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) mixing the powder A with a first active metal source, and grinding to obtain powder AM1; (4) preparing a binder mixed solution C; (5) carrying out ball rolling molding on the powder AM1, the powder B and the binder mixed solution C according to a specific mode to obtain a spherical molded body D; optionally, (6) carrying out surface coating treatment on the spherical molded body D by adopting 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 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] At present, the number of large-scale oil refining and chemical plants in China continues to increase, and the number of residual oil hydroprocessing plants is also growing rapidly, reaching more than 30 sets. As the quality and heaviness of crude oil increase, the raw material properties of residual oil hydroprocessing plants are also deteriorating overall. They often need to process residual oil raw materials with high metal content, high sulfur content, and high carbon residue. The impurity removal and impurity tolerance of the entire residual oil hydroprocessing catalyst system directly affect whether the plant can operate stably for a long period of time. Residue oil hydroprocessing catalysts will produce some catalyst dust during the production process, 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) mixing powder A and a first active metal M1 source, grinding, and obtaining powder AM1;

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

[0012] (5) Powder AM1 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 AM1 and powder B is added each time, the amount of powder AM1 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 AM1 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 AM1 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 AM1 and the current portion of powder B, according to step (5-2), the ball is continuously enlarged 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 calcining, a spherical body D is obtained;

[0017] Optionally, (6) the spherical body D is subjected to surface coating treatment with a carbon source, and then calcined in an inert atmosphere to obtain a catalyst intermediate E;

[0018] (7) The catalyst intermediate E or the spherical molded 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.

[0019] 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.

[0020] 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.

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

[0022] 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.

[0023] 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.).

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.).

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

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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).

[0035] In step (3), the amount of the first active metal added in terms of 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 performed by ball milling, sand milling, etc., and the average particle size of the ground sample is 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), at least 0.5 μm smaller, preferably at least 2.0 μm smaller.

[0037] 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.

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

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

[0040] 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.

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

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

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

[0044] 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 AM1 and the powder B added.

[0045] In step (5), during the balling process of each corresponding portion of powder AM1 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 AM1 and powder B.

[0046] In step (5), the ball-forming time of each corresponding portion of powder AM1 and powder B is controlled to be 0.5 to 1.5 hours.

[0047] In step (5), the spraying rate of the binder mixture C is not strictly limited, as long as it can ensure uniform ball formation.

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

[0049] 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.

[0050] In step (6), 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%.

[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 usage 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.

[0054] In step (6), 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.

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

[0056] In step (7), 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.

[0057] In step (7), 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.

[0058] In step (7), 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.

[0059] In step (7), the standing conditions are: temperature of 20°C to 40°C, and time of 2 to 12 hours.

[0060] In step (7), 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.

[0061] In step (7), 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.

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

[0063] In the present invention, the specific surface area of ​​the catalyst is 165 to 190 m 2 / g, and the pore volume is 0.55 to 0.80 mL / g, preferably 0.55 to 0.75 mL / g.

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

[0065] 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 30% 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.

[0066] 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, introduced during the preparation of the carrier, or introduced after the preparation of the carrier.

[0067] 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.

[0068] Compared with the prior art, the hydrodemetallization catalyst prepared by the method of the present invention has the following advantages:

[0069] 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 the carrier has higher reaction activity and metal capacity; secondly, a non-ammonium alkaline compound is used to treat the 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 the hydrogenation catalyst according to the situation), so as to make full use of the carrier component in the catalyst dust, and at the same time, the non-ammonium alkaline compound is used to treat the catalyst Dust or alumina can form partial hydroxyl groups on the surface of alumina, providing more alkaline sites for the loading of active metals and improving the dispersion of active metals in the subsequent impregnation process; thirdly, a membrane coating treatment is carried out on the matrix carrier containing the first active metal, and it is calcined by inert gas, 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 calcined, the film is burned off, 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.

[0070] 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

[0071] The scheme and effect of the present invention are further described below in conjunction with embodiments, but are not limited to the following embodiments.

[0072] 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.

[0073] 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.

[0074] Example 1

[0075] (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 84.3%, the molybdenum oxide content is 12.5%, and the nickel oxide content is 3.2%) 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 5.5 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 150° C. for 6 h to obtain powder A; a sufficient amount of powder A is synthesized by the same method for standby use;

[0076] (2) 84 g of ρ-type alumina and 2 g of sodium hydroxide were added to 2 L of clean water, and the mixture was ground using a ball mill to obtain a slurry with an average particle size of 2.2 μm and a pH value of 10.0. The mixture was hydrothermally reacted at 260° C. for 8 h. After the reaction, the obtained product was filtered in a conventional manner, and the filtered product was dried at 170° C. for 4 h to obtain powder B. A sufficient amount of powder B was synthesized in the same manner for later use;

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

[0078] (4) Add 20 g of nitric acid and 16 g of sesbania powder to 1 L of aqueous solution, and then add 56.7 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;

[0079] (5) Powder AM1 and powder B are divided into six portions, namely the first portion to the sixth portion, and the total mass of powder AM1 and powder B in each corresponding portion is 100g. Each time a portion of powder AM1 and powder B is added, the amount of powder AM1 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 AM1 to the first portion of powder B 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, and when each portion of powder AM1 and powder B is balled, the amount of binder mixed liquid C added is 110% of the mass sum of the current portion of powder AM1 and powder B. The process includes:

[0080] (5~1) Place the first powder AM1 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, the forming time is 0.5h, and the material is formed into spherical particles.

