Residue hydrodesulfurization catalyst, its preparation method and application

Abstract

The application discloses a residue oil hydrodesulfurization catalyst and a preparation method and application thereof. The residue oil hydrodesulfurization catalyst comprises a carrier and an active metal component, wherein the carrier comprises gallium and fluorine modified metakaolin and aluminum oxide, and the mass ratio of the gallium and fluorine modified metakaolin and the aluminum oxide is 15-30:7-13; in the gallium and fluorine modified metakaolin, the mass content of gallium is 2.0%-5.0%, and the mass content of fluorine is 0.8%-1.5%. The catalyst is used in a residue oil hydroprocessing process, and has good desulfurization activity and stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst preparation, and particularly relates to a residue hydrodesulfurization catalyst and a preparation method and application thereof. BACKGROUND

[0002] In recent years, the heavy and poor quality of crude oil resources is obvious, and the processing of poor quality crude oil faces severe challenges. Most of the sulfur in the crude oil exists in the form of sulfides (30-40%) and thiophenes (60-70%) in the residue, which is mainly distributed in aromatic hydrocarbons, resins and asphaltenes. The hydrodesulfurization process can convert organic sulfur compounds in oil products into hydrogen sulfide which is easy to be removed by reaction with hydrogen, thereby realizing the process of deep desulfurization. In recent years, environmental protection regulations have become increasingly stringent, and the market demand for product quality is also increasing. Therefore, the residue hydrodesulfurization technology needs to be further improved.

[0003] CN1458236A discloses a preparation method of a heavy oil hydrodemetallization and hydrodesulfurization catalyst. The preparation method of the catalyst uses two different forms of aluminum-containing materials, one is calcined alumina, and the other is aluminum hydroxide dry gel powder. Alkali metal and / or alkaline earth metal elements are used as additives. The additives are pre-mixed with the aluminum hydroxide dry gel powder, and part of the additives are loaded on the catalyst by impregnation method, so that the additives are unevenly distributed on the catalyst. The average pore size of the catalyst obtained by the method is 15-19 nm, which is still too small for asphaltene micelles, and is not conducive to residue hydrodesulfurization and hydrodemetallization reactions. The activity and stability of the catalyst need to be further improved. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a residue hydrodesulfurization catalyst and a preparation method and application thereof. The hydrodesulfurization catalyst prepared by the method has good macromolecular diffusion performance, strong desulfurization capacity, and good anti-carbon deposition performance. The hydrodesulfurization catalyst is particularly suitable for use in a residue hydrodesulfurization treatment process, and has good desulfurization activity and stability.

[0005] The first aspect of the present application provides a residue hydrodesulfurization catalyst, which comprises a carrier and an active metal component, wherein the carrier comprises gallium and fluorine modified metakaolin and alumina, and the mass ratio of the gallium and fluorine modified metakaolin to the alumina is 15-30:7-13. In the gallium and fluorine modified metakaolin, the mass content of gallium is 2.0%-5.0%, and the mass content of fluorine is 0.8%-1.5%.

[0006] In the present application, the active metal comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The Group VIII metal is preferably nickel and / or cobalt, and the Group VIB metal is preferably molybdenum and / or tungsten.

[0007] In the present application, the mass content of the carrier is 75% to 85% based on the mass of the catalyst, the content of the Group VIII metal in terms of oxide is 2% to 6%, and the content of the Group VIB metal in terms of oxide is 10% to 20%.

[0008] In the present application, the catalyst has the following properties: the specific surface area is 180 to 220 m 2 / g, the pore volume is 0.5 to 0.7 mL / g, and the average pore diameter is 10 to 30 nm.

[0009] The second aspect of the present application provides a preparation method of the above-mentioned residue hydrodesulfurization catalyst, comprising:

[0010] (1) mixing metakaolin, gallium nitrate, ammonium fluoride and water, performing sealed hydrothermal treatment, drying, and calcining to obtain a modified material;

[0011] (2) mixing and kneading the modified material obtained in step (1), pseudoboehmite, a glue adhesive, a extrusion aid, a pore-expanding agent and water into a shape, drying, and calcining to obtain a catalyst carrier;

[0012] (3) preparing an impregnation solution containing an amine, an alcohol, thiourea and an active metal;

[0013] (4) impregnating the catalyst carrier obtained in step (2) with the impregnation solution obtained in step (3), and drying and calcining to obtain a hydrodesulfurization catalyst.

