Preparation method of hydrodemetallization catalyst

Abstract

The invention discloses a preparation method of a hydrodemetallization catalyst. The method comprises the following steps: (1) mixing catalyst powder, an alkaline auxiliary agent and water to obtain slurry, and performing grinding, hydrothermal treatment, filtering and drying to obtain powder A; (2) mixing aluminum oxide, an alkaline auxiliary agent and water to obtain slurry, and performing grinding, hydrothermal treatment and drying to obtain powder B; (3) loading first active metal M1 on activated carbon X to obtain M1 / activated carbon X, mixing the M1 / activated carbon X and the powder A, and grinding to obtain powder AXM1; (4) preparing a binder mixed solution C; (5) carrying out ball rolling molding on the powder AXM1, the powder B and the binder mixed solution C according to a specific mode to obtain a spherical molded body D; and (6) impregnating the spherical molded body D with an impregnation liquid containing a second active metal to prepare the hydrodemetallization catalyst. According to the method for preparing the catalyst, industrial dust generated in the production process of the catalyst is recycled, and meanwhile the activity and stability of the catalyst are improved.

Description

Technical Field

[0001] The invention relates to a method for preparing a hydrodemetallization catalyst, in particular to a method for preparing a hydrodemetallization catalyst used for residual oil hydroprocessing. Background Art

[0002] As crude oil becomes increasingly inferior and heavy, the raw material properties of the residue oil hydroprocessing unit are also deteriorating overall. It is often necessary to process residue oil raw materials with high metal content, high sulfur content, and high carbon residue. The impurity removal and impurity tolerance of the entire residue oil hydroprocessing catalyst system directly affect whether the unit can operate stably for a long period of time. During the production process of residue oil hydroprocessing catalysts, some catalyst dust will be generated, and these catalyst dusts are often accumulated in the dust removal system and become solid waste for recycling. The recycling process often causes great pollution to the environment and is not conducive to reducing costs in the catalyst production process.

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

[0004] CN101492612A discloses a hydrogenation treatment catalyst and a preparation method thereof, wherein suitable small-pore alumina and large-pore alumina are selected and kneaded to form an alumina carrier, and then the hydrogenation active component and the alkaline metal component are loaded to form a catalyst. However, the capacity of the catalyst still needs to be further improved.

[0005] At present, most residue oil hydrogenation catalysts are loaded with metal components at one time. Due to the different adsorption capacities of the active components on the carrier, the components with strong adsorption capacity tend to be enriched at the pore mouth, while the components with weak adsorption capacity are distributed in the pores, resulting in uneven distribution of active metals. Therefore, the catalyst's ability to remove metals and accommodate metals is limited. Summary of the invention

[0006] In order to overcome the deficiencies in the prior art, the present invention provides a method for preparing a hydrodemetallization catalyst, in particular a method for preparing a residual oil hydrodemetallization catalyst. The catalyst preparation method provided by the present invention can not only fully utilize the catalyst powder generated in the catalyst production process to prepare a hydrogenation catalyst, in particular a residual oil hydrodemetallization catalyst, but also recycle the industrial dust generated in the catalyst production process, while 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 the present invention provides a method for preparing a hydrodemetallization catalyst, comprising:

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

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

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

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

[0012] (5) Powder AXM1 and powder B are divided into N portions (N is greater than 2), that is, from the first portion to the Nth portion, one portion of powder AXM1 and powder B is added each time, the amount of powder AXM1 added in the current portion is reduced, and the amount of powder B added in the current portion is increased. The process includes:

[0013] (5-1) Place the first powder AXM1 and the first powder B on the turntable of the ball rolling machine, spray the binder mixture C on the turntable, rotate the ball rolling machine to form spherical particles.

[0014] (5-2) Add the second powder AXM1 and the second powder B, and continue to spray the binder mixture C. The ball continues to grow.

[0015] (5-3) Using the current portion of powder AXM1 and the current portion of powder B, continue to enlarge 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;

[0016] (5-4) After drying and calcining, a spherical body D is obtained;

[0017] (6) The spherical body D is impregnated with an impregnation solution containing the second active metal M2, allowed to stand, dried, and calcined to obtain a hydrodemetallization catalyst.

