Residue hydrodenitrogenation catalyst, method for preparing the same and use thereof

Abstract

The present application provides a residue hydrodenitrogenation catalyst, a preparation method and application thereof. The catalyst comprises a carrier and an active metal component, the carrier comprises modified Y molecular sieve and alumina, the modified Y molecular sieve is small crystal grain mesoporous modified Y molecular sieve, and the properties are as follows: the crystal grain size is 500 nm or less, the molar ratio of silicon oxide to alumina is 8-55, the specific surface area is 640-800 m 2 / g, the cell parameter is 2.433-2.460 nm, and the average pore size is 10-30 nm. The catalyst is used in a residue hydrodenitrogenation process, and can improve the denitrogenation activity and stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of catalyst preparation, and particularly relates to a residue oil hydrodenitrogenation 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. Residue oil hydroprocessing technology is mainly used to provide feedstock for catalytic cracking process. The increase of nitrogen compounds and residual carbon value in residue oil feedstock will cause the decrease of catalyst activity of downstream catalytic cracking device, and the product distribution will also be poor, so it is necessary to develop a higher activity hydrodenitrogenation catalyst to improve the residue oil hydrodenitrogenation rate and the residual carbon removal rate.

[0003] Due to the limitation of the properties of the existing residue oil hydrodenitrogenation catalyst, the residue oil hydrodenitrogenation catalyst generally only has good denitrification function, but the metal removal function is weak, and only the outer surface of the catalyst can be used for metal removal reaction, and the metal precipitates are precipitated in the voids. Therefore, when denitrification is carried out, the metal removal agent must remove as much metal as possible to make the metal content as low as possible when entering the hydrodenitrogenation catalyst bed, so that the hydrodenitrogenation catalyst can operate for a long period.

[0004] CN1098433A discloses a preparation method of a hydrofining catalyst. In the method, powdery basic nickel carbonate is mixed in the extrusion process of one water aluminum oxide to provide the required Ni content of the catalyst, and a small amount of powdery industrial ammonium molybdate is mixed in, and then a molybdenum ammonia water solution is impregnated once to prepare the final catalyst. The catalyst prepared by the method has high hydrodenitrogenation performance, but the pore is too small to facilitate the diffusion of macromolecules, and the metal cannot be precipitated in the pore. CN1257103A discloses a preparation method of a hydroprocessing catalyst. In the method, the mixing process of one water aluminum hydroxide and metal salts and other materials is optimized to promote metal dispersion. After all the materials are mixed into a plastic body, they are extruded into a catalyst through steam-air high temperature activation. The catalyst prepared by the method has too small pores, and cannot prepare a dual functional catalyst with both denitrification performance and high metal impurity capacity. SUMMARY

[0005] In view of the shortcomings of the prior art, the present application provides a residue oil hydrodenitrogenation catalyst and a preparation method and application thereof. The hydrodenitrogenation catalyst prepared by the method has good macromolecular diffusion performance, strong denitrification capacity, strong metal capacity and good anti-carbon deposition performance. The hydrodenitrogenation catalyst is particularly suitable for use in residue oil hydrodenitrogenation treatment process, and has good metal removal and denitrification activity and good activity stability.

[0006] The first aspect of the present application provides a hydrodenitrogenation catalyst, comprising a carrier and an active metal component, wherein the carrier comprises a modified Y molecular sieve and alumina, and the modified Y molecular sieve is a small crystal mesoporous modified Y molecular sieve with the following properties: a crystal size of 500 nm or less, preferably 300-500 nm, a molar ratio of silicon oxide to alumina of 8-55, a specific surface area of 640-800 m 2 / g, a cell parameter of 2.433-2.460 nm, and an average pore size of 10-30 nm.

[0007] In the present application, the sodium content in the modified Y molecular sieve is 1 wt% or less.

[0008] 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.

[0009] In the present application, the mass content of the carrier is 74-85% based on the mass of the catalyst, the content of the Group VIII metal in terms of oxides is 2-6%, and the content of the Group VIB metal in terms of oxides is 15-24%.

[0010] In the present application, the content of the modified Y molecular sieve is 40-70% based on the mass of the carrier, and the content of the alumina is 14-40%.

[0011] In the present application, the catalyst has the following properties: a specific surface area of 190-250 m 2 / g, a pore volume of 0.4-0.6 mL / g, and an average pore size of 10-20 nm.

