A catalyst support material having a hierarchical pore and a method for preparing the same

Abstract

This invention discloses a catalyst support material with hierarchical pores and its preparation method. The preparation method first treats starch under extraction conditions, then mixes the supernatant obtained after treatment with an aluminum source, an alkali source, and water for further processing to obtain a first material. Next, a silicon source is introduced into the first material stream to initiate a crystallization reaction. The reaction product is then separated, washed, dried, and carbonized to obtain the catalyst support material. This invention also provides a catalyst support material with hierarchical pores obtained using the above preparation method. The catalyst support material with hierarchical pores provided by this invention is a carbon-silicon-aluminum composite porous material, possessing macropore volume, micropore-mesopore-macropore hierarchical channels, exhibiting molecular sieve characteristics, and is suitable for use as a catalyst support, particularly for use as a support for heavy oil hydrogenation catalysts.

Description

Technical Field

[0001] This invention belongs to the field of catalytic materials technology, and relates to a method for preparing a catalyst support material and its application. Background Technology

[0002] Residue feedstocks have large molecules and high nitrogen content, so mesoporous silica-alumina materials are typically used as catalyst supports for hydrocracking. However, since the walls of mesoporous silica-alumina materials are all amorphous silica-alumina, their hydrothermal stability and acidity need further improvement. Molecular sieve materials with mesoporous and macroporous structures have higher hydrothermal stability and acidity. However, molecular sieve catalysts suffer from Brønsted acid concentration, leading to over-cracking and rapid deactivation. Therefore, hierarchical porous molecular sieve materials with suitable Brønsted acid content are more suitable as catalyst support materials for residue hydrocracking processes.

[0003] The preparation methods of hierarchical porous inorganic materials are generally divided into soft template methods and hard template methods. The template agents used in the soft template method are mostly expensive materials, which are difficult to apply to the residue hydrocracking process; the hard template method usually requires the synthesis of molecular sieves followed by reverse etching, which is complex, energy-intensive, and not conducive to industrial applications.

[0004] CN201811238466.X discloses a method for synthesizing a highly crystalline Y-type molecular sieve with mesopores. The method includes: adding an alkali source and water to a 2,3-epoxypropyltrimethylammonium chloride-modified cationic starch template agent, and hydrolyzing it at 30-150°C to obtain a hydrolysis product; mixing the silicon source, hydrolysis product, crystallization directing agent, aluminum source and alkali in the order of addition, and crystallizing them in a closed crystallization kettle at 60-180°C for 0.5-60 hours and recovering the product.

[0005] CN201710152348.6 discloses a porous zeolite catalyst support, its preparation method, and the catalyst. This method involves loading La(NO3)3 onto the surface of a porous aluminosilicate molecular sieve produced by sintering Al2O3 powder, SiO2 powder, corn starch, a dispersant, and carbon fibers, forming a La2O3-modified porous aluminosilicate molecular sieve. Experimental verification optimized the composition and ratio of the porous zeolite catalyst support. Utilizing the particle size distribution principle, corn starch was added as a pore-forming agent to the raw materials for preparing the aluminosilicate molecular sieve from a mixture of Al2O3 powder and SiO2 powder, enabling low-temperature sintering. Simultaneously, the addition of carbon fibers significantly improved the strength and toughness of the prepared aluminosilicate molecular sieve, extending its service life.

[0006] CN201811238481.4 discloses a method for preparing a mesoporous, highly crystalline Y-type molecular sieve. The method involves mixing and hydrolyzing a cationic starch template agent modified with 2,3-epoxypropyltrimethylammonium chloride (0.01%–10% substitution degree) with an alkali source and water to obtain a hydrolysis product; adding the hydrolysis product to a reactive silica-alumina gel to obtain an initial mixture; thoroughly mixing the initial mixture to obtain a gel mixture; and then dynamically crystallizing the resulting gel mixture in a closed crystallization vessel. Summary of the Invention

[0007] To overcome the shortcomings of existing technologies, this invention provides a catalyst support material with hierarchical pores and its preparation method. The preparation method directly synthesizes the catalyst support material with hierarchical pores by crystallizing and carbonizing a molecular sieve precursor with starch, followed by boiling water reflux. The provided catalyst support material with hierarchical pores is a carbon-silicon-aluminum composite porous material, exhibiting macropore volume, micropore-mesopore-macropore hierarchical channels, and exhibiting molecular sieve characteristics. However, it can significantly reduce cracking side reactions caused by the concentration of Brønsted acid in the molecular sieve. Furthermore, this material has moderate interactions with metals, making it more suitable for hydrogenation reactions and possessing high hydrothermal stability. It is suitable for use as a catalyst support, especially for heavy oil hydrogenation catalysts.

