Method for preparing hydrodemetallization catalyst

Abstract

The invention discloses a method for preparing 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 and grinding the modified activated carbon X loaded with the first active metal M1 and the powder A to obtain powder AXM1; (4) preparing a binder mixed solution C; (5) preparing high-temperature activated carbon powder D; (6) firstly balling the powder AXM1, the powder B and the binder mixed solution C, and continuously balling the powder D and the binder mixed solution C to obtain a spherical molded body E; and (7) impregnating E with an impregnation liquid containing a second active metal to prepare the 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) oxidizing the activated carbon X to obtain modified activated carbon X, loading the first active metal M1 on the modified activated carbon X to obtain M1 / modified activated carbon X, and mixing and grinding M1 / modified activated carbon X and powder A to obtain powder AXM1;

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

[0012] (5) preparing high temperature activated carbon powder D;

[0013] (6) First, the powder AXM1, the powder B and the binder mixture C are formed into balls by rolling ball forming, and then the high temperature activated carbon powder D and the binder mixture C are further formed into balls by rolling ball forming on the basis of the above spherical bodies to obtain a spherical body E;

[0014] (7) The spherical body E is impregnated with an impregnation solution containing the second active metal M2, allowed to stand, dried, and calcined to obtain a hydrodemetallization catalyst.

[0015] 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.

[0016] 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.

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

[0018] 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.

[0019] 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.).

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.).

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

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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℃.

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

[0032] In step (3), the first active metal source is selected from nickel salts and / or cobalt salts, such as at least one of acetates, chlorides, nitrates and sulfates.

[0033] In step (3), the content of the first active metal in terms of first active metal nitrate accounts for 20.0% to 80.0% of the mass of the modified activated carbon X.

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

[0035] 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.

[0036] 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.

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

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

[0039] 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.

[0040] In step (5), the minimum heat-resistant temperature of the high-temperature activated carbon powder D is 750° C. The particle size of the high-temperature activated carbon powder D is 0.1 to 6.0 μm.

[0041] In step (6), the powder AXM1, the powder B and the binder mixture C are first formed into balls by rolling ball forming, and then the high-temperature activated carbon powder D and the binder mixture C are further formed into balls by rolling ball forming on the basis of the above spherical body to obtain a spherical formed body E. The specific preferred method is as follows: the powder AXM1 and the powder B are divided into N portions (N is greater than 2), that is, the first portion to the Nth portion, and one portion of powder AXM1 and powder B is added each time, the addition amount of powder AXM1 in the current portion is reduced, and the addition amount of powder B in the current portion is increased. The process includes:

[0042] (6-1) 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.

[0043] (6-2) Add the second powder AXM1 and the second powder B, and continue to spray the binder mixture C. The ball continues to grow.

[0044] (6-3) Using the current portion of powder AXM1 and the current portion of powder B, according to step (6-2), continuously enlarge the ball until the Nth portion of powder AXM1 and the Nth portion of powder B are all spherical, preferably with a particle size of 2-4 mm;

[0045] (6-4) Stop adding other powders, add high temperature activated carbon powder D, and continue spraying the binder mixture C to obtain a spherical precursor;

[0046] (6-5) The spherical precursor is dried and calcined to obtain a spherical body E.

[0047] In step (6), 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.

[0048] In step (6), the total mass of each corresponding portion of powder AXM1 and powder B is 0.90 to 1.10 times the (total mass of the first portion of powder AXM1 and the first portion of powder B). For example, when powder AXM1 and powder B are added for the xth time, the total mass of the xth portion of powder AXM1 and the xth portion of powder B is 0.90 to 1.10 times the (total mass of the first portion of powder AXM1 and the first portion of powder B), where x is 1 to N.

[0049] In step (6), 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.

[0050] In step (6), preferably, the mass ratio of the Nth portion of powder AXM1 to the Nth portion of powder B is 50-70:30-50.

[0051] In step (6), 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, the powder B and the high-temperature activated carbon powder D added.

