A poor-quality residual oil hydrodemetallization catalyst and a method for preparing the same

Abstract

The application discloses a preparation method of a poor-quality residual oil hydrogenation demetallization catalyst, which comprises the following steps: mixing hydrated alumina, phenolic resin and a binder, adding a water solution containing low-carbon alcohol, and performing mixing, kneading, molding, drying and calcination to obtain an alumina carrier; dissolving metal compounds by using organic acid and hydrogen peroxide, adding a composite complexing agent, and preparing a metal impregnation solution; wherein the active metal compounds comprise metals of group VIII and group 6B; the specific surface area of the poor-quality residual oil hydrogenation demetallization catalyst is 80-180 m 2 / g, the pore volume is 0.5-1.1 cm 3 / g, and the proportion of the pore volume of the pore channel with a pore diameter greater than 100 nm to the total pore volume is ≮10%. In the application, the phenolic resin is used as a pore-expanding agent, is partially dissolved under the action of low-carbon alcohol, and forms a diffusion channel with a large pore of more than 100 nm in the alumina carrier after extension and crosslinking, so that the cost is low, the application has thermoplasticity and thermosetting property, is easy to be molded, and the carrier strength is high.

Description

TECHNICAL FIELD

[0001] The present application relates to a poor quality residual oil hydrodemetallization catalyst and a preparation method thereof, in particular to a residual oil hydrodemetallization catalyst with a bimodal pore structure, good activity stability, and high metal capacity, and a preparation method thereof, which is suitable for the hydroprocessing of high metal content heavy poor quality residual oil. BACKGROUND

[0002] Currently, the world oil refining industry is facing the severe challenge of increasingly heavy and poor quality of crude oil resources. Residual oil accounts for usually 45-75% of crude oil, and its properties are significantly poorer than those of gas oil and other distillates with lower boiling ranges. Therefore, the key to maximizing the production of light products and chemical raw materials through deep processing of crude oil lies in the efficient conversion and utilization of residual oil.

[0003] Residual oil hydrogenation is the most effective heavy and residual oil feedstock processing technology. Through hydrogenation, most of the metals, sulfur, nitrogen and other impurities in residual oil are removed, and the carbon residue value is reduced, which is beneficial to its further efficient processing and conversion. The combination of residual oil hydroprocessing and residual oil catalytic cracking (RFCC) has become a key technical path for refining enterprises processing poor quality crude oil to improve economic efficiency. The combination of residual oil hydroprocessing and residual oil catalytic cracking not only maximizes the conversion of residual oil with low utilization value and easy environmental pollution, significantly increasing the yield of light oil; but also obtains clean oil products with high added value and excellent quality. In a sense, the crude oil has been converted by 100%, realizing the desire to extract every drop of oil in the oil refining process. This technical combination has become the core technology for refining enterprises processing sulfur-containing crude oil to improve economic efficiency.

[0004] Catalysts are the core of residual oil hydrogenation technology, and play a decisive role in the smooth and efficient operation of residual oil hydrogenation units. Residual oil hydroprocessing is different from distillate hydroprocessing, and its operating space velocity and operating cycle are much smaller than the latter. The catalyst loading is large, and the deactivation is fast. Statistical data shows that about 40-50% of all types of hydrogenation catalysts are used for residual oil hydroprocessing.

[0005] Residue is the heaviest and poorest component of petroleum, which contains large amount of colloid and asphaltene, has high molecular weight, density, viscosity, polarity, sulfur and carbon residue content, and is rich in almost all metal impurities in petroleum. The deposition of Na, Ca, Ni, V and other metals in residue on the hydrogenation catalyst during the process of residue hydrotreating will cause permanent poisoning, which is the core factor to be considered in the process of heavy and poor residue hydrogenation. Hydrodemetallization (HDM) catalyst is one of the key technologies in the process of heavy oil hydrotreating, which mainly removes most of the Ni and V metal impurities in the feedstock to protect the downstream hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) catalysts, and has a certain desulfurization capacity. Such catalysts not only need to have good metal removal capacity, but also need to have high metal impurity accommodation capacity. Since most of the metal impurities in residue exist in colloid and asphaltene, the diffusion resistance is large. The demetallization agent is restricted by the mass transfer and diffusion efficiency of the carrier, and is prone to pore blockage, uneven deposition and distribution of removed impurities, and limited metal accommodation capacity. All the above cause serious waste of internal space of the catalyst, and the efficiency of the catalyst cannot be maximized. Therefore, such catalysts must have large pore volume, pore size and good pore permeability to facilitate the diffusion, reaction and deposition of metal impurities in asphaltene and other large molecular substances in the residue feedstock. One of the solutions is to use a bimodal pore structure carrier. During the reaction, the macromolecular reactants diffuse through the large pores with a pore diameter of more than 100 nm, which promotes the diffusion and deposition of impurities to the internal pores of the catalyst; and the pores with a pore diameter of less than 50 nm provide a reaction surface and deposition site for impurities. The two types of pores work together to make the catalyst have high demetallization activity and high impurity accommodation capacity.

