A 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) mixing powder A and a first active metal source, and grinding to obtain powder AM1; (4) preparing a binder mixture C; (5) rolling the powder AM1, the powder B and the binder mixture C into a ball in a specific manner to obtain a ball-shaped molding body D; optionally, (6) performing surface coating treatment on the ball-shaped molding body D by using a carbon source to obtain a catalyst intermediate E; and (7) impregnating D or E with an impregnation liquid containing a second active metal to obtain the hydrodemetallization catalyst. According to the method, industrial dust generated in the catalyst production process is recovered, and the activity and stability of the catalyst are improved.

Description

Technical Field

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

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

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

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

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

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

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

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

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

[0010] (3) Mix powder A and the first active metal source M1, grind them to obtain powder AM1;

[0011] (4) Prepare adhesive mixture C;

[0012] (5) Divide powder AM1 and powder B into N portions (N is 2 or more), i.e., from the first portion to the Nth portion. Each time, add one portion of powder AM1 and powder B, reducing the amount of powder AM1 added in the current portion while increasing the amount of powder B added in the current portion. The process includes:

[0013] (5-1) Place the first batch of powder AM1 and the first batch of powder B into the turntable of the ball rolling machine, and simultaneously spray the binder mixture C onto the turntable. Rotate the ball rolling machine to form spherical particles.

[0014] (5-2) Add the second part of powder AM1 and the second part of powder B, while continuing to spray the binder mixture C. The ball continues to increase in size.

[0015] (5-3) Using the current portion of powder AM1 and the current portion of powder B, continuously increase the size of the ball in the manner of step (5-2) until the Nth portion of powder AM1 and the Nth portion of powder B are all formed into balls;

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

[0017] Optionally, (6) the surface of the sphere-shaped body D is coated with a carbon source and then calcined in an inert atmosphere to obtain the catalyst intermediate E;

[0018] (7) Impregnate catalyst intermediate E or spherical form D with impregnation solution containing second active metal M2, let stand, dry, and calcine to obtain hydrogenation demetallization catalyst.

[0019] In step (1), the catalyst powder refers to the catalyst powder produced during the catalyst production process, which can be one or more of the following: residue oil hydrodemetallization catalyst powder, residue oil hydrodesulfurization catalyst powder, and residue oil hydrodecarbonization catalyst powder. The particle size of the catalyst powder is between 0.01 and 1.00 mm. The catalyst powder refers to waste catalyst that does not meet the requirements for catalyst use in at least one aspect such as particle size and bulk density.

[0020] In step (1), the catalyst powder comprises an alumina support and an active metal component, wherein the active metal is at least one of a Group VIII metal and / or at least one of a Group VIB metal. Preferably, the Group VIII metal is Co and / or Ni, and the Group VIB metal is preferably Mo and / or W. Based on the mass of the catalyst powder, the alumina content is 50.0%–90.0%, the Group VIII metal content (based on oxides) is 0.5%–10.0%, and the Group VIB metal content (based on oxides) is 4.0%–30.0%. The catalyst powder may also contain conventional auxiliary components, such as at least one of silicon, phosphorus, and boron, accounting for less than 15.0% of the catalyst powder mass.

[0021] In step (1), the catalyst powder is calcined catalyst powder.

[0022] In step (1), the slurry contains 2-50 g of catalyst powder per 100 ml and 0.01-0.5 g of alkaline additive per 100 ml.

[0023] In step (1), the alkaline auxiliary is one or more of the following non-ammonium alkaline compounds: sodium hydroxide, potassium hydroxide, sodium carboxylate (such as sodium acetate, sodium formate, etc.).

[0024] In step (1), the powder grinding can be carried out by ball milling, sand milling or other processing methods, and the ground sample with an average particle size of 1 to 10 μm is obtained after grinding.

[0025] In step (1), the hydrothermal reaction conditions are: temperature of 120-200℃, pH of 7.0-9.0, and reaction time of 4-20h.

[0026] In step (1), the drying conditions are as follows: the drying temperature is 90-180℃ and the drying time is 1-24h.

[0027] In step (2), the alkaline auxiliary agent is one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, and sodium carboxylate (e.g., sodium acetate, sodium formate).