[0014] In the present application, the mass ratio of the gallium nitrate and the ammonium fluoride in step (1) is 1 to 10:1, and the total mass of the gallium nitrate and the ammonium fluoride accounts for 5% to 60%, preferably 15% to 40%, of the mass of the metakaolin. In step (1), the water is added in a mass ratio of 5:1 to 10:1 to the total mass of the metakaolin, the gallium nitrate and the ammonium fluoride. The metakaolin, the gallium nitrate, the ammonium fluoride and the water can be mixed in any order, for example, the water can be added to the mixture of the metakaolin, the gallium nitrate and the ammonium fluoride, or the metakaolin can be immersed in an aqueous solution of the gallium nitrate and the ammonium fluoride.

[0015] In the present application, the sealed hydrothermal treatment in step (1) is performed at a temperature of 80 to 130°C for 3 to 10 hours, and the temperature increasing rate is 3 to 10°C / min. The sealed hydrothermal treatment is generally performed in a high-pressure reaction kettle under autogenous pressure. Preferably, the hydrothermal treatment is performed in two stages, and the temperature of the second stage is at least 20°C higher, preferably at least 30°C higher, than the temperature of the first stage.

[0016] In the present application, the drying temperature in step (1) is 120 to 160°C, the drying time is 2 to 6 hours, the calcining temperature is 550 to 700°C, and the calcining time is 4 to 6 hours.

[0017] In the present application, the mass ratio of the pseudo-boehmite to the modifier in step (2) is 7-13:15-30 in terms of aluminum oxide. The adhesive can be at least one of nitric acid, acetic acid, and citric acid, the extrusion aid can be sesbania powder, and the pore-expanding agent can be one or more of graphite, activated carbon, wood chips, or cellulose. The adhesive and the extrusion aid are added according to the actual molding needs, and the present application does not have a specific requirement. The pore-expanding agent is added in an amount of 4wt%-13wt% of the total mass of the pseudo-boehmite and the modifier in terms of aluminum oxide.

[0018] In the present application, the molding can be performed by using a conventional molding method, such as extrusion molding or tablet molding.

[0019] In the present application, the drying temperature in step (2) is 120-160°C, the drying time is 2-6 hours, the calcination temperature is 550-750°C, and the calcination time is 2-6 hours.

[0020] In the present application, phosphoric acid can be added to the impregnation solution in step (3).

[0021] In the present application, the alcohol compound in step (3) is one or more of pentaerythritol, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol, and neopentyl glycol; the amine compound is one or more of hexamethylenetetramine, ethylenediamine, ethanolamine, diethanolamine, and triethanolamine; the mass ratio of the alcohol compound to the amine compound is 1:1-16:1; and the amount of thiourea added is such that the concentration of thiourea in the impregnation solution is 5-70g / L, preferably 8-50g / L. The concentration of the alcohol compound in the impregnation solution in step (3) is 5-60g / L, preferably 7-30g / L.

[0022] In the present application, the active metal in step (3) includes at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The metal component selected from Group VIII is preferably nickel and / or cobalt, and the metal component selected from Group VIB is preferably molybdenum and / or tungsten. The concentration of the active metal in the impregnation solution in step (3) in terms of metal oxide is as follows: the content of the metal component selected from Group VIB is 150-450g / L, preferably 300-400g / L; the content of the metal component selected from Group VIII is 10-120g / L, preferably 40-60g / L; and the concentration of phosphorus is 20-80g / L, preferably 40-60g / L. 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 molybdophosphate, 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. The phosphorus-containing compound is phosphoric acid.

[0023] In the present application, the impregnation in step (4) is preferably carried out by spraying, and the impregnation can be carried out by equal-volume impregnation or supersaturation impregnation. Preferably, after impregnation, the sample is placed in a closed condition at room temperature for 6-12 hours before drying. In step (4), the drying condition is constant temperature at 100-160℃ for 1-8 hours; the calcination condition is constant temperature at 450-650℃ for 2-7 hours, preferably constant temperature at 480-600℃ for 2-7 hours.