[0006] On the other hand, in addition to having good hydrodemetallization activity, the stability of the residue hydrotreating catalyst is also crucial. The activity stability of the residue hydrotreating catalyst is closely related to its active phase structure, and the active metal needs to be highly dispersed on the surface of the carrier. Generally, the shorter the size of the active metal platelets, the fewer the layers, the better the dispersion, and the better the activity stability of the catalyst. By developing a new type of active metal solution system that is simple to operate, environmentally friendly and has excellent stability, reducing the interaction between the carrier and the active metal, improving the dispersion of the active metal of the residue hydrotreating catalyst, reducing the length and number of layers of MoS2 platelets, generating a higher proportion of 1-2 layer MoS2 crystal platelets, the activity and stability of the catalyst can be improved, the processing adaptability of poor feedstock during hydrogenation reaction can be improved, the operation cycle can be prolonged, and the operation efficiency can be improved.

[0007] In existing alumina carrier preparation technologies, acidic substances such as nitric acid, acetic acid, and aluminum nitrate are mostly required to be added as peptizing agents during alumina molding. However, the addition of acidic substances will destroy the particle structure of alumina and reduce the pore volume and pore size of the carrier. Using organic binders instead of peptizing acids for carrier molding can increase the pore volume and pore size of the carrier to a certain extent, but the effect is limited. Existing methods simply increase the macropore ratio of the carrier by adding pore expanders. However, when preparing carriers and catalysts with a bimodal pore structure with a high macropore ratio, they face problems such as increased cost, difficulty in molding, and decreased strength.

[0008] In the preparation of residue oil hydroprocessing catalysts, conventional ammonia-containing alkaline metal impregnation systems utilize large amounts of aqueous ammonia, which causes environmental pollution. During the production process, ammonia gas overflows in large quantities, creating a strong odor and environmentally unfriendly conditions. To address this ammonia pollution issue, existing technologies use phosphoric acid and other agents to prepare active metal impregnation solutions. However, catalysts prepared using phosphoric acid have poor dispersion of active metals, and their high phosphorus content leads to excessive acidity. This leads to catalysts prone to coking and rapid deactivation during the hydroprocessing process, resulting in insufficient stability and making them unsuitable for the hydroprocessing of low-quality heavy residue oil. Summary of the Invention

[0009] The present invention aims to address the problems of existing residue oil hydrodemetallization catalysts such as poor pore structure, high pollution and environmental unfriendliness in the preparation process, and insufficient stability due to poor dispersion of active metals. By developing a new carrier preparation and active metal loading method, the present invention provides a residue oil hydrodemetallization catalyst and preparation method having a bimodal pore structure, large pore volume and pore diameter, excellent stability, and an environmentally friendly preparation process.

[0010] In response to the problems existing in the prior art, the present invention provides a method for preparing a low-quality residue oil hydrodemetallization catalyst. A macroporous alumina carrier with a bimodal pore structure is prepared using phenolic resin as a pore-expanding agent, thereby solving the diffusion problem of macromolecular metal compounds and asphaltenes in low-quality residue oil. By developing a new, environmentally friendly active metal solution system and corresponding loading technology, the emission of pollutants such as ammonia during the production process is effectively reduced, making catalyst production cleaner. At the same time, highly dispersed loading of active metals is achieved, resulting in a high-performance residue oil hydrodemetallization catalyst. The present invention provides a low-quality residue oil hydrodemetallization catalyst and a preparation method thereof. The catalyst has an excellent bimodal pore structure, large pore volume and pore diameter, and an environmentally friendly and pollution-free production process. The active metal on the catalyst exhibits a highly dispersed, low-stacking, short platelet state. When used in residue oil hydroprocessing, the catalyst exhibits excellent hydrogenation reaction performance.

[0011] The basic technical solution to solve the problem of the present invention is:

[0012] A method for preparing a catalyst for hydrodemetallization of low-quality residual oil comprises the following steps:

[0013] (1) mixing hydrated alumina, phenolic resin and binder, adding water solution containing low carbon alcohol, mixing, shaping, drying and baking to obtain alumina carrier

[0014] (2) dissolving metal compound with organic acid and hydrogen peroxide, adding complexing agent to prepare metal impregnation solution; impregnating the carrier in step (1), aging, drying and baking to obtain catalyst.

[0015] The preferred technical scheme of the present application is:

[0016] The hydrated alumina is selected from one or more than one mixture of boehmite, diaspore, pseudo-boehmite and amorphous aluminum hydroxide, preferably pseudo-boehmite. They can be commercially available or prepared by any method in the prior art, such as pseudo-boehmite prepared by aluminum sulfate-sodium metaaluminate method;

[0017] The phenolic resin is a condensate of phenol and formaldehyde, which can be thermosetting or thermoplastic or a mixture of the two, and the particle size is 80-3000 mesh, preferably 120-2000 mesh; the addition amount is 2-25wt%, preferably 5-20wt% based on alumina;

[0018] The binder is synthetic cellulose, selected from one or more of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, preferably hydroxypropyl methyl cellulose; the addition amount is 1-5wt% based on alumina;

[0019] The 2% mass concentration aqueous solution of the synthetic cellulose has a viscosity of not less than 50000 mPa·s at 20℃;

[0020] The low carbon alcohol is selected from one or more of methanol, ethanol, ethylene glycol, propanol, isopropanol and glycerol, preferably methanol or ethanol; the addition amount is 0.5-5wt% based on alumina;

[0021] The temperature of the water solution containing low carbon alcohol is 30-100℃, preferably 40-80℃;

[0022] The drying temperature of the alumina carrier is 100-180℃, preferably 120-160℃; the carrier baking temperature is 500-1200℃, preferably 700-1000℃; the baking time is 1-4 hours;

[0023] The shape of the alumina carrier can be changed as needed, including but not limited to strip, sphere, Rasai ring, tooth ball, honeycomb, impeller, etc., wherein the strip includes but is not limited to cylinder, trilobes, quadrilobes, butterfly, etc.