[0028] In step (2), the alumina is p-type alumina or x-type alumina.

[0029] In step (2), the slurry contains 3 to 20 g of alumina per 100 ml and 0.05 to 2.0 g of alkaline additives per 100 ml.

[0030] In step (2), the powder grinding can be carried out by ball milling, sand milling or other processing methods, and the ground sample with an average particle size of 0.1 to 5 μm is obtained after grinding.

[0031] In step (2), the hydrothermal reaction conditions are: temperature of 180-320℃, pH of 9.0-13.0, and reaction time of 6-48h.

[0032] In step (2), the drying conditions are as follows: the drying temperature is 120℃~180℃, and the drying time is 2~6h.

[0033] In step (3), the first active metal is at least one of Group VIII metals. Preferably, the Group VIII metal is Co and / or Ni.

[0034] 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).

[0035] In step (3), the amount of the first active metal added, calculated as an oxide, accounts for 0.5 to 8.0% of the total mass of the final catalyst.

[0036] In step (3), the powder grinding can be carried out by ball milling, sand milling, or other methods to obtain a ground sample with an average particle size of 1 to 10 μm. The average particle size after grinding in step (2) is smaller than the average particle size after grinding in step (3), by at least 0.5 μm, and preferably at least 2.0 μm smaller.

[0037] In step (4), the adhesive mixture C includes an acid, water and a colloid. The acid is one or more of nitric acid, citric acid, acetic acid, sulfuric acid, oxalic acid, acetic acid, etc., and the colloid is at least one of methylcellulose, guar gum, polyethylene glycol, etc.

[0038] In step (4), the mass concentration of acid in the adhesive mixture C is 0.5% to 4.5%.

[0039] In step (4), the mass concentration of the colloid in the adhesive mixture C is 0.5% to 2.5%.

[0040] In step (4), the adhesive mixture C may also contain an additive, which is selected from at least one of fluorine, phosphorus, silicon or boron, preferably phosphorus.

[0041] In step (5), powder AM1 and powder B are divided into N parts, where N is 2 or more, preferably 3 to 20, and more preferably 3 to 10. In step (5), the total mass of each corresponding part of powder AM1 and powder B is 0.90 to 1.10 times (the total mass of the first part of powder AM1 and the first part of powder B). For example, when powder AM1 and powder B are added for the xth time, the total mass of the xth part of powder AM1 and the xth part of powder B is 0.90 to 1.10 times (the total mass of the first part of powder AM1 and the first part of powder B), where x is 1 to N.

[0042] In step (5), the mass ratio of the first part of powder AM1 to the first part of powder B is 90-98:2-10, and the amount of powder AM1 added in the current part is 77%-95% of the amount of powder AM1 added in the previous part.

[0043] In step (5), preferably, the mass ratio of the Nth part of powder AM1 to the Nth part of powder B is 50-70:30-50.

[0044] In step (5), the total amount of the binder mixture C added accounts for 80.0% to 150.0% of the total mass of powder AM1 and powder B added.

[0045] In step (5), during the spheroidizing process of each corresponding part of powder AM1 and powder B, the amount of binder mixture C added accounts for 80% to 150% of the mass of each corresponding part of powder AM1 and powder B.

[0046] In step (5), the spheroidization time of powder AM1 and powder B in each corresponding part is controlled between 0.5 and 1.5 h.

[0047] In step (5), there is no strict limit to the spraying rate of the adhesive mixture C, as long as it is to ensure uniform ball formation.

[0048] In step (5), the diameter of the spherical shape D is 2 to 5 mm.

[0049] In step (5), the drying conditions are as follows: drying temperature is 100℃~180℃, and drying time is 2~6h. The calcination conditions are as follows: calcination temperature is 400℃~650℃, and calcination time is 2~6h. The calcination atmosphere is one or more of air, nitrogen, water vapor, etc., preferably an air atmosphere.

[0050] In step (6), the coating treatment uses an aqueous emulsion containing a polymer compound and water-soluble cellulose. The polymer compound in the aqueous emulsion has a mass content of 5%–15%, and the water-soluble cellulose has a mass content of 0.5%–3.0%.

[0051] In step (6), the polymer compound is one or more of polyimide, polyfurfuryl alcohol, phenolic resin, etc.