[0024] The third aspect of the present application provides the use of the above-mentioned residue hydrodesulfurization catalyst in residue hydroprocessing.

[0025] Compared with the prior art, the present application has the following advantages:

[0026] 1. The residue hydrodesulfurization catalyst of the present application comprises a carrier and an active metal component, wherein the carrier comprises alumina and gallium and fluorine modified metakaolin. The catalyst of the present application is suitable for the hydroconversion of sulfides in asphaltene in the residue hydroprocessing process, has high hydrodesulfurization activity and good stability.

[0027] 2. In the preparation process of the residue hydrodesulfurization catalyst of the present application, the metakaolin is first modified by hydrothermal treatment in the presence of gallium nitrate and ammonium fluoride, which introduces gallium species to form Si-O-Ga bonds while increasing the silica-alumina ratio by removing aluminum. The removal of aluminum exposes more unsaturated aluminum ions and silicon oxide on the surface of the silica-alumina material. Then, the carrier is prepared by mixing alumina, pore-expanding agent, etc. The carrier is then impregnated with an impregnating solution containing alcohol, amine, thiourea and active metal. During the contact between the impregnating solution and the carrier, the unsaturated sites and SH groups in the mixture of active metal ions, alcohol, amine and thiourea generate Lewis acid and Br nsted acid sites on the surface of the carrier, respectively, thereby obtaining a catalyst with suitable pore structure, high acid amount and suitable acid strength distribution, which is particularly suitable for residue hydrodesulfurization.

[0028] 3. In the preparation process of the residue hydrodesulfurization catalyst of the present application, the impregnating solution containing alcohol, amine, thiourea and active metal can complex the Group VIII metal ions to form a complex, and at the same time form phosphomolybdate (tungstate), which effectively prevents the formation of strong Mo(W)-O-Al bonds in the Ga species located on the surface and near-surface region, thereby further weakening the acid regulation and interaction between the active metal and the carrier. The catalyst has strong anti-coking performance and is particularly suitable for use as a residue hydrodesulfurization catalyst, which is beneficial to improving the hydrodesulfurization activity and stability. DETAILED DESCRIPTION

[0029] The technical solutions of the present application will be described in detail below in conjunction with examples.

[0030] ​In the present application, the determination of total infrared acid, L acid or B acid is carried out by infrared spectroscopy, and the instrument is a Fourier infrared spectrometer-6700 from Nicot, USA. The determination method is as follows: 20 mg of sample with particle size less than 200 mesh is pressed into a thin slice with a diameter of 20 mm, and is loaded on the sample holder of the absorption cell. 200 mg of sample is placed in the instrument hanging cup, and the absorption cell and the adsorption tube are connected. After vacuum treatment, the vacuum degree reaches 4x10 -2 Pa, and the temperature is raised to 500℃ and kept for 1 hour to remove the adsorbed substances on the surface of the sample. After the temperature is lowered to room temperature, pyridine is adsorbed to saturation, and then the temperature is continuously raised to 160℃ and kept for 1 hour to desorb the physically adsorbed pyridine. Thus, the acid amount of total infrared acid, B acid and L acid can be obtained. The acid amount is in mmol / g. Then, the temperature is raised to 250℃, 350℃ and 450℃ in turn, and each is kept for 1 hour to obtain the acid amount of corresponding infrared acid, B acid and L acid. The absorption peak near 1450 cm -1 is L acid, the absorption peak near 1540 cm -1 is B acid.

[0031] In the present application, the specific surface area, pore volume and pore distribution are determined by using an ASAP2420 full-automatic physical adsorption instrument from Micromeritics, USA. The determination method is as follows: after the sample is treated at 300℃ and 0.1 MPa for 4 hours, liquid N2 is used as the adsorbate, and the adsorption temperature is -196℃. After accurate weighing, the sample is analyzed and tested. The specific surface area is calculated by BET method, and the pore volume and pore distribution are calculated by BJH method.