[0008] The first aspect of this invention provides a method for preparing a catalyst support material with hierarchical pores, the method comprising the following:

[0009] (1) Under extraction conditions, starch is placed in water for treatment, and the supernatant is obtained after treatment;

[0010] (2) Under contact conditions, the supernatant obtained in step (1), aluminum source, alkali source and water are mixed and processed to obtain the first material:

[0011] (3) Under mixed conditions, a silicon source is introduced into the first material stream obtained in step (2), and a second material is obtained after the reaction;

[0012] (4) The second material obtained in step (3) is subjected to a crystallization reaction, and the reaction product is separated, washed and dried to obtain the third material;

[0013] (5) The third material obtained in step (4) is carbonized to obtain the catalyst support material.

[0014] Furthermore, according to a preferred embodiment of the present invention, the starch in step (1) may be selected from one or more of mung bean starch, corn starch, potato starch, sweet potato starch, and millet starch, preferably corn starch.

[0015] Furthermore, according to a preferred embodiment of the present invention, the temperature of the water in step (1) is 70-100°C, preferably 80-90°C.

[0016] Furthermore, according to a preferred embodiment of the present invention, the processing procedure in step (1) is as follows: the starch is placed in hot water (the temperature of the hot water is 70-100°C, preferably 80-90°C), and then extraction is performed. After the extraction, the supernatant is taken. The extraction can be performed in a Soxhlet extraction apparatus.

[0017] Furthermore, according to a preferred embodiment of the present invention, the alkali source mentioned in step (2) is one or more of triethylamine, tetrapropylammonium bromide, ethylenediamine, tetrapropylammonium hydroxide, and ammonium hydroxide, preferably tetrapropylammonium bromide;

[0018] Furthermore, according to a preferred embodiment of the present invention, the aluminum source mentioned in step (2) is one or a mixture of several of aluminum sulfate, aluminum nitrate, sodium aluminate, aluminum oxide, aluminum trichloride, and aluminum hydroxide, preferably aluminum sulfate;

[0019] Furthermore, according to a preferred embodiment of the present invention, the processing temperature in step (2) is 40-70°C, preferably 50-60°C.

[0020] Furthermore, according to a preferred embodiment of the present invention, the silicon source mentioned in step (3) is a silicon-containing alkaline compound. Specifically, the silicon source can be one or more of ethyl silicate, sodium silicate, silica sol, and aluminum silicate, preferably silica sol.

[0021] Furthermore, according to a preferred embodiment of the present invention, the reaction conditions in step (3) are: the reaction temperature is 20-70°C, preferably 30-60°C.

[0022] Furthermore, according to a preferred embodiment of the present invention, the crystallization reaction conditions in step (4) are: crystallization temperature of 100-250°C and crystallization time of 6-50 hours.

[0023] Furthermore, according to a preferred embodiment of the present invention, the drying conditions in step (4) are: drying temperature of 100-150°C and drying time of 2-6 hours.

[0024] Furthermore, according to a preferred embodiment of the present invention, the carbonization process in step (5) is carried out under an inert atmosphere, wherein the inert atmosphere is one or more of nitrogen, carbon dioxide, and inert gases, preferably carbon dioxide; and the inert gas is one or more of helium, neon, argon, krypton, and xenon.

[0025] Furthermore, according to a preferred embodiment of the present invention, the carbonization conditions in step (5) are: carbonization temperature of 400-1200°C and carbonization time of 2-6 hours.

[0026] Furthermore, according to a preferred embodiment of the present invention, the catalyst support material obtained in step (5) is further refluxed in hot water and then dried to obtain the product. The hot water temperature is 90-100°C, and the reflux time is 6-120 hours. The drying is generally carried out at 80-120°C for 2-6 hours.