[0052] In step (6), the water-soluble cellulose is one or more of hydroxymethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, etc.

[0053] In step (6), the ratio of the amount of the aqueous emulsion (in ml) to the amount of the spheroid D (in g) is 0.8 to 1.5 ml / g.

[0054] In step (6), the inert atmosphere calcination conditions are: calcination at a temperature of 500–700℃ for 2–8 hours. The inert atmosphere is one or more of nitrogen and argon.

[0055] In step (7), the impregnation method can be any impregnation method used in industry, such as saturated impregnation, vacuum impregnation, etc.

[0056] In step (7), the second active metal M2 is at least one of the group VIB metals. Preferably, the group VIB metal is Mo and / or W.

[0057] In step (7), the content of Group VIB metals (calculated as oxides) in the impregnation solution containing the second active metal M2 is 8.0 to 48.0 g / 100 ml.

[0058] In step (7), the source of the second active metal M2 in the impregnation solution containing the second active metal M2 can be one or two of ammonium tetramolybdate, ammonium heptamolybdate, etc.

[0059] In step (7), the conditions for standing are: temperature of 20℃~40℃ and time of 2~12h.

[0060] In step (7), the drying conditions are as follows: drying temperature is 100℃~180℃, and drying time is 2~6h. The calcination conditions are as follows: calcination temperature is 600℃~750℃, and calcination time is 2~6h. The calcination atmosphere is one or more of air, nitrogen, water vapor, etc., preferably an air atmosphere.

[0061] In step (7), the hydrogenation demetallization catalyst, based on the weight of the catalyst, contains 0.5% to 8.0% of Group VIII metals as oxides and 4.0% to 18.0% of Group VIB metals as oxides.

[0062] The second aspect of the present invention provides a residue oil hydrodemetallization catalyst prepared by the above method.

[0063] In this invention, the catalyst has a specific surface area of ​​165–190 m². 2 / g, with a pore volume of 0.55-0.80mL / g, preferably 0.55-0.75mL / g.

[0064] In this invention, the mechanical strength of the catalyst is 10.0 to 25.0 N / mm.

[0065] In this invention, the pore distribution of the catalyst is as follows: pores with a diameter <10nm account for 15% to 30% of the total pore volume, pores with a diameter of 10-30nm account for 55% to 65% of the total pore volume, and pores with a diameter >30nm account for less than 25% of the total pore volume.

[0066] In this invention, the catalyst further includes an auxiliary component, which is selected from at least one of fluorine, phosphorus, silicon, or boron, preferably phosphorus. Based on the mass of the catalyst, the content of the auxiliary component, calculated as oxides, is 0.5% to 8.0%. The auxiliary component can be derived from catalyst powder, introduced during the preparation of the support, or introduced after the preparation of the support.

[0067] The third aspect of this invention provides the application of the residue hydrodemetallization catalyst prepared by the above method in residue hydrotreating.

[0068] Compared with existing technologies, the hydrogenation demetallization catalyst prepared by the method of this invention has the following advantages:

[0069] The method of this invention has two main aspects: First, by using spherical molding to control the particle size of two powders of different sizes, a support with a continuously distributed pore structure from the inside out is prepared. This solves the problem of the inability to continuously transition between the inner and outer pore structures when using different pore structures in previous methods. Therefore, the catalyst prepared with this support has higher reactivity and metal-containing capacity. Second, a non-ammonium alkaline compound is used to treat the catalyst dust, and hydrothermal treatment is used to efficiently separate the alumina support from the active metal (the separated active metal can be used to prepare hydrogenation catalysts as needed). This fully utilizes the support component in the catalyst dust, while the non-ammonium alkaline compound treatment of the catalyst... Dust or alumina can form some hydroxyl groups on the alumina surface, providing more alkaline sites for the loading of active metals and improving the dispersion of active metals during subsequent impregnation. Third, a membrane coating treatment is performed on a matrix support containing the first active metal, and the latex particles are gradually squeezed to form a thin film by inert gas calcination. The film contains crosslinkable groups and crosslinks to form a three-dimensional network film. This film temporarily provides loading sites for the second active metal. After the catalyst is calcined, the film is burned off, and the second active metal is uniformly dispersed on the matrix support and cooperates with the first active metal, which is beneficial to improving the activity and stability of hydrogenation demetallization.

