Residue hydrodemetallization catalyst and method for making same

Abstract

The application discloses a residual oil hydrodemetallization catalyst and a preparation method thereof. The method comprises the following steps: (1) an acid aluminum salt aqueous solution, an alkaline aluminum salt aqueous solution and a kaolin suspension liquid containing a surfactant are subjected to a first reaction to obtain slurry I; (2) an alkaline solution is introduced into the slurry I of step (1) to perform a second reaction to obtain slurry II; (3) the slurry II obtained in step (2) is subjected to hydrothermal treatment with a gallium nitrate solution, and then washed and dried to obtain a gallium-containing macroporous silica-aluminum material; (4) the gallium-containing macroporous silica-aluminum material is mixed with a plasticizing agent and a cementing agent, and then kneaded into a shape, and then dried and calcined to obtain a catalyst carrier; and (5) the catalyst carrier of step (4) is impregnated with an active metal impregnation liquid containing an organic acid and an alcohol compound, and then dried and calcined to obtain the residual oil hydrodemetallization catalyst. The catalyst can improve the demetallization activity and use stability of the catalyst in a residual oil hydroprocessing process.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst preparation, and particularly relates to a preparation method of a residual oil hydrodemetallization catalyst. BACKGROUND

[0002] With the increasingly heavy and poor quality of crude oil, and increasingly stringent environmental regulations, processing of heavy and poor quality crude oil is facing severe challenges. Residual oil is the heaviest and most complex fraction of petroleum distillates, and is rich in most impurities in crude oil, such as sulfur, nitrogen, heterocyclic compounds, soluble metal compounds, gum, asphaltene, etc., and is therefore the most difficult fraction to process. Gum and asphaltene contain a large amount of unstable compounds with a dense ring aromatic structure. These unstable compounds are prone to condensation reactions, and coke and carbon are deposited on the surface of the catalyst, covering and blocking the metal active sites and the micropores of the catalyst. Metal impurities such as Fe, Ca, Ni, and V exist in the form of soluble organic metal compounds, which are deposited on the surface and pores of the catalyst after decomposition during the hydrogenation process, causing loss of active sites and permanent deactivation of the catalyst. Therefore, the carbon and metal capacity of the fixed-bed residual oil hydrodemetallization catalyst is the key to the long-term stable operation of the residual oil hydroprocessing unit.

[0003] Currently, the industrialized hydrodemetallization catalysts use alumina as the carrier and Group VIB and Group VIII metals as the active components. The hydrodemetallization catalysts are usually prepared by adding a pore-expanding agent during kneading to prepare the carrier, and then impregnating and loading the active metals. Although this method can produce some large pores, the connectivity between the pores is poor, which still affects the diffusion of macromolecular asphaltene molecules and more easily causes the deposited coke to block the pores. In addition, the production of large pores also reduces the mechanical strength of the catalyst and affects the activity of the catalyst. The high activity and good stability of the hydrodemetallization catalyst are not only related to the large pores and the mechanical strength, but also related to the surface properties of the catalyst and the existence state of the metal and other factors. Therefore, the improvement of the activity and stability of the hydrodemetallization catalyst still needs to be further explored.

[0004] CN1160602A discloses a method for preparing a large-pore alumina carrier. The method is to add a physical pore-expanding agent such as carbon black and a chemical pore-expanding agent such as a phosphorus compound during kneading of pseudo-boehmite and water or an aqueous solution, to knead the plastic body, to form a strip on a strip extruder, and to calcine the dried strip at 840-1000℃ for 1-5h. This method uses the conventional kneading method to prepare the carrier, and therefore the activity and stability of the hydrodemetallization catalyst prepared therefrom need to be improved. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a residue demetallization catalyst and a preparation method thereof. The catalyst is used in a residue hydroprocessing process, and can improve the demetallization activity and use stability of the catalyst.

[0006] The present application provides a preparation method of a residue hydrodemetallization catalyst, comprising the following steps:

[0007] (1) acid aluminum salt aqueous solution, alkaline aluminum salt aqueous solution and kaolin suspension liquid containing surfactant are parallelly reacted to obtain slurry I;

[0008] (2) the slurry I of step (1) is introduced into an alkaline solution to perform secondary reaction to obtain slurry II;

[0009] (3) the slurry II obtained in step (2) is subjected to hydrothermal treatment with gallium nitrate solution, and then washed and dried to obtain a gallium-containing macroporous silica-alumina material;

[0010] (4) the gallium-containing macroporous silica-alumina material is mixed and kneaded with a plasticizing agent and a cementing agent, and then dried and calcined to obtain a catalyst carrier;

[0011] (5) the catalyst carrier of step (4) is impregnated with an active metal impregnation solution containing an organic acid and an alcohol compound, and then dried and calcined to obtain a residue hydrodemetallization catalyst.

[0012] In the present application, the surfactant in step (1) is one or more of long-chain fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, polyoxyethylene alkylamines, polyoxyethylene alkyl alcohol amides and polyethers, and the amount of the surfactant is 0.3% to 3.0% of the mass of kaolin, preferably 0.5% to 2.5%.

[0013] In the present application, the pH value of the reaction in step (1) is controlled to be 1.2 to 1.8, and the pH value is adjusted by adding at least one of hydrochloric acid, nitric acid or sulfuric acid.