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

[0019] In step (1), the catalyst powder includes an alumina carrier and an active metal component, wherein the active metal is at least one of the metals of Group VIII and / or at least one of the metals of Group VIB. The metals of Group VIII are preferably Co and / or Ni, and the metals of Group VIB are preferably Mo and / or W. Based on the mass of the catalyst powder, the mass content of alumina is 50.0% to 90.0%, the mass content of the metals of Group VIII as oxide is 0.5% to 10.0%, and the mass content of the metals of Group VIB as oxide is 4.0% to 30.0%. The catalyst powder may also contain conventional auxiliary components, such as at least one of silicon, phosphorus, boron, etc., accounting for less than 15.0% of the mass of the catalyst powder.

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

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

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

[0023] In step (1), the powder can be ground by ball milling, sand milling or the like, and a ground sample having an average particle size of 1 to 10 μm is obtained after grinding.

[0024] In step (1), the hydrothermal reaction conditions are: temperature of 120-200° C., pH of 7.0-9.0, and reaction time of 4-20 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 hours.

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

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

[0028] In step (2), in the slurry, the content of aluminum oxide is 3-20 g / 100 ml, and the content of alkaline auxiliary agent is 0.05-2.0 g / 100 ml.

[0029] In step (2), the powder can be ground by ball milling, sand milling or the like, and a ground sample having an average particle size of 0.1 to 5 μm is obtained after grinding.

[0030] In step (2), the hydrothermal reaction conditions are: temperature of 180-320° C., pH of 9.0-13.0, and reaction time of 6-48 h.

[0031] In step (2), the drying conditions are as follows: the drying temperature is 120° C. to 180° C., and the drying time is 2 to 6 hours.

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

[0033] In step (3), the first active metal source is selected from nickel salts (or cobalt salts), such as at least one of nickel acetate, nickel chloride, nickel nitrate and nickel sulfate (or corresponding cobalt salts).

[0034] In step (3), the content of the first active metal in terms of first active metal nitrate accounts for 20.0% to 65.0% of the mass of the activated carbon.

[0035] In step (3), the specific surface area of ​​the activated carbon X is 800 to 1500 m 2 / g, can be burned in an air roasting 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, etc., and the average particle size of the ground sample is 1-10 μm. The average particle size after grinding in step (2) is smaller than the average particle size after grinding in step (3), at least 0.5 μm smaller, preferably at least 2.0 μm smaller.

[0038] In step (4), the binder mixture C comprises acid, water and 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, sesbania powder, polyethylene glycol, etc.

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

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

[0041] In step (4), the binder mixture C may further contain an auxiliary agent, wherein the auxiliary agent is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus.

[0042] In step (5), powder AXM1 and powder B are divided into N portions, respectively, N is greater than 2, preferably 3-20, and more preferably 3-10. 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, and x is 1 to N.

[0043] 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.

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

[0045] In step (5), the total amount of the binder mixed solution C added accounts for 80.0% to 150.0% of the total mass of the powder AXM1 and the powder B added.

[0046] In step (5), during the balling process of each corresponding portion of powder AXM1 and powder B, the amount of binder mixed liquid C added accounts for 80% to 150% of the mass of each corresponding portion of powder AXM1 and powder B.

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

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

[0049] In step (5), the diameter of the spherical molding D is 2 to 5 mm.

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

[0051] In step (5), step (5-5) is added after step (5-4), that is, the spherical forming body D is first surface coated with a carbon source, and then calcined in an inert atmosphere before step (6).

[0052] In step (5-5), the coating treatment is performed using an aqueous emulsion containing a polymer compound and water-soluble cellulose, wherein the mass content of the polymer compound in the aqueous emulsion is 5% to 15%, and the mass content of the water-soluble cellulose is 0.5% to 3.0%.

[0053] In step (5-5), the polymer compound is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc.

[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 aqueous emulsion (by volume ml) to the spherical forming body D (by mass g) is 0.8 to 1.5 ml / g;

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

[0057] In step (6), the impregnation method is any impregnation method in industry, such as saturated impregnation, vacuum impregnation, etc.

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

[0059] In step (6), the content of Group VIB metal (in terms of oxide) in the impregnation solution containing the second active metal M2 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 may be one or two of ammonium tetramolybdate, ammonium heptamolybdate, and the like.

[0061] In step (6), the standing condition is as follows: the temperature is 20°C to 40°C and the time is 2 to 12 hours.

