals. Preferably, the Group VIII metal is Co and / or Ni.

[0033] 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).

[0034] In step (3), the content of the first active metal, calculated as the first active metal nitrate, is 20.0%-65.0% of the mass of the activated carbon.

[0035] In step (3), the specific surface area of the activated carbon X is 800-1500m 2 / g, which can be burned off in an air calcination atmosphere at 500-700℃.

[0036] In step (3), the mass ratio of M1 / activated carbon X and powder A is 1.0:2.0-5.0.

[0037] In step (3), the powder grinding can be performed by ball milling, sand milling or the like, and the ground sample has an average particle size of 1-10μm. The average particle size after step (2) grinding is smaller than that after step (3) grinding, at least 0.5μm smaller, preferably at least 2.0μm smaller.

[0038] In step (4), the binder mixture C comprises an acid and a colloid, the acid is one or more of nitric acid, citric acid, acetic acid, sulfuric acid, oxalic acid, acetic acid, and the colloid is at least one of methyl cellulose, sesbania powder, polyethylene glycol, etc.

[0039] In step (4), the mass concentration of the acid in the binder mixture C is 0.5%-4.5%.

[0040] In step (4), the mass concentration of the colloid in the binder mixture C is 0.5%-2.5%.

[0041] In step (4), the binder mixture C can also contain an additive, the additive is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus.

[0042] In step (5), the powder AXM1 and the powder B are each divided into N parts, N is 2 or more, preferably 3-20, and further preferably 3-10. In step (5), the total mass of the powder AXM1 and the powder B in each corresponding part is 0.90-1.10 times the total mass of the first part of the powder AXM1 and the first part of the powder B. For example, when the powder AXM1 and the powder B are added for the xth time, the total mass of the xth part of the powder AXM1 and the xth part of the powder B is 0.90-1.10 times the total mass of the first part of the powder AXM1 and the first part of the powder B, x is 1-N.

[0043] In step (5), the mass ratio of the first part of the powder AXM1 to the first part of the powder B is 90-98:2-10, and the addition amount of the current part of the powder AXM1 is 77%-95% of the addition amount of the previous part of the powder AXM1.

[0044] In step (5), preferably, the mass ratio of the Nth part of the powder AXM1 to the Nth part of the powder B is 50-70:30-50.

[0045] In step (5), the total addition amount of the binder mixture C is 80.0%-150.0% of the total mass of the powder AXM1 and the powder B.

[0046] In step (5), the addition amount of the binder mixture C in the ball forming process of each corresponding part of the powder AXM1 and the powder B is 80%-150% of the mass of each corresponding part of the powder AXM1 and the powder B.

[0047] In step (5), the ball forming time of each corresponding part of the powder AXM1 and the powder B is controlled to be 0.5-1.5 h.

[0048] In step (5), the spraying rate of the binder mixture C is not strictly limited, as long as uniform ball formation is ensured.

[0049] In step (5), the diameter of the ball-formed body D is 2-5 mm.

[0050] In step (5), the drying conditions are as follows: the drying temperature is 100°C-180°C, and the drying time is 2-6 h. The calcination conditions are as follows: the calcination temperature is 400°C-650°C, and the calcination time is 2-6 h. The calcination atmosphere is one or a combination of air, nitrogen, water vapor, etc., and is preferably an air atmosphere.

[0051] In step (5), step (5-5) is added after step (5-4), that is, the ball-formed body D is first coated with a carbon source, and then subjected to inert atmosphere calcination before step (6).

[0052] In step (5-5), the coating treatment is carried out using an aqueous emulsion containing a high molecular compound and water-soluble cellulose. In the aqueous emulsion, the high molecular compound has a mass content of 5% to 15%, and the water-soluble cellulose has a mass content of 0.5% to 3.0%.

[0053] In step (5-5), the high molecular compound is one or more of polyimide, polyfurfuryl alcohol, phenol formaldehyde resin, and the like.

[0054] In step (5-5), the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and the like.

[0055] In step (5-5), the ratio of the amount of the aqueous emulsion (in volume ml) to the amount of the spherical formed body D (in mass g) is 0.8 to 1.5 ml / g.