[0014] In the present application, the acidic aluminum salt in step (1) is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate, and the concentration of the acidic aluminum salt solution is 20-100 g / 100 mL in terms of Al2O3. The basic aluminum salt is at least one of sodium aluminate or potassium aluminate, and the concentration of the basic aluminum salt solution is 20-100 g / 100 mL in terms of Al2O3. The concentration of kaolin in the kaolin suspension containing surfactant is 0.5-5 g / 100 mL. The volume ratio of the kaolin suspension containing surfactant, the acidic aluminum salt solution and the basic aluminum salt solution is 1:1-5:1-3. The reaction time of step (1) is 60-180 min, and the reaction temperature is 60-90℃. The reaction is preferably carried out under stirring, and the stirring rate is 100-500 rad / min, preferably 150-450 rad / min.

[0015] In the present application, the basic solution in step (2) is a solution of at least one of sodium hydroxide or sodium carbonate. The concentration of the basic solution is 50-70 g / 100 mL, the reaction time of the secondary reaction is 60-120 min, and the reaction temperature is 120-180℃. The reaction is preferably carried out under stirring, and the stirring rate is 100-500 rad / min, preferably 250-500 rad / min. The pH value of the secondary reaction is controlled to be 8.5-9.7.

[0016] In the present application, the concentration of the gallium nitrate solution in step (3) is 0.3-2.5 mol / L. The mass ratio of the slurry II obtained in step (2) to the gallium nitrate solution is 3:1-7:1 in terms of Al2O3 and Ga2O3.

[0017] In the present application, in step (3), the hydrothermal treatment temperature is 200-500℃, the pressure is 10-20 MPa, and the time is 2-4 hours. The washing can be carried out by using conventional washing methods in the art, preferably using deionized water, and further preferably at 50-90℃. The drying conditions are 120-160℃, and the drying time is 3-6 hours.

[0018] In the present application, the preparation process of the catalyst carrier in step (4) is to knead the extrusion aid, the adhesive and the gallium-containing macroporous silica-alumina material into a plastic body, and then to shape, which can be carried out by using conventional shaping methods, such as extrusion, tabletting, etc., preferably extrusion. Then, drying and calcination are carried out. The drying temperature is 110-160℃, and the drying time is 2-8 hours. The calcination temperature is 600-750℃, and the calcination time is 6-10 hours.

[0019] In the present application, the extrusion aid in step (4) is pearl millet powder, and the amount is 1% to 5% of the mass of the carrier; the adhesive is nitric acid, formic acid, acetic acid, citric acid, methyl cellulose, or polyethylene glycol, and the amount is 0.5% to 3% of the mass of the gallium-containing large-pore silicon-aluminum material.

[0020] In the present application, in step (5), the impregnation solution contains phosphorus, and the phosphorus source is preferably phosphoric acid.

[0021] In the present application, the active metal component in step (5) is a metal of Group VIB and a metal of Group VIII. The metal of Group VIB is selected from one or more of W and Mo, and the metal of Group VIII is selected from one or more of Co and Ni. The content of the active metal oxide is 8% to 18.0%, preferably 9.5% to 18.0%, based on the weight of the hydrodemetallization catalyst, and further preferably the content of the metal of Group VIB is 5% to 13% as metal oxide, and the content of the metal of Group VIII is 1.5% to 3.5% as metal oxide.

[0022] In the present application, in the impregnation solution in step (5), the content of the metal of Group VIB as metal oxide is 150 to 450 g / L, preferably 300 to 400 g / L, and the content of the metal of Group VIII is 10 to 120 g / L, preferably 40 to 60 g / L; and / or the concentration of phosphorus is 20 to 80 g / L, preferably 40 to 60 g / L.

[0023] In the present application, in step (5), the organic acid is one or more of maleic acid, fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid, and the alcohol compound is one or more of diethylene glycol, triethylene glycol, 1,2-propanediol, 1,4-butanediol, and neopentyl glycol. In the active metal impregnation solution containing the organic acid and the alcohol compound, the concentration of the organic acid is 2 to 45 g / L, preferably 4 to 25 g / L, and the concentration of the alcohol compound is 5 to 50 g / L, preferably 7 to 35 g / L.

[0024] In the present application, in the impregnation solution in step (5), the tungsten source is a tungstate or a tungsten oxide, and is preferably ammonium metatungstate; the molybdenum source can be one or more of molybdenum trioxide, a molybdate, and a paramolybdate, and is preferably molybdenum trioxide; the nickel source is one or more of nickel nitrate, nickel acetate, basic nickel carbonate, and nickel chloride, and is preferably basic nickel carbonate; and the cobalt source is one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, and is preferably basic cobalt carbonate.

[0025] In the present application, after impregnation in step (5), aging is preferably performed, and then drying and calcination are performed. The aging is performed at 10 to 30℃ for 6 to 10 hours under a closed condition.

[0026] In the present application, the impregnation in step (5) is carried out by spraying, and the impregnation is carried out by equal volume impregnation or supersaturation impregnation.

[0027] In the present application, in step (5), the drying condition is constant temperature at 100-160℃ for 2-10 hours, and the calcination condition is constant temperature at 480-550℃ for 6-10 hours.