[0052] In step (6), 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.

[0053] In step (6), the ball-forming time of each corresponding portion of powder AXM1 and powder B is controlled at 0.5-1.5 h.

[0054] In step (6), the spraying rate of the binder mixture C is not strictly limited, as long as it can ensure uniform ball formation.

[0055] In step (6), there is no strict limit on the spraying rate of the binder C and the high-temperature activated carbon powder D, as long as uniform ball formation is ensured.

[0056] In step (6-4), the amount of the binder mixture C added is 80% to 150% of the mass of the high-temperature activated carbon powder D.

[0057] In step (6-4), the mass of the high-temperature activated carbon powder D is 15.0% to 35.0% of the mass of the Nth part of powder AXM1 and the Nth part of powder B.

[0058] In step (6-4), the time for forming balls of high temperature activated carbon powder D and binder mixture C is not limited, and the final ball formation is based on the mass.

[0059] In step (6-5), the diameter of the spherical molded body E is 2.5 to 5.0 mm.

[0060] In step (6-5), 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.

[0061] In step (7), the impregnation method is any impregnation method in industry, such as saturated impregnation, vacuum impregnation, etc.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] In step (7), the standing condition is as follows: the temperature is 20°C to 40°C and the time is 2 to 12 hours.

[0066] 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.

[0067] 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.

[0068] The second aspect of the present invention provides a residue hydrodemetallization catalyst prepared by the above method.

[0069] In the present invention, the specific surface area of ​​the catalyst is 175 to 195 m 2 / g, and the pore volume is 0.80~1.00mL / g.

[0070] In the present invention, the mechanical strength of the catalyst is 10.0 to 18.0 N / mm.

[0071] 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 10% to 20% of the total pore volume, the pore volume occupied by pores with a pore diameter of 10-30nm accounts for 60% to 65% of the total pore volume, and the pore volume occupied by pores with a pore diameter >30nm accounts for less than 30% of the total pore volume.

[0072] 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.

[0073] 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.

[0074] Compared with the prior art, the hydrodemetallization catalyst prepared by the method of the present invention has the following advantages:

[0075] 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 component in the catalyst dust. At the same time, the non-ammonium alkaline compound is used to treat the catalyst dust or alumina, which can form partial hydroxyl groups on the surface of alumina, provide more alkaline sites for the loading of active metals, and improve the dispersion of active metals in the subsequent impregnation process; thirdly, In order to further control the distribution of active components, the activated carbon powder is oxidized to produce a large number of hydrophilic groups, which play an anchoring role on the first active metal, improve the dispersion of the first active metal, and further prevent the interaction between the metal nickel and the alumina carrier. The metal nickel is first loaded on the activated carbon carrier, ground into powder, and then formed into balls. This method can effectively disperse the metal nickel first and reduce the formation of inactive nickel aluminum spinel; fourth, high-temperature activated carbon is introduced to form a stable fixed activated carbon layer on the surface of the matrix carrier, which not only provides more pores for the catalyst, but also provides more attachment points for the second active metal on the catalyst surface, avoiding its aggregation on the surface of the matrix carrier. The high-temperature activated carbon layer will not disappear during the calcination process and still exists in the later reaction process, which can effectively enhance the metal capacity of the catalyst.

[0076] 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

[0077] The scheme and effect of the present invention are further described below in conjunction with embodiments, but are not limited to the following embodiments.

[0078] In the present invention, the pore structure is tested by low-temperature liquid nitrogen adsorption and 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 detected by an intelligent particle strength tester; and the metal component content is analyzed by spectrophotometry. The catalyst powder used in the embodiment is the calcined powder generated by the catalyst in the actual production process and collected by a collector.