[0012] The second aspect of the present application provides a preparation method of the above-mentioned hydrodenitrogenation catalyst, comprising the following steps:

[0013] (1) NaY molecular sieve is subjected to ammonium ion exchange, filtration and washing to obtain NH4Y molecular sieve filter cake;

[0014] (2) The NH4Y molecular sieve filter cake obtained in step (1) is mixed with an organic acid, a water-soluble polymer and water, and then subjected to hydrothermal treatment to obtain a modified Y molecular sieve;

[0015] (3) The modified Y molecular sieve obtained in step (2), pseudoboehmite, a glue adhesive, a extrusion aid, a pore-expanding agent and water are mixed and kneaded into a shape, dried, and calcined to obtain a catalyst carrier;

[0016] (4) The catalyst carrier obtained in step (3) is immersed in a gallium nitrate solution, dried, and then subjected to high-temperature steam treatment to obtain a catalyst carrier;

[0017] (5) preparing an impregnation solution containing amines, alcohols and thiourea and active metals;

[0018] (6) impregnating the catalyst carrier obtained in step (4) with the impregnation solution obtained in step (5), drying and calcining to obtain a hydrodenitrogenation catalyst.

[0019] In the method of the present application, the NaY zeolite in step (1) has the following properties: the molar ratio of silicon oxide to aluminum oxide is 3-7:1, and the sodium content is 6wt%-12wt%.

[0020] In the method of the present application, the ammonium ion exchange of the NaY zeolite in step (1) can be carried out by a conventional method, i.e. mixing the NaY zeolite with an ammonium salt solution, beating the slurry, adjusting the pH value of the slurry (the pH value can be adjusted by at least one of nitric acid or hydrochloric acid), carrying out ammonium ion exchange, filtering and washing to obtain a NH4Y zeolite filter cake. The mass ratio of the NaY zeolite, water and ammonium salt is 1:6-25:0.2-0.4, the pH value of the slurry is adjusted to 3-4, the ammonium ion exchange temperature is adjusted to 70-90℃, the ammonium ion exchange time is 2-4 hours, and the ammonium ion exchange is carried out for 1-3 times. The ammonium salt can be one or more of ammonium chloride, ammonium nitrate, ammonium sulfate and ammonium phosphate.

[0021] In the method of the present application, the filtering and washing in step (1) can be carried out by a conventional method, and the washing can be carried out by deionized water.

[0022] In the method of the present application, the organic acid in step (2) is at least one of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid and malic acid. The water-soluble polymer is at least one of polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone and water-soluble polysaccharide (such as methyl cellulose). The weight average molecular weight of the water-soluble polymer is 10000-40000.

[0023] In the method of the present application, the mass ratio of the NH4Y zeolite, the organic acid, the water-soluble polymer and water in step (2) is 1:0.01-0.05:0.05-0.25:15-40, based on the NaY zeolite in step (1).

[0024] In the method of the present application, the hydrothermal treatment in step (2) is carried out under the following conditions: the temperature is 100-150℃, and the treatment time is 5-12 hours. Preferably, the temperature increasing rate is 8-15℃ / min. Preferably, the hydrothermal treatment is carried out by two-stage hydrothermal treatment, and the temperature of the second stage is at least 15℃ higher than that of the first stage, preferably at least 20℃ higher. The hydrothermal treatment is generally carried out in a sealed high-pressure reaction kettle under autogenous pressure. After the hydrothermal treatment in step (2), drying is carried out, and the drying conditions are as follows: the drying temperature is 100-160℃, and the drying time is 3-8 hours.

[0025] In the method, the mass ratio of the pseudo-boehmite to the modified Y molecular sieve is 7-13:15-30. The adhesive can be at least one of nitric acid, acetic acid and citric acid, the extrusion aid can be a kind of Euphorbia, and the pore-expanding agent can be one or more of graphite, activated carbon, wood chips or cellulose. The adhesive, the extrusion aid and water are added according to the actual molding needs, and the application does not have a special requirement. The pore-expanding agent is added in an amount of 2wt%-10wt% of the total mass of the pseudo-boehmite and the modified Y molecular sieve.

[0026] In the method, the molding can be performed by using a conventional molding method, such as extrusion molding or tablet molding.

[0027] In the method, the drying temperature in step (3) is 120-160°C, the drying time is 3-6 hours, the calcination temperature is 550-700°C, and the calcination time is 2-6 hours.

[0028] In the method, the concentration of the gallium nitrate solution in step (4) is 0.5-2.5 mol / L. The immersion method in step (4) is saturated immersion or unsaturated immersion. The high-temperature water vapor treatment is performed under the following conditions: temperature of 500-700°C and time of 60-90 min.

[0029] In the method, the phosphoric acid can be added to the immersion solution in step (5).

[0030] In the method, the alcohol compound in step (5) is one or more of pentaerythritol, ethylene glycol, glycerol, 1,2-propanediol, 1,4-butanediol and neopentyl glycol; and 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. The thiourea is added in an amount such that the concentration of the thiourea in the immersion solution is 5-70 g / L, preferably 8-50 g / L. In the immersion solution in step (5), the concentration of the alcohol compound is 2-60 g / L, preferably 7-30 g / L.