[0028] The present application provides a hydrodemetallization catalyst prepared by the above method.

[0029] In the present application, the catalyst comprises a carrier and an active metal component, and the carrier comprises kaolin and alumina.

[0030] In the present application, the content of the active metal oxide is 8.0%-18.0% based on the weight of the hydrodemetallization catalyst, preferably 9.5%-18.0%, and further preferably, the content of the Group VIB metal is 5.0%-13.0% based on the metal oxide, and the content of the Group VIII metal is 1.5%-3.5% based on the metal oxide.

[0031] In the present application, the content of the carrier is 70%-90% based on the weight of the hydrodemetallization catalyst.

[0032] In the present application, the content of the kaolin is 6%-25% based on the weight of the carrier, and the content of the alumina is 50%-80% based on the weight of the carrier.

[0033] In the present application, the content of the gallium is 2.0%-5.0% based on the weight of the carrier.

[0034] In the present application, the catalyst has the following properties: the specific surface area is 180-280m 2 / g, the pore volume is 0.5-1.3mL / g, the average pore size is 15-30nm, and the mechanical strength is 110-130N / cm.

[0035] In the present application, the catalyst has the following pore distribution: the pore volume of the pores with a pore size less than 10nm accounts for 5%-10% of the total pore volume, the pore volume of the pores with a pore size of 10-20nm accounts for 60%-75% of the total pore volume, and the pore volume of the pores with a pore size greater than 20nm accounts for 20%-30% of the total pore volume.

[0036] The present application provides the use of the above hydrodemetallization catalyst in the residue oil hydroprocessing.

[0037] Compared with the prior art, the present application has the following advantages:

[0038] 1. In the method of the present invention, acidic aluminum salt aqueous solution, alkaline aluminum salt aqueous solution and kaolin suspension containing surfactant are co-flowed to form a gel. The acidified active silicon is adsorbed on the aluminum hydroxide colloid, providing crystal nuclei for subsequent reactions and helping to form new silicon-aluminum structures. At the same time, the surfactant forms hydrogen bonds with the hydroxyl groups of the aluminum hydroxide hydrosol, which can prevent the particles from adhering and agglomerating with each other, so that the gel particles are oriented to form ordered crystal precipitates or colloidal particles with crystalline structures. During the secondary reaction, the incomplete small crystals are redissolved and recrystallized or adsorbed onto other crystals, which promotes the increase of the crystal size of the prepared silicon-aluminum material, reduces the formation of amorphous silicon-aluminum, and is conducive to the formation of silicon-aluminum materials with large pore volume and large pore size.

[0039] 2. In the method of the present invention, the sol particles with complete crystal form in slurry II react with gallium nitrate solution under high temperature, high pressure and high pH value to generate a large number of particles with complete crystal form to form gallium-containing silicon-aluminum material precipitate, thereby resulting in a material with high crystal purity and concentrated pore size distribution. The presence of silicon and gallium improves the corresponding catalyst's resistance to carbon deposition and sintering, thereby increasing the catalyst's service life.

[0040] 3. In the method of the present invention, an active metal impregnation solution containing organic acids and alcohols is used. The organic acids and alcohols can form complexes with active metal ions, reducing the number of crystalline species such as molybdenum (tungsten) salts, thereby increasing the proportion of the active phase. Gallium species located in the surface and near-surface regions effectively prevent the formation of strong Mo(W)-O-Al bonds, which can reduce the amount of metal deposition near the catalyst surface, delay pore blockage, and allow the active components in the pores to fully exert their hydrogenation effect, thereby improving the utilization rate of active metals and enhancing the activity of the residue oil hydrogenation catalyst.

[0041] 4. The catalyst prepared by the method of the present invention has good demetallization activity and stability when used in the hydrotreating process of residual oil. Detailed Implementation

[0042] The technical solution of the present invention will be described in detail below with reference to the embodiments.

[0043] In this invention, the specific surface area, pore volume, and pore distribution were measured using an ASAP2420 fully automated physical adsorption analyzer from Micron Instruments, Inc., USA. The measurement method is as follows: the sample was treated at 300℃ and 0.1MPa for 4 hours, with liquid N2 as the adsorbate and an adsorption temperature of -196℃. The sample was accurately weighed and then analyzed. The specific surface area was calculated using the BET method, and the pore volume and pore distribution were calculated using the BJH method.

[0044] In this invention, mechanical strength is expressed as lateral compressive strength, which is tested using a ZQJ-Ⅲ type particle strength tester manufactured by Dalian Intelligent Testing Machine Factory.