[0079] Example 1

[0080] (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 85.0%, the molybdenum oxide content is 12.0%, and the nickel oxide content is 3.0%) 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 6.0 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 4 h to obtain powder A; a sufficient amount of powder A is synthesized in the same way for standby use;

[0081] (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 2.5 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 160° C. for 5 h to obtain powder B. Use the same method to synthesize a sufficient amount of powder B for later use;

[0082] (3) Activated carbon X (with a specific surface area of ​​1000 m 2 / g) is subjected to oxidation treatment (treatment conditions are: the oxidation liquid is a nitric acid solution, the volume mass ratio of the oxidation liquid to the activated carbon X is 1.5 ml / g, the concentration of the nitric acid solution is 8.0 mol / L, the treatment temperature is 90°C, and the treatment time is 8 h) to obtain modified activated carbon X, the first active metal M1 (Ni) is loaded on the modified activated carbon X (the Ni source is nickel nitrate, and the amount is 77.5% of the mass of the activated carbon X) to obtain M1 / modified activated carbon X, and M1 / modified activated carbon X and powder A are mixed at a mass ratio of 1:5 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;

[0083] (4) Add 24 g of nitric acid and 18 g of sesbania powder to 1 L of aqueous solution, and then add 48.4 g of phosphoric acid to prepare a binder mixture C;

[0084] (5) Weigh 25.0 g of high-temperature activated carbon powder D (particle size 0.1-6.0 μm);

[0085] (6) Powder AXM1 and powder B are divided into four portions, namely the first portion to the fourth portion, and the total mass of powder AXM1 and powder B in each corresponding portion 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 92:8, the amount of powder AXM1 added in the current portion is 87% of the amount of powder AXM1 added in the previous portion, when each portion of powder AXM1 and powder B is balled, the amount of binder mixed liquid C added is 140% of the sum of the masses of the current portion of powder AXM1 and powder B, and when high-temperature activated carbon powder D is balled, the amount of binder mixed liquid C added is 140% of the mass of high-temperature activated carbon powder D. The process includes:

[0086] (6-1) 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 the particles. The forming time is 0.6 hours, and the materials are formed into spherical particles.

[0087] (6-2) 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 0.6h.

[0088] (6-3) Using the current portion of powder AXM1 and the current portion of powder B, continue to enlarge the ball in the manner of step (6-2) until the Nth portion of powder AXM1 and the Nth portion of powder B are all formed into balls;

[0089] (6-4) Stop adding other powders and only add binder C and high-temperature activated carbon powder D until a 3-5 mm spherical precursor is finally obtained;

[0090] (6-5) drying at 170°C for 6 h, and then calcining at 550°C for 3 h to obtain a spherical body E;

[0091] (7) The spherical body 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 14.83 g / 100 ml). After the metal was impregnated, the support was allowed to stand at 35° C. for 6 h, dried at 140° C. for 6 h, and then calcined in air at 700° 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.

[0092] Example 2

[0093] 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 8.5. The hydrothermal reaction temperature is 190°C, the reaction time is 15 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 3.0 μm. Finally, the hydrodemetallization catalyst CAT-2 is obtained. Other physicochemical properties of catalyst CAT-2 are shown in Table 1.

[0094] Example 3

[0095] Compared with Example 1, the difference is that in step (1), a slurry with an average particle size of 4.5 μm 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 AXM1 with an average particle size of 3.5 μm. Finally, the hydrodemetallization catalyst CAT-3 is obtained. Other physicochemical properties of catalyst CAT-3 are shown in Table 1.