[0062] In step (6), the drying conditions are as follows: the drying temperature is 100°C to 180°C, and the drying time is 2 to 6 hours. The roasting conditions are as follows: the roasting temperature is 600°C to 750°C, and the roasting time is 2 to 6 hours. The roasting atmosphere is one or more of air, nitrogen, water vapor, etc., preferably air atmosphere.

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

[0064] The second aspect of the present invention provides a residue hydrodemetallization catalyst prepared by the above method.

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

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

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

[0068] In the present invention, the catalyst further comprises 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 in terms of oxide is 0.5% to 8.0%. The auxiliary component can be derived from catalyst powder, or introduced during the preparation of the carrier, or introduced after the preparation of the carrier.

[0069] The third aspect of the present invention provides the use of the residue oil hydrodemetallization catalyst prepared by the above method in residue oil hydroprocessing.

[0070] Compared with the prior art, the hydrodemetallization catalyst prepared by the method of the present invention has the following advantages:

[0071] The method of the present invention comprises the following steps: firstly, two powders with different particle sizes are regulated by rolling ball forming, and a carrier with a pore structure that is continuously distributed from large to small from the inside to the outside is prepared, which solves the problem that the inner and outer pore structures with different pore structures cannot be continuously transitioned in the past, so that the catalyst prepared by this carrier has higher reaction activity and metal capacity; secondly, non-ammonium alkaline compounds are used to treat catalyst dust, and the alumina carrier and the active metal are efficiently separated by hydrothermal treatment (the separated active metal can be used to prepare hydrogenation catalyst according to the situation), so as to make full use of the carrier components in the catalyst dust. At the same time, the non-ammonium alkaline compounds are used to treat the catalyst dust or alumina, so that partial hydroxyl groups can be formed on the surface of alumina, which provides more alkaline sites for the loading of active metals, thereby improving the catalyst performance. The dispersion of active metals in the subsequent impregnation process is high; thirdly, it is preferred to carry out membrane coating treatment on the matrix carrier containing the first active metal, and through inert gas roasting, the water gradually evaporates, the latex particles are gradually squeezed to form a film, and the structure contains cross-linkable groups, which are cross-linked to form a three-dimensional network film. The film temporarily provides a loading position for the second active metal. After the catalyst is roasted, the film disappears, and the second active metal is evenly dispersed on the matrix carrier and cooperates with the first active metal, which is beneficial to improve the hydrogenation demetallization activity and stability; fourth, in order to further prevent the interaction between metallic nickel and alumina carrier, metallic nickel is first loaded on an activated carbon carrier, ground into powder, and then formed into balls. This method can effectively disperse metallic nickel first and reduce the formation of inactive nickel aluminum spinel.

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

[0073] The scheme and effect of the present invention are further described below in conjunction with embodiments, but are not limited to the following embodiments.

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

[0075] The catalyst powder used in the embodiment is the calcined powder generated during the actual production process of the catalyst and collected by a collector.

[0076] Example 1

[0077] (1) 150 g of catalyst powder (residue oil hydrodemetallization catalyst powder, particle size 0.01-1.00 mm, based on the mass of the catalyst, the aluminum oxide content is 86.0%, the molybdenum oxide content is 11.5%, and the nickel oxide content is 2.5%) and 2 g of sodium hydroxide are added to 2 L of clean water, and ground by a ball mill to obtain a slurry with an average particle size of 6.5 μm. The pH value of the slurry is adjusted to 8.0, and then transferred to a 5 L autoclave for hydrothermal reaction at a reaction temperature of 180° C. for a reaction time of 10 h. After the reaction is completed, the obtained product is filtered by a conventional method, and the filtered product is dried at 130° C. for 4 h to obtain powder A; a sufficient amount of powder A is synthesized by the same method for standby use;

[0078] (2) Add 84 g of ρ-type alumina and 2 g of sodium hydroxide to 2 L of clean water, grind with a ball mill to obtain a slurry with an average particle size of 3.0 μm, and perform a hydrothermal reaction at 260° C. for 8 h. After the reaction, the obtained product is filtered in a conventional manner, and the filtered product is dried at 150° C. for 6 h to obtain powder B. Use the same method to synthesize a sufficient amount of powder B for later use;

