Preparation method of a residual oil hydrodemetallization catalyst

Abstract

The application discloses a preparation method of a residual oil hydrodemetallization catalyst. The method comprises the following steps: (1) performing a co-current precipitation reaction on an acidic aluminum salt aqueous solution and an alkaline aluminum salt aqueous solution to obtain a slurry; (2) adding an alkaline solution and a water-soluble polymer to the slurry in step (1) to perform a secondary reaction, aging, drying, and obtaining material A; (3) impregnating activated carbon with a solution containing silicon and gallium to obtain material B; (4) mixing and kneading material A obtained in step (2) and material B obtained in step (3) into a shape, drying and calcining to obtain a carrier; and (5) impregnating the carrier in step (4) with an active metal impregnating solution containing an organic acid and an alcohol compound, drying and calcining to obtain the residual oil hydrodemetallization catalyst. The catalyst can improve the demetallization activity of the catalyst and prolong the service life of the catalyst when used 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 the 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, 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, V, etc. 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 preparation method of a residual oil hydrodemetallization catalyst. The catalyst is used in a residual oil hydroprocessing process, can improve the demetallization activity of the catalyst, and can prolong the service life of the catalyst.

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

[0007] (1) The acid aluminum salt aqueous solution and the basic aluminum salt aqueous solution are subjected to a precipitation reaction in parallel flow to obtain a slurry;

[0008] (2) The slurry of step (1) is added with a basic solution and a water-soluble polymer for a secondary reaction, aging, drying to obtain material A;

[0009] (3) The active carbon is impregnated with a solution containing silicon and gallium to obtain material B;

[0010] (4) The material A obtained in step (2) and the material B obtained in step (3) are kneaded and formed, dried and calcined to obtain a carrier;

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

[0012] In the present application, the acid aluminum salt in step (1) is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate, and the concentration of the acid 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 ratio of the addition volume rate of the acid aluminum salt solution to the basic aluminum salt solution is 1:1-3:1. The pH value of the reaction in step (1) is controlled to be 1.2-1.8, and the pH value is adjusted by adding at least one of hydrochloric acid, nitric acid or sulfuric acid. The parallel flow reaction time in 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.

[0013] 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 amount of the water-soluble polymer added is 0.1%-5% of the mass of the slurry obtained in step (1) in terms of aluminum oxide, preferably 0.5%-3%. The pH value of the secondary reaction in step (2) is 8.5-9.7. The reaction time of the secondary reaction in step (2) is 60-120 min, 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 water-soluble polymer is selected from at least one of polyvinyl alcohol, polyethylene oxide and polyvinyl pyrrolidone. The weight average molecular weight of the water-soluble polymer is 10,000-40,000.

[0014] In the present application, the aging temperature in step (2) is 200-500℃, the aging time is 2-4 hours, and after aging, deionized water is preferably used for washing, further preferably at 50-90℃, and the drying condition is 120-160℃, and the drying time is 2-6 hours.

[0015] In the present application, the specific surface area of the activated carbon in step (3) is 2,000-3,000 m 2 / g, and the particle size is 2-15 μm.

[0016] In the present application, the solution containing silicon and gallium in step (3) is an ethanol solution containing silicate and gallium nitrate, the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate, the concentration of silicon in the solution containing silicon and gallium is 0.1-5 g / mL in terms of SiO2, and the mass ratio of silicon and gallium in the solution containing silicon and gallium is 2:1-5:1 in terms of SiO2 and Ga2O3. The amount of the solution containing silicon and gallium used is 30%-50% of the saturated water absorption of the activated carbon in terms of volume. The impregnation in step (3) is preferably carried out by spraying.

[0017] In the present application, in step (3), the silicon and gallium introduced into the activated carbon from the solution containing silicon and gallium account for 2%-9% of the mass of the activated carbon in terms of SiO2 and Ga2O3.

[0018] In the present application, in step (4), the mass ratio of the material A obtained in step (2) in terms of aluminum oxide and the material B obtained in step (3) in terms of activated carbon is 2:1-10:1.

[0019] In the present application, the preparation of the carrier in step (4) can be added according to the actual needs of the forming agent, such as extrusion aid, adhesive and other forming agents. The forming can use conventional forming methods, such as extrusion forming, tabletting forming and the like. The drying conditions after forming are as follows: the drying temperature is 100-160℃, and the drying time is 2-10 hours. The calcination conditions are as follows: the calcination temperature is 600-750℃, and the calcination time is 2-10 hours. The extrusion aid can be amaranth powder, and the amount is 1%-5% of the mass of the carrier. The adhesive is nitric acid, formic acid, acetic acid, citric acid, methyl cellulose, polyethylene glycol, or one or more of them, and the amount is 0.5%-3.0% of the mass of the carrier.