[0027] Furthermore, according to a preferred embodiment of the present invention, in step (2), the amount of alkali solution is controlled to ensure that the pH value of the solution is 7 to 13, preferably 8 to 12.

[0028] Furthermore, according to a preferred embodiment of the present invention, the ratio of aluminum source, starch, alkali source and water in the first material by mass is 1:0.05-200:0.05-20:50-1000.

[0029] Furthermore, according to a preferred embodiment of the present invention, the aluminum content in the second material is 3-40 gAl2O3 / L, and the silicon content is 60-250 gSiO2 / L, calculated as SiO2.

[0030] A second aspect of the present invention provides a catalyst support material obtained by the above preparation method.

[0031] Furthermore, according to a preferred embodiment of the present invention, the pore distribution of the catalyst support material has the following characteristics: the pore volume of pores with a diameter <10 nm accounts for 10% to 30% of the total pore volume, the pore volume of pores with a diameter of 10 to 50 nm accounts for 60% to 80% of the total pore volume, and the pore volume of pores with a diameter >50 nm accounts for ≤10% of the total pore volume; preferably, the pore volume of pores with a diameter <10 nm accounts for 12% to 22% of the total pore volume, the pore volume of pores with a diameter of 10 to 50 nm accounts for 70% to 80% of the total pore volume, and the pore volume of pores with a diameter >50 nm accounts for ≤8% of the total pore volume.

[0032] Furthermore, according to a preferred embodiment of the present invention, the Brønsted acid content of the catalyst support material is greater than 0.18 mmol / g, preferably 0.18 to 0.25 mmol / g, and more preferably 0.20 to 0.23 mmol / g.

[0033] Furthermore, according to a preferred embodiment of the present invention, the catalyst support material has the following properties: pore volume not less than 1.0 mL / g, preferably greater than 1.05 mL / g, generally 1.05–1.5 mL / g; specific surface area of ​​330–480 m². 2 / g, preferably 350-420m 2 / g.

[0034] Furthermore, according to a preferred embodiment of the present invention, the average pore size of the catalyst support material is 3 to 15 nm, preferably 8 to 13 nm.

[0035] A third aspect of the present invention provides a catalytic material comprising the catalyst support material described above or a catalyst support material manufactured according to the aforementioned method; more preferably, the catalytic material further comprises an active component, the active component being an active metal component, specifically selected from at least one of Group VIB and Group VIII metals of the periodic table, particularly at least one of Mo, W, Ni and Co.

[0036] The fourth aspect of the present invention provides a hydrogenation process for hydrocarbon-containing materials, wherein the hydrocarbon-containing materials and hydrogen-containing gas are brought into contact and reacted under hydrogenation reaction conditions in the presence of the aforementioned catalytic material.

[0037] In the above hydrogenation process, the hydrocarbon-containing material can be at least one selected from diesel oil, wax oil, heavy oil, coal tar, ethylene tar, and catalytic slurry.

[0038] In the above hydrogenation process, the hydrogen-containing gas is hydrogen or a mixture of hydrogen and other gases. The volume content of hydrogen in the mixture is generally not less than 80%, preferably not less than 85%, and even more preferably not less than 95%.

[0039] In the above hydrogenation process, the hydrogenation reaction conditions are: reaction pressure of 5–20 MPaG, reaction temperature of 300–450 °C, and liquid hourly space velocity of 0.1–0.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100–1000.

[0040] Compared with the prior art, the catalyst support material with hierarchical pores, its preparation method, and its application described in this invention have the following advantages:

[0041] (1) The novel catalyst support material with multi-level pores provided by the present invention has molecular sieve characteristics and low impurity content. It also has a large pore volume and a three-level gradient pore structure of macropores-mesopores-micropores, making it suitable for use as a support for heavy oil hydrogenation catalysts.

[0042] (2) After the supernatant obtained after starch extraction is mixed with the molecular sieve precursor, the cavity structure formed restricts the growth of molecular sieve crystals during the molecular sieve crystallization process, reduces the excessive cracking reaction of raw oil caused by the concentration of Brønsted acid, and thus avoids the problem of catalyst deactivation due to excessive carbon deposition.