[0079] (3) The first active metal Ni is loaded on the activated carbon X (with a specific surface area of ​​1000 m 2 / g) (Ni source is nickel nitrate, and the amount is 41.94% of the mass of activated carbon X), and the activated carbon and powder A are mixed at a mass ratio of 1:4 and ground evenly, with an average particle size of 5.0 μm to obtain powder AXM1; a sufficient amount of powder AXM1 is synthesized in the same way for standby use;

[0080] (4) Add 25 g of nitric acid and 14 g of sesbania powder to 1 L of aqueous solution, and then add 37.3 g of phosphoric acid to prepare a binder mixture C; synthesize a sufficient amount of binder mixture C in the same way for later use;

[0081] (5) Powder AXM1 and powder B are divided into seven portions, namely the first portion to the seventh portion, and the total mass of each corresponding portion of powder AXM1 and powder B is 100g. Each time a portion of powder AXM1 and powder B is added, the amount of powder AXM1 added in the current portion is reduced, and the amount of powder B added in the current portion is increased; wherein, the mass ratio of the first portion of powder AXM1 to the first portion of powder B is 96:4, and the amount of powder AXM1 added in the current portion is 91% of the amount of powder AXM1 added in the previous portion. When each portion of powder AXM1 and powder B is balled, the amount of binder mixed liquid C added is 120% of the mass sum of the current portion of powder AXM1 and powder B. The process includes:

[0082] (5-1) Place the first powder AXM1 and the first powder B on the turntable of the ball rolling machine, spray the binder mixture C on the turntable, and rotate the ball rolling machine to form spherical particles. The forming time is 0.8h.

[0083] (5-2) Add the second powder AXM1 and the second powder B, and continue to spray the binder mixture C. The ball continues to grow. The molding time is 0.8h.

[0084] (5-3) Using the current portion of powder AXM1 and the current portion of powder B, continue to enlarge 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;

[0085] (5-4) drying at 150°C for 6 h, and then calcining at 650°C for 4 h to obtain a spherical molding D, wherein the diameter of the spherical molding D is 3-5 mm;

[0086] (5-5) The spherical molding body D is subjected to surface coating treatment, using an aqueous emulsion containing polyimide and hydroxymethyl cellulose, wherein the mass content of polyimide in the aqueous emulsion is 10.0%, and the mass content of hydroxymethyl cellulose is 1.0%. The amount ratio of the aqueous emulsion (by volume ml) to the spherical molding body D (by mass g) is 1.2 ml / g. The spherical molding body D is calcined in a nitrogen atmosphere, and the calcination conditions are: calcination at a temperature of 700° C. for 4 hours. After calcination, a three-dimensional network structure film can be formed on the surface of the spherical molding body D to obtain a catalyst intermediate E;

[0087] (6) The catalyst intermediate E was saturatedly impregnated in an impregnation solution containing a second active metal Mo (the molybdenum source was ammonium heptamolybdate) (the content of Mo (in terms of oxide) was 13.75 g / 100 ml). After the metal was impregnated, the support was allowed to stand at 30° C. for 6 h, dried at 150° C. for 5 h, and then calcined in air at 650° C. for 3 h to obtain a hydrodemetallization catalyst CAT-1. Other physical and chemical properties of the catalyst CAT-1 are shown in Table 1.

[0088] Example 2

[0089] Compared with Example 1, the difference is that in step (1), a slurry with an average particle size of 5.5 μm is obtained after grinding with a ball mill, and the pH value of the slurry is adjusted to 8.5. The hydrothermal reaction temperature is 190°C, the reaction time is 14 hours, and after the reaction is completed, the obtained product is filtered in a conventional manner, and the filtered product is dried at 160°C for 6 hours to obtain powder A; step (3) is ground with a ball mill to obtain powder AXM1 with an average particle size of 4.5 μm. Finally, the hydrodemetallization catalyst CAT-2 is obtained. Other physicochemical properties of catalyst CAT-2 are shown in Table 1.

[0090] Example 3

[0091] Compared with Example 1, the difference is that in step (1), a slurry with an average particle size of 5.0 μm is obtained after grinding with a ball mill, and the pH value of the slurry is adjusted to 8.0. The hydrothermal reaction temperature is 200°C, the reaction time is 12 hours, and after the reaction is completed, the obtained product is filtered in a conventional manner, and the filtered product is dried at 180°C for 5 hours to obtain powder A; step (3) is ground with a ball mill to obtain powder AXM1 with an average particle size of 4.0 μm. Finally, the hydrodemetallization catalyst CAT-3 is obtained. Other physicochemical properties of catalyst CAT-3 are shown in Table 1.