[0020] In the present application, the active metal impregnation solution containing organic acid and alcohol compound in step (5) contains phosphorus. Among them, the phosphorus source is preferably phosphoric acid.

[0021] In the present application, the active metal in step (5) is a group VIB and group VIII metal. The group VIB metal is preferably selected from one or more of W, Mo, and the group VIII metal is preferably selected from one or more of Co, Ni. The content of active metal oxide is 8.0%-18.0%, preferably 9.5%-18.0%, further preferably, the content of group VIB metal is 5.0%-13.0% as metal oxide, and the content of group VIII metal is 1.5%-3.5% as metal oxide.

[0022] In the present application, in the impregnation solution in step (5), the tungsten source can be tungstate or tungsten oxide, preferably ammonium metatungstate; the molybdenum source can be one or more of molybdenum trioxide, molybdate, and secondary molybdate, preferably molybdenum trioxide; the nickel source can be one or more of nickel nitrate, nickel acetate, basic nickel carbonate, and nickel chloride, preferably basic nickel carbonate; the cobalt source can be one or more of cobalt nitrate, cobalt acetate, basic cobalt carbonate, and cobalt chloride, preferably basic cobalt carbonate.

[0023] In the present application, the organic acid in step (5) 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. The concentration of organic acid in the active metal impregnation solution containing organic acid and alcohol compound is 2-45g / L, preferably 4-25g / L, and the concentration of alcohol compound is 5-50g / L, preferably 7-35g / L.

[0024] In the present application, the active metal in the impregnation solution in step (5) is calculated as metal oxide, wherein the content of Group VIB metal is 150-450 g / L, preferably 300-400 g / L, the content of Group VIII metal is 10-120 g / L, preferably 40-60 g / L; and / or the concentration of phosphorus is 20-80 g / L, preferably 40-60 g / L.

[0025] In the present application, the impregnation in step (5) can be carried out by spraying impregnation, and the impregnation can be carried out by saturated impregnation or supersaturated impregnation.

[0026] In the present application, after impregnation in step (5), the product is preferably aged, and then dried and calcined, and the aging is carried out at 10-30℃ for 6-10 hours in a closed condition.

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

[0028] The second aspect of 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 is alumina containing silicon and gallium.

[0030] In the present application, the content of active metal oxide is 8.0%-18.0%, preferably 9.5%-18.0%, based on the weight of the hydrodemetallization catalyst, and further preferably, the content of Group VIB metal is 5.0%-13.0% calculated as metal oxide, and the content of Group VIII metal is 1.5%-3.5% calculated as 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, in the carrier, the content of silicon and gallium calculated as SiO2 and Ga2O3 is 0.2%-4.5% of the mass of the alumina, and the mass ratio of silicon and gallium calculated as SiO2 and Ga2O3 is 2:1-5:1.

[0033] In the present application, the catalyst has the following properties: the specific surface area is 180-280 m 2 / g, the pore volume is 0.5-1.2 mL / g, the average pore diameter is 15-30 nm, and the mechanical strength is 110-130 N / cm.

[0034] In the present application, the pore distribution of the catalyst is as follows: the pore volume of the pore with a pore size less than 10 nm accounts for 5-10% of the total pore volume, the pore volume of the pore with a pore size of 10-20 nm accounts for 60-75% of the total pore volume, and the pore volume of the pore with a pore size greater than 20 nm accounts for 20-30% of the total pore volume.

[0035] The third aspect of the present application provides the use of the above-mentioned hydrodemetallization catalyst in a residue oil hydroprocessing.

[0036] Compared with the prior art, the present application has the following advantages:

[0037] 1. In the catalyst preparation method, by controlling the co-current gelation process and conditions of the acidic aluminum salt aqueous solution and the basic aluminum salt aqueous solution, uniform particles are formed by rapid crystallization in the first reaction, and then by adding a basic solution and a water-soluble polymer in the secondary reaction, the water-soluble polymer forms a physical cross-linking bridge with the aluminum hydroxide sol, which can bind the movement between the particles to avoid the collision and adhesion between the sol-gel molecules or ions, so that the gel particles are arranged in an ordered crystal precipitation or gel particles with a crystal structure, which helps to continue to generate larger pseudo-boehmite particles, and higher crystallinity pseudo-boehmite is obtained, so that the final obtained alumina carrier has larger pore volume and pore size, concentrated pore distribution, and good mechanical strength, which is beneficial to improve the activity and stability of the catalyst.