[0031] In the method of the present application, the active metal in step (5) comprises at least one metal component selected from Group VIII and at least one metal component selected from Group VIB. The metal component of Group VIII is preferably nickel and / or cobalt, and the metal component of Group VIB is preferably molybdenum and / or tungsten. In the impregnation solution in step (5), the content of the metal component of Group VIB is 150-450 g / L, preferably 300-400 g / L, the content of the metal component of Group VIII is 10-120 g / L, preferably 40-60 g / L, and the concentration of phosphorus is 20-80 g / L, preferably 40-60 g / L. The source of molybdenum is one or more of molybdenum trioxide, molybdate and paramolybdate, preferably molybdenum trioxide; the source of tungsten is tungstate or tungsten oxide, preferably ammonium metatungstate; the source of nickel is one or more of nickel nitrate, nickel acetate, basic nickel carbonate and nickel chloride, preferably basic nickel carbonate; the source of cobalt is 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.

[0032] In the method of the present application, the impregnation in step (6) is preferably carried out by spraying impregnation, 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 (6), the drying condition is constant temperature at 100-160℃ for 1-8 hours; the calcination condition is constant temperature at 450-650℃ for 3-7 hours, preferably constant temperature at 480-600℃ for 4-7 hours.

[0033] The third aspect of the present application provides the use of the above-mentioned residue hydrodenitrogenation catalyst in residue hydroprocessing.

[0034] Compared with the prior art, the present application has the following advantages:

[0035] 1. The hydrodenitrogenation catalyst of the present application comprises a carrier and an active metal component, wherein the carrier comprises alumina and modified Y molecular sieve. The catalyst of the present application is suitable for the hydroconversion of nitrogen compounds in asphaltene in the process of residue hydroprocessing, and has high hydrodenitrogenation activity and good stability.

[0036] 2. In the preparation process of the hydrodenitrogenation catalyst of the present application, the NH4Y molecular sieve filter cake is first subjected to hydrothermal treatment in the presence of an organic acid and a water-soluble polymer. The hydrothermal treatment removes non-framework aluminum and improves the silica-alumina ratio, and improves the pore distribution state. The catalyst carrier is impregnated in a gallium nitrate solution and then subjected to high-temperature steam treatment, so that Ga species is anchored in the carrier material to form Si-O-Ga bonds. The Ga species effectively prevents the formation of strong Mo(W)-O-Al bonds, thereby weakening the acid adjustment and interaction between the active metal and the carrier, and facilitating the hydrodenitrogenation catalyst to have a suitable pore structure, acid amount and acid distribution.

[0037] 3、The hydrodenitrogenation catalyst of the present application is prepared by using impregnation solution containing amine, alcohol and thiourea and active metal, so that the Group VIII metal ions form complex and the Group VIB metal forms phosphomolybdic (tungstic) acid structure, and the adsorption heat generated during the contact of solution and carrier surface in the impregnation process is reduced, the interaction between active metal and alumina is reduced, the catalyst has suitable acid strength distribution, better pore size distribution, stronger anti-carbon deposition performance and other characteristics, and is particularly suitable for use as a residue hydrodenitrogenation catalyst, which is beneficial to improve the hydrodenitrogenation activity and stability and metal capacity. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be described in detail below in combination with examples.

[0039] 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 of Nicot, USA. The determination method is as follows: 20 mg of sample with particle size less than 200 mesh is pressed into a thin sheet 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 hanging cup of the instrument, 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, so that the acid amount of total infrared acid, B acid and L acid can be obtained. Then, the temperature is raised to 250℃, 350℃ and 450℃ in turn, and each is kept for 1 hour, so that the acid amount of corresponding infrared acid, B acid and L acid is obtained. The absorption peak near 1450cm -1 is L acid, and the absorption peak near 1540cm -1 is B acid.

[0040] In the present application, the specific surface area, pore volume and pore distribution are determined by using the full-automatic physical adsorption instrument ASAP2420 of Micromeritics Corporation, USA. The determination method is as follows: after the sample is treated at 300℃ and 0.1MPa for 4h, liquid N2 is used as 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.

[0041] Example 1

[0042] Take 100 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 6:1, sodium content is 7 wt%), 20 g ammonium chloride and 800 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with hydrochloric acid, ion exchange is carried out at 90℃ for 2 hours, ammonium ion exchange is 2 times, then filtration and washing are carried out, and NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 3 g citric acid, 20 g polyvinyl alcohol (molecular weight is 25000) and 1500 g deionized water are stirred uniformly, the above-mentioned materials are transferred into an autoclave, and hydrothermal treatment is carried out; after being sealed, the temperature is increased to 100℃ at a speed of 15℃ / min, then constant temperature is kept for 3 hours, then the temperature is increased to 140℃ at a speed of 10℃ / min, constant temperature is kept for 6 hours, filtration and washing are carried out, then the materials are dried at 120℃ for 6 hours, and modified molecular sieve is obtained.