[0081] (5-2) Add the second powder AM1 and the second powder B, and continue to spray the binder mixture C. The ball continues to grow. The molding time is 0.5h.

[0082] (5-3) Using the current portion of powder AM1 and the current portion of powder B, continue to enlarge the balls 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) drying at 170°C for 6 h, and then calcining at 550°C for 3 h to obtain a spherical molding D, wherein the diameter of the spherical molding D is 2.5-4.5 mm;

[0084] (6) 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 8.0%, and the mass content of hydroxymethyl cellulose is 0.8%. The amount ratio of the aqueous emulsion (by volume ml) to the spherical molding body D (by mass g) is 1.0 ml / g. The spherical molding body D is calcined in a nitrogen atmosphere, and the calcination conditions are: calcination at a temperature of 650° C. for 5 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;

[0085] (7) 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 15.70 g / 100 ml). After the metal was impregnated, the support was allowed to stand at 30° C. for 6 h, dried at 140° C. for 4 h, and then calcined in air at 600° 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.

[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 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 AM1 with an average particle size of 3.5 μm. Finally, the hydrodemetallization catalyst CAT-2 is obtained. 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 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 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 AM1 with an average particle size of 5.0 μm. Finally, the hydrodemetallization catalyst CAT-3 is 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, and the amount is 15.9% of the mass of powder A) are mixed and ground evenly, and the average particle size is 4.5 μm to obtain powder AM1; in step (4), 25 g nitric acid and 14 g sesbania powder are added to 1 L aqueous solution, and then 62.6 g phosphoric acid is added to prepare a binder mixed solution C; in step (5), powder AM1 and powder B are divided into four parts, namely the first to fourth parts, and the first part of powder AM1 is mixed with the first part of powder B. The mass ratio of the catalyst intermediate E to the catalyst intermediate B is 90:10, and the amount of the current powder AM1 added is 85% of the amount of the previous powder AM1 added; in step (7), 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 17.40g / 100ml), and the carrier after metal impregnation is allowed to stand at 35°C for 6h, and the obtained product is dried at 160°C for 6h, and then calcined at 600°C for 4h to obtain the carrier. Finally, the hydrodemetallization catalyst CAT-4 is obtained. Other physical and chemical properties of the 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, and the amount is 17.42% of the mass of powder A) are mixed and ground evenly, and the average particle size is 4.5 μm to obtain powder AM1; a sufficient amount of powder AM1 is synthesized in the same way for standby use; in step (4), 30 g of nitric acid and 12 g of sesbania powder are added to 1 L of aqueous solution, and then 71.4 g of phosphoric acid is added to prepare a binder mixture C; a sufficient amount of binder mixture C is synthesized in the same way for standby use; in step (5), powder AM1 and powder B are divided into three parts, namely, the first to third parts, the first The mass ratio of the first powder AM1 to the first powder B is 90:10, and the amount of the current powder AM1 added is 80% of the amount of the previous powder AM1 added; 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 saturatedly impregnated in an impregnation solution containing a second active metal Mo (the molybdenum source is ammonium heptamolybdate) (the content of Mo (in terms of oxide) is 19.72g / 100ml), and the carrier after metal impregnation is allowed to stand at a temperature of 25°C for 6h. Finally, the hydrogenation demetallization catalyst CAT-5 is obtained. Other physical and chemical properties of the catalyst CAT-5 are shown in Table 1.

[0094] Example 6

[0095] Compared with Example 1, the difference is that in step (2), ρ-type alumina is changed to χ-type alumina; in step (3), powder A and the first active metal Ni (nickel source is nickel nitrate, and the amount is 12.75% of the mass of powder A) are mixed and ground evenly, and the average particle size is 4.5 μm to obtain powder AM1; in step (4), 35 g nitric acid and 10 g sesbania powder are added to 1 L aqueous solution, and then 51.7 g phosphoric acid is added to prepare a binder mixed solution C; in step (5), powder AM1 and The powder B is divided into eight portions, namely the first portion to the eighth portion, the mass ratio of the first portion of powder AM1 to the first portion of powder B is 98:2, 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 (7), the catalyst intermediate E is saturatedly impregnated in an impregnation solution containing a second active metal Mo (the molybdenum source is ammonium heptamolybdate) (the content of Mo (in terms of oxide) is 14.48 g / 100 ml), and the carrier after metal impregnation is allowed to stand at a temperature of 35°C for 6 hours. Finally, the hydrodemetallization catalyst CAT-6 is obtained. Other physicochemical properties of the catalyst CAT-6 are shown in Table 1.