[0096] Example 4

[0097] Compared with Example 1, the difference is that in step (3), the activated carbon X is oxidized (the treatment conditions are: the oxidizing liquid is a nitric acid solution, the volume mass ratio of the oxidizing liquid to the activated carbon X is 1.2 ml / g, the concentration is 10.0 mol / L, the treatment temperature is 80°C, and the treatment time is 6 h) to obtain modified activated carbon X, and the first active metal M1 (Ni) is loaded on the modified activated carbon X (the Ni source is nickel nitrate, and the amount is 61.2% of the mass of the activated carbon X) to obtain M1 / modified activated carbon X, and M1 / modified activated carbon X 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; in step (4), 22 g nitric acid and 20 g sesbania powder are added to 1 L of aqueous solution, and then 31.5 g phosphoric acid is added to prepare a binder mixed solution C; in step (5), high temperature activated carbon powder D is weighed 20.0g; in step (6), the powder AXM1 and powder B are divided into six parts, namely the first to the sixth parts, and the total mass of the powder AXM1 and powder B in each corresponding part is 100g. Each time a part of powder AXM1 and powder B is added, the addition amount of powder AXM1 in the current part is reduced, and the addition amount of powder B in the current part is increased; wherein, the mass ratio of the first part of powder AXM1 to the first part of powder B is 94:6, and the addition amount of powder AXM1 in the current part is 90% of the addition amount of powder AXM1 in the previous part; in step (7), the spherical body 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 14.17g / 100ml), and the carrier after impregnation with the metal is left to stand for 6h. The obtained product is dried at 160°C for 5h, and then calcined at 600°C for 4h. Finally, the hydrodemetallization catalyst CAT-4 was prepared. Other physical and chemical properties of the catalyst CAT-4 are shown in Table 1.

[0098] Example 5

[0099] The same as Example 1, except that in step (3), the activated carbon X is oxidized (the treatment conditions are: the oxidizing liquid is a nitric acid solution, the volume mass ratio of the oxidizing liquid to the activated carbon X is 1.4 ml / g, the concentration is 8.0 mol / L, the treatment temperature is 90°C, and the treatment time is 8 h) to obtain modified activated carbon X, and the first active metal M1 (Ni) is loaded on the modified activated carbon X (the Ni source is nickel nitrate, and the amount is 44.85% of the mass of the activated carbon X) to obtain M1 / modified activated carbon X, and M1 / modified activated carbon X and powder A are mixed at a mass ratio of 1:3 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; in step (4), 20 g nitric acid and 22 g sesbania powder are added to 1 L of aqueous solution, and then 46.9 g phosphoric acid is added to prepare a binder mixed solution C; in step (5), high temperature activated carbon powder D is weighed 30.0g; in step (6), the powder AXM1 and powder B are divided into seven parts, namely the first to the seventh parts, and the total mass of the powder AXM1 and powder B in each corresponding part is 100g. Each time a part of powder AXM1 and powder B is added, the addition amount of powder AXM1 in the current part is reduced, and the addition amount of powder B in the current part is increased; wherein, the mass ratio of the first part of powder AXM1 to the first part of powder B is 92:8, and the addition amount of powder AXM1 in the current part is 94% of the addition amount of powder AXM1 in the previous part; in step (7), the spherical body 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 14.40g / 100ml), and the carrier after impregnation with the metal is left to stand for 6h. The obtained product is dried at 150°C for 4h, and then calcined at 650°C for 4h. Finally, the hydrodemetallization catalyst CAT-5 was prepared. Other physical and chemical properties of the catalyst CAT-5 are shown in Table 1.

[0100] Example 6

[0101] The same as Example 1, except that in step (2), ρ-type alumina is replaced by χ-type alumina; in step (3), activated carbon X is oxidized (treatment conditions are: the oxidizing liquid is nitric acid solution, the volume mass ratio of the oxidizing liquid to the activated carbon X is 1.0 ml / g, the concentration is 12.0 mol / L, the treatment temperature is 100°C, and the treatment time is 8 h) to obtain modified activated carbon X, and the first active metal M1 (Ni) is loaded on the modified activated carbon X (the Ni source is nickel nitrate, and the amount is 31.24% of the mass of the activated carbon X) to obtain M1 / modified activated carbon X, and M1 / modified activated carbon X and powder A are mixed at 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), 24 g nitric acid and 24 g sesbania powder are added to 1 L of aqueous solution, and then 48.29 g phosphoric acid is added to prepare a binder mixed solution C; in step (5), high temperature activated carbon powder D is weighed 35.0g; in step (6), the powder AXM1 and powder B are divided into five parts, namely the first to fifth parts, and the total mass of each corresponding part of the powder AXM1 and powder B is 100g. Each time a part of powder AXM1 and powder B is added, the amount of powder AXM1 added in the current part is reduced, and the amount of powder B added in the current part is increased; wherein, the mass ratio of the first part of powder AXM1 to the first part of powder B is 95:5, and the amount of powder AXM1 added in the current part is 88% of the amount of powder AXM1 added in the previous part; in step (7), the spherical body 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 14.83g / 100ml), and the carrier after metal impregnation is left to stand for 6h. The obtained product is dried at 140°C for 6h, and then calcined at 650°C for 6h. Finally, the hydrodemetallization catalyst CAT-6 was prepared. Other physical and chemical properties of the catalyst CAT-6 are shown in Table 1.