[0092] Example 4

[0093] Compared with Example 1, the difference is that in step (3), the first active metal Ni is loaded on the activated carbon X (the Ni source 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 mixed in a mass ratio of 1:3 and ground evenly, and the average particle size is 5.0 μm to obtain powder AXM1; in step (4), 22 g nitric acid and 16 g sesbania powder are added to 1L aqueous solution, and then 40.08 g phosphoric acid is added to prepare a binder mixed solution C; in step (5), the powder AXM1 and the powder B are divided into five parts, namely the first to fifth parts, the mass ratio of the first powder AXM1 to the first powder B is 90:10, and the amount of powder AXM1 added to the current part is 88% of the amount of powder AXM1 added to the previous part. The obtained product was dried at 160°C for 5h, and then calcined at 650°C for 4h to obtain a spherical body D; in step (6), the catalyst intermediate E was saturated with an impregnation solution containing a second active metal Mo (the molybdenum source was ammonium heptamolybdate) (the content of Mo (in terms of oxide) was 14.73g / 100ml), and the carrier after metal impregnation was allowed to stand for 8h. Finally, the hydrodemetallization catalyst CAT-4 was obtained. Other physical and chemical properties of the catalyst CAT-4 are shown in Table 1.

[0094] Example 5

[0095] The same as Example 1, except that in step (3), the first active metal Ni is loaded on the activated carbon X (the Ni source is nickel nitrate, and the amount is 61.50% of the mass of the activated carbon X), and the activated carbon X and the powder A are mixed in a mass ratio of 1:5 and ground evenly, and the average particle size is 5.0 μm to obtain powder AXM1; in step (4), 24 g nitric acid and 18 g sesbania powder are added to 1L aqueous solution, and then 43.32 g phosphoric acid is added to prepare a binder mixture C; in step (5), the powder AXM1 and the powder B are divided into four parts, namely the first to fourth parts, the mass ratio of the first powder AXM1 to the first powder B is 90:10, and the amount of powder AXM1 added to the current part is 86% of the amount of powder AXM1 added to the previous part. The obtained product was dried at 160°C for 5h, and then calcined at 650°C for 4h to obtain a spherical body D; in step (5-5), an aqueous emulsion containing polyimide and hydroxymethyl cellulose was used, the mass content of polyimide in the aqueous emulsion was 11.0%, and the mass content of hydroxymethyl cellulose was 1.5%. In step (6), the catalyst intermediate E was saturatedly impregnated in an impregnation solution containing a second active metal Mo (the molybdenum source was ammonium heptamolybdate) (the content of Mo (in terms of oxide) was 16.15g / 100ml), and the carrier after metal impregnation was allowed to stand for 8h. Finally, the hydrodemetallization catalyst CAT-5 was obtained. Other physical and chemical properties of the catalyst CAT-5 are shown in Table 1.

[0096] Example 6

[0097] The same as Example 1, except that in step (2), ρ-type alumina is changed to χ-type alumina; in step (3), the first active metal Ni is loaded on the activated carbon X (the Ni source is nickel nitrate, and the amount is 20.34% of the mass of the activated carbon X), and the activated carbon X and the powder A are mixed in a mass ratio of 1:2 and ground evenly, with an average particle size of 5.0 μm to obtain powder AXM1; in step (4), 26 g nitric acid and 20 g sesbania powder are added to 1 L of aqueous solution, and then 35.22 g phosphoric acid is added to prepare a binder mixture. Liquid C; in step (5), powder AM1 and powder B are divided into eight portions, namely the first to the eighth portion, the mass ratio of the first portion of powder AM1 to the first portion of powder B is 97:3, and the amount of powder AM1 added in the current portion is 92% of the amount of powder AM1 added in the previous portion; in step (6), the catalyst intermediate E is saturatedly impregnated in an impregnation solution containing the second active metal Mo (the molybdenum source is ammonium heptamolybdate) (the content of Mo (in terms of oxide) is 12.92g / 100ml), and the carrier after metal impregnation is allowed to stand for 10 hours. Finally, the hydrodemetallization catalyst CAT-6 is obtained. Other physical and chemical properties of catalyst CAT-6 are shown in Table 1.