[0045] Example 1

[0046] A reaction kettle was charged with 2.0 L of pure water and heated to 60°C at a stirring rate of 200 rad / min. An aluminum sulfate solution with a concentration of 20 g / 100 mL and a sodium metaaluminate solution with a concentration of 15 g / 100 mL and a kaolin suspension with a concentration of 3.5 g / 100 mL (the amount of nonylphenol polyoxyethylene ether-10 was 1.2% of the mass of the kaolin) were continuously added to the reaction kettle at flow rates of 20 mL / min, 15 mL / min and 10 mL / min, respectively. The pH of the reaction was controlled at 1.4 by adding hydrochloric acid during the reaction. The reaction time was 70 min. After the reaction was completed, the temperature was adjusted to 120°C and the stirring rate was adjusted to 300 rad / min. A sodium carbonate solution with a concentration of 55 g / 100 mL was passed into the reaction kettle to perform a secondary reaction. The pH of the reaction was adjusted to 9. The reaction time was 90 min. After the reaction was completed, 0.92 L of a gallium nitrate solution with a concentration of 1.5 mol / L was added. The hydrothermal treatment temperature was 250°C, the pressure was 15 MPa, and the time was 2 hours. The slurry after the reaction was washed with hot water at 90°C until it was neutral. The drying conditions were 120°C and the drying time was 3 hours to obtain a gallium-containing silicon-aluminum material. 448 g of the gallium-containing silicon-aluminum material was weighed out, 9 g of sesbania powder, 4 g of nitric acid, 3 g of citric acid and 292 g of water were added and mixed, and then kneaded and shaped. After drying at 110°C for 3 hours and calcination at 650°C for 8 hours, a catalyst support A (the mass content of gallium was 3.6%) was obtained.

[0047] 100 g of the catalyst support A was weighed out and its water absorption was measured to be 0.87. 202 g of molybdenum trioxide (containing 99 wt% of molybdenum trioxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide), and 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus) were added to pure water and stirred to gradually heat to boiling until all the raw materials were dissolved. After constant temperature for 40 min, it was cooled to room temperature for standby. An impregnation solution I was obtained. A mixture of maleic acid and diethylene glycol was slowly added to the above solution under stirring. The amount of maleic acid was added to make its concentration in the impregnation solution 16 g / L, and the amount of diethylene glycol was added to make its concentration in the impregnation solution 22 g / L. The solution was made up to 87 mL for standby. The above impregnation solution was impregnated on the support A by spraying to obtain D-A. The D-A was placed in a closed container at room temperature for 6 hours, then dried at 110°C for 3 hours, and finally calcined at 530°C for 6 hours to obtain C-A.

[0048] Example 2

[0049] A reaction kettle was charged with 2.5 L of pure water and heated to 70°C at a stirring rate of 300 rad / min. An aluminum sulfate solution with a concentration of 35 g / 100 mL and a sodium metaaluminate solution with a concentration of 40 g / 100 mL and a kaolin suspension with a concentration of 5 g / 100 mL (the amount of dodecyl fatty alcohol polyoxyethylene ether-11 was 1.4% of the mass of kaolin) were continuously added to the reaction kettle at flow rates of 15 mL / min, 20 mL / min and 15 mL / min, respectively. The pH of the reaction was controlled at 1.3 by adding hydrochloric acid during the reaction. The reaction time was 90 min. After the reaction was completed, the temperature was adjusted to 140°C and the stirring rate was adjusted to 400 rad / min. A sodium hydroxide solution with a concentration of 60 g / 100 mL was passed into the reaction kettle to perform a secondary reaction. The pH of the reaction was adjusted to 8.8. The reaction time was 70 min. After the reaction was completed, 1.25 L of a gallium nitrate solution with a concentration of 1.0 mol / L was added. The hydrothermal treatment temperature was 300°C, the pressure was 18 MPa and the time was 3 hours. The slurry after the reaction was washed with hot water at 70°C until it was neutral. The drying conditions were 140°C and the drying time was 4 hours to obtain a gallium-containing silicon-aluminum material.

[0050] 100 g of the catalyst carrier B was weighed. The water absorption rate of the catalyst carrier B was measured to be 0.88. Molybdenum trioxide (containing molybdenum trioxide 99 wt%) 182 g, basic nickel carbonate (containing nickel oxide 52 wt%) 96.2 g, phosphoric acid solution (containing phosphorus 26.7 wt%) 59.9 g were added to pure water. The mixture was stirred and gradually heated to boiling until all the raw materials were dissolved. The solution was kept at a constant temperature for 60 min and then cooled to room temperature for standby. An impregnation solution I was obtained. Maleic acid and triethylene glycol were slowly added to the above solution under stirring. The amount of maleic acid was added to make the concentration in the impregnation solution 14 g / L. The amount of triethylene glycol was added to make the concentration in the impregnation solution 19 g / L. The solution was made up to 88 mL for standby. The above impregnation solution was impregnated on the carrier B by spraying to obtain D-B. The D-B was placed in a closed container at room temperature for 6 hours, then dried at 130°C for 4 hours, and finally calcined at 500°C for 6 hours to obtain C-B.

[0051] Example 3

[0052] A 3L reactor was charged with 3L of pure water and heated to 80°C at a stirring rate of 350 rad / min. An aluminum sulfate solution with a concentration of 55 g / 100 mL and a sodium metaaluminate solution with a concentration of 50 g / 100 mL and a kaolin suspension with a concentration of 4 g / 100 mL (the amount of dodecyl alkyl phenol polyoxyethylene ether-10 was 1.1% of the mass of kaolin) were continuously added to the reactor at flow rates of 30 mL / min, 35 mL / min and 25 mL / min, respectively. The pH of the reaction was controlled at 1.7 by adding hydrochloric acid during the reaction. The reaction time was 120 min. After the reaction was completed, the temperature was increased to 160°C and the stirring rate was adjusted to 500 rad / min. A sodium hydroxide solution with a concentration of 55 g / 100 mL was introduced into the reactor for a secondary reaction. The pH of the reaction was adjusted to 9.0 and the reaction time was 100 min. After the reaction was completed, 1.12 L of a gallium nitrate solution with a concentration of 2.2 mol / L was added. The hydrothermal treatment temperature was 400°C, the pressure was 16 MPa and the time was 4 hours. The slurry after the reaction was washed with hot water at 90°C until it was neutral. The drying conditions were 130°C and the drying time was 5 hours to obtain a gallium-containing silicon-aluminum material.