[0070] In summary, the catalyst prepared by this invention not only has good activity but also good stability, which is beneficial for extending the operating cycle of the device. Detailed Implementation

[0071] The present invention and its effects are further described below with reference to embodiments, but are not limited to the following embodiments.

[0072] In this invention, the pore structure is tested using a low-temperature liquid nitrogen adsorption-desorption method, 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 using an intelligent particle strength testing machine; and the metal component content is analyzed using spectrophotometry.

[0073] The catalyst powder used in the examples is the calcined powder generated during the actual production process of the catalyst and collected by a collector.

[0074] Example 1

[0075] (1) Add 150g of catalyst powder (residue oil hydrodemetallization catalyst powder, particle size 0.01~1.00mm, based on the mass of the catalyst, alumina content 84.3%, molybdenum oxide content 12.5%, nickel oxide content 3.2%) and 2g of sodium hydroxide to 2L of purified water, grind with a ball mill to obtain a slurry with an average particle size of 5.5μm, adjust the pH of the slurry to 8.0, and then transfer it to a 5L high-pressure reactor for hydrothermal reaction at a reaction temperature of 180℃ for 10h. After the reaction, the obtained product is filtered by conventional means, and the filtered product is dried at 150℃ for 6h to obtain powder A; synthesize sufficient powder A in the same way for later use.

[0076] (2) Add 84g of p-type alumina and 2g of sodium hydroxide to 2L of purified water, and grind them using a ball mill to obtain a slurry with an average particle size of 2.2μm and a pH of 10.0. The slurry is then subjected to hydrothermal reaction at 260℃ for 8h. After the reaction is completed, the product is filtered by conventional methods. The filtered product is then dried at 170℃ for 4h to obtain powder B. Sufficient powder B is synthesized in the same way for later use.

[0077] (3) Powder A and the first active metal Ni (nickel source is nickel nitrate, the amount is 13.9% of the mass of powder A) are mixed and ground evenly, with an average particle size of 4.5 μm, to obtain powder AM1; sufficient amount of powder AM1 is synthesized in the same way for later use;

[0078] (4) Add 20g of nitric acid and 16g of guar gum powder to 1L of aqueous solution, then add 56.7g of phosphoric acid to prepare adhesive mixture C; synthesize sufficient adhesive mixture C in the same way for later use;

[0079] (5) Divide powder AM1 and powder B into six portions, namely the first to the sixth portion. The total mass of powder AM1 and powder B in each corresponding portion is 100g. Each time one portion of powder AM1 and powder B is added, the amount of powder AM1 added in the current portion is reduced, while the amount of powder B added in the current portion is increased. The mass ratio of powder AM1 to powder B in the first portion is 95:5. The amount of powder AM1 added in the current portion is 90% of the amount of powder AM1 added in the previous portion. When each portion of powder AM1 and powder B forms balls, the amount of binder mixture C added is 110% of the total mass of powder AM1 and powder B in the current portion. The process includes:

[0080] (5-1) Place the first powder AM1 and the first powder B into the turntable of the ball rolling machine, and simultaneously spray the binder mixture C onto the turntable. Rotate the ball rolling machine to form spherical particles. The forming time is 0.5 hours.

[0081] (5~2) Add the second part of powder AM1 and the second part of powder B, while continuing to spray the binder mixture C. The ball continues to increase in size, and the molding time is 0.5h.

[0082] (5-3) Using the current portion of powder AM1 and the current portion of powder B, continuously increase the size of the ball in the manner of step (5-2) until the sixth portion of powder AM1 and the sixth portion of powder B are all formed into balls;

[0083] (5~4) Dry at 170℃ for 6 hours, and then calcine at 550℃ for 3 hours to obtain spherical shape D, wherein the diameter of spherical shape D is 2.5~4.5mm;

[0084] (6) Surface coating treatment was performed on the spheroid D using an aqueous emulsion containing polyimide and hydroxymethyl cellulose. The mass content of polyimide in the aqueous emulsion was 8.0%, and the mass content of hydroxymethyl cellulose was 0.8%. The ratio of aqueous emulsion (by volume, ml) to spheroid D (by mass, g) was 1.0 ml / g. Calcination was carried out under a nitrogen atmosphere at 650℃ for 5 hours. After calcination, a three-dimensional network structure film was formed on the surface of the spheroid D, yielding catalyst intermediate E.