[0024] The alumina carrier may be added with various additives as needed, including but not limited to one or more of silicon, phosphorus, boron, titanium, zirconium, chlorine, fluorine and the like. Various molecular sieves may be added with the alumina carrier as needed, including but not limited to one or more of X, Y, ZSM-5, β, phosphorus aluminum, titanium silicon, ZSM-41, SBA-15 and the like;

[0025] The alumina carrier has a specific surface area of ​​80-240m 2 / g, preferably 100-200m 2 / g; pore volume of 0.5-1.5cm 3 / g, preferably 0.6-1.2cm 3 / g, the proportion of the pore volume corresponding to the pores with a pore diameter greater than 100 nm to the total pore volume is ≮10%.

[0026] In the present invention, the preparation steps of the metal impregnation solution in step (2) are as follows:

[0027] (A) mixing an active metal compound, an organic acid, hydrogen peroxide and purified water to prepare an active metal aqueous solution;

[0028] (B) adding a complex complexing agent to the aqueous solution of step (A) to obtain an active metal impregnation solution.

[0029] The active metal compound in step (A) comprises at least one metal selected from Group VIII and one metal selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt, most preferably nickel, and the Group VIB metal is preferably molybdenum and / or tungsten, most preferably molybdenum. The Group VIII nickel metal is one or more of basic nickel carbonate, nickel sulfate, nickel nitrate, nickel acetate, and nickel chloride, preferably nickel nitrate and nickel acetate. The Group VIB molybdenum raw material is one or more of molybdenum trioxide, ammonium heptamolybdate (ammonium molybdate tetrahydrate), ammonium tetramolybdate, ammonium orthomolybdate, ammonium octamolybdate, and ammonium dodecomolybdate, preferably molybdenum trioxide and ammonium heptamolybdate.

[0030] The organic acid in step (A) comprises at least one or more of tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and maleic acid, preferably oxalic acid, and the amount added is 1.0-12.0 g / 100 cm 3 .

[0031] The amount of hydrogen peroxide added in step (A) is 0.1-3.0 g / 100 cm 3 .

[0032] The specific preparation process of the active metal aqueous solution in step (A) is as follows:

[0033] a) Mixing the Group VIB metal raw material and the organic acid in a container, adding deionized water, heating at 60-100° C. and stirring to completely dissolve;

[0034] b) adding a Group VIII metal raw material to the solution obtained in step a), stirring and dissolving, and heating appropriately if necessary, to obtain an active metal mixture solution;

[0035] c) adding hydrogen peroxide to the solution obtained in step b) to obtain an active metal aqueous solution.

[0036] The composite complexing agent in step (B) is a combination of a polycarboxylic acid scale inhibitor and an organic phosphorus compound. The polycarboxylic acid scale inhibitor includes at least one or more of polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylic acid-hydroxypropyl acrylate copolymer (T-225), and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, and the addition amount is 0.5-15.0 g / 100 cm 3 The organic phosphorus-containing compound includes at least one or more of aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hydroxyethylenediphosphonic acid, and ethylenediaminetetramethylenephosphonic acid, and the addition amount is 0.5-10.0 g / 100 cm 3 .

[0037] The impregnation method in step (2) can be an equal volume impregnation method or a supersaturated impregnation method, etc.; the impregnation method can spray the solution onto the surface of the carrier, or immerse the carrier in the solution; the impregnation process can be performed by vacuuming the carrier or directly impregnating it; the impregnation process can be performed by heating the carrier or at room temperature; the impregnation process can be performed using auxiliary technologies such as ultrasound or microwaves.

[0038] In the step (2), the sample after immersion is cured under closed conditions at a temperature of 20-100°C, preferably 20-60°C, for 0.5-6 hours, preferably 1.0-4 hours; the drying conditions are 80-180°C, preferably 100-140°C, and the drying time is 1-6 hours, preferably 2-4 hours.

[0039] In the step (2), the calcination temperature is 400-700° C., preferably 420-600° C.; the calcination time is 0.5-6 hours, preferably 1-4 hours.

[0040] In the inferior residue oil hydrodemetallization catalyst, calculated as oxide, the VIB group metal accounts for 2-12% of the total weight of the catalyst, and the VIII group metal accounts for 0.4-3% of the total weight of the catalyst.

[0041] The low-quality residue oil hydrodemetallization catalyst has a specific surface area of ​​80-180m2 / g, pore volume of 0.5-1.1cm 3 / g, the proportion of the pore volume corresponding to the pores with a pore diameter greater than 100 nm to the total pore volume is ≮10%.