[0056] In step (5-5), the inert atmosphere firing condition is a condition of firing at a temperature of 500 to 700°C for 2 to 8 h. The inert atmosphere is one or more of nitrogen and argon.

[0057] In step (6), the impregnation method is any one of the impregnation methods in industry, such as saturation impregnation, vacuum impregnation, and the like.

[0058] In step (6), the second active metal M2 is at least one of the Group VIB metals. Among them, the Group VIB metal is preferably Mo and / or W.

[0059] In step (6), in the impregnation solution containing the second active metal M2, the content of the Group VIB metal (calculated as an oxide) is 8.0 to 48.0 g / 100 ml.

[0060] In step (6), in the impregnation solution containing the second active metal M2, the source of the second active metal M2 can be one or both of ammonium tetramolybdate and ammonium heptamolybdate.

[0061] In step (6), the standing condition is a temperature of 20°C to 40°C and a time of 2 to 12 h.

[0062] In step (6), the drying condition is a drying temperature of 100°C to 180°C and a drying time of 2 to 6 h. The firing condition is a firing temperature of 600°C to 750°C and a firing time of 2 to 6 h. The firing atmosphere is one or more of air, nitrogen, water vapor, and the like, and is preferably an air atmosphere.

[0063] In step (6), the hydrogen demetallization catalyst has a content of Group VIII metal in the form of an oxide of 0.5% to 8.0% and a content of Group VIB metal in the form of an oxide of 4.0% to 18.0%, based on the weight of the catalyst.

[0064] The second aspect of the present application provides a residue hydrogen demetallization catalyst prepared by the above method.

[0065] In the present application, the specific surface area of the catalyst is 150 to 210 m 2 / g, and the pore volume is 0.65 to 0.85 mL / g.

[0066] In the present application, the mechanical strength of the catalyst is 10.0 to 22.0 N / mm.

[0067] In the present application, the pore distribution of the catalyst is as follows: the pore volume of the pores with a pore diameter of <10 nm accounts for 15% to 20% of the total pore volume, the pore volume of the pores with a pore diameter of 10-30 nm accounts for 55% to 65% of the total pore volume, and the pore volume of the pores with a pore diameter of >30 nm accounts for 25% or less of the total pore volume.

[0068] In the present application, the catalyst further comprises an auxiliary component selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus. The content of the auxiliary component in the form of an oxide is 0.5% to 8.0%, based on the mass of the catalyst. The auxiliary component can be derived from the catalyst powder, can be introduced during the preparation of the carrier, or can be introduced after the preparation of the carrier.

[0069] The third aspect of the present application provides the use of the residue hydrogen demetallization catalyst prepared by the above method in residue hydroprocessing.

[0070] Compared with the prior art, the hydrogen demetallization catalyst prepared by the method of the present application has the following advantages:

[0071] The method of the present application has the following advantages: 1. The carrier with the pore structure continuously distributed from large to small from inside to outside is prepared by using two kinds of powders with different particle sizes to be formed by rolling ball, which solves the problem of non-continuous transition of the inner layer and the outer layer pore structure of the previous catalysts, so that the catalyst prepared by the carrier has higher reaction activity and metal capacity; 2. The catalyst dust is treated by using non-ammonium alkaline compound, and the alumina carrier and the active metal are efficiently separated through hydrothermal treatment (the separated active metal can be used to prepare hydrogenation catalyst according to the situation), so that the carrier component in the catalyst dust is fully utilized, and the alumina treated by the non-ammonium alkaline compound or the catalyst dust can form part of the hydroxyl group on the surface of the alumina, so as to provide more alkaline sites for the loading of the active metal, and improve the dispersion degree of the active metal in the subsequent impregnation process; 3. The film coating treatment is preferably carried out on the substrate carrier containing the first active metal, and the water is gradually evaporated through the inert gas roasting, so that the latex particles are gradually extruded to form a thin film, and the structure contains a cross-linkable group, which is cross-linked to form a three-dimensional network film. The film temporarily provides a loading position for the second active metal, and after the catalyst is roasted, the film disappears, and the second active metal is uniformly dispersed on the substrate carrier and cooperates with the first active metal, which is beneficial to improve the hydrogen demetallization activity and stability; 4. In order to further prevent the interaction between the metal nickel and the alumina carrier, the metal nickel is first loaded on the activated carbon carrier, and then ground into powder, and then formed into a ball, which can effectively disperse the metal nickel and reduce the formation of inactive nickel aluminum spinel.