[0043] Take 179 g pseudo-boehmite (alumina mass content is 69.2%), 269 g modified molecular sieve, 9 g sesbania powder, 4.5 g nitric acid, 3 g citric acid, 12 g activated carbon with a particle size of 4 microns, and 178 g water are mixed and kneaded into a shape, then dried at 120℃ for 3 hours and calcined at 550℃ for 3 hours, and catalyst carrier A-0 is obtained. The obtained carrier A-0 is saturatedly immersed in a 1.5 mol / L gallium nitrate solution under the condition of 100% water vapor at 550℃ for 90 min, and catalyst carrier A-1 is obtained.

[0044] Take 100 g catalyst carrier A-1, and measure the water absorption rate to be 0.9. Take 202 g molybdenum trioxide (containing 99 wt% molybdenum oxide), 96.2 g basic nickel carbonate (containing 52 wt% nickel oxide), 52.4 g phosphoric acid solution (containing 26.7 wt% phosphorus), add clean water, stir, gradually heat to boiling until the raw materials are completely dissolved, keep constant temperature for 40 min, then reduce to room temperature for standby, and obtain impregnation solution I. In a stirring state, slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above-mentioned solution, the ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea is added so that the concentration in the impregnation solution is 20 g / L, and the amount of pentaerythritol is added so that the concentration in the impregnation solution is 16 g / L, and the solution is constant volume 90 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier A-1 in a spraying mode to obtain A-2. A-2 is placed in a closed container at room temperature for 6 hours, then dried at 120℃ for 4 hours, and finally calcined at 500℃ for 4 hours to obtain CA-2.

[0045] Example 2

[0046] Take 200 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 4:1, sodium content is 11 wt%), 40 g ammonium chloride and 1400 g deionized water are mixed, beaten, the slurry pH is adjusted to about 4 with nitric acid, ion exchange is carried out at 85°C for 3 hours, ammonium ion exchange is carried out twice, then filtration and washing are carried out, and NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 6 g citric acid, 20 g methyl cellulose (molecular weight is 20000) and 4000 g deionized water are stirred uniformly, and the above-mentioned materials are transferred into an autoclave for hydrothermal treatment, after being sealed, the temperature is increased to 110°C at a rate of 10°C / min, then constant temperature is maintained for 2.5 hours, then the temperature is increased to 130°C at a rate of 10°C / min, constant temperature is maintained for 6 hours, filtration and washing are carried out, then the materials are dried at 120°C for 4 hours to obtain modified molecular sieve.

[0047] Take 147 g pseudoboehmite (alumina mass content is 68.7%), 359 g modified molecular sieve, 12 g sesbania powder, 6 g nitric acid, 4 g citric acid, 22 g activated carbon with a particle size of 4 microns, 258 g water are mixed and kneaded into a shape, then dried at 140°C for 3 hours and calcined at 550°C for 3 hours to obtain catalyst carrier B-0. The obtained carrier A-0 is saturatedly immersed in a 2.0 mol / L gallium nitrate solution under the condition of 100% water vapor at 550°C for 70 min to obtain catalyst carrier B-1.

[0048] Take 100 g catalyst carrier B-1, measure its water absorption rate, which is 0.88, take 183 g molybdenum trioxide (containing 99 wt% molybdenum oxide), 96.2 g basic nickel carbonate (containing 52 wt% nickel oxide), 59.9 g phosphoric acid solution (containing 26.7 wt% phosphorus), add clean water, stir and gradually heat to boiling until the raw materials are completely dissolved, then reduce the temperature to room temperature after constant temperature for 60 min for standby. In a stirring state, slowly add a mixture of 1,4-butanediol and diethanolamine and thiourea to the above-mentioned solution, the ratio of 1,4-butanediol and diethanolamine is 5:1, the amount of thiourea is added so that its concentration in the impregnation solution is 33 g / L, the amount of 1,4-butanediol is added so that its concentration in the impregnation solution is 22 g / L, and the solution is constant volume to 88 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier B-1 by spraying to obtain B-2. B-2 is placed in a closed container at room temperature for 8 hours, then dried at 120°C for 4 hours, and finally calcined at 490°C for 4 hours to obtain CB-2.

[0049] Example 3

[0050] Take 152 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 5:1, sodium content is 7 wt%), 46 g ammonium chloride and 1672 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with nitric acid, ion exchange is carried out at 90℃ for 3 hours, ammonium ion exchange is 2 times, then filtration and washing are carried out, and an NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 5 g adipic acid, 17 g polyvinylpyrrolidone (molecular weight is 30000), 3200 g deionized water are added to the above-mentioned material and stirred uniformly, the above-mentioned material is transferred into an autoclave for hydrothermal treatment, after sealing, the temperature is increased to 110℃ at a rate of 10℃ / min, then constant temperature is kept for 4 hours, then the temperature is increased to 130℃ at a rate of 10℃ / min, constant temperature is kept for 6 hours, filtration and washing are carried out, and then the material is dried at 130℃ for 4 hours to obtain a modified molecular sieve.