[0032] Example 1

[0033] 360 g of metakaolin, 88 g of gallium nitrate, 36 g of ammonium fluoride, 2520 g of distilled water are added to the above materials and stirred for 20 minutes. The above materials are transferred into a high-pressure kettle and sealed. The temperature is raised to 80℃ at a speed of 10℃ / min, and then kept constant for 3 hours. The temperature is raised to 110℃ at a speed of 5℃ / min, and then kept constant for 5 hours. After filtration and washing, the materials are dried at 120℃ for 6 hours, and then calcined at 600℃ for 5 hours to obtain gallium and fluorine modified material I (the mass content of gallium is 3.6%, and the mass content of fluorine is 1.1%). 179 g of pseudoboehmite (the mass content of alumina is 69.1%), 269 g of material I, 9 g of sesbania powder, 4.5 g of nitric acid, 3 g of citric acid, 18 g of activated carbon with a particle size of 4 microns, and 228 g of water are mixed and kneaded to form a shape. After drying at 120℃ for 3 hours and calcining at 700℃ for 4 hours, catalyst carrier A-0 is obtained.

[0034] Take 100 g of catalyst carrier A-0, measure its water absorption rate of 0.9, take molybdenum trioxide (containing 99 wt% of molybdenum oxide) 202 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 96.2 g, phosphoric acid solution (containing 26.7 wt% of phosphorus) 52.4 g, add clean water and stir to gradually heat to boiling until the raw materials are completely dissolved, and then reduce to room temperature after constant temperature for 40 minutes, and get the impregnation solution I. Slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above solution under stirring, the mass ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea is 20 g / L in the impregnation solution, and the amount of pentaerythritol is 16 g / L in the impregnation solution. The solution is constant volume 90 mL for standby. The above impregnation solution is impregnated on the carrier A-0 by spraying to obtain A-1. A-1 is placed in a sealed container at room temperature for 6 hours, then dried at 120℃ for 4 hours, and finally calcined at 550℃ for 4 hours to obtain CA-1.

[0035] Example 2

[0036] Take 500 g of metakaolin, 92 g of gallium nitrate, 25 g of ammonium fluoride, add 4388 g of distilled water to the above materials and stir for 30 minutes, then transfer the above materials into a high-pressure kettle and seal, then heat to 90℃ at a rate of 8℃ / min and keep constant temperature for 4 hours, then heat to 120℃ at a rate of 10℃ / min and keep constant temperature for 3 hours, then filter, wash, and then dry the materials at 130℃ for 4 hours, and then calcine at 650℃ for 4 hours to obtain gallium and fluorine modified material I (the mass content of gallium is 2.8%, and the mass content of fluorine is 1.3%). Take 146 g of pseudoboehmite (the mass content of alumina is 68.6%), 358 g of material I, 12 g of sesbania powder, 6 g of nitric acid, 4 g of citric acid, 22 g of activated carbon with a particle size of 4 microns, and 304 g of water, and then knead and shape, then dry at 130℃ for 2 hours, and then calcine at 730℃ for 3 hours to obtain catalyst carrier B-0.

[0037] Take 100 g of catalyst carrier B-0, measure its water absorption rate of 0.88, take molybdenum trioxide (containing 99 wt% of molybdenum oxide) 182 g, basic nickel carbonate (containing 52 wt% of nickel oxide) 96.2 g, phosphoric acid solution (containing 26.7 wt% of phosphorus) 59.9 g, add clean water and stir to gradually heat to boiling until the raw materials are completely dissolved, and then reduce to room temperature after constant temperature for 60 minutes, get the impregnation solution I. Slowly add 1,4-butanediol and ethylenediamine and thiourea mixture to the above solution under stirring, the mass ratio of 1,4-butanediol and ethylenediamine is 6:1, the amount of thiourea is 32 g / L in the impregnation solution, the amount of 1,4-butanediol is 22 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-0 by spraying to obtain B-1. B-1 is placed in a sealed container at room temperature for 8 hours, then dried at 130°C for 2 hours, and finally calcined at 530°C for 3 hours to obtain CB-1.