[0038] 2. In the catalyst preparation method, due to the presence of the water-soluble polymer in the active carbon containing silicon and gallium and the alumina dry gel, when the two are kneaded and formed into a carrier, it is helpful to form a good through-hole structure, the introduction of silicon and gallium species can form Si-O-Ga bonds at large pores, which can effectively prevent the formation of strong Mo(W)-O-Al bonds during subsequent loading of active metals, and help to evenly distribute the active components, and at the same time, avoid agglomeration of the active components during sulfidation. In addition, Ga is a weak electron acceptor, and the method of the present application can also weaken the acidity of the catalyst at the large pores to some extent, improve the carbon deposition resistance and sintering resistance of the corresponding catalyst, and improve the activity and stability of the catalyst.

[0039] 3. In the catalyst preparation method, the addition of organic acids and alcohols in the active metal impregnation solution can form complexes with active metal ions, which can reduce the number of molybdate (tungstate) and other crystalline species during catalyst preparation, thereby increasing the proportion of active phases and making the active components in the pore fully play a hydrogenation role, improving the utilization rate of active metals, and improving the activity and stability of the residue oil hydrogenation catalyst.

[0040] 4. The catalyst prepared by the method of the present application has good demetallization activity and stability when used in the residue oil hydroprocessing process. DETAILED DESCRIPTION

[0041] The technical solutions of the present application are described in detail below in combination with examples.

[0042] In the present application, the specific surface area, pore volume and pore distribution are determined by using an ASAP2420 full-automatic physical adsorption instrument of American Micromeritics Company, and the determination method is as follows: after the sample is treated at 300℃ and 0.1 MPa for 4 h, liquid N2 is used as the adsorbate, the adsorption temperature is -196℃, and the sample is accurately weighed and then analyzed and tested. The specific surface area is calculated by the BET method, and the pore volume and pore distribution are calculated by the BJH method.

[0043] In the present application, the mechanical strength is represented by the side pressure strength, and the side pressure strength is tested by using a ZQJ-III type particle strength tester produced by Dalian Intelligent Tester Factory.

[0044] Example 1

[0045] A 3L reaction kettle is charged with pure water, heated to 60℃, and stirred at a speed of 200 rad / min. 35g / 100mL aluminum sulfate solution and 23g / 100mL sodium metaaluminate are continuously added to the reaction kettle at flow rates of 30mL / min and 20mL / min, respectively. During the reaction, hydrochloric acid is added to control the reaction pH to 1.4, and the reaction time is 70 min. After the reaction is completed, the temperature is adjusted to 120℃, the stirring speed is adjusted to 300 rad / min, polyvinyl alcohol (molecular weight 25000) (1.2% of the content of aluminum oxide) is introduced into the reaction kettle, and a 55g / 100mL sodium carbonate solution is introduced into the reaction kettle for secondary reaction. The reaction pH is adjusted to 9, the reaction time is 90 min, and the aging temperature is 260℃. After filtration, washing with hot water at 90℃ until neutral, and drying at 130℃ for 3 hours, pseudo-boehmite is obtained.

[0046] 75g of activated carbon with a particle size of 4μm is placed in a spray-impregnation rolling pot, and 22.5ml of an ethanol solution containing 3g of tetraethyl orthosilicate and 1.5g of gallium nitrate containing 3g of silicon dioxide and 1.5g of gallium nitrate is sprayed into the activated carbon in the rolling pot in a rotating state in a misting manner. After impregnation, the activated carbon is mixed with 348g of pseudo-boehmite (alumina mass content of 69.1%), 7.2g of sesbania powder, 3.58g of nitric acid, 2.4g of citric acid and 313g of water, and then kneaded and formed. After drying at 120℃ for 3 hours and calcining at 600℃ for 6 hours, catalyst carrier A is obtained.

[0047] Take 100 g of catalyst carrier A, measure its water absorption rate of 0.87, take molybdenum trioxide (containing molybdenum oxide 99wt%) 202 g, basic nickel carbonate (containing nickel oxide 52wt%) 96.2 g, phosphoric acid solution (containing phosphorus 26.7wt%) 52.4 g, after adding clean water, stirring gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 40 minutes, then reduce to room temperature for standby, get the impregnation solution I. In the stirring state, slowly add maleic acid and diethylene glycol mixture to the above solution, the amount of maleic acid is 16 g / L in the impregnation solution, the amount of diethylene glycol is 22 g / L in the impregnation solution, and the solution is constant volume 87 mL for standby. The above impregnation solution is impregnated on the carrier A by spraying method to obtain D-A. After placing D-A in a closed container at room temperature for 6 hours, drying at 110℃ for 3 hours, finally calcining at 530℃ for 6 hours to obtain C-A.