[0098] Example 7

[0099] The same as Example 1, except that the step (5-5) of surface coating the spherical body D is omitted. Finally, the hydrodemetallization catalyst CAT-7 is obtained. Other physical and chemical properties of the catalyst CAT-7 are shown in Table 1.

[0100] Comparative Example 1

[0101] Compared with Example 1, the difference is that in step (1), a ball mill is not used for grinding to obtain a slurry with an average particle size of 16.5 μm, and in step (3), a ball mill is used for grinding to obtain a powder AXM1 with an average particle size of 14.5 μm. Finally, a hydrodemetallization catalyst DAT-1 is obtained. Other physical and chemical properties of the catalyst DAT-1 are shown in Table 2.

[0102] Comparative Example 2

[0103] 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 a ball mill is used to grind to obtain a powder AXM1 with an average particle size of 3.0 μm. Finally, the hydrodemetallization catalyst DAT-2 is obtained. Other physical and chemical properties of the catalyst DAT-2 are shown in Table 2.

[0104] Comparative Example 3

[0105] Compared with Example 1, the difference is that in step (5), all materials are directly mixed, extruded and formed. Finally, the hydrodemetallization catalyst DAT-3 is prepared. Other physical and chemical properties of the catalyst DAT-3 are shown in Table 2.

[0106] Comparative Example 4

[0107] Compared with Example 1, the difference is that powder A and powder B are exchanged, and the pore distribution trend of the prepared catalyst is a continuous distribution of small inside and large outside. Finally, the hydrodemetallization catalyst DAT-4 is prepared. Other physical and chemical properties of catalyst DAT-4 are shown in Table 2.

[0108] Comparative Example 5

[0109] Compared with Example 1, the difference is that no alkaline auxiliary agent is introduced during the preparation of powders A and B. Finally, a hydrodemetallization catalyst DAT-5 is prepared. Other physical and chemical properties of the catalyst DAT-5 are shown in Table 2.

[0110] Comparative Example 6

[0111] Compared with Example 1, the difference is that each of the powder AXM1 and the powder B is added to the ball rolling machine at a mass ratio of 1:1 for molding. Finally, the hydrodemetallization catalyst DAT-6 is prepared. Other physical and chemical properties of the catalyst DAT-6 are shown in Table 2.

[0112] Table 1 Physicochemical properties of the hydrodemetallization catalysts of various examples

[0113]

[0114] Table 2 Physicochemical properties of the hydrodemetallization catalysts of the comparative examples

[0115] Serial number Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Catalyst No. DAT-1 DAT-2 DAT-3 DAT-4 DAT-5 DAT-6 <![CDATA[Specific surface area, m 2 / g]]> 166 167 161 168 162 165 <![CDATA[Pore volume, cm 3 / g]]> 0.65 0.62 0.61 0.68 0.63 0.66 Mechanical strength, N / mm 13.4 13.5 13.1 13.6 13.2 13.0 Active ingredient content <![CDATA[MoO3,wt%]]> 14.6 14.7 14.4 14.5 14.6 14.4 NiO, wt% 2.5 2.6 2.5 2.4 2.6 2.5 Additive content <![CDATA[P2O5,wt%]]> 2.3 2.3 2.5 2.4 2.3 2.5 Pore ​​distribution <10nm,% 22.3 21.7 21.5 21.7 22.7 22.4 10-30nm, % 55.1 55.5 55.9 55.7 55.2 55.3 >30nm,% 22.6 22.8 22.6 22.6 22.1 22.3

[0116] Evaluation test

[0117] The activity stability test of the catalysts obtained in Examples 1 to 7 and Comparative Examples 1 to 6 was carried out on a 200 ml fixed bed hydrogenation test device. The raw oil was residual oil with a density of 993.7 kg / m 3 (20°C), S content 3.26wt%, metal Ni and V contents 35.4μg / g and 70.6μg / g respectively, CCR content 12.8wt%. The demetallization rate of comparative example 6 when running for 1200h is 100%, and the other embodiments and comparative examples are all relative demetallization rates when running for 1200h, calculated as Ni+V. Specific test conditions are shown in Table 3, and test results are shown in Tables 4 and 5.