[0042] A low-quality residual oil hydrodemetallization catalyst prepared by the above method.

[0043] Compared with the prior art, the low-quality residue oil hydrodemetallization catalyst and its preparation method of the present invention have the following advantages:

[0044] (1) Phenolic resin is used as a pore-enlarging agent, which is partially dissolved under the action of low-carbon alcohols. After extension and cross-linking, a macroporous diffusion channel with a diameter of more than 100 nm is formed in the alumina carrier. It has low cost, is both thermoplastic and thermosetting, is easy to shape, and has high carrier strength.

[0045] (2) Use organic acids to prepare the metal solution system. Organic acid radical ions have coordination sites that can form coordination bonds with metal ions. By coordinating with active metal ions, organic acid radical ions can form stable complexes with them. Organic acids are weakly acidic and can reduce the corrosion loss of the carrier. The addition of hydrogen peroxide can cause redox reactions under acidic conditions, promote the active metal to form relatively stable oxidation products, weaken the interaction between the active components and the alumina carrier, and have a positive effect on the activity and stability of the final residue oil hydroprocessing catalyst. The metal impregnation solution preparation process does not use volatile ammonia, the solution system is green and environmentally friendly, and the production process is environmentally friendly.

[0046] (3) Use a composite complexing agent, which has strong complexing ability and good solution stability. Through efficient complexing, the length of the metal active phase crystal is shortened, the number of crystal layers is reduced, and a larger proportion of 1-2 layer crystal structures are generated, achieving a high dispersion load of active metals and improving catalyst activity and stability. The use of organic phosphorus-containing compounds in the composite complexing agent introduces an appropriate amount of phosphorus into the acidic active metal solution system, which can effectively weaken the strong interaction between the active components and the carrier, optimize the metal active phase structure, and thus improve the dispersion of active metals in the residue oil hydroprocessing catalyst. At the same time, it avoids the problems of excessive phosphorus, excessive acidity, and aggregation of metal components caused by the use of phosphoric acid to prepare the active metal solution acidic system, prevents the increase in the number and length of the catalyst active phase, avoids the decrease in stability during the catalyst hydrogenation reaction, and has stronger processing adaptability for inferior residue oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 : TEM transmission electron microscope image of catalyst B in Example 2.

[0048] Figure 2 : TEM transmission electron microscope image of catalyst D in Example 4.

[0049] Figure 3 : TEM image of catalyst G in comparative example 1.

[0050] Figure 4 : Mercury intrusion pore size distribution diagram of catalyst A in Example 1. DETAILED DESCRIPTION

[0051] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Those skilled in the art may make some non-essential improvements and adjustments to the present invention based on the above disclosure.

[0052] Example 1:

[0053] Weigh 500g of the PN-2 macroporous pseudo-boehmite dry rubber powder (dry basis content 71.5wt%) produced by Binzhou Poly Innovation Materials Co., Ltd., add 35.8g of 1000-mesh phenolic resin powder and 10.7g of hydroxypropyl methylcellulose having a viscosity of 150,000 mPa·s (referring to the viscosity of a 2% aqueous solution at 20°C), and mix uniformly; dissolve 10g of ethanol in 607.8g of purified water, heat to 60°C, slowly add to the aforementioned materials, mix to form a plastic, and then extrude into a clover shape with a diameter of 1.6mm on a single-screw extruder; dry at 140°C for 2.0 hours, then place in a high-temperature roasting furnace, and keep at 900°C for 3 hours to obtain carrier a. The physicochemical properties of carrier a are shown in Table 1.

[0054] Weigh 2.0g of molybdenum trioxide and 1.0g of oxalic acid respectively, place them in a beaker, add 60g of deionized water, and heat at 95℃ to dissolve; weigh 2.08g of nickel nitrate and add it, stirring to dissolve; cool the solution to room temperature, and gradually add 0.5g of 20% hydrogen peroxide under stirring; add 0.5g of polyacrylic acid and 0.5g of diethylenetriaminepentamethylenephosphonic acid, stir to dissolve, and then standardize to 100cm 3 , obtaining an active metal impregnation solution. Weigh 50 g of carrier a and apply the impregnation solution to carrier a using an equal volume impregnation method by spraying. The impregnated sample was cured under closed conditions at 20°C for 1 hour, dried at 110°C for 2 hours, and then calcined at 550°C for 4 hours to obtain residue oil hydrotreating catalyst A. After sulfurization, the active phase transmission electron microscopy (TEM) analysis results are shown in Table 2.

[0055] Example 2:

[0056] Weigh 500g of PN-2 type macroporous pseudo-boehmite dry glue powder (dry basis content 71.5wt%) produced by Binzhou Poly Innovation Materials Co., Ltd., add 71.5g of phenolic resin powder with a particle size of 120 mesh and 17.9g of hydroxypropyl methylcellulose with a viscosity of 50,000 mPa·s (referring to the viscosity of a 2% mass concentration aqueous solution at 20°C), and mix uniformly; 17.9g of ethanol is dissolved in 607.8g of clean water, heated to 80°C, slowly added to the aforementioned materials, kneaded into a plastic, and then extruded into a clover shape with a diameter of 1.6mm on a single-screw extruder; dried at 160°C for 1.0 hour, then placed in a high-temperature roasting furnace, and kept at 700°C for 4 hours to obtain carrier b. The physicochemical properties of carrier b are shown in Table 1.