[0048] Example 2

[0049] Into the reaction kettle, 4L of clean water was added and heated to 60℃, the stirring rate was 300 rad / min, 35 g / 100 mL of aluminum sulfate solution and 40 g / 100 mL of sodium metaaluminate were continuously added to the reaction kettle at flow rates of 45 mL / min and 30 mL / min respectively. During the reaction, hydrochloric acid was added to control the reaction pH to 1.6. After the reaction was completed, the temperature was adjusted to 140℃, the stirring rate was adjusted to 400 rad / min, and polyethylene oxide with a molecular weight of 20000 (2.2% of the aluminum oxide content) was introduced into the reaction kettle. Then, a 60 g / 100 mL sodium hydroxide solution was introduced into the reaction kettle for secondary reaction, the reaction pH was adjusted to 8.8, and the reaction time was 70 min. Aging was carried out at 300℃ for 4 hours. After filtration and washing with hot water at 70℃ until neutral, drying was carried out at 120℃ for 4 hours to obtain pseudoboehmite;

[0050] Take 80 grams of activated carbon with a particle size of 10 microns and place it in a spray impregnation rolling pot. In the rotating state, 32 ml of ethyl alcohol solution containing 5 grams of tetraethyl orthosilicate and 1.5 grams of gallium nitrate containing gallium oxide is sprayed into the activated carbon in the rolling pot in an atomized manner. After impregnation, the activated carbon is mixed with 418 g of pseudoboehmite (alumina mass content of 67.8%), 8.4 g of sesbania powder, 4.1 g of nitric acid, 2.8 g of citric acid, and 366 g of water. After kneading and forming, drying is carried out at 120℃ for 3 hours, and calcination is carried out at 600℃ for 4 hours to obtain catalyst carrier B.

[0051] Take 100 g of catalyst carrier B, measure its water absorption rate of 0.88, take molybdenum trioxide (containing molybdenum oxide 99wt%) 182 g, basic nickel carbonate (containing nickel oxide 52wt%) 96.2 g, phosphoric acid solution (containing phosphorus 26.7wt%) 59.9 g, after adding clean water, stirring gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 60 minutes, then reduce to room temperature for standby, get the impregnation solution I. In the stirring state, slowly add maleic acid and triethylene glycol mixture to the above solution, the amount of maleic acid is 14 g / L in the impregnation solution, the amount of triethylene glycol is 19 g / L in the impregnation solution, and the solution is constant volume 88 mL for standby. The above impregnation solution is impregnated on the carrier B by spraying method to obtain D-B. After placing D-B in a closed container at room temperature for 6 hours, it is dried at 130℃ for 4 hours, and finally calcined at 500℃ for 6 hours to obtain C-B.

[0052] Example 3

[0053] Into the reaction kettle, 3L of clean water was charged and heated to 70℃, the stirring rate was 350 rad / min, 55 g / 100 mL of aluminum sulfate solution and 50 g / 100 mL of sodium metaaluminate were continuously added to the reaction kettle at flow rates of 30 mL / min and 15 mL / min respectively, and the pH of the reaction was controlled at 1.3 by adding hydrochloric acid during the reaction. After the reaction was completed, the temperature was adjusted to 160℃, the stirring rate was adjusted to 500 rad / min, polyvinylpyrrolidone (molecular weight 30000) (1.2% of the content of aluminum oxide) was introduced into the reaction kettle, and then a 55 g / 100 mL sodium hydroxide solution was introduced into the reaction kettle for secondary reaction, the pH value was adjusted to 9.0, the reaction time was 100 min, and the aging was carried out at 70℃ for 3 hours. After filtration, washing with hot water at 90℃ until neutral, drying at 130℃ for 2 hours, pseudo-boehmite was obtained;

[0054] Take 71 grams of activated carbon with a particle size of 4 μm and place it in a spray impregnation rolling pot. In the rotating state, 32 ml of ethyl alcohol solution containing 4 grams of tetraethyl orthosilicate and 1 gram of gallium nitrate containing gallium oxide is sprayed into the activated carbon in the rolling pot in an atomized manner. After impregnation, the activated carbon is mixed with 298 g of pseudo-boehmite (alumina mass content of 68.4%), 6 g of sesbania powder, 2.9 g of nitric acid, 2 g of citric acid and 261 g of water, and then kneaded and formed. After drying at 130℃ for 4 hours and calcining at 670℃ for 3 hours, catalyst carrier C is obtained.

[0055] Take 100 g of catalyst carrier C, measure its water absorption rate of 0.93, take molybdenum trioxide (containing molybdenum oxide 99wt%) 192 g, basic nickel carbonate (containing nickel oxide 52wt%) 101 g, phosphoric acid solution (containing phosphorus 26.7wt%) 52.4 g, after adding clean water, stirring gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 60 minutes, then reduce to room temperature for standby, get the impregnation solution I. In the state of stirring, slowly add the mixture of citric acid and diethylene glycol to the above solution, the amount of citric acid is 20 g / L in the impregnation solution, the amount of diethylene glycol is 33 g / L in the impregnation solution, and the solution is constant volume 93 mL for standby. The above impregnation solution is impregnated on the carrier C by spraying method to obtain D-C. After placing D-C in a closed container at room temperature for 6 hours, drying at 140℃ for 5 hours, and finally calcining at 495℃ for 6 hours, C-C is obtained.