[0072] In summary, the catalyst prepared by the present application not only has good activity, but also has good stability, which is beneficial to prolong the operation period of the device. DETAILED DESCRIPTION

[0073] The scheme and effect of the present application will be further described below in combination with examples, but are not limited to the following examples.

[0074] In the present application, the pore structure is tested by low-temperature liquid nitrogen adsorption and desorption method, the specific surface area is obtained according to BET equation, the pore size distribution is obtained according to BJH model, and the crushing resistance is detected by intelligent particle strength tester; the content of metal component is analyzed by spectrophotometry.

[0075] The catalyst powder used in the examples is the powder collected by the collector after the catalyst is roasted in the actual production process. Example 1

[0076] (1) 2L pure water is added with 150g catalyst powder (residual oil hydrodemetalization catalyst powder, particle size 0.01-1.00mm, taking the mass of the catalyst as the basis, alumina content 86.0%, molybdenum oxide content 11.5%, nickel oxide content 2.5%) and 2g sodium hydroxide, and a ball mill is used for grinding to obtain a slurry with an average particle size of 6.5μm, the pH value of the slurry is adjusted to 8.0, and then it is transferred to a 5L autoclave for hydrothermal reaction, the reaction temperature is 180℃, the reaction time is 10h, after the reaction is completed, the product is filtered by a conventional method, and the filtered product is dried at 130℃ for 4h to obtain powder A; sufficient powder A is synthesized by the same method for later use;

[0077] (2) 2L pure water is added with 84g of ρ-type alumina and 2g of sodium hydroxide, and a ball mill is used for grinding to obtain a slurry with an average particle size of 3.0μm, which is subjected to hydrothermal reaction at 260℃ for 8h, after the reaction is completed, the product is filtered by a conventional method, and the filtered product is dried at 150℃ for 6h to obtain powder B; sufficient powder B is synthesized by the same method for later use;

[0078] (3) The first active metal Ni is loaded on activated carbon X (specific surface area 1000m 2 / g) (the source of Ni is nickel nitrate, and the amount used is 41.94% of the mass of activated carbon X), and the activated carbon and powder A are uniformly mixed and ground in a mass ratio of 1:4, with an average particle size of 5.0μm, to obtain powder AXM1; sufficient powder AXM1 is synthesized by the same method for later use;

[0079] (4) 1L of an aqueous solution is added with 25g of nitric acid and 14g of sesbania powder, and then 37.3g of phosphoric acid is added to prepare binder mixture C; sufficient binder mixture C is synthesized by the same method for later use;

[0080] (5) The powder AXM1 and the powder B are each divided into seven parts, i.e. the first part to the seventh part, and the total mass of the powder AXM1 and the powder B in each corresponding part is 100g, one part of the powder AXM1 and the powder B is added each time, the addition amount of the powder AXM1 in the current part is reduced while the addition amount of the powder B in the current part is increased; wherein the mass ratio of the first part of the powder AXM1 to the first part of the powder B is 96:4, the addition amount of the powder AXM1 in the current part is 91% of the addition amount of the powder AXM1 in the previous part, and when the powder AXM1 and the powder B in each part are formed into a ball, the addition amount of the binder mixture C is 120% of the mass sum of the powder AXM1 and the powder B in the current part, and the process includes:

[0081] (5-1) Put the first portion of powder AXM1 and the first portion of powder B into the rotating disc of the ball forming machine, and spray the binder mixture C onto the rotating disc, rotate the ball to form, the forming time is 0.8h, the material is formed into spherical particles,

[0082] (5-2) Add the second portion of powder AXM1 and the second portion of powder B, and continue to spray the binder mixture C, and the ball continues to grow, the forming time is 0.8h,