[0053] 100 g of the catalyst carrier C was weighed and its water absorption was measured to be 0.93. Molybdenum trioxide (containing 99 wt% of molybdenum trioxide) 192 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 101 g, phosphoric acid solution (containing 26.7 wt% of phosphorus) 52.4 g, and pure water were added and stirred to gradually heat to boiling until all the raw materials were dissolved. After constant temperature for 60 min, it was cooled to room temperature for standby. An impregnation solution I was obtained. In a stirred state, a mixture of citric acid and diethylene glycol was slowly added to the above solution. The amount of citric acid was added to make the concentration in the impregnation solution 20 g / L, and the amount of diethylene glycol was added to make the concentration in the impregnation solution 33 g / L. The solution was made up to 93 mL for standby. The above impregnation solution was impregnated on the carrier C by spraying to obtain D-C. The D-C was placed in a sealed container at room temperature for 6 hours, then dried at 140°C for 5 hours, and finally calcined at 495°C for 6 hours to obtain C-C.

[0054] Example 4

[0055] A 2.5 L reaction kettle was charged with 2.5 L of pure water and heated to 90°C at a stirring rate of 250 rad / min. An aluminum sulfate solution with a concentration of 45 g / 100 mL and a sodium metaaluminate solution with a concentration of 40 g / 100 mL and a kaolin suspension with a concentration of 4.5 g / 100 mL (the amount of dodecyl alkyl phenol polyoxyethylene ether-10 was 2% of the mass of kaolin) were continuously added to the reaction kettle at flow rates of 35 mL / min, 30 mL / min and 20 mL / min, respectively. The pH of the reaction was controlled at 1.2 by adding hydrochloric acid during the reaction. The reaction time was 100 min. After the reaction was completed, the temperature was adjusted to 180°C and the stirring rate was adjusted to 400 rad / min. A sodium bicarbonate solution with a concentration of 60 g / 100 mL was passed into the reaction kettle to perform a secondary reaction. The pH of the reaction was adjusted to 9.5. The reaction time was 120 min. After the reaction was completed, 1.17 L of a gallium nitrate solution with a concentration of 1.5 mol / L was added. The hydrothermal treatment temperature was 500°C, the pressure was 11 MPa, and the time was 3 hours. The reacted slurry was washed with hot water at 80°C until it was neutral. The drying conditions were 140°C and the drying time was 4 hours to obtain a gallium-containing silicon-aluminum material.

[0056] 100 g of the catalyst support D was weighed. The water absorption rate was measured to be 0.87. Molybdenum trioxide (containing 99 wt% of molybdenum trioxide) 192 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 101 g, and phosphoric acid solution (containing 26.7 wt% of phosphorus) 52.4 g were added to pure water. The mixture was stirred and gradually heated to boiling until all the raw materials were dissolved. The temperature was kept at 70°C for 70 min and then lowered to room temperature for standby. An impregnation solution I was obtained. Maleic acid and diethylene glycol were slowly added to the above solution under stirring. The amount of maleic acid was added to make the concentration in the impregnation solution 26 g / L. The amount of diethylene glycol was added to make the concentration in the impregnation solution 19 g / L. The solution was made up to 87 mL for standby. The above impregnation solution was impregnated on the support D by spraying to obtain D-D. The D-D was placed in a sealed container at room temperature for 6 hours, then dried at 130°C for 4 hours, and finally calcined at 520°C for 6 hours to obtain C-D.

[0057] Comparative Example 1

[0058] Compared with Example 1, no secondary reaction was performed in the preparation process. Finally, a catalyst DC-A was obtained, as follows:

[0059] A 2.0 L reaction kettle was charged with 2.0 L of pure water and heated to 60°C at a stirring rate of 200 rad / min. An aluminum sulfate solution with a concentration of 20 g / 100 mL and a sodium metaaluminate solution with a concentration of 15 g / 100 mL and a kaolin suspension with a concentration of 3.5 g / 100 mL (the amount of nonylphenol polyoxyethylene ether-10 was 1.2% of the mass of the kaolin) were added to the reaction kettle at flow rates of 20 mL / min, 15 mL / min and 10 mL / min, respectively, continuously. The pH of the reaction was controlled at 1.4 by adding hydrochloric acid during the reaction. The reaction time was 70 min. After the reaction was completed, 0.92 L of a gallium nitrate solution with a concentration of 1.5 mol / L was added. The hydrothermal treatment temperature was 250°C, the pressure was 15 MPa, and the time was 2 hours. The slurry after the reaction was washed with hot water at 90°C until it was neutral. The drying conditions were 120°C and the drying time was 3 hours to obtain a gallium-containing silicon-aluminum material. 448 g of the gallium-containing silicon-aluminum material was weighed out, mixed with 9 g of sesbania powder, 4 g of nitric acid, 3 g of citric acid and 292 g of water, and then kneaded and shaped. The shaped product was dried at 110°C for 3 hours and calcined at 650°C for 8 hours to obtain a catalyst carrier DA.