[0057] Weigh 7.68g of molybdenum trioxide and 4.0g of oxalic acid, place them in a beaker, add 60g of deionized water, and heat and stir at 60°C to dissolve; weigh 5.54g of nickel nitrate, add it, and stir to dissolve; cool the solution to room temperature, and gradually add 6.0g of 20% hydrogen peroxide under stirring; add 4.0g of epoxysuccinic acid and 3.0g of aminotrimethylenephosphonic acid under stirring, and stir to dissolve at room temperature. The solution is calibrated to 100cm 3 50 g of carrier b was weighed and the impregnation solution was sprayed onto the alumina carrier b using an equal volume impregnation method. The impregnated sample was cured under closed conditions at 40°C for 4 hours and dried at 100°C for 4 hours. The dried sample was then calcined at 500°C for 2 hours to obtain residue oil hydrotreating catalyst B. After sulfurization, the active phase transmission electron microscopy (TEM) analysis results are shown in Table 2.

[0058] Example 3:

[0059] 500 g of PN-2 macroporous pseudo-boehmite dry rubber powder (dry basis content 71.5 wt%) produced by Binzhou Poly Innovation Materials Co., Ltd. was weighed, 17.9 g of phenolic resin powder with a particle size of 2000 mesh and 3.6 g of hydroxypropyl methylcellulose with a viscosity of 200,000 mPa·s (referring to the viscosity of a 2% aqueous solution at 20° C.) were added, and mixed uniformly; 1.8 g of ethanol was dissolved in 607.8 g of clean water, heated to 40° C., slowly added to the above materials, kneaded into a plastic mass, and then extruded into a clover shape with a diameter of 1.6 mm on a single-screw extruder; dried at 120° C. for 3.0 hours, then placed in a high-temperature roasting furnace and kept at a constant temperature of 1000° C. for 1 hour to obtain carrier c. The physicochemical properties of carrier c are shown in Table 1.

[0060] Take the ammonium heptamolybdate 11.53 g, oxalic acid 6.0 g, placed in a beaker, add 60 g of deionized water, heated to 98 ℃ stirring to dissolve; take the nickel acetate 6.47 g, stirring to dissolve; the solution is reduced to room temperature, under stirring conditions to add 20% hydrogen peroxide 7.5 g; under stirring conditions to add hydrolyzed poly maleic anhydride 4.0 g, hydroxy ethylene diphosphonic acid 10.0 g, stirring to dissolve at room temperature, the solution is calibrated to 100 cm 3 . Take the carrier c 50 g, using equal volume of impregnation method to spray the above impregnation solution to the alumina carrier c, the impregnated sample is incubated at 45 ℃ under closed conditions for 2 hours; 120 ℃ drying for 2 hours; the dried sample is incubated at 600 ℃ for 1 hour, to get the residue oil hydroprocessing catalyst C. After sulfidation of the catalyst, the active phase transmission electron microscopy (TEM) analysis results are shown in Table 2.

[0061] Example 4:

[0062] Take the aforementioned pseudo-boehmite dry gel powder 500 g, add the phenolic resin powder with particle size of 300 mesh 53.6 g, add the hydroxypropyl methylcellulose with viscosity of 150 million mPa·s 10.7 g, mix evenly; dissolve 14.3 g of methanol in 600.0 g of pure water, heat to 50 ℃, slowly add the above material into the mixture, and then knead into a plastic body on a single screw extruder to form a clover shape with a diameter of 1.6 mm; dry at 130 ℃ for 3 hours, then put it into a high temperature calcination furnace, incubate at 800 ℃ for 2 hours, to get the carrier d, the physicochemical properties of the carrier d are shown in Table 1.

[0063] Take the molybdenum trioxide 11.81 g, oxalic acid 8.0 g, placed in a beaker, add 65 g of deionized water, heated to 100 ℃ stirring to dissolve; take the nickel nitrate 8.33 g, stirring to dissolve; the solution is reduced to room temperature, under stirring conditions to add 20% hydrogen peroxide 9.0 g; under stirring conditions to add hydrolyzed poly maleic anhydride 6.0 g, ethylenediaminetetramethylene phosphonic acid 4.0 g, stirring to dissolve at room temperature, the solution is calibrated to 100 cm 3 . Take the aforementioned carrier d 50 g, using equal volume of impregnation method to spray the above impregnation solution to the alumina carrier d, the impregnated sample is incubated at 60 ℃ under closed conditions for 3 hours; 140 ℃ drying for 2 hours; the dried sample is incubated at 480 ℃ for 2 hours, to get the residue oil hydroprocessing catalyst D. After sulfidation of the catalyst, the active phase transmission electron microscopy (TEM) analysis results are shown in Table 2.