[0102] Example 7

[0103] The same as Example 1, except that in step (4), 30 g nitric acid and 20 g sesbania powder are added to 1 L aqueous solution, and then 48.4 g phosphoric acid is added to prepare a binder mixed solution C; in step (6-5), the mixture is dried at 140° C. for 5 h, and then calcined at 650° C. for 4 h to obtain a spherical body E. Finally, a hydrodemetallization catalyst CAT-7 is obtained. Other physical and chemical properties of the catalyst CAT-7 are shown in Table 1.

[0104] Comparative Example 1

[0105] Compared with Example 1, the difference is that in step (1), a ball mill is not used for grinding to obtain a slurry with an average particle size of 17.8 μm, and in step (3), a ball mill is used for grinding to obtain a powder AXM1 with an average particle size of 15.5 μm. Finally, a hydrodemetallization catalyst DAT-1 is obtained. Other physical and chemical properties of the catalyst DAT-1 are shown in Table 2.

[0106] Comparative Example 2

[0107] 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 3.5 μm. Finally, the hydrodemetallization catalyst DAT-2 is obtained. Other physical and chemical properties of the catalyst DAT-2 are shown in Table 2.

[0108] Comparative Example 3

[0109] Compared with Example 1, the difference is that all materials in step (6) 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.

[0110] Comparative Example 4

[0111] 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.

[0112] Comparative Example 5

[0113] Compared with Example 1, the difference is that no alkaline auxiliary agent is introduced during the treatment 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.

[0114] Comparative Example 6

[0115] 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.

[0116] Table 1 Physicochemical properties of the hydrodemetallization catalysts of various examples

[0117] 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]]> 182 184 187 179 183 185 181 <![CDATA[Pore volume, cm 3 / g]]> 0.85 0.90 0.88 0.85 0.83 0.85 0.92 Mechanical strength, N / mm 12.4 12.6 12.1 12.5 12.2 12.4 12.5 Active ingredient content <![CDATA[MoO3,wt%]]> 13.8 13.7 13.6 13.7 13.8 13.6 13.7 NiO, wt% 3.5 3.6 3.4 3.5 3.7 3.6 3.5 Additive content <![CDATA[P2O5,wt%]]> 3.2 3.1 3.0 3.2 3.1 3.0 3.2 Pore ​​distribution <10nm,% 13.1 13.4 13.7 13.2 13.8 13.5 13.0 10-30nm, % 61.0 60.9 61.7 61.5 61.3 61.4 61.8 >30nm,% 25.9 25.7 24.6 25.3 24.9 25.1 25.2

[0118] Table 2 Physicochemical properties of the hydrodemetallization catalysts of the comparative examples

[0119]

[0120]

[0121] Evaluation test

[0122] 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 992.8 kg / m 3 (20°C), S content 3.31wt%, metal Ni and V contents 34.6μg / g and 66.9μg / g respectively, CCR content 12.3wt%. 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. Specific test conditions are shown in Table 3, and test results are shown in Table 4 and Table 5.