[0038] Example 3

[0039] Take 600 g of metakaolin, 102 g of gallium nitrate, 36 g of ammonium fluoride, add 5540 g of distilled water to the above materials and stir for 60 minutes, then transfer the above materials into an autoclave and seal, then heat to 80°C at a rate of 6°C / min and keep constant temperature for 3 hours, then heat to 130°C at a rate of 8°C / min and keep constant temperature for 3 hours, then filter, wash, then dry the materials at 120°C for 3 hours, and then calcine at 600°C for 5 hours to obtain gallium and fluorine modified material I (the mass content of gallium is 2.6%, and the mass content of fluorine is 0.9%). Take 224 g of pseudoboehmite (alumina mass content is 69%), 538 g of material I, 15 g of sesbania powder, 7 g of nitric acid, 5 g of citric acid, 36 g of activated carbon with a particle size of 4 microns, and 462 g of water, and then knead and shape, then dry at 120°C for 2 hours, and then calcine at 750°C for 3 hours to obtain catalyst carrier C-0.

[0040] Take 100 g of catalyst carrier C-0, measure its water absorption rate of 0.93, take 192 g of molybdenum trioxide (containing 99 wt% of molybdenum oxide), 101 g of basic nickel carbonate (containing 52 wt% of nickel oxide), 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus), add clean water and stir to gradually heat to boiling until the raw materials are completely dissolved, then reduce to room temperature after constant temperature for 60 minutes, and get the impregnation solution I. Slowly add a mixture of ethylene glycol and hexamethyl tetramine and thiourea to the above solution under stirring, the mass ratio of ethylene glycol and hexamethyl tetramine is 4:1, the amount of thiourea is 43 g / L in the impregnation solution, and the amount of ethylene glycol is 19 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-0 by spraying to obtain C-1. C-1 is placed in a sealed container at room temperature for 8 hours, then dried at 120℃ for 2 hours, and finally calcined at 500℃ for 3 hours to obtain CC-1.

[0041] Example 4

[0042] Take 750 g of metakaolin, 132 g of gallium nitrate, 44 g of ammonium fluoride, add 5741 g of distilled water to the above materials and stir for 90 minutes, then transfer the above materials into an autoclave and seal, then heat to 90℃ at a rate of 5℃ / min and keep constant temperature for 4 hours, then heat to 130℃ at a rate of 8℃ / min and keep constant temperature for 3 hours, then filter, wash, then dry the materials at 140℃ for 2 hours, then calcine at 550℃ for 5 hours to obtain gallium and fluorine modified material I (the mass content of gallium is 3.8%, and the mass content of fluorine is 1.0%). Take 251 g of pseudoboehmite (the mass content of alumina is 67.9%), 532 g of material I, 15 g of sesbania powder, 7 g of nitric acid, 5 g of citric acid, 36 g of activated carbon with a particle size of 4 microns, and 462 g of water, then mix and knead to form, then dry at 120℃ for 2 hours, and calcine at 750℃ for 3 hours to obtain catalyst carrier D-0.

[0043] Take 100 g of catalyst carrier D-0, measure its water absorption rate of 0.93, take molybdenum trioxide (containing 99wt% of molybdenum trioxide) 192g, basic nickel carbonate (containing 52wt% of nickel oxide) 101g, phosphoric acid solution (containing 26.7wt% of phosphorus) 52.4g, add clean water after stirring, gradually heat to boiling until all raw materials are dissolved, constant temperature for 60 minutes, then reduce to room temperature for standby. Slowly add a mixture of glycerol and ethanolamine and thiourea to the above solution under stirring, the mass ratio of glycerol and ethanolamine is 6:1, the amount of thiourea is 52g / L in the impregnation solution, the amount of glycerol is 26g / L in the impregnation solution, and the solution is constant volume 93mL for standby. The above impregnation solution is impregnated on the carrier D-0 by spraying to obtain D-1. D-1 is placed in a closed container at room temperature for 8 hours, then dried at 130℃ for 3 hours, and finally calcined at 490℃ for 3 hours to obtain CD-1.