[0043] (3) In the preparation method of the catalyst support material with multi-level pores described in this invention, during the process of step (8), the inert gas can not only protect the carbon material from oxidation, but also act as a pore expander. At the same time, the carbon-silicon-aluminum composite catalyst support material obtained has a moderate interaction force with the active metal compared with conventional alumina material. The active metal can be better dispersed and sulfided to form more hydrogenation active centers, which is conducive to the occurrence of hydrogenation reaction.

[0044] (4) In the preparation method of the catalyst support material with multi-level pores described in this invention, during the boiling water reflux process in step (9), some amorphous silicon-aluminum materials dissolve in water, which at the same time plays a role in expanding the pores of carbon materials, and the resulting catalyst support material has good hydrothermal stability. Attached Figure Description

[0045] Figure 1 This is a scanning electron microscope image of the sample obtained in Example 1 of the present invention. Detailed Implementation

[0046] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings and specific examples. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims.

[0047] In the context of this specification, material pore volume, specific surface area, and pore size distribution were measured using a low-temperature nitrogen adsorption method. Total acid, Brønsted acid, and Lewis acid were measured using a pyridine infrared adsorption method.

[0048] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0049] In this paper, the catalyst wear index was measured using an MH-1 fluidized bed wear tester via the air jet method.

[0050] In the context of this specification, any two or more embodiments of the present invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0051] Example 1

[0052] Preparation of a hierarchical porous molecular sieve material: 500g of corn starch was extracted in 90℃ warm water for 2h to obtain 2.5L of supernatant. 42.5g of aluminum sulfate (0.124mol) and 335g of tetrapropylammonium bromide were added to the supernatant. After stirring in a 60℃ water bath for 4 hours, 1kg of silica sol with a silica content of 30wt% was added dropwise. Stirring continued at 60℃ until solidification into a gel. The gel was transferred to a reaction vessel and crystallized at 140℃ for 8h. After cooling and filtration, the filter cake was washed with hot water until neutral and dried at 120℃ for 4h to obtain a white powder sample. The powder sample was carbonized in a carbon dioxide atmosphere for 3h at a carbonization temperature of 750℃ to obtain a black powder product. This product was then refluxed in boiling water at 100℃ for 24h and dried at 100℃ for 4h to obtain a hierarchical porous molecular sieve material S-1, the properties of which are shown in Table 1.

[0053] Take 500g of the prepared S-1 sample, add 7g of guar gum powder, 15.38g of nitric acid (65wt%), and 450g of water, mix evenly and then form into spheres. Dry the spheres at 120℃ for 5h to obtain carrier Z1 with a particle size of 0.3-0.8mm.

[0054] Weigh 28.57 g of phosphoric acid and add 800 mL of distilled water. Then, add 77.58 g of molybdenum oxide and 35.56 g of basic nickel carbonate sequentially. Heat and stir until completely dissolved. Dilute the solution to 1000 mL with distilled water to obtain solution L1. Saturate the support Z1 with solution L1, dry at 110 °C for 2 h, and calcine at 450 °C under a nitrogen atmosphere for 3 h to obtain catalyst C1. The specific properties are shown in Table 2.

[0055] Example 2

[0056] Preparation of a hierarchical porous molecular sieve material: 600g of potato starch was extracted in 90℃ warm water for 2h to obtain 2.5L of supernatant. 42.5g of aluminum sulfate (0.124mol) and 335g of tetrapropylammonium bromide were added to the supernatant. After stirring in a 60℃ water bath for 4 hours, 1040g of tetraethyl orthosilicate was added dropwise, and stirring continued at 60℃ until solidification into a gel. The gel was transferred to a reaction vessel and crystallized at 140℃ for 8h. After cooling and filtration, the filter cake was washed with hot water until neutral and dried at 110℃ for 4h to obtain a white powder sample. The powder sample was carbonized in a carbon dioxide atmosphere for 2h at a carbonization temperature of 750℃ to obtain a black powder product. This product was then refluxed in boiling water at 100℃ for 24h and dried at 100℃ for 4h to obtain a hierarchical porous molecular sieve material S-2, the properties of which are shown in Table 1.

[0057] Take 500g of the prepared S-2 sample, add 25.3g of acetic acid (85wt%) and 420g of water, mix evenly and then form into spheres. Dry the spheres at 110℃ for 5h to obtain carrier Z2 with a particle size of 0.3-0.8mm.