[0118] Table 3 Test conditions

[0119]

[0120]

[0121] Table 4 Test results of hydrodemetallization catalysts of various embodiments

[0122]

[0123] Table 5 Test results of the hydrodemetallization catalysts of the comparative examples

[0124]

[0125] It can be seen from Tables 1-5 that, compared with the comparative example catalyst, the hydrodemetallization catalyst prepared by the method of the present invention has higher reaction activity and stability, and can well meet the requirements of heavy and residual oil hydrodemetallization process.

Claims

1. A method for preparing a hydrodemetallization catalyst, comprising: (1) mixing catalyst powder, alkaline auxiliary agent and water to obtain slurry, grinding, hydrothermal reaction, filtering and drying to obtain powder A; (2) mixing alumina, an alkaline additive and water to obtain a slurry, grinding, hydrothermal reaction and drying to obtain powder B; (3) loading the first active metal M1 on the activated carbon X to obtain M1 / activated carbon X, and mixing M1 / activated carbon X and powder A and grinding them to obtain powder AXM1; (4) preparing a binder mixed solution C; (5) Powder AXM1 and powder B are divided into N portions (N is greater than 2), that is, from the first portion to the Nth portion, one portion of powder AXM1 and powder B is added each time, the amount of powder AXM1 added in the current portion is reduced, and the amount of powder B added in the current portion is increased. The process includes: (5-1) Place the first powder AXM1 and the first powder B on the turntable of the ball rolling machine, spray the binder mixture C on the turntable, rotate the ball rolling machine to form spherical particles. (5-2) Add the second powder AXM1 and the second powder B, and continue to spray the binder mixture C. The ball continues to grow. (5-3) Using the current portion of powder AXM1 and the current portion of powder B, continue to enlarge 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; (5-4) After drying and calcining, a spherical body D is obtained; (6) The spherical body D is impregnated with an impregnation solution containing the second active metal M2, allowed to stand, dried, and calcined to obtain a hydrodemetallization catalyst.

2. The method according to claim 1, characterized in that In step (1), the catalyst powder refers to the calcined catalyst powder produced in the catalyst production process (preferably one or more of residual oil hydrodemetallization catalyst powder, residual oil hydrodesulfurization catalyst powder, and residual oil hydrodecarbonization catalyst powder); the particle size of the catalyst powder is 0.01 to 1.00 mm.

3. The method according to claim 1 or 2, characterized in that: In step (1), the catalyst powder comprises an alumina carrier and an active metal component, wherein the active metal is at least one of a Group VIII metal and a Group VIB metal; wherein the Group VIII metal is preferably Co and / or Ni, and the Group VIB metal is preferably Mo and / or W; based on the mass of the catalyst powder, the mass content of alumina is 50.0% to 90.0%, the mass content of the Group VIII metal as oxide is 0.5% to 10.0%, and the mass content of the Group VIB metal as oxide is 4.0% to 30.0%.

4. The method according to claim 1 or 2, characterized in that: In step (1), in the slurry, the content of catalyst powder is 2-50 g / 100 ml, and the content of alkaline auxiliary agent is 0.01-0.5 g / 100 ml; And / or, in step (1), the alkaline auxiliary agent is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate; and / or, in step (1), the average particle size of the catalyst powder after grinding is 1 to 10 μm; And / or, in step (1), the hydrothermal reaction conditions are: temperature of 120-200° C., pH of 7.0-9.0, and reaction time of 4-20 h; And / or, 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 hours.

5. The method according to claim 1, characterized in that: In step (2), the alkaline auxiliary agent is one or more of sodium hydroxide, potassium hydroxide, and sodium carboxylate; And / or, in step (2), the alumina is ρ-type alumina or χ-type alumina; And / or, in step (2), in the slurry, the content of aluminum oxide is 3 to 20 g / 100 ml, and the content of alkaline auxiliary agent is 0.05 to 2.0 g / 100 ml; In step (2), the average particle size of the aluminum oxide after grinding is 0.1 to 5 μm; preferably, the average particle size of the aluminum oxide after grinding in step (2) is smaller than the average particle size of the powder after grinding in step (3), at least 0.5 μm smaller, preferably at least 2.0 μm smaller; And / or, in step (2), the hydrothermal reaction conditions are: temperature of 180-320° C., pH of 9.0-13.0, and reaction time of 6-48 h; And / or, in step (2), the drying conditions are as follows: the drying temperature is 120° C. to 180° C., and the drying time is 2 to 6 hours.