[0085] (7) The catalyst intermediate E was saturated and impregnated in an impregnation solution containing the second active metal Mo (molybdenum source was ammonium heptamolybdate) (Mo content (based on oxides) was 15.70 g / 100 ml). The metal-impregnated support was allowed to stand at 30 °C for 6 h, then dried at 140 °C for 4 h, and then calcined in air at 600 °C for 3 h to obtain the hydrodemetallization catalyst CAT-1. Other physicochemical properties of catalyst CAT-1 are shown in Table 1.

[0086] Example 2

[0087] Compared with Example 1, the difference is that in step (1), a slurry with an average particle size of 4.5 μm was obtained by grinding with a ball mill, and the pH value of the slurry was adjusted to 8.5. The hydrothermal reaction temperature was 190℃, the reaction time was 14h, and after the reaction was completed, the product was filtered by conventional methods, and the filtered product was dried at 160℃ for 6h to obtain powder A; in step (3), powder AM1 with an average particle size of 3.5 μm was obtained by grinding with a ball mill. Finally, the hydrogenation demetallization catalyst CAT-2 was prepared. Other physicochemical properties of catalyst CAT-2 are shown in Table 1.

[0088] Example 3

[0089] Compared with Example 1, the difference is that in step (1), a slurry with an average particle size of 6.0 μm was obtained by grinding with a ball mill, and the pH value of the slurry was adjusted to 8.5. The hydrothermal reaction temperature was 200℃, the reaction time was 12h, and after the reaction was completed, the product was filtered by conventional methods, and the filtered product was dried at 180℃ for 5h to obtain powder A; in step (3), powder AM1 with an average particle size of 5.0 μm was obtained by grinding with a ball mill. Finally, the hydrogenation demetallization catalyst CAT-3 was obtained. Other physicochemical properties of catalyst CAT-3 are shown in Table 1.

[0090] Example 4

[0091] Compared with Example 1, the difference is that in step (3), powder A and the first active metal Ni (nickel source is nickel nitrate, the amount of which is 15.9% of the mass of powder A) are mixed and ground evenly with an average particle size of 4.5 μm to obtain powder AM1; in step (4), 25 g of nitric acid and 14 g of guar gum powder are added to 1 L of aqueous solution, and then 62.6 g of phosphoric acid is added to prepare binder mixture C; in step (5), powder AM1 and powder B are divided into four parts, namely the first part to the fourth part, the first part of powder AM1 and the first part of powder B are mixed together. The mass ratio of body B is 90:10, and the amount of powder AM1 added in the current batch is 85% of the amount of powder AM1 added in the previous batch. In step (7), the catalyst intermediate E is saturated and impregnated in an impregnation solution containing the second active metal Mo (molybdenum source is ammonium heptamolybdate) (Mo content (calculated as oxide) is 17.40 g / 100 ml). After impregnation, the support is allowed to stand at 35 °C for 6 h, and the resulting product is dried at 160 °C for 6 h, and then calcined at 600 °C for 4 h to obtain the support. Finally, the hydrogenation demetallization catalyst CAT-4 is obtained. Other physicochemical properties of catalyst CAT-4 are shown in Table 1.