[0056] Example 4

[0057] A 2.5L reaction kettle is charged with 90℃ clean water, and the stirring rate is 250 rad / min. 45g / 100mL aluminum sulfate solution and 40g / 100mL sodium metaaluminate are continuously added to the reaction kettle at flow rates of 36mL / min and 30mL / min respectively. During the reaction, hydrochloric acid is added to control the reaction pH to 1.3. After the reaction is completed, the temperature is adjusted to 180℃, the stirring rate is adjusted to 400 rad / min, polyvinyl alcohol (molecular weight 25000) (1.2% of the content of aluminum oxide) is introduced into the reaction kettle, and a 60g / 100mL sodium bicarbonate solution is introduced into the reaction kettle for secondary reaction. The reaction pH is adjusted to 9.5, the reaction time is 120 min, and the aging is carried out at 70℃ for 3 hours. After filtration and washing with 90℃ hot water until neutral, the product is dried at 130℃ for 2 hours to obtain pseudoboehmite;

[0058] Take 114 grams of activated carbon with a particle size of 16μm and place it in a spray impregnation rolling pot. In the state of rotation, 45ml of ethyl alcohol solution containing 6g of tetraethyl orthosilicate containing silicon dioxide and 2g of gallium nitrate containing gallium oxide is sprayed into the activated carbon in the rolling pot in an atomized manner. After impregnation, the activated carbon is mixed with 388 pseudoboehmite (alumina content 69.1%), 6g of sesbania powder, 2.9g of nitric acid, 2g of citric acid and 261g of water, and then kneaded and formed. After drying at 130℃ for 4 hours and calcining at 670℃ for 3 hours, the catalyst carrier D is obtained.

[0059] Take 100 g of catalyst carrier D, measure its water absorption rate of 0.87, take molybdenum trioxide (containing molybdenum oxide 99wt%) 192 g, basic nickel carbonate (containing nickel oxide 52wt%) 101 g, phosphoric acid solution (containing phosphorus 26.7wt%) 52.4 g, after adding clean water, stirring and gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 70 minutes, then reduce to room temperature for standby, get the impregnation solution I. Slowly add maleic acid and diethylene glycol mixture to the above solution under stirring, the amount of maleic acid is 26g / L in the impregnation solution, the amount of diethylene glycol is 19g / L in the impregnation solution, and the solution is constant volume 87mL for standby. The above impregnation solution is impregnated on the carrier D by spraying method to obtain D-D. After placing D-D in a closed container at room temperature for 6 hours, it is dried at 130℃ for 4 hours, and finally calcined at 520℃ for 6 hours to obtain C-D.

[0060] Comparative example 1

[0061] Compared with example 1, no secondary reaction is carried out in the preparation process, and finally the catalyst DC-A is obtained, as follows:

[0062] Into the reaction kettle, 3L of clean water is added and heated to 60℃, the stirring rate is 200 rad / min, 35g / 100mL aluminum sulfate solution and 23g / 100mL sodium metaaluminate are continuously added to the reaction kettle at flow rates of 30mL / min and 20mL / min respectively, the reaction pH is controlled to be 1.4 by adding hydrochloric acid during the reaction, and the reaction time is 70min. After the reaction is completed, the temperature is adjusted, and the pseudo-boehmite is obtained by aging at 260℃ for 2 hours, filtering, washing to neutral with hot water at 90℃, and drying at 130℃ for 3 hours;

[0063] Take 75 grams of activated carbon with a particle size of 4μm and place it in a spray impregnation rolling pot. Under the rotating state, 22.5ml of ethanol solution containing 3g of tetraethyl orthosilicate containing silicon dioxide and 1.5g of gallium nitrate containing gallium oxide is sprayed to the activated carbon in the rolling pot in an atomized manner. After impregnation, the activated carbon is mixed with 348g of pseudo-boehmite (alumina mass content of 69.1%), 7.2g of sesbania powder, 3.58g of nitric acid, 2.4g of citric acid and 313g of water, and then kneaded and formed. After drying at 120℃ for 3 hours and calcining at 600℃ for 6 hours, the catalyst carrier DA is obtained.