[0058] The support Z2 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 580℃ under nitrogen atmosphere for 3 h to obtain catalyst C2. The specific properties are shown in Table 2.

[0059] Example 3

[0060] Preparation of a hierarchical porous molecular sieve material: 500g of corn starch was extracted in 80℃ warm water for 2h to obtain 2.5L of supernatant. 42.5g of aluminum sulfate (0.124mol) and 255g of tetrapropylammonium hydroxide were added to the supernatant. After stirring in a 60℃ water bath for 4 hours, 1kg of silica sol with a silica content of 30wt% was added dropwise. Stirring continued at 60℃ until solidification into a gel. The gel was transferred to a reaction vessel and crystallized at 140℃ for 8h. After cooling and filtration, the filter cake was washed with hot water until neutral and then dried at 100℃ for 4h to obtain a white powder sample. The powder sample was carbonized in a nitrogen atmosphere at 700℃ for 3h to obtain a black powder product. This product was then refluxed in boiling water at 100℃ for 24h and dried at 100℃ for 4h to obtain a hierarchical porous molecular sieve material S-3, the properties of which are shown in Table 1.

[0061] Take 500g of the prepared S-3 sample, add 10.0g of methylcellulose and 450g of water, mix evenly and form into spheres. Dry the spheres at 110℃ for 5h to obtain carrier Z3 with a particle size of 0.3-0.8mm.

[0062] The support Z3 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 480℃ under nitrogen atmosphere for 4 h to obtain catalyst C3. The specific properties are shown in Table 2.

[0063] Example 4

[0064] Preparation of a hierarchical porous molecular sieve material: 500g of corn starch was extracted in 80℃ warm water for 2h to obtain 2.5L of supernatant. 42.5g of aluminum sulfate (0.124mol) was added to the supernatant and stirred until dissolved in a 60℃ water bath. 1040g of tetraethyl orthosilicate was added, followed by tetrapropylammonium bromide until the pH reached 10.5. The solution was stirred at 35℃ for 0.5h to obtain a clear solution. This solution was transferred to a reaction vessel and crystallized at 160℃ for 48h. After cooling and filtration, the filter cake was washed with hot water until neutral and then dried at 120℃ for 4h to obtain a white powder sample. The powder sample was carbonized in a carbon dioxide atmosphere for 2h at a carbonization temperature of 750℃ to obtain a black powder product. This product was then refluxed in boiling water at 100℃ for 24h and dried at 100℃ for 4h to obtain a hierarchical porous molecular sieve material S-4, the properties of which are shown in Table 1.

[0065] Take 500g of the prepared S-4 sample, add 7g of guar gum powder, 31.3g of nitric acid (65wt%), and 410g of water, mix evenly and then form into spheres. Dry the spheres at 140℃ for 5h to obtain carrier Z4 with a particle size of 0.3-0.8mm.

[0066] Weigh 78.88 g of phosphoric acid and add 800 mL of distilled water. Then, add 185.68 g of molybdenum oxide and 50.81 g of basic cobalt carbonate sequentially. Heat and stir until completely dissolved, then dilute the solution to 2000 mL with distilled water to obtain solution L2. Saturate the support Z4 with solution L2, dry at 110 °C for 4 h, and calcine at 500 °C under a nitrogen atmosphere to obtain catalyst C4. The specific properties are shown in Table 2.

[0067] Example 5

[0068] Preparation of a hierarchical porous molecular sieve material: 500g of corn starch was extracted in 80℃ warm water for 2h to obtain 2.5L of supernatant. 42.5g of aluminum sulfate (0.124mol) was added to the supernatant and stirred until dissolved under a 60℃ water bath. 1040g of tetraethyl orthosilicate was added, followed by tetrapropylammonium hydroxide until the pH reached 10.0. The solution was stirred at 60℃ for 0.5h to obtain a clear solution. This solution was transferred to a reaction vessel and crystallized at 120℃ for 24h. After cooling and filtration, the filter cake was washed with hot water until neutral and then dried at 130℃ for 4h to obtain a white powder sample. The powder sample was carbonized in a carbon dioxide atmosphere for 2h at a carbonization temperature of 750℃ to obtain a black powder product. This product was then refluxed in 90℃ hot water for 60h and dried at 100℃ for 4h to obtain a hierarchical porous molecular sieve material S-5, the properties of which are shown in Table 1.