[0092] Example 5

[0093] Compared with Example 1, the difference is that in step (3), powder A and the first active metal Ni (nickel source is nickel nitrate, the amount of which is 17.42% of the mass of powder A) are mixed and ground evenly, with an average particle size of 4.5 μm, to obtain powder AM1; sufficient powder AM1 is synthesized in the same way for later use; in step (4), 30 g of nitric acid and 12 g of guar gum powder are added to 1 L of aqueous solution, and then 71.4 g of phosphoric acid is added to prepare binder mixture C; sufficient binder mixture C is synthesized in the same way for later use; in step (5), powder AM1 and powder B are divided into three parts, namely the first part to the third part, the first part... The mass ratio of powder AM1 to powder B is 90:10, and the amount of powder AM1 added in the current batch is 80% of the amount of powder AM1 added in the previous batch. In step (6), an aqueous emulsion containing polyimide and hydroxymethyl cellulose is used. The mass content of polyimide in the aqueous emulsion is 12.0%, and the mass content of hydroxymethyl cellulose is 1.2%. In step (7), the catalyst intermediate E is saturated and impregnated in an impregnation solution containing the second active metal Mo (molybdenum source is ammonium heptamolybdate) (the content of Mo (calculated as oxide) is 19.72 g / 100 ml). The support after impregnation is allowed to stand at 25 °C for 6 h. Finally, the hydrogenation demetallization catalyst CAT-5 is obtained. Other physicochemical properties of catalyst CAT-5 are shown in Table 1.

[0094] Example 6

[0095] Compared with Example 1, the difference is that in step (2), p-type alumina is replaced with x-type alumina; in step (3), powder A and the first active metal Ni (nickel source is nickel nitrate, the amount is 12.75% of the mass of powder A) are mixed and ground evenly, with an average particle size of 4.5 μm, to obtain powder AM1; in step (4), 35 g of nitric acid and 10 g of guar gum powder are added to 1 L of aqueous solution, and then 51.7 g of phosphoric acid is added to prepare binder mixture C; in step (5), powder AM1 and Powder B was divided into eight portions, namely the first to the eighth portions. The mass ratio of the first portion of powder AM1 to the first portion of powder B was 98:2. The amount of powder AM1 added in the first portion was 92% of the amount of powder AM1 added in the previous portion. In step (7), the catalyst intermediate E was saturated and impregnated in an impregnation solution containing the second active metal Mo (molybdenum source was ammonium heptamolybdate) (Mo content (calculated as oxide) was 14.48 g / 100 ml). The support after impregnation was allowed to stand at 35 °C for 6 h. Finally, the hydrogenation demetallization catalyst CAT-6 was obtained. Other physicochemical properties of catalyst CAT-6 are shown in Table 1.

[0096] Example 7

[0097] Compared with Example 1, the step (6) of surface coating treatment of the sphere-shaped body D was omitted. The hydrogenation demetallization catalyst CAT-7 was finally obtained. Other physicochemical properties of catalyst CAT-7 are shown in Table 1.

[0098] Comparative Example 1

[0099] Compared with Example 1, the difference is that in step (1), a ball mill was not used for grinding to obtain a slurry with an average particle size of 17.6 μm, while in step (3), a ball mill was used to grind the particles to obtain powder AM1 with an average particle size of 15.6 μm. Finally, the hydrodemetallization catalyst DAT-1 was obtained. Other physicochemical properties of catalyst DAT-1 are shown in Table 2.

[0100] Comparative Example 2

[0101] Compared with Example 1, the difference is that powder A obtained in step (1) is removed. In step (3), powder A is replaced by an equal amount of powder B, and the powder is ground using a ball mill to obtain powder AM1 with an average particle size of 2.2 μm. Finally, the hydrodemetallization catalyst DAT-2 is obtained. Other physicochemical properties of catalyst DAT-2 are shown in Table 2.

[0102] Comparative Example 3

[0103] Compared with Example 1, the difference is that in step (5), all materials are directly mixed, extruded, and shaped. The hydrogenation demetallization catalyst DAT-3 is finally obtained. Other physicochemical properties of catalyst DAT-3 are shown in Table 2.

[0104] Comparative Example 4

[0105] Compared to Example 1, the difference lies in the exchange of powder A and powder B, resulting in a catalyst with a continuous distribution of smaller pores at the inside and larger pores at the outside. The final hydrogenation demetallization catalyst DAT-4 was thus obtained. Other physicochemical properties of catalyst DAT-4 are shown in Table 2.

[0106] Comparative Example 5

[0107] Compared to Example 1, the difference lies in that no alkaline additives were introduced during the preparation of powders A and B. The final hydrogenation demetallization catalyst DAT-5 was obtained. Other physicochemical properties of catalyst DAT-5 are shown in Table 2.

[0108] Comparative Example 6

[0109] Compared to Example 1, the difference lies in that powder AM1 and powder B are added to a ball rolling machine at a mass ratio of 1:1 for molding. The resulting hydrogenation demetallization catalyst DAT-6 is thus prepared. Other physicochemical properties of catalyst DAT-6 are shown in Table 2.