[0044] Example 5

[0045] Take 360g of metakaolin, 88g of gallium nitrate, 36g of ammonium fluoride, add 2520g of distilled water to the above materials and stir for 20 minutes, then transfer the materials into an autoclave and seal, then heat to 110℃ at a rate of 5℃ / min and keep constant temperature for 5 hours, then filter, wash, then dry the materials at 120℃ for 6 hours, then calcine at 600℃ for 5 hours to obtain gallium and fluorine modified material I (mass content of gallium is 3.6%, mass content of fluorine is 1.1%). Take 179g of pseudoboehmite (mass content of alumina is 69.1%), 269g of material I, 9g of sesbania powder, 4.5g of nitric acid, 3g of citric acid, 18g of activated carbon with particle size of 4 microns, and 228g of water, then mix and shape, then dry at 120℃ for 3 hours, then calcine at 700℃ for 4 hours to obtain catalyst carrier E-0.

[0046] Take 100g of catalyst carrier E-0, measure its water absorption rate of 0.9, take molybdenum trioxide (containing 99wt% of molybdenum trioxide) 202g, basic nickel carbonate (containing 52wt% of nickel oxide) 96.2g, phosphoric acid solution (containing 26.7wt% of phosphorus) 52.4g, add clean water after stirring, gradually heat to boiling until all raw materials are dissolved, constant temperature for 40 minutes, then reduce to room temperature for standby to obtain impregnation solution I. Slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above solution under stirring, the mass ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea is 20g / L in the impregnation solution, the amount of pentaerythritol is 16g / L in the impregnation solution, and the solution is constant volume 90mL for standby. The above impregnation solution is impregnated on the carrier E-0 by spraying to obtain E-1. E-1 is placed in a closed container at room temperature for 6 hours, then dried at 120℃ for 4 hours, and finally calcined at 550℃ for 4 hours to obtain CE-1.

[0047] Comparative Example 1

[0048] Comparative hydrogen desulfurization catalyst DCA-1 was prepared by kneading the metakaolin with the pseudo-boehmite and other materials without modification.

[0049] Comparative Example 2

[0050] Comparative hydrogen desulfurization catalyst DCA-2 was prepared by mixing the metakaolin with gallium nitrate and ammonium fluoride without modification and without hydrothermal treatment in an autoclave.

[0051] Comparative Example 3

[0052] Comparative hydrogen desulfurization catalyst DCA-3 was prepared by impregnating the carrier with the conventional impregnation solution I without adding the mixture of pentaerythritol, diethanolamine and thiourea.

[0053] Comparative Example 4

[0054] Comparative hydrogen desulfurization catalyst DCA-4 was prepared by impregnating the carrier with the impregnation solution I containing pentaerythritol and diethanolamine without adding thiourea.

[0055] Comparative Example 5

[0056] Comparative hydrogen desulfurization catalyst DCA-5 was prepared by modifying the metakaolin with gallium only without adding ammonium fluoride, and using the same amounts of other materials and preparation conditions as in Example 1.

[0057] Comparative Example 6

[0058] Comparative hydrogen desulfurization catalyst DCA-6 was prepared by modifying the metakaolin with fluorine only without adding gallium nitrate, and using the same amounts of other materials and preparation conditions as in Example 1.

[0059] Table 1 Compositions and properties of the catalysts obtained in the examples and comparative examples

[0060] Item Example 1 Example 2 Example 3 Example 4 Example 5 Composition MoO3, wt.% 15.2 15.8 15.4 15.6 15.5 NiO, wt% 3.7 3.9 3.8 3.6 3.7 Property Specific surface area, m 2 / g]] 187 185 192 188 181 Pore volume, cm3 / g 3 / g]]> 0.52 0.59 0.57 0.61 0.50 Average pore diameter, nm 11.45 10.66 11.29 13.18 10.09

[0061] Table 1 (continued)

[0062] Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Composition MoO3, wt.% 15.6 15.1 15.9 15.4 15.9 15.2 NiO, wt% 3.5 3.7 3.8 3.4 3.5 3.1 Property Specific surface area, m 2 / g]] 159 147 178 172 168 171 Pore volume, cm3 / g 3 / g]]> 0.39 0.42 0.47 0.41 0.43 0.46 Average pore diameter, nm 7.90 8.40 9.85 9.39 8.20 9.30

[0063] Table 2 Infrared acid properties of the catalysts obtained in the examples and comparative examples

[0064]

[0065]

[0066] Application Example

[0067] The catalysts obtained in the examples and comparative examples were evaluated using the feedstock oils in Table 3, the reaction conditions are shown in Table 3, the evaluation results are shown in Table 4, and the stability evaluation results are shown in Table 5.