[0069] Take 500g of the prepared S-5 sample, add 15g of guar gum powder and 470g of water, mix evenly and form into spheres. Dry the spheres at 100℃ for 3h to obtain carrier Z5 with a particle size of 0.3-0.8mm.

[0070] The support Z5 was saturated with solution L2, dried at 100℃ for 2 hours, and calcined at 550℃ under a nitrogen atmosphere to obtain catalyst C5. The specific properties are shown in Table 2.

[0071] Comparative Example 1

[0072] 42.5 g of aluminum sulfate (0.124 mol) and 335 g of tetrapropylammonium bromide were added to 2.5 kg of deionized water and stirred for 4 hours in a water bath at 60 °C. Then, 1 kg of silica sol with a silica content of 30 wt% was added dropwise, and stirring was continued at 60 °C until it solidified into a gel. The gel was transferred to a reaction vessel and crystallized at 140 °C for 8 hours. After cooling and filtration, the filter cake was washed with hot water until neutral and then dried at 120 °C for 4 hours to obtain a white powder sample. The powder sample was then carbonized at 750 °C for 2 hours under a carbon dioxide atmosphere to obtain a black powder product. The product was then refluxed in boiling water at 100 °C for 24 hours and dried at 100 °C for 4 hours to obtain SK-1, a molecular sieve material with hierarchical pores. Its properties are shown in Table 1.

[0073] Take 500g of the prepared SK-1 sample, add 7g of guar gum powder, 15.38g of nitric acid (65wt%), and 450g of water, mix evenly and then form into spheres. Dry the spheres at 120℃ for 5h to obtain carrier ZK1 with a particle size of 0.3-0.8mm.

[0074] The support ZK1 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ under nitrogen atmosphere for 3 h to obtain catalyst CK1. The specific properties are shown in Table 2.

[0075] Comparative Example 2

[0076] 500g of corn starch, 42.5g of aluminum sulfate (0.124mol), and 335g of tetrapropylammonium bromide were added to 2.5kg of deionized water. After stirring for 4 hours in a 60℃ water bath, 1kg of silica sol with a silica content of 30wt% was added dropwise, stirring until a uniform suspension was obtained. The suspension was transferred to a reaction vessel and crystallized at 140℃ for 8 hours. After cooling and filtration, the filter cake was washed with hot water until neutral and then dried at 120℃ for 4 hours to obtain a white powder sample. The powder sample was then carbonized at 750℃ for 2 hours under a carbon dioxide atmosphere to obtain a black powder product. This product was then refluxed in boiling water at 100℃ for 24 hours and dried at 100℃ for 4 hours to obtain SK-2, a molecular sieve material with hierarchical pores. Its properties are shown in Table 1.

[0077] Take 500g of the prepared SK-2 sample, add 7g of guar gum powder, 15.38g of nitric acid (65wt%), and 450g of water, mix evenly and then form into spheres. Dry the spheres at 120℃ for 5h to obtain carrier ZK2 with a particle size of 0.3-0.8mm.

[0078] The support ZK2 was saturated with solution L1, dried at 110℃ for 2 h, and calcined at 450℃ under nitrogen atmosphere for 3 h to obtain catalyst CK2. The specific properties are shown in Table 2.

[0079] Table 1 Properties of molecular sieve materials with hierarchical pores

[0080]

[0081] Table 2 Catalyst Properties

[0082]

[0083] The above catalysts were evaluated for activity in an autoclave. The evaluation of feedstock properties and evaluation conditions are shown in Table 3. The activity of Comparative Example 1 was set as 100, and the evaluation results compared with the activity of Comparative Example 3 are shown in Table 4.

[0084] Table 3. Properties and Evaluation Conditions of Feed Oil

[0085] project numerical values properties of crude oil sulfur,% 5.76 Carbon residue,% 24.86 <![CDATA[Nickel + Vanadium / μg·g -1 > 214.38 >500℃ residue oil yield, % 93.2 Process conditions Reaction temperature / °C 420 Reaction pressure / MPa 15 Oil volume ratio 13:1 Reaction time / h 1

[0086] Table 4 Catalyst Evaluation Results

[0087]

[0088] The data in the tables show that the carbon-silicon-aluminum composite material prepared using this invention has a large pore volume and a higher Brønsted acid content than commonly used macroporous silica-alumina materials, but lower than molecular sieves. The hydrogenation catalyst prepared using this material, compared to the catalyst prepared in the comparative example, increases the impurity removal rate and residue oil conversion rate, making it particularly suitable for use as a hydrogenation catalyst for heavy oil or residue oil.