[0064] Take 100 g of catalyst carrier DA, measure its water absorption rate of 0.87, take molybdenum trioxide (containing molybdenum oxide 99wt%) 202g, basic nickel carbonate (containing nickel oxide 52wt%) 96.2g, phosphoric acid solution (containing phosphorus 26.7wt%) 52.4g, after adding clean water, stirring gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 40 minutes, then reduce to room temperature for standby, get the impregnation solution I. In the stirring state, slowly add maleic acid and diethylene glycol mixture to the above solution, the amount of maleic acid is 16g / L in the impregnation solution, the amount of diethylene glycol is 22g / L in the impregnation solution, and the solution is constant volume 87ml for standby. The above impregnation solution is impregnated on the carrier DA by spraying method to obtain D-DA. After placing D-DA in a closed container at room temperature for 6 hours, it is dried at 110℃ for 3 hours, and finally calcined at 530℃ for 6 hours to obtain DC-A.

[0065] Comparative example 2

[0066] Compared with example 1, no acid is added to adjust the pH value in the first reaction process, and finally the catalyst DCB is obtained.

[0067] Into the reaction kettle 3L of clean water, heated to 60℃, stirring rate 200rad / min, 35g / 100mL aluminum sulfate solution and 23g / 100mL sodium metaaluminate were continuously added into the reaction kettle at flow rate of 30mL / min and 20mL / min respectively, the reaction time was 70min. After the reaction was completed, the temperature was adjusted to 120℃, the stirring rate was adjusted to 300rad / min, polyvinyl alcohol (molecular weight 25000) (1.2% of the content of aluminum oxide) was introduced into the reaction kettle, and then the concentration of 55g / 100mL sodium carbonate solution was introduced into the reaction kettle for secondary reaction, the reaction pH value was adjusted to 9, the reaction time was 90min, and the aging was carried out at 260℃ for 2 hours. After filtration and washing with hot water at 90℃ to neutral, drying at 130℃ for 3 hours, pseudo-boehmite was obtained;

[0068] Take 75 grams of activated carbon with particle size of 4μm and place it in a spray impregnation rolling pot. In the rotating state, 22.5ml of ethyl alcohol solution containing 3g of tetraethyl orthosilicate containing silicon dioxide and 1.5g of gallium nitrate containing gallium oxide is sprayed into the activated carbon in the rolling pot in an atomized manner. After impregnation, the activated carbon is mixed with 348g of pseudo-boehmite (alumina mass content of 69.1%), 7.2g of sesbania powder, 3.58g of nitric acid, 2.4g of citric acid and 313g of water, and then kneaded and formed. After drying at 120℃ for 3 hours and calcining at 600℃ for 6 hours, the catalyst carrier DB is obtained.

[0069] Take 100 g of catalyst carrier DB, measure its water absorption rate of 0.87, take molybdenum trioxide (containing molybdenum oxide 99wt%) 202 g, basic nickel carbonate (containing nickel oxide 52wt%) 96.2 g, phosphoric acid solution (containing phosphorus 26.7wt%) 52.4 g, after adding clean water, stirring gradually heating to boiling until the raw materials are completely dissolved, constant temperature for 40 minutes, then reduce to room temperature for standby, get the impregnation solution I. Slowly add maleic acid and diethylene glycol mixture to the above solution under stirring, the amount of maleic acid is 16 g / L in the impregnation solution, the amount of diethylene glycol is 22 g / L in the impregnation solution, and the solution is constant volume 87 mL for standby. The above impregnation solution is impregnated on the carrier DB by spraying to obtain D-DB. D-DB is placed in a closed container at room temperature for 6 hours, then dried at 110℃ for 3 hours, and finally calcined at 530℃ for 6 hours to obtain DC-B.

[0070] Comparative Example 3

[0071] Compared with Example 1, the mixture of organic acid and alcohol compound is not added in the preparation process of impregnation solution, the conventional impregnation solution I is impregnated on the carrier, and finally the catalyst DC-C is obtained.

[0072] Comparative Example 4

[0073] Compared with Example 1, only maleic acid is added to the above solution after preparing the impregnation solution I under stirring, and the amount of maleic acid is 16 g / L in the impregnation solution. The solution is constant volume 90 mL for standby. The impregnation solution is impregnated on the carrier, and finally the catalyst DC-D is obtained.