[0068] Table 3 Properties of feedstock oils and reaction conditions

[0069] Item Property Feed oil property Density / kg m -3 ]] 970.0 S / wt% 2.2 N / wt% 0.54 Ni + V / μg·g -1 ]]> 72 Reaction condition Reaction temperature / °C 360 Pressure / MPa 15.3 Volume space velocity / h -1 ]] 0.35 Hydrogen / oil volume ratio 550

[0070] Table 4 Evaluation results of the activity of the catalysts obtained in each example

[0071] Removal rate Example 1 Example 2 Example 3 Example 4 Example 5 HDS, % 94.3 94.8 95.4 95.6 92.6 HDN, % 73.6 72.4 72.8 74.1 71.3

[0072] Table 4 (continued)

[0073] Removal rate Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 HDS, % 68.6 73.5 71.2 76.7 72.3 69.2 HDN, % 63.1 63.7 62.8 65.8 64.9 60.3

[0074] Table 5 Evaluation results of the activity and stability of the catalysts in each example and comparative example

[0075] Removal rate Operation time, h Example 1 Example 2 Example 3 Example 4 Example 5 HDS, % 200 94.3 94.8 95.4 95.6 92.6 HDS, % 2000 92.4 90.3 91.2 89.4 88.2 HDN, % 200 73.6 72.4 72.8 74.1 71.3 HDN, % 2000 69.4 65.8 69.4 67.9 63.8

[0076] Table 5 (continued)

[0077] Removal rate Operation time, h Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 HDS, % 200 68.6 73.5 71.2 76.7 72.3 69.2 HDS, % 2000 59.9 60.4 58.7 58.4 55.8 54.4 HDN, % 200 63.1 63.7 62.8 65.8 64.9 60.3 HDN, % Removal rate Operation time, h 2000 45.2 50.4 52.1 54.8 49.2 44.8

[0078] From the evaluation results of the catalysts in Table 4 and Table 5, the desulfurization and denitrification performance of the catalyst prepared by the method provided in the present application is better than that of the catalyst in the comparative example.

Claims

1. A residue hydrodesulfurization catalyst comprising a carrier and an active metal component, wherein the carrier comprises a gallium and fluorine modified metakaolin and alumina, the mass ratio of which is 15-30:7-13, the mass content of gallium in the gallium and fluorine modified metakaolin is 2.0%-5.0%, and the mass content of fluorine is 0.8%-1.5%; the active metal component comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB; the mass content of the carrier is 75%-85% based on the mass of the catalyst, the content of Group VIII in terms of oxides is 2%-6%, and the content of Group VIB metal in terms of oxides is 10%-20%; the properties of the catalyst are as follows: the specific surface area is 180-220 m2 / g, the pore volume is 0.5-0.7 mL / g, and the average pore diameter is 10.0-30.0 nm. 2 ​ The preparation method of the catalyst comprises: (1) mixing metakaolin, gallium nitrate, ammonium fluoride and water, sealing and hydrothermal treatment, drying, and calcining to obtain a modified material; (2) mixing and kneading the modified material obtained in step (1), pseudo-boehmite, a glue adhesive, a extrusion aid, a pore-expanding agent and water, drying, and calcining to obtain a catalyst carrier; (3) preparing an impregnation solution containing an amine, an alcohol, thiourea and an active metal; (4) impregnating the catalyst carrier obtained in step (2) with the impregnation solution obtained in step (3), drying and calcining to obtain a hydrodesulfurization catalyst. In step (3), the mass ratio of the alcohol compound to the amine compound is 1:1-16:1; the amount of thiourea added is such that the concentration of thiourea in the impregnation solution is 5-70 g / L, and the concentration of the alcohol compound in the impregnation solution obtained in step (3) is 5-60 g / L.