[0123] Table 3 Test conditions

[0124] Reaction temperature, °C 370 Reaction pressure, MPa 15.7 <![CDATA[Liquid hourly space velocity, h -1 > 1.0 Hydrogen to oil ratio, V / V 800

[0125] Table 4 Test results of hydrodemetallization catalysts of various embodiments

[0126]

[0127] Table 5 Test results of the hydrodemetallization catalysts of the comparative examples

[0128]

[0129] 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) oxidizing the activated carbon X to obtain modified activated carbon X, loading the first active metal M1 on the modified activated carbon X to obtain M1 / modified activated carbon X, and mixing and grinding M1 / modified activated carbon X and powder A to obtain powder AXM1; (4) preparing a binder mixed solution C; (5) preparing high temperature activated carbon powder D; (6) First, the powder AXM1, the powder B and the binder mixture C are formed into balls by rolling ball forming, and then the high temperature activated carbon powder D and the binder mixture C are further formed into balls by rolling ball forming on the basis of the above spherical bodies to obtain a spherical body E; (7) The catalyst intermediate E 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 oxidation treatment conditions are: the solution is a nitric acid solution, the concentration is 5-12 mol / L, the volume mass ratio of the oxidation solution to the activated carbon X is 0.9-1.8 ml / g, the temperature is 80-100° C., and the treatment time is 6-12 h; and / or, in step (3), the first active metal is at least one of the Group VIII metals, wherein the Group VIII metal is 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 80.0% of the mass of the modified activated carbon; In step (3), the ratio of M1 / modified 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), the minimum heat-resistant temperature of the high-temperature activated carbon powder D is 750°C; and the particle size of the high-temperature activated carbon powder D is 0.1 to 6.0 μm.

9. The method according to claim 1, characterized in that: In step (6), the powder AXM1, the powder B and the binder mixture C are first formed into balls by rolling ball forming, and then the high-temperature activated carbon powder D and the binder mixture C are further formed into balls by rolling ball forming on the basis of the above spherical bodies to obtain a spherical body E, which is specifically as follows: the powder AXM1 and the powder B are divided into N portions (N is greater than 2), that is, the first portion to the Nth portion, and one portion of powder AXM1 and powder B is added each time, the addition amount of powder AXM1 in the current portion is reduced, and the addition amount of powder B in the current portion is increased. The process includes: (6-1) 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. (6-2) Add the second powder AXM1 and the second powder B, and continue to spray the binder mixture C. The ball continues to grow. (6-3) Using the current portion of powder AXM1 and the current portion of powder B, according to step (6-2), continuously enlarge the ball until the Nth portion of powder AXM1 and the Nth portion of powder B are all spherical, preferably with a particle size of 2-4 mm; (6-4) Stop adding other powders, add high temperature activated carbon powder D, and continue spraying the binder mixture C to obtain a spherical precursor; (6-5) The spherical precursor is dried and calcined to obtain a spherical body E.

10. The method according to claim 9, characterized in that In step (6), 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 (6), 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, in step (6), 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 (6), 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 (6), 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 (6), 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 the high-temperature activated carbon powder D; and / or, in step (6), 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 (6-4), the amount of the binder mixture C added is 80% to 150% of the mass of the high-temperature activated carbon powder D; And / or, in step (6-4), the mass of the high temperature activated carbon powder D is 15.0% to 35.0% of the mass of the Nth part of powder AXM1 and the Nth part of powder B; And / or, in step (6-5), 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, the roasting time is 2 to 6 hours, and the roasting atmosphere is air; And / or, in step (6-5), the diameter of the spherical molded body E is 2.5 to 5.0 mm.

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 impregnation solution containing the second active metal M2 has a content of the Group VIB metal in the form of oxide of 8.0 to 48.0 g / 100 ml; And / or, in step (7), the standing conditions are: temperature of 20°C to 40°C, time of 2 to 12 hours; 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, and 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 175 to 195 m 2 / g, a pore volume of 0.80-1.00 mL / g, and / or a mechanical strength of the catalyst of 10.0-18.0 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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