[0083] (5-3) Use the current portion of powder AXM1 and the current portion of powder B, and continuously grow the ball in the manner of step (5-2) until the seventh portion of powder AXM1 and the seventh portion of powder B are all formed into balls;

[0084] (5-4) Dry at 150℃ for 6h, and then calcine at 650℃ for 4h to obtain the spherical forming body D, wherein the diameter of the spherical forming body D is 3-5mm;

[0085] (5-5) The spherical forming body D is subjected to surface coating treatment, and an aqueous emulsion containing polyimide and hydroxymethyl cellulose is used, the mass content of polyimide in the aqueous emulsion is 10.0%, and the mass content of hydroxymethyl cellulose is 1.0%. The usage ratio of the aqueous emulsion (by volume ml) to the spherical forming body D (by mass g) is 1.2ml / g. The calcination is carried out in a nitrogen atmosphere, and the calcination conditions are: calcination at a temperature of 700℃ for 4h, and after calcination, a thin film with a three-dimensional network structure is formed on the surface of the spherical forming body D to obtain the catalyst intermediate E;

[0086] (6) The catalyst intermediate E is saturatedly impregnated in an impregnation liquid containing the second active metal Mo (the molybdenum source is ammonium heptamolybdate), the content of Mo (calculated as the oxide) is 13.75g / 100ml, the carrier after impregnation of the metal is placed at a temperature of 30℃ for 6h, then dried at a temperature of 150℃ for 5h, and then air calcined at 650℃ for 3h to obtain the hydrodemetallization catalyst CAT-1. The other physicochemical properties of the catalyst CAT-1 are shown in Table 1. Example 2

[0087] Compared with Example 1, the difference is that in step (1), the slurry with an average particle size of 5.5μm is obtained after grinding by a ball mill, and the pH value of the slurry is adjusted to 8.5. The hydrothermal reaction temperature is 190℃, and the reaction time is 14h, after the reaction, the product is filtered by a conventional method, and the product obtained by filtration is dried at a temperature of 160℃ for 6h to obtain the powder A; in step (3), the powder AXM1 with an average particle size of 4.5μm is obtained after grinding by a ball mill. Finally, the hydrodemetallization catalyst CAT-2 is obtained. The other physicochemical properties of the catalyst CAT-2 are shown in Table 1. Example 3

[0088] Compared with Example 1, the difference is that in step (1), the slurry with an average particle size of 5.0 μm is obtained after grinding by a ball mill, and the pH value of the slurry is adjusted to 8.0. The hydrothermal reaction temperature is 200 ℃, and the reaction time is 12 h. After the reaction, the product is filtered by a conventional method, and the product obtained by filtration is dried at 180 ℃ for 5 h to obtain powder A. In step (3), the powder AXM1 with an average particle size of 4.0 μm is obtained after grinding by a ball mill. Finally, the hydrogen demetallization catalyst CAT-3 is prepared. The other physical and chemical properties of the catalyst CAT-3 are shown in Table 1. Example 4

[0089] Compared with Example 1, the difference is that in step (3), the first active metal Ni is loaded on the activated carbon X (the source of Ni is nickel nitrate, and the amount is 34.56% of the mass of the activated carbon X), and the activated carbon X and the powder A are uniformly mixed and ground at a mass ratio of 1:3, and the average particle size is 5.0 μm, to obtain the powder AXM1. In step (4), 22 g of nitric acid and 16 g of sesbania powder are added to 1 L of water, and then 40.08 g of phosphoric acid is added to prepare the binder mixture C. In step (5), the powder AXM1 and the powder B are divided into five parts, i.e., the first part to the fifth part. The mass ratio of the first part of the powder AXM1 to the first part of the powder B is 90:10, and the addition amount of the current part of the powder AXM1 is 88% of the addition amount of the previous part of the powder AXM1. The product is dried at 160 ℃ for 5 h, and then calcined at 650 ℃ for 4 h to obtain the spherical shaped body D. In step (6), the catalyst intermediate E is saturatedly impregnated in an impregnation solution containing the second active metal Mo (the source of Mo is ammonium heptamolybdate), and the content of Mo (calculated as an oxide) is 14.73 g / 100 ml. The carrier after impregnation of the metal is placed for 8 h. Finally, the hydrogen demetallization catalyst CAT-4 is prepared. The other physical and chemical properties of the catalyst CAT-4 are shown in Table 1. Example 5