2. The catalyst according to claim 1, characterized in that, The Group VIII metal is nickel and / or cobalt, and the Group VIB metal is molybdenum and / or tungsten.

3. The preparation method of the residual oil hydrodesulfurization catalyst according to any one of claims 1-2, comprising: (1) mixing metakaolin, gallium nitrate, ammonium fluoride and water, sealing and hydrothermal treatment, drying, and calcining to obtain a modified material; (2) mixing and kneading the modified material obtained in step (1), pseudo-boehmite, a glue adhesive, a extrusion aid, a pore-expanding agent and water, drying, and calcining to obtain a catalyst carrier; (3) preparing an impregnation solution containing an amine, an alcohol, thiourea and an active metal; (4) impregnating the catalyst carrier obtained in step (2) with the impregnation solution obtained in step (3), drying and calcining to obtain a hydrodesulfurization catalyst. In step (3), the mass ratio of the alcohol compound to the amine compound is 1:1-16:1; the amount of thiourea added is such that the concentration of thiourea in the impregnation solution is 5-70 g / L, and the concentration of the alcohol compound in the impregnation solution obtained in step (3) is 5-60 g / L.

4. The production method according to claim 3, characterized by, In step (1), the mass ratio of the gallium nitrate to the ammonium fluoride is 1-10:1, and the total mass of the gallium nitrate and the ammonium fluoride accounts for 5%-60% of the mass of the metakaolin; and / or, in step (1), the amount of water added is such that the mass ratio of water to the sum of the metakaolin, the gallium nitrate and the ammonium fluoride is 5:1-10:

1.

5. The preparation method according to claim 4, characterized in that, The total mass of the gallium nitrate and the ammonium fluoride accounts for 15%-40% of the mass of the metakaolin.

6. The preparation method according to claim 3, characterized in that, In step (1), the sealing and hydrothermal treatment is performed under the following conditions: the hydrothermal treatment temperature is 80-130℃, and the hydrothermal treatment time is 3-10 hours.

7. The preparation method according to claim 6, characterized in that, The hydrothermal treatment is performed in two stages, and the temperature of the second stage is at least 20℃ higher than that of the first stage.

8. The preparation method according to claim 7, characterized in that, The temperature of the second stage is 30℃ higher than that of the first stage.

9. The preparation method according to claim 3, characterized in that, In step (1), the drying temperature is 120-160℃, the drying time is 2-6 hours, the calcining temperature is 550-700℃, and the calcining time is 4-6 hours; and / or, in step (2), the drying temperature is 120-160℃, the drying time is 2-6 hours, the calcining temperature is 550-750℃, and the calcining time is 2-6 hours.

10. The method of claim 3, wherein, In step (2), the amount of the pore-expanding agent added is 4wt%-13wt% of the total mass of the pseudo-boehmite calculated as alumina and the modified material.

11. The method of claim 5, wherein, The alcohol compound in step (3) is one or more of pentaerythritol, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol, and neopentyl glycol; the amine compound is one or more of hexamethylenetetramine, ethylenediamine, ethanolamine, diethanolamine, and triethanolamine; the amount of thiourea added is such that the concentration of thiourea in the impregnating solution is 8-50 g / L; and the concentration of the alcohol compound in the impregnating solution in step (3) is 7-30 g / L.

12. The method of claim 3, wherein, In step (4), the impregnation is performed by spraying, and the impregnation is performed by equal-volume impregnation or supersaturation impregnation; after impregnation, the sample is placed in a closed condition at room temperature for 6-12 hours and then dried; and / or, in step (4), the drying condition is constant temperature at 100-160°C for 1-8 hours; and the calcination condition is constant temperature at 450-650°C for 2-7 hours.

13. The method of claim 12, wherein, In step (4), the calcination condition is constant temperature at 480-600°C for 2-7 hours.

14. Use of the catalyst of any one of claims 1-2 or the catalyst prepared by the method of any one of claims 3-13 in residue hydroprocessing.

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