[0074] Comparative Example 5

[0075] Compared with Example 1, only the solution containing silicon is used to impregnate activated carbon to prepare the comparative hydrogen demetallization catalyst DC-E, as follows:

[0076] Into the reaction kettle, 3L of clean water is loaded and heated to 60℃, the stirring rate is 200 rad / min, 35 g / 100 mL aluminum sulfate solution and 23 g / 100 mL sodium metaaluminate are continuously added to the reaction kettle at flow rates of 30 mL / min and 20 mL / min respectively, the pH value of the reaction is controlled to be 1.4 by adding hydrochloric acid during the reaction, and the reaction time is 70 min. After the reaction is completed, the temperature is adjusted to 120℃, the stirring rate is adjusted to 300 rad / min, polyvinyl alcohol (molecular weight 25000) (1.2% of the content of aluminum oxide) is introduced into the reaction kettle, and then a 55 g / 100 mL sodium carbonate solution is introduced into the reaction kettle for secondary reaction, the pH value of the reaction is adjusted to 9, the reaction time is 90 min, and the aging is carried out at 260℃ for 2 hours. After filtration, washing with hot water at 90℃ until neutral, drying at 130℃ for 3 hours, pseudo-boehmite is obtained.

[0077] Take 75 grams of activated carbon with a particle size of 4 μm and place it in a spray-impregnation rolling kettle. While rotating, spray-impregnate the activated carbon in the rolling kettle with 22.5 ml of an ethanol solution of tetraethyl orthosilicate containing 3 grams of silicon dioxide in an atomized manner. After impregnation, mix the activated carbon with 348 grams of pseudoboehmite (alumina content of 69.1%), 7.2 grams of sesbania powder, 3.58 grams of nitric acid, 2.4 grams of citric acid, and 313 grams of water, and then knead and shape. After drying at 120°C for 3 hours and calcining at 600°C for 6 hours, a catalyst carrier DE is obtained.

[0078] Take 100 grams of the catalyst carrier DE and measure its water absorption rate, which is 0.87. Take 202 grams of molybdenum trioxide (containing 99 wt% of molybdenum trioxide), 96.2 grams of basic nickel carbonate (containing 52 wt% of nickel oxide), and 52.4 grams of phosphoric acid solution (containing 26.7 wt% of phosphorus). After adding clean water, gradually heat and boil the mixture until the raw materials are completely dissolved. After constant temperature for 40 minutes, lower the temperature to room temperature for standby. An impregnation solution I is obtained. While stirring, slowly add a mixture of maleic acid and diethylene glycol to the above solution. The amount of maleic acid added is such that its concentration in the impregnation solution is 16 g / L, and the amount of diethylene glycol added is such that its concentration in the impregnation solution is 22 g / L. The solution is then made up to 87 ml for standby. The above impregnation solution is impregnated on the carrier DE in a spraying manner to obtain D-DE. After placing D-DE in a closed container at room temperature for 6 hours, dry it at 110°C for 3 hours, and finally calcine it at 530°C for 6 hours to obtain DC-E.

[0079] Table 1 Catalyst composition and properties of examples and comparative examples

[0080]

[0081]

[0082] Continued table 1

[0083]

[0084] Application example

[0085] In this application example, the catalysts of examples 1, 2, 3, 4 and comparative examples 1, 2, 3, 4, and 5 are respectively subjected to activity tests in a small fixed-bed hydrogenation device. The properties of the raw oil and the reaction conditions are shown in Table 3, and the evaluation results are shown in Tables 4 and 5.

[0086] Table 3 Properties of raw oil and reaction conditions

[0087]

[0088]

[0089] Activity evaluation of each catalyst in Table 4

[0090] Removal Example 1 Example 2 Example 3 Example 4 HDS, % 67.7 71.2 69.9 77.2 HDM, % 84.3 84.8 85.4 85.6

[0091] Table 4 (continued)

[0092] Removal Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 HDS, % 51.7 54.9 54.2 55.3 56.7 HDM, % 61.5 63.8 68.3 70.3 69.4

[0093] Activity and stability evaluation results of catalysts in each example and comparative example in Table 5

[0094] Removal Run time, h Example 1 Example 2 Example 3 Example 4 HDS, % 200 67.7 71.2 69.9 77.2 HDS, % 2000 64.4 66.4 64.7 71.4 HDM, % 200 84.3 84.8 85.4 85.6 HDM, % 2000 80.4 79.4 80.1 81.8

[0095] Table 5 (continued)

[0096] Removal Run time, h Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 HDS, % 200 51.7 54.9 54.2 55.3 56.7 HDS, % 2000 32.6 36.3 34.1 32.4 39.3 HDM, % 200 61.5 63.8 68.3 70.3 69.4 HDM, % 2000 43.2 44.6 45.8 45.3 41.2

[0097] The catalyst prepared by the method has 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) performing a precipitation reaction between an acidic aqueous aluminum salt solution and a basic aqueous aluminum salt solution in a parallel flow to obtain a slurry; (2) adding a basic solution and a water-soluble polymer to the slurry of step (1) to perform a secondary reaction, aging, drying, and obtaining a material A; (3) impregnating activated carbon with a solution containing silicon and gallium to obtain a material B; (4) mixing and shaping the material A obtained in step (2) and the material B obtained in step (3), drying, and calcining to obtain a carrier; (5) impregnating the carrier of step (4) with an active metal impregnating solution containing an organic acid and an alcohol compound, drying, and calcining to obtain the residue hydrodemetallization catalyst; In step (1), the reaction is controlled to have a pH value of 1.2-1.