[0064] Example 5:

[0065] 500 g of the aforementioned pseudo-boehmite dry rubber powder was weighed, 25.0 g of 600-mesh phenolic resin powder was added, and 10.7 g of hydroxypropyl methylcellulose with a viscosity of 150,000 mPa·s was added and mixed uniformly; 7.2 g of ethanol and 7.2 g of methanol were dissolved in 603.0 g of purified water, heated to 50°C, and slowly added to the aforementioned materials. The mixture was kneaded into a plastic mass, and then extruded into a clover-shaped mass with a diameter of 1.6 mm on a single-screw extruder; the mixture was dried at 130°C for 3 hours and then placed in a high-temperature roasting furnace at a constant temperature of 950°C for 3 hours to obtain carrier e. The physicochemical properties of carrier e are shown in Table 1.

[0066] Weigh 14.31g of molybdenum trioxide and 11.0g of oxalic acid, place them in a beaker, add 65g of deionized water, and heat at 85°C with stirring to dissolve; weigh 8.73g of nickel nitrate, add it, and stir to dissolve; cool the solution to room temperature, and gradually add 12.0g of 20% hydrogen peroxide while stirring; add 15.0g of polyacrylic acid and 6.0g of ethylenediaminetetramethylenephosphonic acid while stirring, and stir to dissolve at room temperature. The solution is calibrated to 100cm 3 50 g of the aforementioned carrier e was weighed and impregnated onto the alumina carrier e using an equal volume impregnation method by spraying the impregnation solution. The impregnated sample was cured under closed conditions at 40°C for 4 hours, dried at 120°C for 3 hours, and then calcined at 460°C for 3 hours to obtain residue oil hydrotreating catalyst E. After sulfurization, the active phase transmission electron microscopy (TEM) analysis results are shown in Table 2.

[0067] Example 6:

[0068] 500 g of the aforementioned pseudo-boehmite dry rubber powder was weighed, 28.6 g of 200-mesh phenolic resin powder was added, and 10.7 g of hydroxypropyl methylcellulose with a viscosity of 150,000 mPa·s was added, and mixed uniformly; 10.7 g of ethanol was dissolved in 600.0 g of purified water, heated to 55°C, and slowly added to the aforementioned materials, kneaded into a plastic mass, and then extruded into a clover-shaped mass with a diameter of 1.6 mm on a single-screw extruder; dried at 120°C for 3 hours, and then placed in a high-temperature roasting furnace and kept at a constant temperature of 850°C for 3 hours to obtain carrier f. The physicochemical properties of carrier f are shown in Table 1.

[0069] Weigh 18.0g of molybdenum trioxide and 12.0g of oxalic acid, place them in a beaker, add 60g of deionized water, and heat at 90°C to dissolve; weigh 20.83g of nickel nitrate, add it, and stir to dissolve; cool the solution to room temperature, and gradually add 15.0g of 20% hydrogen peroxide under stirring; add 8.0g of epoxysuccinic acid and 5.0g of hydroxyethylidene diphosphonic acid under stirring, and stir to dissolve at room temperature. The solution is calibrated to 100cm 350 g of the aforementioned carrier f was weighed and impregnated onto the alumina carrier f using an equal volume impregnation method by spraying the impregnation solution. The impregnated sample was cured under closed conditions at 55°C for 2 hours, dried at 110°C for 3 hours, and then calcined at 420°C for 3 hours to obtain residue oil hydrotreating catalyst F. After sulfurization, the active phase transmission electron microscopy (TEM) analysis results are shown in Table 2.

[0070] Comparative Examples 1-3 illustrate the prior art process and residue hydrotreating catalysts prepared by the prior art process.

[0071] Comparative Example 1:

[0072] In Comparative Example 1, the alumina carrier was prepared according to the method described in CN105983443B, and the metal impregnation solution was prepared according to the method provided in CN114425354B. The catalyst metal loading was the same as that in Example 2.

[0073] 500 g of macroporous pseudo-boehmite dry rubber powder (71.5 wt% dry basis) produced by Yantai Henghui Chemical Co., Ltd. was weighed, 10.7 g of hydroxypropyl methylcellulose with a viscosity of 150,000 mPa·s (the viscosity of a 2% aqueous solution) and 17.9 g of polyvinyl alcohol powder with a particle diameter of 90-150 μm were added, and the mixture was uniformly mixed. 14.3 g of boric acid was dissolved in 390 g of purified water and slowly added to the above materials. The mixture was kneaded into a plasticized mass, which was then extruded into a clover-shaped mass with a diameter of 1.6 mm on a forward-extrusion single-screw extruder. The mixture was dried at 120°C for 2 hours and then placed in a roasting oven at 800°C for 3 hours to obtain carrier g. Its physicochemical properties are shown in Table 1.

[0074] Weigh 7.68g of molybdenum trioxide and 2.61g of basic nickel carbonate, place them in a beaker, add water and stir, weigh 3.76g of phosphoric acid, dilute with water and slowly add it to the beaker, react at room temperature for 15 minutes; heat to 95°C and heat for 35 minutes; weigh 3.0g of citric acid and add it, continue to heat at constant temperature for 25 minutes, wait until all the raw materials are dissolved, turn off the heating and cool to room temperature; add 10.0g of triethanolamine and 3g of Tween-80 while stirring, stir and dissolve, and calibrate to 100cm 3 The impregnation solution was sprayed onto carrier G. The impregnated sample was dried and then kept at 500°C for 2 hours to obtain catalyst G. After the catalyst was sulfurized, the results of transmission electron microscopy (TEM) analysis of the active phase are shown in Table 2.