[0110] Table 1. Physicochemical properties of the hydrogenation demetallization catalysts in each example.

[0111] Serial Number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Catalyst number CAT-1 CAT-2 CAT-3 CAT-4 CAT-5 CAT-6 CAT-7 <![CDATA[Specific surface area, m 2 / g]]> 175 178 169 177 174 179 167 <![CDATA[Pore volume, cm 3 / g]]> 0.65 0.61 0.67 0.63 0.62 0.66 0.58 Mechanical strength, N / mm 15.2 15.6 15.3 16.1 15.9 16.4 15.5 Active ingredient content <![CDATA[MoO3,wt%]]> 15.3 15.4 15.2 15.3 15.4 15.2 15.1 NiO, wt% 3.2 3.3 3.1 3.0 3.2 3.1 3.2 Additive content <![CDATA[P2O5,wt%]]> 3.1 3.0 3.1 3.2 3.1 3.2 3.0 Pore ​​distribution <10nm,% 19.2 20.5 21.5 20.3 20.8 21.8 21.1 10-30nm, % 58.2 57.2 56.1 57.6 57.0 56.3 56.6 >30nm, % 22.6 22.3 22.4 22.1 22.2 21.9 22.3

[0112] Table 2 Physicochemical properties of the comparative hydrogenation demetallization catalysts

[0113]

[0114]

[0115] Evaluation test

[0116] The catalysts obtained in Examples 1-7 and Comparative Examples 1-6 were subjected to activity and stability tests on a 200ml fixed-bed hydrogenation test apparatus. The feedstock was residual oil with a density of 989.2 kg / m³. 3 (20℃), S content 2.68wt%, Ni and V contents 25.5μg / g and 62.7μg / g respectively, CCR content 11.4wt%. The demetallization rate of Comparative Example 6 after 1500h of operation was 100%. The demetallization rates for other examples and comparative examples are relative demetallization rates after 1500h of operation, calculated as Ni+V. Specific experimental conditions are shown in Table 3, and experimental results are shown in Tables 4 and 5.

[0117] Table 3 Experimental conditions

[0118] Reaction temperature, °C 370 Reaction pressure, MPa 15.7 <![CDATA[Liquid hourly space velocity, h ～1 > 1.2 Hydrogen-to-oil ratio, V / V 650

[0119] Table 4. Test results of the hydrogenation demetallization catalysts in each example.

[0120]

[0121]

[0122] Table 5. Experimental results of hydrogenation demetallization catalysts in each comparative example.

[0123]

[0124] As can be seen from Tables 1-5, compared with the comparative catalyst, the hydrodemetallization catalyst prepared according to the method of the present invention has higher reactivity and stability. It can process relatively good feedstock residue oil at higher space velocities and lower hydrogen-to-oil volume ratios, and can maintain a good demetallization rate over a longer period of time. It can well meet the requirements of hydrodemetallization processes for heavy and residue oils.

Claims

1. A method for preparing a hydrodemetallization catalyst, comprising: (1) mixing a catalyst powder, a non-ammonium basic additive and water to obtain a slurry, grinding, hydrothermal reaction, filtering, drying, and obtaining a powder A; (2) mixing alumina, a non-ammonium basic additive and water to obtain a slurry, grinding, hydrothermal reaction, drying, and obtaining a powder B; (3) mixing the powder A and a first active metal M1 source, and grinding to obtain a powder AM1; (4) preparing a binder mixture C; (5) dividing the powder AM1 and the powder B into N parts, N being 2 or more, i.e. a first part to an Nth part, adding one part of the powder AM1 and the powder B each time, reducing the amount of the powder AM1 in the current part while increasing the amount of the powder B in the current part, the process comprising: (5-1) placing the first part of the powder AM1 and the first part of the powder B on a rotating disc of a ball-rolling machine, spraying the binder mixture C onto the rotating disc, and rolling the ball to form a spherical particle, (5-2) adding the second part of the powder AM1 and the second part of the powder B, and continuing to spray the binder mixture C, and continuously increasing the size of the ball, (5-3) continuously increasing the size of the ball by using the powder AM1 in the current part and the powder B in the current part according to the method of step (5-2) until the Nth part of the powder AM1 and the Nth part of the powder B are all formed into balls; (5-4) drying and calcining to obtain a spherical formed body D; optionally, (6) performing surface coating treatment on the spherical formed body D using a carbon source, and after calcination in an inert atmosphere, obtaining a catalyst intermediate E; (7) impregnating the catalyst intermediate E or 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 catalyst powder after grinding in step (3); in step (3), the powder AM1 has an average particle size of 1-10 μm after grinding.