[0060] 100 g of the catalyst carrier DA was weighed out and its water absorption was measured to be 0.87. 202 g of molybdenum trioxide (containing 99 wt% of molybdenum trioxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide) and 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus) were added to pure water and stirred to gradually heat and boil until the raw materials were completely dissolved. After being kept at a constant temperature for 40 min, the solution was cooled to room temperature and was ready for use. An impregnation solution I was obtained. A mixture of maleic acid and diethylene glycol was slowly added to the above solution under stirring. The amount of maleic acid added was such that the concentration of maleic acid in the impregnation solution was 16 g / L. The amount of diethylene glycol added was such that the concentration of diethylene glycol in the impregnation solution was 22 g / L. The solution was made up to 87 mL and was ready for use. The above impregnation solution was impregnated on the carrier DA by spraying to obtain D-DA. The D-DA was placed in a closed container at room temperature for 6 hours, then dried at 110°C for 3 hours, and finally calcined at 530°C for 6 hours to obtain DC-A.

[0061] Comparative Example 2

[0062] Compared with Example 1, no acid was added to adjust the pH value during the one-step reaction. Finally, a catalyst DC-B was obtained, as follows:

[0063] A 2.0 L reactor was charged with purified water and heated to 60°C at a stirring rate of 200 rad / min. An aluminum sulfate solution with a concentration of 20 g / 100 mL and a sodium metaaluminate solution with a concentration of 15 g / 100 mL and a kaolin suspension with a concentration of 3.5 g / 100 mL (nonylphenol polyoxyethylene glycol-10 was used in an amount of 1.2% of the mass of the kaolin) were continuously fed into the reactor at flow rates of 20 mL / min, 15 mL / min and 10 mL / min, respectively. The reaction time was 70 min. After the reaction was completed, the temperature was increased to 120°C, the stirring rate was adjusted to 300 rad / min, and a sodium carbonate solution with a concentration of 55 g / 100 mL was fed into the reactor to perform a secondary reaction. The pH value of the reaction was adjusted to 9, and the reaction time was 90 min. After the reaction was completed, 0.92 L of a gallium nitrate solution with a concentration of 1.5 mol / L was added. The hydrothermal treatment temperature was 250°C, the pressure was 15 MPa, and the time was 2 hours. The reacted slurry was washed with hot water at 90°C until it was neutral. The drying conditions were 120°C and a drying time of 3 hours to obtain a gallium-containing silicon-aluminum material. 448 g of the gallium-containing silicon-aluminum material was mixed with 9 g of sesbania powder, 4 g of nitric acid, 3 g of citric acid and 292 g of water. After kneading and molding, the mixture was dried at 110°C for 3 hours and calcined at 650°C for 8 hours to obtain a catalyst carrier DB.

[0064] 100 g of the catalyst carrier DB was weighed, and its water absorption rate was measured to be 0.87. 202 g of molybdenum trioxide (containing 99 wt% of molybdenum trioxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide), and 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus) were added to purified water and stirred to gradually heat to boiling until all the raw materials were dissolved. After constant temperature for 40 minutes, it was cooled to room temperature for standby. An impregnation solution I was obtained. A mixture of maleic acid and diethylene glycol was slowly added to the above solution under stirring. The amount of maleic acid added was such that the concentration of maleic acid in the impregnation solution was 16 g / L, and the amount of diethylene glycol added was such that the concentration of diethylene glycol in the impregnation solution was 22 g / L. The solution was made up to 87 mL for standby. The above impregnation solution was impregnated on the carrier DB by spraying to obtain D-DB. The D-DB was placed in a closed container at room temperature for 6 hours, then dried at 110°C for 3 hours, and finally calcined at 530°C for 6 hours to obtain DC-B.

[0065] Comparative Example 3

[0066] In comparison with Example 1, no mixture of organic acid and alcohol compound was added in the preparation process of the impregnation solution. The conventional impregnation solution I was impregnated on the carrier to finally obtain a catalyst DC-C.

[0067] Comparative Example 4

[0068] Comparative Example 1

[0069] Comparative Example 5

[0070] Comparative Example 1 was repeated except that the gallium nitrate solution was not added to produce a comparative hydrodemetallization catalyst DC-E as follows:

[0071] A reaction kettle was charged with 2.0 L of purified water and heated to 60°C. The stirring rate was 200 rad / min. The flow rates of the 20 g / 100 mL aluminum sulfate solution, 15 g / 100 mL sodium metaaluminate solution, and 3.5 g / 100 mL kaolin suspension (nonylphenol polyoxyethylene ether-10 was used in an amount of 1.2% of the mass of the kaolin) were 20 mL / min, 15 mL / min, and 10 mL / min, respectively, and were continuously added to the reaction kettle. The pH of the reaction was controlled at 1.4 by adding hydrochloric acid during the reaction. The reaction time was 70 min. After the reaction was complete, the temperature was adjusted to 120°C, the stirring rate was adjusted to 300 rad / min, and a 55 g / 100 mL sodium carbonate solution was passed into the reaction kettle at a flow rate of 20 mL / min to perform a secondary reaction. The pH of the reaction was adjusted to 9, and the reaction time was 90 min. After the reaction was complete, the reaction was hydrothermally treated at a temperature of 250°C, a pressure of 15 MPa, and for a time of 2 hours. The slurry after the reaction was washed with hot water at 90°C until it was neutral. The drying conditions were 120°C and a drying time of 3 hours to obtain a gallium-containing silicon-aluminum material. 448 g of the gallium-containing silicon-aluminum material was weighed out, mixed with 9 g of sesbania powder, 4 g of nitric acid, 3 g of citric acid, and 292 g of water, and then kneaded and shaped. The shaped product was dried at 110°C for 3 hours and calcined at 650°C for 8 hours to obtain a catalyst carrier DE.

[0072] A gallium-containing silicon-aluminum material was prepared according to the method of Comparative Example 1. 100 g of the catalyst carrier DE was weighed out and its water absorption was measured to be 0.87. 202 g of molybdenum trioxide (containing 99 wt% of molybdenum trioxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide), and 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus) were added to purified water and stirred while gradually heating to boiling until the raw materials were completely dissolved. After being kept at a constant temperature for 40 min, the solution was cooled to room temperature and used as impregnation solution I. Maleic acid and diethylene glycol were slowly added to the above solution under stirring until the concentration of maleic acid in the impregnation solution was 16 g / L and the concentration of diethylene glycol in the impregnation solution was 22 g / L. The solution was made up to 87 mL with purified water and used as impregnation solution. The impregnation solution was sprayed onto the catalyst carrier DE to obtain D-DE. D-DE was placed in a sealed container at room temperature for 6 hours, dried at 110°C for 3 hours, and finally calcined at 530°C for 6 hours to obtain DC-E.

[0073] Table 1 Catalyst composition and properties of examples and comparative examples

[0074]

[0075]

[0076] Table 1 (continued)

[0077]

[0078] Application examples

[0079] The application examples are activity tests of the catalysts of examples 1, 2, 3, 4 and comparative examples 1, 2, 3, 4, 5 on a small fixed-bed hydrogenation device. The properties of the raw oil and the reaction conditions are shown in Table 2, and the evaluation results are shown in Tables 3 and 4.

[0080] Table 2 Properties of raw oil and reaction conditions

[0081] Item Feed oil properties Density / kg m -3 ]] 970.0 S / wt% 1.9 Ni / μg·g -1 ]]> 28.7 V / μg·g -1 ]] 46.9 Reaction conditions Temperature / °C 320 Pressure / MPa 7.5 Volume space velocity / h -1 ]] 1.5 Hydrogen / oil volume ratio 500

[0082] Table 3 Activity evaluation of catalysts of examples

[0083] Removal rate Example 1 Example 2 Example 3 Example 4 HDS, % 66.9 72.1 71.7 76.7 HDM, % 84.5 85.1 84.9 85.4

[0084] Table 3 (continued)

[0085] Removal rate Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 HDS, % 52.4 54.5 54.7 55.3 60.3 HDM, % 62.2 64.6 68.1 71.0 70.6

[0086] Table 4 Evaluation results of catalyst activity and stability in examples and comparative examples

[0087] Removal rate Operation time, h Example 1 Example 2 Example 3 Example 4 HDS, % 200 66.9 72.1 69.9 76.7 HDS, % 2000 62.4 67.2 65.5 69.8 HDM, % 200 84.5 85.1 85.5 85.4 HDM, % 2000 80.3 79.6 81.2 80.7

[0088] Table 4 (continued)

[0089] Removal rate Operation time, h Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 HDS, % 200 52.4 54.5 54.7 55.3 60.3 HDS, % 2000 32.4 35.3 34.6 33.4 39.5 HDM, % 200 62.2 64.6 68.1 71.0 70.6 HDM, % 2000 43.4 44.7 45.4 45.7 41.5

[0090] The catalyst prepared by the method has a large pore size and pore volume, and has high hydrodemetallization activity and activity stability. The catalyst prepared by the method is suitable for the field of residue hydrodemetallization.

Claims

1. A method for preparing a residue hydrodemetallization catalyst, comprising the following steps: (1) a first reaction of a acidic aqueous aluminum salt solution, a basic aqueous aluminum salt solution and a kaolin suspension containing a surfactant to obtain a slurry I; (2) a second reaction of the slurry I of step (1) with a basic solution to obtain a slurry II; (3) a hydrothermal treatment of the slurry II of step (2) with a gallium nitrate solution, washing, drying to obtain a gallium-containing macroporous silica-alumina material; (4) a kneading and molding of the gallium-containing macroporous silica-alumina material with a extrusion aid and a binder, drying, calcining to obtain a catalyst carrier; (5) an impregnation of the catalyst carrier of step (4) with an active metal impregnation solution containing an organic acid and an alcohol compound, drying and calcining to obtain the residue hydrodemetallization catalyst; the pH value of the reaction of step (1) is controlled to be 1.2-1.8; the reaction time of the second reaction of step (2) is 60-120 min, the reaction temperature is 120-180℃, and the pH value of the second reaction is controlled to be 8.5-9.7; the mass ratio of the slurry II of step (2) to the gallium nitrate solution, calculated based on Al2O3 and Ga2O3, is 3:1-7:1; the active metal component of step (5) is a Group VIB and a Group VIII metal; the content of the Group VIB metal, calculated based on the metal oxide, is 5%-13%, and the content of the Group VIII metal, calculated based on the metal oxide, is 1.5%-3.5%, based on the weight of the hydrodemetallization catalyst; the concentration of the organic acid in the active metal impregnation solution containing an organic acid and an alcohol compound of step (5) is 2-45 g / L, and the concentration of the alcohol compound is 5-50 g / L.