[0096] Example 7

[0097] Compared with Example 1, the difference is that the step (6) of surface coating the spherical body D is omitted. Finally, the hydrodemetallization catalyst CAT-7 is prepared. Other physical and chemical properties of the 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 is not used for grinding to obtain a slurry with an average particle size of 17.6 μm, and in step (3), a ball mill is used for grinding to obtain a powder AM1 with an average particle size of 15.6 μm. Finally, a hydrodemetallization catalyst DAT-1 is obtained. Other physical and chemical properties of the catalyst DAT-1 are shown in Table 2.

[0100] Comparative Example 2

[0101] 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 AM1 with an average particle size of 2.2 μm. Finally, the hydrodemetallization catalyst DAT-2 is obtained. Other physical and chemical properties of the 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 formed. Finally, the hydrodemetallization catalyst DAT-3 is prepared. Other physical and chemical properties of the catalyst DAT-3 are shown in Table 2.

[0104] Comparative Example 4

[0105] 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.

[0106] Comparative Example 5

[0107] Compared with Example 1, the difference is that no alkaline auxiliary agent is introduced during the preparation of powder A and powder B. Finally, a hydrodemetallization catalyst DAT-5 is prepared. Other physical and chemical properties of catalyst DAT-5 are shown in Table 2.

[0108] Comparative Example 6

[0109] Compared with Example 1, the difference is that the powder AM1 and the powder B are 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.

[0110] Table 1 Physicochemical properties of the hydrodemetallization catalysts of various examples

[0111] Serial number Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Catalyst No. 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 hydrodemetallization catalysts of the comparative examples

[0113]

[0114]

[0115] Evaluation test

[0116] The activity stability test of the catalysts obtained in Examples 1-7 and Comparative Examples 1-6 was carried out on a 200 ml fixed bed hydrogenation test device. The raw oil was residual oil with a density of 989.2 kg / m 3 (20°C), S content 2.68wt%, metal Ni and V contents 25.5μg / g and 62.7μg / g respectively, CCR content 11.4wt%. The demetallization rate of comparative example 6 when running for 1500h is 100%, and the other embodiments and comparative examples are all relative demetallization rates when running for 1500h, calculated as Ni+V. Specific test conditions are shown in Table 3, and test results are shown in Tables 4 and 5.

[0117] Table 3 Test 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 hydrodemetallization catalysts of various embodiments

[0120]

[0121]

[0122] Table 5 Test results of the hydrodemetallization catalysts of the comparative examples

[0123]

[0124] 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, can process residual oil with relatively good raw material properties at a higher space velocity and a lower hydrogen-to-oil volume ratio, can maintain a good demetallization rate over a longer period, and can well meet the 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) mixing powder A and a first active metal M1 source, grinding, and obtaining powder AM1; (4) preparing a binder mixed solution C; (5) Powder AM1 and powder B are divided into N portions respectively, where N is greater than 2, i.e., from the first portion to the Nth portion, one portion of powder AM1 and powder B is added each time, the amount of powder AM1 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 AM1 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 AM1 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 AM1 and the current portion of powder B, according to step (5-2), the ball is continuously enlarged until the Nth portion of powder AM1 and the Nth portion of powder B are all formed into balls; (5-4) After drying and calcining, a spherical body D is obtained; Optionally, (6) the spherical body D is subjected to surface coating treatment with a carbon source, and then calcined in an inert atmosphere to obtain a catalyst intermediate E; (7) The catalyst intermediate E or the spherical molded 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 alumina after grinding is 0.1 to 5 μm; preferably, 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), 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.

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% to 4.5%; And / or, in step (4), the mass concentration of the colloid in the binder mixed solution C is 0.5% to 2.5%.

8. The method according to claim 1, characterized in that In step (5), powder AM1 and powder B are divided into N parts respectively, where N is greater than 2, preferably 3 to 20, and more preferably 3 to 10; and / or, in step (5), the total mass of each corresponding portion of powder AM1 and powder B is 0.90 to 1.10 times (the total mass of the first portion of powder AM1 and the first portion of powder B); and / or, the mass ratio of the first powder AM1 to the first powder B is 90-98:2-10, and the amount of the current powder AM1 added is 77%-95% of the amount of the previous powder AM1 added; and / or, in step (5), the mass ratio of the Nth portion of powder AM1 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 AM1 and B added; preferably, in step (5), during the balling process of each corresponding portion of the powders AM1 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 AM1 and B; And / or, in step (5), the balling time of each corresponding portion of powder AM1 and powder B is controlled within 0.5 to 1.5 hours; 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 (6), the coating treatment is performed by 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.; And / or, in step (6), the ratio of the volume of the aqueous emulsion to the mass of the spherical forming body D 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 (7), 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 (7), 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 (7), 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 (7), 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 165 to 190 m 2 / g, the pore volume is 0.55-0.80 mL / g, and / or the mechanical strength of the catalyst is 10.0-25.0 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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