6. The method according to claim 1, characterized in that In step (3), the first active metal is at least one of the Group VIII metals, wherein the Group VIII metal is preferably Co and / or Ni; And / or, in step (3), the content of the first active metal in terms of first active metal nitrate accounts for 20.0% to 65.0% of the 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.

7. The method according to claim 1, characterized in that 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 acetic acid, and the colloid is at least one of methylcellulose, 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 mixed solution C is 0.5%-2.5%.

8. The method according to claim 1, characterized in that: In step (5), powder AXM1 and powder B are divided into N parts respectively, where N is greater than 2, preferably 3-20, and more preferably 3-10; and / or, in step (5), the total mass of each corresponding portion of powder AXM1 and powder B is 0.90-1.10 times (the total mass of the first portion of powder AXM1 and the first portion of powder B); and / or, 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; and / or, in step (5), the mass ratio of the Nth portion of powder AXM1 to the Nth portion of powder B is 50-70:30-50; And / or, in step (5), the total amount of the binder mixed liquid C added accounts for 80.0% to 150.0% of the total mass of the powders AXM1 and B added; preferably, in step (5), during the balling process of each corresponding portion of the powders AXM1 and B, the amount of the binder mixed liquid C added accounts for 80% to 150% of the mass of each corresponding portion of the powders AXM1 and B; and / or, in step (5), the spheronization time of each corresponding portion of powder AXM1 and powder B is controlled within 0.5 to 1.5 h; And / or, in step (5), the diameter of the spherical molding D is 2 to 5 mm.

9. The method according to claim 1, characterized in that: In step (5), the drying conditions are as follows: the drying temperature is 100°C to 180°C, and the drying time is 2 to 6 hours; the roasting conditions are as follows: the roasting temperature is 400°C to 650°C, and the roasting time is 2 to 6 hours; and the roasting atmosphere is air.

10. The method according to claim 1, characterized in that In step (5), after step (5-4), step (5-5) is added, that is, the spherical forming body D is firstly subjected to surface coating treatment with a carbon source, and then calcined in an inert atmosphere, and then step (6) is performed; Preferably, the coating treatment is performed using an aqueous emulsion containing a polymer compound and water-soluble cellulose; in the aqueous emulsion, the mass content of the polymer compound is 5% to 15%, and the mass content of the water-soluble cellulose is 0.5% to 3.0%; Preferably, the polymer compound is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc., and the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, etc.; Preferably, the dosage ratio of the aqueous emulsion by volume ml to the spherical forming body D by mass g is 0.8 to 1.5 ml / g; And / or, in step (6), the inert atmosphere calcination conditions are: calcination at a temperature of 500-700° C. for 2-8 hours.

11. The method according to claim 1, characterized in that: In step (6), the second active metal M2 is at least one of the Group VIB metals, wherein the Group VIB metal is preferably Mo and / or W; and / or, in step (6), the content of the Group VIB metal in the impregnation solution containing the second active metal M2, calculated as oxide, is 8.0 to 48.0 g / 100 ml; And / or, in step (6), the drying conditions are as follows: the drying temperature is 100°C to 180°C, and the drying time is 2 to 6 hours; the roasting conditions are as follows: the roasting temperature is 600°C to 750°C, the roasting time is 2 to 6 hours, and the roasting atmosphere is air.

12. The method according to claim 1, characterized in that In step (6), the hydrodemetallization catalyst has a content of 0.5% to 8.0% of Group VIII metal in terms of oxide, and a content of 4.0% to 18.0% of Group VIB metal in terms of oxide, based on the weight of the catalyst.

13. A residue hydrodemetallization catalyst prepared by the method of any one of claims 1 to 12.

14. The catalyst according to claim 13, characterized in that The specific surface area of ​​the catalyst is 150 to 210 m 2 / g, the pore volume is 0.65-0.85 mL / g, and / or the mechanical strength of the catalyst is 10.0-22.0 N / mm.

15. Use of the residue oil hydrodemetallization catalyst prepared by the method of any one of claims 1 to 12 in residue oil hydrotreatment.

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