[0051] Take 251 g pseudoboehmite (alumina mass content is 69%), 532 g modified molecular sieve, 9 g sesbania powder, 4.5 g nitric acid, 3 g citric acid, 17 g activated carbon with a particle size of 4 microns, 328 g water are mixed and kneaded into a shape, then dried at 130℃ for 4 hours and calcined at 650℃ for 3 hours to obtain a catalyst carrier C-0. The obtained carrier C-0 is saturatedly impregnated with a 1.7 mol / L gallium nitrate solution under the condition of 100% water vapor and 600℃ for 60 min to obtain a catalyst carrier C-1.

[0052] Take 100 g of the catalyst carrier C-1, and measure the water absorption rate to be 0.9. Take 202 g of molybdenum trioxide (containing 99 wt% of molybdenum oxide), 96.2 g of basic nickel carbonate (containing 52 wt% of nickel oxide), and 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus), add clean water, stir and gradually heat to boiling until the raw materials are completely dissolved, then reduce the temperature to room temperature after constant temperature for 40 minutes. In a stirred state, slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above-mentioned solution, the ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea is added to make its concentration in the impregnation solution be 20 g / L, and the amount of pentaerythritol is added to make its concentration in the impregnation solution be 19 g / L, and the solution is constant volume to 90 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier C-1 by spraying to obtain C-2. The C-2 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 CC-2.

[0053] Example 4

[0054] Take 100 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 7:1, sodium content is 10 wt%), 25 g ammonium chloride and 800 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with hydrochloric acid, ion exchange is carried out at 90°C for 2 hours, the number of ammonium ion exchange is 3 times, then filtration and washing are carried out, and an NH4Y molecular sieve filter cake is obtained; the obtained NH4Y molecular sieve filter cake, 3 g citric acid, 20 g methyl cellulose (molecular weight is 20000) and 1500 g deionized water are stirred uniformly, and the above-mentioned materials are transferred into an autoclave for hydrothermal treatment, after sealing, the temperature is increased to 100°C at a rate of 15°C / min, then the temperature is kept constant for 3 hours, then the temperature is increased to 140°C at a rate of 10°C / min, and the temperature is kept constant for 6 hours, then filtration and washing are carried out, and then the materials are dried at 120°C for 6 hours to obtain a modified molecular sieve.

[0055] Take 224 g pseudo-boehmite (alumina mass content is 67.8%), 538 g modified molecular sieve, 15 g sesbania powder, 7 g nitric acid, 5 g citric acid, 36 g activated carbon with a particle size of 4 microns, and 462 g water are mixed and kneaded into a shape, then dried at 120°C for 3 hours and calcined at 550°C for 3 hours to obtain a catalyst carrier D-0. The obtained carrier D-0 is saturatedly immersed in a 1.5 mol / L gallium nitrate solution under the condition of 100% water vapor and 600°C for 80 min to obtain a catalyst carrier D-1.

[0056] Take 100 g of the catalyst carrier D-1, and measure the water absorption rate to be 0.93. Take 192 g of molybdenum trioxide (containing 99 wt% of molybdenum oxide), 102 g of basic nickel carbonate (containing 52 wt% of nickel oxide), and 52.4 g of phosphoric acid solution (containing 26.7 wt% of phosphorus), add clean water, stir and gradually heat to boiling until the raw materials are completely dissolved, then keep the temperature constant for 70 min, and then reduce the temperature to room temperature for standby. In a stirred state, slowly add a mixture of neopentyl glycol and hexamethylenetetramine and thiourea to the above-mentioned solution, the ratio of neopentyl glycol and hexamethylenetetramine is 4:1, the amount of thiourea is added so that its concentration in the impregnation solution is 39 g / L, and the amount of neopentyl glycol is added so that its concentration in the impregnation solution is 27 g / L, and the solution is made up to 93 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier D-1 by spraying to obtain D-2. After placing D-2 in a closed container at room temperature for 6 hours, drying at 120°C for 4 hours, and finally calcining at 495°C for 4 hours, CD-2 is obtained.

[0057] Example 5

[0058] Take 100 g NaY molecular sieve (properties as follows: molar ratio of silicon oxide to aluminum oxide is 6:1, sodium content is 7 wt%), 20 g ammonium chloride and 800 g deionized water are mixed, beaten, the slurry pH is adjusted to about 3.5 with hydrochloric acid, ion exchange is carried out at 90℃ for 2 hours, the ammonium ion exchange times is 2, then filtered and washed to obtain NH4Y molecular sieve filter cake; the obtained NH4Y molecular sieve filter cake, 3 g citric acid, 20 g polyvinyl alcohol (molecular weight is 25000) are added to 1500 g deionized water and stirred uniformly, and the above-mentioned materials are transferred into an autoclave for hydrothermal treatment, the temperature is raised to 140℃ at a rate of 10℃ / min and kept constant for 6 hours, then filtered, washed, and then the materials are dried at 120℃ for 6 hours to obtain modified molecular sieve.