[0075] Comparative Example 2:

[0076] Comparative Example 2: An alumina carrier was prepared according to the method described in CN1103009A, and a metal impregnation solution was prepared according to the method disclosed in CN103007949B. The catalyst metal loading was the same as that in Example 2.

[0077] 34.1 g of aluminum hydroxide dry rubber powder (alkyl aluminum hydrolysis product containing 75% aluminum oxide) and 39.3 g of aluminum hydroxide powder obtained by the aluminum sulfate method were mixed, and then 4.7 g of high-wear-resistant carbon black, 3.5 g of surfactant SA-20, 2.1 g of aluminum nitrate, and 66 ml of water were added and thoroughly ground and mixed. The mixture was extruded into a clover-shaped shape with a diameter of 1.8 mm on an extruder, dried at 120°C, and calcined at 600°C for 4 hours to obtain carrier h. Its physicochemical properties are shown in Table 1.

[0078] Take 30% hydrogen peroxide and add it dropwise to 9.48g ammonium heptamolybdate, stirring to dissolve; add 5.54g nickel nitrate, stirring to dissolve, add 1.5g terephthalic acid, and calibrate to 100cm 3 The solution was added dropwise to carrier h, impregnated at room temperature for 6 hours, dried at 110°C for 2 hours, and calcined at 500°C for 4 hours to obtain catalyst H. After the catalyst was sulfurized, the results of transmission electron microscopy (TEM) analysis of the active phase are shown in Table 2.

[0079] Comparative Example 3:

[0080] Comparative Example 3: An alumina carrier was prepared according to the method described in patent CN1647857A, and a metal impregnation solution was prepared according to the method disclosed in patent CN1230491C. The catalyst metal loading was the same as that in Example 2.

[0081] 500 g of PN-2 macroporous pseudo-boehmite dry rubber powder (aluminum sulfate-sodium aluminate method, dry basis content 71.5 wt%) produced by Binzhou Poly Innovation Materials Co., Ltd. was weighed, 10.7 g of polyethylene glycol with a molecular weight of 2000 was added, and water was added to slurry to finally obtain 6 liters of slurry. The slurry was then spray-dried at an inlet temperature of 580°C and an outlet temperature of 180°C. The resulting composition was extruded and dried, and calcined at 800°C for 3 hours to obtain carrier i. Its physicochemical properties are shown in Table 1.

[0082] Take 75cm 3 Place 18% ammonia water in an ultrasonic transducer, control the transmission power to 350W and the frequency to 25kHz, add 9.48g of ammonium heptamolybdate and dissolve it, then add 5.54g of nickel nitrate. After the metal salt is completely dissolved, turn off the ultrasonic transducer and adjust the solution volume to 100cm with ammonia water. 3 The solution was added dropwise to support i, impregnated at room temperature for 4 hours, dried at 120°C for 2 hours, and calcined at 500°C for 3 hours to obtain catalyst I. After the catalyst was sulfurized, the results of transmission electron microscopy (TEM) analysis of the active phase are shown in Table 2.

[0083] Example 7:

[0084] This example is an activity evaluation test of the catalysts obtained in Examples 1-6 and Comparative Examples 1-3, and is used to compare the hydrogenation reaction performance of catalysts prepared by different methods.

[0085] Catalysts B, G, H, and I were tested for performance in a fixed-bed residue oil hydroprocessing evaluation unit using the same feedstock and process conditions. The feedstock properties and process conditions are listed in Table 3, and the evaluation results are listed in Table 4.

[0086] In summary, it can be seen from Examples 1-7 and Comparative Examples 1-3 that:

[0087] (1) As shown in Table 1, the carrier obtained in the present invention has the characteristics of large pore volume and pore diameter, high proportion of macropores larger than 100 nm, and good strength compared with the prior art, and can better adapt to the hydrodemetallization process of low-quality residual oil;

[0088] (2) The TEM characterization results in Table 2 show that the catalyst for hydrotreating residual oil obtained in the present invention has a small number of lamellae, mainly single-layer and double-layer MoS2, with short lamellae length and good dispersion of active phase, showing obvious high dispersion, low stacking and short lamellae characteristics, and is more suitable for hydrotreating heavy and inferior residual oil; while the catalyst obtained in the comparative example has a high proportion of lamellae structure with more than 3 layers, a large lamellae length and poor dispersion of active components;

[0089] (3) As can be seen from the evaluation results in Table 4, compared with the comparative example catalyst, the catalyst prepared by the present invention has better desulfurization, carbon removal and demetallization activities, good activity stability, and stronger adaptability to processing inferior raw materials, which is conducive to extending the operation cycle of the device and improving economic benefits.