[0090] The same as example 1, except that in step (3), the first active metal Ni is supported on activated carbon X (the Ni source is nickel nitrate, and the amount used is 61.50% of the mass of activated carbon X), and activated carbon X and powder A are uniformly mixed at a mass ratio of 1:5 and then uniformly ground, with an average particle size of 5.0 μm, to obtain powder AXM1; in step (4), 24 g of nitric acid and 18 g of sesbania powder are added to 1 L of an aqueous solution, and then 43.32 g of phosphoric acid is added to prepare binder mixture C; in step (5), powder AXM1 and powder B are each divided into four parts, i.e., first to fourth parts, the mass ratio of the first part of powder AXM1 to the first part of powder B is 90:10, and the addition amount of the current part of powder AXM1 is 86% of the addition amount of the previous part of powder AXM1. The resulting product is dried at 160°C for 5 h, and then calcined at 650°C for 4 h to obtain spherical shaped body D; in step (5-5), an aqueous emulsion containing polyimide and hydroxymethyl cellulose is used, the mass content of polyimide in the aqueous emulsion is 11.0%, and the mass content of hydroxymethyl cellulose is 1.5%. In step (6), the catalyst intermediate E is saturatedly impregnated in an impregnation solution containing the second active metal Mo (the Mo source is ammonium heptamolybdate), the Mo content (calculated as the oxide) is 16.15 g / 100 ml, the carrier after metal impregnation is allowed to stand for 8 h. And finally the hydrogen demetallization catalyst CAT-5 is prepared. The other physicochemical properties of catalyst CAT-5 are shown in Table 1. Example 6

[0091] The same as example 1, except that in step (2), the p-type alumina is replaced by χ-type alumina; in step (3), the first active metal Ni is supported on activated carbon X (the Ni source is nickel nitrate, and the amount used is 20.34% of the mass of activated carbon X), and activated carbon X and powder A are uniformly mixed at a mass ratio of 1:2 and then uniformly ground, with an average particle size of 5.0 μm, to obtain powder AXM1; in step (4), 26 g of nitric acid and 20 g of sesbania powder are added to 1 L of an aqueous solution, and then 35.22 g of phosphoric acid is added to prepare binder mixture C; in step (5), powder AM1 and powder B are each divided into eight parts, i.e., first to eighth parts, the mass ratio of the first part of powder AM1 to the first part of powder B is 97:3, and the addition amount of the current part of powder AM1 is 92% of the addition amount of the previous part of powder AM1; in step (6), the catalyst intermediate E is saturatedly impregnated in an impregnation solution containing the second active metal Mo (the Mo source is ammonium heptamolybdate), the Mo content (calculated as the oxide) is 12.92 g / 100 ml, the carrier after metal impregnation is allowed to stand for 10 h. And finally the hydrogen demetallization catalyst CAT-6 is prepared. The other physicochemical properties of catalyst CAT-6 are shown in Table 1. Example 7

[0092] The same as example 1, except that the step (5-5) of surface coating treatment of the sphere-forming body D is omitted. And finally the hydrogen demetallization catalyst CAT-7 is prepared. The other physical and chemical properties of the catalyst CAT-7 are shown in Table 1. Comparative Example 1

[0093] Compared with example 1, the difference is that the ball mill is not used for grinding in step (1), and the slurry with an average particle size of 16.5 μm is obtained, and the ball mill is used for grinding in step (3), and the powder AXM1 with an average particle size of 14.5 μm is obtained. And finally the hydrogen demetallization catalyst DAT-1 is prepared. The other physical and chemical properties of the catalyst DAT-1 are shown in Table 2. Comparative Example 2

[0094] Compared with example 1, the difference is that the powder A obtained in step (1) is removed. In step (3), the powder A is replaced by an equal amount of powder B, and the ball mill is used for grinding, and the powder AXM1 with an average particle size of 3.0 μm is obtained. And finally the hydrogen demetallization catalyst DAT-2 is prepared. The other physical and chemical properties of the catalyst DAT-2 are shown in Table 2. Comparative Example 3