[0059] Take 179 g pseudoboehmite (alumina mass content is 69.2%), 269 g modified molecular sieve, 9 g sesbania powder, 4.5 g nitric acid, 3 g citric acid, 12 g activated carbon with a particle size of 4 microns, and 178 g water are mixed and kneaded into a shape, then dried at 120℃ for 3 hours and calcined at 550℃ for 3 hours to obtain catalyst carrier E-0. The obtained carrier E-0 is saturatedly immersed in a 1.5 mol / L gallium nitrate solution under the condition of 100% water vapor at 550℃ for 90 min to obtain catalyst carrier E-1.

[0060] Take 100 g catalyst carrier E-1, and measure its water absorption rate to be 0.9. Take 202 g molybdenum trioxide (containing 99 wt% molybdenum oxide), 96.2 g basic nickel carbonate (containing 52 wt% nickel oxide), and 52.4 g phosphoric acid solution (containing 26.7 wt% phosphorus), add clean water, stir, gradually heat to boiling until the raw materials are completely dissolved, keep constant temperature for 40 min, then reduce to room temperature for standby, to obtain impregnation solution I. In a stirred state, slowly add a mixture of pentaerythritol and diethanolamine and thiourea to the above-mentioned solution, the ratio of pentaerythritol and diethanolamine is 3:1, the amount of thiourea is added so that its concentration in the impregnation solution is 20 g / L, and the amount of pentaerythritol is added so that its concentration in the impregnation solution is 16 g / L, and the solution is made up to 90 mL for standby. The above-mentioned impregnation solution is impregnated on the carrier E-1 by spraying to obtain E-2. E-2 is placed in a closed container at room temperature for 6 hours, then dried at 120℃ for 4 hours, and finally calcined at 500℃ for 4 hours to obtain CE-2.

[0061] Comparative Example 1

[0062] Compared with Example 1, only the NH4Y molecular sieve is not modified by adding organic acid and water-soluble polymer, and is directly mixed and kneaded with pseudoboehmite to prepare the carrier, and the comparative hydrogen denitrification catalyst DCA-1 is prepared.

[0063] Comparative Example 2

[0064] Comparative hydrogenation denitrification catalyst DCA-2 was prepared by the same method as in Example 1 except that the catalyst carrier was not impregnated in gallium nitrate solution and treated by high-temperature steam.

[0065] Comparative Example 3

[0066] Comparative hydrogenation denitrification catalyst DCA-3 was prepared by the same method as in Example 1 except that the mixture of pentaerythritol and diethanolamine and thiourea was not added in the preparation of the impregnation solution, and the conventional impregnation solution I was used to impregnate the carrier.

[0067] Comparative Example 4

[0068] Comparative hydrogenation denitrification catalyst DCA-4 was prepared by the same method as in Example 1 except that thiourea was not added in the preparation of the impregnation solution, and the impregnation solution I containing pentaerythritol and diethanolamine was used to impregnate the carrier.

[0069] Properties of modified Y molecular sieves in each example and comparative example in Table 1

[0070] Properties Example 1 Example 2 Example 3 Example 4 Example 5 Crystal particle size, nm 463 436 391 401 495 molar ratio of SiO2 / Al2O3 25 19 31 37 10 Specific surface area, m 2 / g]] 705 668 683 711 643 Cell parameter, nm 2.442 2.453 2.449 2.452 2.435 Average pore size, nm 12.5 11.9 11.1 12.4 10.3

[0071] Continued Table 1

[0072] Properties Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Crystal particle size, nm 658 461 472 456 molar ratio of SiO2 / Al2O3 7 21 23 24 Specific surface area, m 2 / g]] 382 598 630 625 Cell parameter, nm 2.128 2.448 2.446 2.444 Average pore size, nm 8.2 10.8 10.9 12.2

[0073] Catalyst composition and properties in each example and comparative example in Table 2

[0074] Item Example 1 Example 2 Example 3 Example 4 Example 5 Composition MoO3, wt.% 18.2 18.8 18.4 18.4 18.5 NiO, wt% 4.7 4.9 4.8 4.8 4.6 Properties Specific surface area, m 2 / g]] 215 207 232 197 194 Pore volume, cm3 / g 3 / g]]> 0.52 0.59 0.47 0.55 0.57 Average pore size, nm 11.9 12.2 13.7 11.3 11.9

[0075] Continued Table 2

[0076] Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Composition MoO3, wt.% 18.6 18.1 18.9 18.8 NiO, wt% 4.5 4.7 4.8 4.6 Properties Specific surface area, m 2 / g]] 157 168 195 189 Pore volume, cm3 / g 3 / g]]> 0.33 0.43 0.47 0.44 Average pore size, nm 7.9 9.7 9.6 10.1

[0077] Infrared acid properties of catalysts in each example and comparative example in Table 3

[0078]

[0079]

[0080] Application Example

[0081] The catalysts obtained in the examples and comparative examples were evaluated by using the feedstock oils in Table 4, and the reaction conditions are shown in Table 4, the evaluation results are shown in Table 5, and the stability evaluation results are shown in Table 6.