[0090] Table 1 Physicochemical properties of carriers

[0091]

[0092]

[0093] Table 2 TEM characterization results of catalysts

[0094]

[0095] Table 3 Evaluation test raw oil and process conditions

[0096] Raw oil properties Middle East residual oil Density (20°C) / g-cm -3 ]] 0.9884 Sulfur content, w% 4.478 Residual carbon value, w% 13.20 Metal (Ni + V), pg g -1 ]] 79.44 Process conditions Reaction temperature, °C 380 Hydrogen partial pressure, MPa 16.0 <![CDATA[体积空速,h -1 ]]> 1.0 Hydrogen / oil ratio, V / V 700

[0097] Table 4 Catalyst evaluation results

[0098]

Claims

1. A method for preparing a catalyst for hydrodemetallization of low-quality residual oil, characterized in that: The following steps are involved: (1) Hydrated alumina, phenolic resin and a binder are mixed, an aqueous solution containing a low-carbon alcohol is added, and the mixture is kneaded, formed, dried and calcined to obtain an alumina carrier; (2) dissolving the active metal compound with organic acid and hydrogen peroxide, adding a complexing agent, and preparing a metal impregnation solution; impregnating the carrier in step (1), curing, drying and calcining to obtain a catalyst; The active metal compound comprises a metal selected from Group VIII and a metal selected from Group VIB, wherein, calculated as oxide, the Group VIB metal accounts for 2-12% of the total weight of the catalyst and the Group VIII metal accounts for 0.4-3% of the total weight of the catalyst; The specific surface area of ​​the inferior residue oil hydrodemetallization catalyst is 80-180 m 2 / g, pore volume of 0.5-1.1 cm 3 / g, the proportion of pore volume corresponding to pores with pore diameter greater than 100 nm to the total pore volume is ≮10%; The organic acid includes one or more of tartaric acid, oxalic acid, malic acid, citric acid, succinic acid, and maleic acid; The composite complexing agent is a combination of a polycarboxylic acid scale inhibitor and an organic phosphorus-containing compound; The binder is synthetic cellulose.

2. The preparation method according to claim 1, characterized in that The steps of preparing the metal impregnation solution in step (2) include: (A) mixing an active metal compound, an organic acid, hydrogen peroxide and purified water to prepare an active metal aqueous solution; (B) adding a complex complexing agent to the aqueous solution of step (A) to obtain an active metal impregnation solution; The polycarboxylic acid scale inhibitor includes one or more of polyepoxysuccinic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, polyaspartic acid, acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer; The organic phosphorus-containing compound includes one or more of aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hydroxyethylenediphosphonic acid, and ethylenediaminetetramethylenephosphonic acid.

3. The preparation method according to claim 2, wherein: The specific preparation process of the active metal aqueous solution in step (A) is as follows: (a) Mixing a Group VIB metal raw material and an organic acid in a container, adding deionized water, heating at 60-100° C. and stirring to completely dissolve the mixture; (b) adding a Group VIII metal raw material to the solution obtained in step (a), stirring and dissolving, and heating appropriately if necessary, to obtain an active metal mixture solution; (c) adding hydrogen peroxide to the solution obtained in step (b) to obtain an active metal aqueous solution.

4. The preparation method according to claim 1, characterized in that In step (2): The impregnated samples are cured in a sealed environment at a temperature of 20-100°C for 0.5-6 hours; The drying condition is 80-180°C and the drying time is 1-6 hours; The calcination temperature is 400-700° C., and the calcination time is 0.5-6 hours.

5. The preparation method according to claim 1, wherein: The hydrated aluminum oxide is selected from one or a mixture of gibbsite, boehmite, pseudo-boehmite and amorphous aluminum hydroxide.

6. The preparation method according to claim 1, wherein: The phenolic resin is a condensation product of phenol and formaldehyde, and is thermosetting or thermoplastic or a mixture of the two. Its particle size is 80-3000 meshes. The addition amount is 2-25wt% based on aluminum oxide.

7. The preparation method according to claim 1, wherein: The synthetic cellulose is selected from one or more of methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the amount added is 1-5 wt% based on aluminum oxide; The viscosity of a 2% mass concentration aqueous solution of the synthetic cellulose at 20° C. is not less than 50,000 mPa·s.

8. The preparation method according to claim 1, wherein: The low-carbon alcohol is selected from one or more of methanol, ethanol, ethylene glycol, propanol, isopropanol and glycerol, and is added in an amount of 0.5-5 wt% based on alumina; The temperature of the aqueous solution containing low-carbon alcohol is 30-100°C.

9. The preparation method according to claim 1, wherein: The alumina carrier is dried at a temperature of 100-180°C; the alumina carrier is calcined at a temperature of 500-1200°C and for a time of 1-4 hours; The shape of the alumina carrier includes any one of a bar, a sphere, a Raschig ring, a toothed ball, a honeycomb, and an impeller; an additive is selectively added to the alumina carrier, and the additive includes one or more of silicon, phosphorus, boron, titanium, zirconium, chlorine, and fluorine; Molecular sieves are selectively added to the alumina carrier, and the molecular sieves include one or more of X, Y, ZSM-5, β, phosphorus aluminum, titanium silicon, ZSM-41, and SBA-15.

10. A low-quality residue oil hydrodemetallization catalyst prepared according to the method for preparing a low-quality residue oil hydrodemetallization catalyst according to any one of claims 1 to 9.

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