[0095] Compared with example 1, the difference is that all the materials are directly mixed and extruded in step (5). And finally the hydrogen demetallization catalyst DAT-3 is prepared. The other physical and chemical properties of the catalyst DAT-3 are shown in Table 2. Comparative Example 4

[0096] Compared with example 1, the difference is that the powder A and powder B are exchanged, and the prepared catalyst has a continuous distribution trend of small inside and large outside. And finally the hydrogen demetallization catalyst DAT-4 is prepared. The other physical and chemical properties of the catalyst DAT-4 are shown in Table 2. Comparative Example 5

[0097] Compared with example 1, the difference is that no alkaline additive is introduced in the preparation of the powder A and B. And finally the hydrogen demetallization catalyst DAT-5 is prepared. The other physical and chemical properties of the catalyst DAT-5 are shown in Table 2. Comparative Example 6

[0098] Compared with example 1, the difference is that the ball mill is used for molding in the powder AXM1 and powder B each with a mass ratio of 1:1. And finally the hydrogen demetallization catalyst DAT-6 is prepared. The other physical and chemical properties of the catalyst DAT-6 are shown in Table 2.

[0099] Table 1 Physical and chemical properties of hydrogen demetallization catalysts of various examples

[0100]

[0101] Table 2 Physical and chemical properties of hydrogen demetallization catalysts of each comparative example

[0102]

[0103] Evaluation test

[0104] The activity stability tests were carried out on the catalysts obtained in Examples 1-7 and Comparative Examples 1-6 respectively in a 200 ml fixed bed hydrogenation test device, and the raw oil was residual oil raw material with a density of 993.7 kg / m 3 (20℃), S content of 3.26wt%, and metal Ni and V contents of 35.4 μg / g and 70.6 μg / g respectively, and CCR content of 12.8wt%. The demetallization rate of Comparative Example 6 after 1200h operation was taken as 100%, and the relative demetallization rate of Ni+V of other examples and comparative examples after 1200h operation was taken. The specific test conditions are shown in Table 3, and the test results are shown in Tables 4 and 5.

[0105] Table 3 Test conditions

[0106]

[0107] Table 4 Test results of hydrogen demetallization catalysts of each example

[0108]

[0109] Table 5 Test results of hydrogen demetallization catalysts of each comparative example

[0110]

[0111] As can be seen from Tables 1-5, compared with the comparative catalysts, the hydrogen demetallization catalysts prepared according to the method of the present application have higher reaction activity and stability, and can well meet the heavy oil and residual oil hydrogen demetallization process.

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 obtaining a powder A; (2) mixing alumina, an alkaline additive and water to obtain a slurry, grinding, hydrothermal reaction, drying, and obtaining a powder B; (3) loading a first active metal M1 on activated carbon X to obtain M1 / activated carbon X, mixing M1 / activated carbon X and the powder A, and grinding to obtain a powder AXM1; (4) preparing a binder mixed solution C; (5) 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 ball-rolling machine, spraying the binder mixed solution C on the rotating disc, and rotating the ball to form a spherical particle, (5-2) adding the second portion of the powder AXM1 and the second portion of the powder B, and continuously spraying the binder mixed solution C to continuously increase the size of the ball, (5-3) continuously increasing the size of the ball by using the powder AXM1 in the current portion and the powder B in the current portion according to 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 a spherical formed body D; (6) impregnating the spherical formed body D with an impregnation solution containing a second active metal M2, standing, drying, and calcining to obtain 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 the catalyst powder, the active metal is the Group VIII metal and the Group VIB metal, the mass content of the alumina is 50.0%-90.0% based on the mass of the catalyst powder, the mass content of the Group VIII metal as calculated based on the oxide is 0.5%-10.0%, and the mass content of the Group VIB metal as calculated based on the oxide is 4.0%-30.0%.