[0082] Properties of feedstock oils and reaction conditions in Table 4

[0083] Item Properties Feed oil properties Density / kg m -3 ]] 970.0 S / wt% 2.2 [Ni + V] / μg·g -1 ]] 72 N / wt% 0.54 Reaction conditions Reaction temperature / °C 360 Pressure / MPa 15.3 Volume space velocity / h -1 ]] 0.35 Hydrogen / oil volume ratio 550

[0084] Evaluation results of activities of catalysts in Table 5

[0085] Removal rate Example 1 Example 2 Example 3 Example 4 Example 5 HDS, % 94.0 92.8 95.2 96.1 91.4 HDN, % 96.7 97.4 98.1 97.1 95.1

[0086] Table 5 (Continued)

[0087]

[0088]

[0089] Table 6 Catalyst activity and stability evaluation results in each example and comparative example

[0090] Removal rate Operation time, h Example 1 Example 2 Example 3 Example 4 Example 5 HDS, % 200 94.0 92.8 95.2 96.1 91.4 HDS, % 2000 91.6 90.3 92.1 92.4 89.3 HDN, % 200 96.7 97.4 98.1 97.1 95.1 HDN, % 2000 93.2 94.6 95.8 95.3 91.2

[0091] Table 6 (Continued)

[0092] Removal rate Operation time, h Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 HDS, % 200 66.7 69.5 71.2 72.2 HDS, % 2000 44.4 46.4 54.7 51.4 HDN, % 200 75.8 77.7 82.8 81.1 HDN, % Removal rate Operation time, h 2000 50.4 52.4 62.1 64.8

[0093] From the catalyst evaluation results in Table 5 and Table 6, the desulfurization and denitrification performance of the catalyst prepared by the method provided in the present application is better than that of the comparative catalyst.

Claims

1. A hydrodenitrification catalyst, comprising a support and an active metal component, wherein the support comprises a modified Y molecular sieve and alumina, and the modified Y molecular sieve is a small-crystal mesoporous modified Y molecular sieve with the following properties: crystal particle size below 500 nm, molar ratio of silica to alumina of 8-55, and specific surface area of ​​640-800 m². 2 The catalyst has a cell parameter of 2.433–2.460 nm and an average pore size of 10–30 nm. The active metal component comprises at least one metal selected from Group VIII and at least one metal selected from Group VIB. Based on the mass of the catalyst, the support contains 74%–85% by mass, the Group VIII metal content (based on oxides) is 2%–6%, and the Group VIB metal content (based on oxides) is 15%–24%. Based on the mass of the support, the modified Y molecular sieve content is 40%–70%, and the alumina content is 14%–40%. The catalyst has the following properties: specific surface area of ​​190–250 m² / g. 2 / g, pore volume is 0.4~0.6mL / g, and average pore size is 10~20nm; The preparation method of the hydrodenitrogenation catalyst comprises the following steps: (1) NaY molecular sieve is exchanged by ammonium ions, filtered and washed to obtain NH4Y molecular sieve filter cake; (2) The NH4Y molecular sieve filter cake obtained in step (1) is mixed with an organic acid, a water-soluble polymer and water, and then subjected to hydrothermal treatment to obtain modified Y molecular sieve; (3) The modified Y molecular sieve obtained in step (2), pseudo-boehmite, a glue adhesive, a extrusion aid, a hole expanding agent and water are mixed and kneaded into a shape, dried, calcined to obtain a catalyst carrier; (4) The catalyst carrier obtained in step (3) is immersed in a gallium nitrate solution, dried and then subjected to high-temperature steam treatment to obtain a catalyst carrier; (5) An impregnation solution containing amine, alcohol and thiourea and active metal is prepared; (6) The catalyst carrier obtained in step (4) is impregnated with the impregnation solution obtained in step (5), dried and calcined to obtain a hydrodenitrogenation catalyst; The water-soluble polymer in step (2) is at least one selected from polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone and water-soluble polysaccharide with a weight average molecular weight of 10,000-40,000; the mass ratio of NH4Y molecular sieve: organic acid: water-soluble polymer: water in step (2) is 1: 0.01-0.05: 0.05-0.25: 15-40; The mass ratio of alcohol compound and amine compound in step (5) 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 alcohol compound in the impregnation solution in step (5) is 2-60 g / L.