8. In step (2), the water-soluble polymer is at least one selected from polyvinyl alcohol, polyethylene oxide, and polyvinyl pyrrolidone, and the weight average molecular weight of the water-soluble polymer is 10,000-40,000; the water-soluble polymer is added in an amount of 0.1%-5% of the mass of the slurry obtained in step (1) in terms of aluminum oxide. In step (2), the secondary reaction is controlled to have a pH value of 8.5-9.7, and the reaction time of the secondary reaction is 60-120 min, and the reaction temperature is 120-180°C. In step (3), the silicon and gallium introduced into the activated carbon in the solution containing silicon and gallium account for 2%-9% of the mass of the activated carbon in terms of SiO2 and Ga2O3. In step (5), the active metal is a metal of Group VIB and Group VIII; the content of the metal of Group VIB is 5.0%-13.0% in terms of metal oxide based on the weight of the hydrodemetallization catalyst, and the content of the metal of Group VIII is 1.5%-3.5% in terms of metal oxide. In step (5), the concentration of the organic acid is 2-45 g / L, and the concentration of the alcohol compound is 5-50 g / L.

2. The method of claim 1, wherein, In step (1), the acidic aluminum salt is at least one selected from aluminum sulfate, aluminum chloride, and aluminum nitrate, and the concentration of the acidic aluminum salt solution in terms of Al2O3 is 20-100 g / 100 mL; the basic aluminum salt is at least one selected from sodium metaaluminate and potassium metaaluminate, and the concentration of the basic aluminum salt solution in terms of Al2O3 is 20-100 g / 100 mL; the ratio of the addition volume rate of the acidic aluminum salt solution to the basic aluminum salt solution is 1:1-3:

1.

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.

4. The method of claim 1, wherein, In step (1), the reaction time of the parallel flow is 60-180 min, the reaction temperature is 60-90°C, and the reaction is performed under stirring at a stirring rate of 100-500 rad / min.

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

6. The method of claim 1, wherein, In step (2), the basic solution 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 water-soluble polymer is added in an amount of 0.5%-3% of the mass of the slurry obtained in step (1) in terms of aluminum oxide.

7. The method of claim 1, wherein, The secondary reaction in step (2) is carried out under stirring, and the stirring rate is 100-500 rad / min; and / or, the aging temperature in step (2) is 200-500 ℃, the aging time is 2-4 hours, the drying temperature is 120-160 ℃, and the drying time is 2-6 hours.

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

9. The method of claim 1, wherein, The specific surface area of the activated carbon in step (3) is 2000-3000 m 2 / g, and the particle size is 2-15 μm; the silicon and gallium-containing solution is an ethanol solution containing silicate and gallium nitrate, the silicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate, the concentration of silicon in the silicon and gallium-containing solution is 0.1-5 g / mL as SiO2, and the mass ratio of silicon and gallium in the silicon and gallium-containing solution is 2:1-5:1 as SiO2 and Ga2O3; the amount of the silicon and gallium-containing solution is 30%-50% of the saturated water absorption capacity of the activated carbon by volume; and the impregnation in step (3) is performed by spraying.

10. The method of claim 1, wherein, In step (4), the mass ratio of the material A obtained in step (2) to the material B obtained in step (3) is 2:1-10:

1.

11. The method of claim 1, wherein, In step (4), the drying conditions are as follows: the drying temperature is 100-160 ℃, and the drying time is 2-10 hours; the calcination conditions are as follows: the calcination temperature is 600-750 ℃, and the calcination time is 2-10 hours; and / or, in step (5), the drying temperature is 100-160 ℃, the drying time is 2-10 hours, the calcination temperature is 480-550 ℃, and the calcination time is 5-10 hours.

12. The method of claim 1, wherein, The impregnation solution in step (5) contains phosphorus; wherein the phosphorus source is phosphoric acid.

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

14. The method of claim 13, wherein, The content of the active metal oxide is 8.0%-18.0% based on the weight of the hydrodemetallization catalyst.

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

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

17. The hydrodemetallization catalyst prepared by any of the methods in claims 1-16.

18. The 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 1.2 mL / g, average pore diameter of 15 to 30 nm, and mechanical strength of 110 to 130 N / cm.

19. The catalyst of claim 17, wherein, The catalyst has the following pore distribution: 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 catalyst in any of claims 17-19 for use in residual oil hydroprocessing.

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