6. The method of claim 1, wherein, In step (1), the catalyst powder content in the slurry is 2-50 g / 100 mL, and the alkaline additive content is 0.01-0.5 g / 100 mL. And / or, in step (1), the alkaline 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: a temperature of 120-200 °C, a pH of 7.0-9.0, and a reaction time of 4-20 h; And / or, in step (1), the drying conditions are as follows: a drying temperature of 90-180 °C and a drying time of 1-24 h.

7. The method of claim 1, wherein, In step (2), the alkaline 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), the content of alumina in the slurry is 3-20 g / 100 mL, and the content of the alkaline 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: a temperature of 180-320 °C, a pH of 9.0-13.0, and a reaction time of 6-48 h; And / or, in step (2), the drying conditions are as follows: a drying temperature of 120-180 °C and a drying time of 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 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, calculated as the first active metal nitrate, is 20.0%-65.0% by mass of the activated carbon; And / or, in step (3), the mass ratio of M1 / activated carbon X and 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, an acid, and a colloid, the acid is one or more of nitric acid, citric acid, acetic acid, sulfuric acid, and oxalic acid, and the colloid is at least one of methyl cellulose, sesbania powder, and polyethylene glycol; And / or, in step (4), the mass concentration of the acid in the binder mixture C is 0.5%-4.5%; And / or, 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; And / or, in step (5), the total mass of each corresponding portion of the powder AXM1 and 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; And / or, 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. And / or, 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; And / or, in step (5), the total amount of the binder mixture C added accounts for 80.0%-150.0% of the total mass of the powder AXM1 and the powder B; And / or, in step (5), the time for each corresponding portion of the powder AXM1 and the powder B to form a ball is controlled to be 0.5-1.5 h; And / or, in step (5-4), the diameter of the ball-formed body D is 2-5 mm.

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 amount of the binder mixture C added during the ball-forming 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 100-180℃, and the drying time is 2-6 h; the calcination conditions are as follows: the calcination temperature is 400-650℃, and the calcination time is 2-6 h; and the calcination atmosphere is air.

16. The method of claim 1, wherein, In step (5), after step (5-4), step (5-5) is added, i.e., the ball-formed body D is first subjected to surface coating treatment using a carbon source, and then subjected to step (6) after inert atmosphere calcination. And / or, in step (6), the inert atmosphere calcination conditions are as follows: the temperature is 500-700℃, and the calcination time is 2-8 h.

17. The method of claim 16, wherein, The coating treatment uses an aqueous emulsion containing a high-molecular compound and water-soluble cellulose; in the aqueous emulsion, 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%.

18. The method of claim 17, wherein, The high-molecular compound is one or more of polyimide, polyfurfuryl alcohol, and phenolic resin; and the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethylmethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, and hydroxyethyl cellulose.

19. The method of claim 17, wherein, The use amount ratio of the aqueous emulsion (volume mL) to the ball-formed body D (mass g) is 0.8-1.5 mL / g.

20. The method of claim 1, wherein, 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; And / or, in step (6), in the impregnation solution containing the second active metal M2, the content of the Group VIB metal, calculated as an oxide, is 8.0-48.0 g / 100 mL; And / or, in step (6), the drying conditions are as follows: the drying temperature is 100-180℃, and the drying time is 2-6 h; the calcination conditions are as follows: the calcination temperature is 600-750℃, the calcination time is 2-6 h, and the calcination atmosphere is air.

21. The method of claim 1, wherein, In step (6), the hydrogen demetallization catalyst contains the Group VIII metal and the Group VIB metal; the content of the Group VIII metal, calculated as an oxide, is 0.5%-8.0% based on the weight of the catalyst; and the content of the Group VIB metal, calculated as an oxide, is 4.0%-18.0% based on the weight of the catalyst.

22. A hydrogen demetallization catalyst prepared by any of the methods in claims 1-21.

23. The catalyst of claim 22, wherein, The specific surface area of the hydrogenation demetallization catalyst is 150-210 m 2 / g, the pore volume is 0.65-0.85 mL / g, and / or the mechanical strength of the hydrogenation demetallization catalyst is 10.0-22.0 N / mm.

24. The use of a hydrodemetallization catalyst produced by any of the methods of claims 1-21 in a residue hydroprocessing.

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