2. The catalyst of claim 1, wherein: The Group VIII metal is nickel and / or cobalt, and the Group VIB metal is molybdenum and / or tungsten.

3. The catalyst of claim 1, wherein: The modified Y molecular sieve is a small crystal mesoporous modified Y molecular sieve with a crystal particle size of 300-500 nm.

4. The preparation method of the hydrodenitrogenation catalyst according to any one of claims 1-3, comprising the following steps: (1) NaY molecular sieve is exchanged by ammonium ions, filtered and washed to obtain NH4Y molecular sieve filter cake; (2) The NH4Y molecular sieve filter cake obtained in step (1) is mixed with an organic acid, a water-soluble polymer and water, and then subjected to hydrothermal treatment to obtain modified Y molecular sieve; (3) The modified Y molecular sieve obtained in step (2), pseudo-boehmite, a glue adhesive, a extrusion aid, a hole expanding agent and water are mixed and kneaded into a shape, dried, calcined to obtain a catalyst carrier; (4) The catalyst carrier obtained in step (3) is immersed in a gallium nitrate solution, dried and then subjected to high-temperature steam treatment to obtain a catalyst carrier; (5) An impregnation solution containing amine, alcohol and thiourea and active metal is prepared; (6) The catalyst carrier obtained in step (4) is impregnated with the impregnation solution obtained in step (5), dried and calcined to obtain a hydrodenitrogenation catalyst; The water-soluble polymer in step (2) is at least one selected from polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone and water-soluble polysaccharide with a weight average molecular weight of 10,000-40,000; the mass ratio of NH4Y molecular sieve: organic acid: water-soluble polymer: water in step (2) is 1: 0.01-0.05: 0.05-0.25: 15-40; The mass ratio of the alcohol compound and the amine compound in step (5) is 1:1-16:1; the amount of the thiourea added is such that the concentration of the thiourea in the impregnation solution is 5-70 g / L, and the concentration of the alcohol compound in the impregnation solution in step (5) is 2-60 g / L.

5. The method of claim 4, wherein: The NaY molecular sieve in step (1) has the following properties: the molar ratio of silicon oxide to aluminum oxide is 3-7:1, and the sodium content is 6 wt%-12 wt%; the NaY molecular sieve is exchanged into NH4Y molecular sieve by mixing the NaY molecular sieve with an ammonium salt solution, adjusting the pH value of the slurry, and performing ammonium ion exchange, and then the NH4Y molecular sieve filter cake is obtained after filtration and washing; the mass ratio of the NaY molecular sieve, water, and the ammonium salt is 1:6-25:0.2-0.4; the pH value of the slurry is adjusted to 3-4; the ammonium ion exchange temperature is adjusted to 70-90 ℃, the ammonium ion exchange time is 2-4 hours, and the ammonium ion exchange is performed 1-3 times.

6. The method of claim 4, wherein: The organic acid in step (2) is at least one selected from the group consisting of fumaric acid, adipic acid, tartaric acid, citric acid, oxalic acid, acetic acid, salicylic acid, and malic acid.

7. The method of claim 4, wherein: The hydrothermal treatment in step (2) is performed under the following conditions: the temperature is 100-150 ℃, and the treatment time is 5-12 hours; and / or, after the hydrothermal treatment in step (2), drying is performed under the following conditions: the drying temperature is 100-160 ℃, and the drying time is 3-8 hours.

8. The method of claim 7, wherein: The hydrothermal treatment is performed in two stages, and the temperature in the second stage is at least 15 ℃ higher than that in the first stage.

9. The method of claim 8, wherein: The temperature in the second stage is at least 20 ℃ higher than that in the first stage.

10. The method of claim 4, wherein: The mass ratio of the pseudo-boehmite to the modified Y molecular sieve in step (3) is 7-13:15-30; the amount of the pore-expanding agent added is 2 wt%-10 wt% of the total mass of the pseudo-boehmite and the modified Y molecular sieve; and / or, the drying temperature in step (3) is 120-160 ℃, the drying time is 3-6 hours, the calcination temperature is 550-700 ℃, and the calcination time is 2-6 hours.

11. The method of claim 4, wherein: The concentration of the gallium nitrate solution in step (4) is 0.5-2.5 mol / L; the impregnation method in step (4) is saturation impregnation or unsaturation impregnation; and the high-temperature water vapor treatment is performed under the following conditions: the temperature is 500-700 ℃, and the time is 60-90 min.

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

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

14. The method of claim 13, wherein: In step (6), the baking condition is constant temperature for 4-7 hours at 480-600°C.

15. Use of the catalyst of any one of claims 1-3 or the catalyst obtained by the preparation method of any one of claims 4-14 in residual oil hydroprocessing.

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