2. The method of claim 1, wherein, the surfactant of step (1) is one or more of long-chain fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene alkylamine and polyoxyethylene alkyl alcohol amide, and the amount of the surfactant is 0.3%-3.0% of the mass of the kaolin; the concentration of the kaolin in the kaolin suspension containing a surfactant is 0.5-5 g / 100 mL.

3. The method of claim 1, wherein, in step (1), the pH value is adjusted by adding at least one of hydrochloric acid, nitric acid or sulfuric acid; and / or, the co-current reaction time of step (1) is 60-180 min, the reaction temperature is 60-90℃, and the reaction is carried out under stirring at a stirring rate of 100-500 rad / min.

4. The method of claim 3, wherein, the stirring rate is 150-450 rad / min.

5. The method of claim 1, wherein, the acidic aluminum salt of step (1) is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate, and the concentration of the acidic aluminum salt solution, calculated based on Al2O3, is 20-100 g / 100 mL; the basic aluminum salt is at least one of sodium aluminate or potassium aluminate, and the concentration of the basic aluminum salt solution, calculated based on Al2O3, is 20-100 g / 100 mL; and / or, the volume rate ratio of the kaolin suspension containing a surfactant, the acidic aluminum salt solution and the basic aluminum salt solution is 1:1-5:1-3.

6. The method of claim 1, wherein, The basic solution in step (2) is a solution of at least one of sodium hydroxide or sodium carbonate, and the concentration of the basic solution is 50-70 g / 100 mL; the secondary reaction is carried out under stirring, and the stirring rate is 100-500 rad / min.

7. The method of claim 6, wherein, The stirring rate is 250-500 rad / min.

8. The method of claim 1, wherein, The concentration of the gallium nitrate solution in step (3) is 0.3-2.5 mol / L.

9. The method of claim 1, wherein, In step (3), the hydrothermal treatment temperature is 200-500 ℃, the pressure is 10-20 MPa, and the time is 2-4 hours; the drying condition is 120-160 ℃, and the drying time is 3-6 hours.

10. The method of claim 1, wherein, In step (4), the drying temperature is 110-160 ℃, and the drying time is 2-8 hours; the calcination temperature is 600-750 ℃, and the calcination time is 6-10 hours.

11. The method of claim 1, wherein, In step (5), the impregnation solution contains phosphorus, and the phosphorus source is phosphoric acid.

12. The method of claim 1, wherein, In step (5), the active metal group, the Group VIB metal is selected from one or more of W and Mo, and the Group VIII metal is selected from one or more of Co and Ni.

13. The method of claim 12, wherein, The content of the active metal oxide is 8%-18.0% based on the weight of the hydrogen demetallization catalyst.

14. The method of claim 13, wherein, The content of the active metal oxide is 9.5%-18.0% based on the weight of the hydrogen demetallization catalyst.

15. The method of claim 1, wherein, In step (5), the organic acid is one or more of maleic acid, fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid, and the alcohol compound is one or more of diethylene glycol, triethylene glycol, 1,2-propanediol, 1,4-butanediol, and neopentyl glycol; in the active metal impregnation solution containing the organic acid and the alcohol compound, the concentration of the organic acid is 4-25 g / L, and the concentration of the alcohol compound is 7-35 g / L.

16. The method of claim 1, wherein, In step (5), the drying condition is constant temperature at 100-160 ℃ for 2-10 hours, and the calcination condition is constant temperature at 480-550 ℃ for 6-10 hours.

17. The hydrogen demetallization catalyst prepared by the method of any one of claims 1-16.

18. The hydrodemetal l ation catalyst of claim 17, wherein, The catalyst has the following properties: specific surface area of 180 to 280 m 2 / g, pore volume of 0.5 to 1.3 mL / g, average pore diameter of 15 to 30 nm, and mechanical strength of 110 to 130 N / cm.

19. The hydrodemetal l ation catalyst of claim 17, wherein, The pore distribution of the catalyst is as follows: the pore volume of the pore channels with a pore diameter less than 10 nm accounts for 5%-10% of the total pore volume, the pore volume of the pore channels with a pore diameter of 10-20 nm accounts for 60%-75% of the total pore volume, and the pore volume of the pore channels with a pore diameter greater than 20 nm accounts for 20%-30% of the total pore volume.

20. The hydrogen demetallization catalyst of any one of claims 17-19 for use in residual oil hydroprocessing.

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