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

3. The method of claim 2, wherein, The catalyst powder is one or more of a residual oil hydrodemetallization catalyst powder, a residual oil hydrodesulfurization catalyst powder, and a residual oil 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 non-ammonium basic additive content is 0.01-0.5 g / 100 mL. And / or, in step (1), the non-ammonium 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: temperature 120-200 ℃, pH 7.0-9.0, and reaction time 4-20 h; And / or, in step (1), the drying conditions are: drying temperature 90-180 ℃, and drying time 1-24 h.

7. The method of claim 1, wherein, In step (2), the non-ammonium alkaline additive 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 alumina is 3-20 g / 100 mL, and the content of non-ammonium 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: temperature 180-320 ℃, pH 9.0-13.0, and reaction time 6-48 h; And / or, in step (2), the drying conditions are: drying temperature 120-180 ℃, and drying time 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 catalyst 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 catalyst powder in step (3).

10. The method of claim 1, wherein, In step (3), the first active metal is at least one of Group VIII metals, wherein the Group VIII metal is Co and / or Ni.

11. The method of claim 1, wherein, In step (4), the binder mixture C comprises water, acid, and colloid, the acid is one or more of nitric acid, citric acid, acetic acid, sulfuric acid, and oxalic acid, and the colloid is at least one of methyl cellulose, sesbania gum, and polyethylene glycol; And / or, in step (4), in the binder mixture C, the mass concentration of the acid is 0.5%-4.5%; And / or, in step (4), in the binder mixture C, the mass concentration of the colloid 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 AM1 and the powder B is 0.90-1.10 times the total mass of the first portion of the powder AM1 and the first portion of the powder B; And / or, the mass ratio of the first portion of the powder AM1 to the first portion of the powder B is 90-98:2-10, and the addition amount of the current portion of the powder AM1 is 77%-95% of the addition amount of the previous portion of the powder AM1; And / or, in step (5), the mass ratio of the Nth portion of the powder AM1 to the Nth portion of the powder B is 50-70:30-50; And / or, in step (5), the total addition amount of the binder mixture C accounts for 80.0%-150.0% of the total mass of the powder AM1 and the powder B. And / or, in step (5), the time for each corresponding part of the powder AM1 and the powder B to form a ball is controlled to be 0.5-1.5 h. And / or, in step (5), the diameter of the ball-formed body D is 2-5 mm.

13. The method of claim 12, wherein, 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 part of the powder AM1 and the powder B is 80%-150% of the mass of each corresponding part of the powder AM1 and the powder B.

15. The method of claim 1, wherein, In step (5), 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; the calcination atmosphere is air.

16. The method of claim 1, wherein, In step (6), the coating treatment is performed using 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%. 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 use amount ratio of the aqueous emulsion (in mL) to the ball-formed body D (in g) is 0.8-1.5 mL / g.

18. The method of claim 16, 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, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose.

19. The method of claim 1, wherein, In step (7), 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 (7), in the impregnation solution containing the second active metal M2, the content of the Group VIB metal, in terms of oxide, is 8.0-48.0 g / 100 mL. And / or, in step (7), 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.

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

21. A hydrogen demetallization catalyst prepared by any of the methods of claims 1-20.

22. The catalyst of claim 21, wherein, The specific surface area of the hydrogenation demetallization catalyst is 165-190 m 2 / g, the pore volume is 0.55-0.80 mL / g, and / or the mechanical strength of the hydrogenation demetallization catalyst is 10.0-25.0 N / mm.

23. The use of a hydrogen demetallization catalyst prepared by any of the methods of claims 1-20 in residual oil hydroprocessing.

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