Claims

1. A method for preparing a catalyst support material with hierarchical pores, the preparation method comprising the following steps: (1) Place the starch in hot water at a temperature of 70-100℃, and then perform extraction. After the extraction, take the supernatant. (2) Under contact conditions, the supernatant obtained in step (1), aluminum source, alkali source and water are mixed and treated to obtain the first material; the alkali source is one or more of triethylamine, tetrapropylammonium bromide, ethylenediamine, ammonium hydroxide and tetrapropylammonium hydroxide. (3) Under mixed conditions, a silicon source is introduced into the first material obtained in step (2), and the second material is obtained after the reaction; (4) The second material obtained in step (3) is subjected to a crystallization reaction. The reaction product is separated, washed and dried to obtain the third material. The crystallization reaction conditions are: crystallization temperature is 100-250℃ and crystallization time is 6-50 hours. (5) The third material obtained in step (4) is carbonized to obtain a catalyst support material. The obtained catalyst support material is refluxed in hot water at a temperature of 90-100°C for 6-120 hours. Then it is dried to obtain the product. The carbonization process is carried out under an inert atmosphere.

2. The method for preparing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The starch in step (1) is selected from one or more of mung bean starch, corn starch, potato starch, sweet potato starch, and millet starch.

3. The method for preparing the catalyst support material with hierarchical pores according to claim 1, characterized in that: The starch in step (1) is corn starch.

4. The method for preparing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The hot water temperature in step (1) is 80-90℃.

5. The method for preparing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The alkali source in step (2) is tetrapropylammonium bromide.

6. The method for preparing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The aluminum source in step (2) is one or more of aluminum sulfate, aluminum nitrate, sodium aluminate, aluminum oxide, aluminum trichloride, and aluminum hydroxide.

7. The method for preparing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The aluminum source in step (2) is aluminum sulfate.

8. The method for preparing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The processing temperature in step (2) is 40 to 70°C.

9. The method of producing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The processing temperature in step (2) is 50-60℃.

10. The method of producing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The silicon source in step (3) is one or more of tetraethyl orthosilicate, sodium silicate, silica sol, and aluminum silicate.

11. The method of producing a catalyst support material having a hierarchical pore according to claim 1 or 10, characterized by: The silicon source in step (3) is silica sol.

12. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: The reaction conditions in step (3) are: reaction temperature of 20-70℃.

13. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: The reaction conditions in step (3) are: the reaction temperature is 30-60℃.

14. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: The drying conditions in step (4) are: drying temperature of 100-150℃ and drying time of 2-6 hours.

15. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: The inert atmosphere in step (5) is one or more of nitrogen, carbon dioxide, and inert gases; the inert gas is one or more of helium, neon, argon, krypton, and xenon.

16. The method of producing a catalyst support material having a hierarchical pore according to claim 1, characterized by: The inert atmosphere in step (5) is carbon dioxide.

17. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: The carbonization conditions in step (5) are: carbonization temperature of 400-1200℃ and carbonization time of 2-6 hours.

18. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: The drying in step (5) is carried out at 80-120°C for 2-6 hours.

19. The method of producing a catalyst support material having a hierarchical pore according to claim 1, characterized by: In step (2), the amount of alkali source is controlled to ensure that the pH value of the solution is 7 to 13.

20. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: In step (2), the amount of alkali source is controlled to ensure that the pH value of the solution is 8 to 12.

21. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: In the first material, the mass ratio of aluminum source, starch, alkali source, and water is 1:0.05~200:0.05~20:50~1000.

22. The method of preparing a catalyst support material having a hierarchy of pores according to claim 1, characterized by: The aluminum content in the second material is 3-40 gAl2O3 / L, and the silicon content is 60-250 gSiO2 / L, calculated as SiO2.

23. A catalyst support material with hierarchical pores, characterized in that: The catalyst support material with hierarchical pores is obtained by the preparation method described in any one of claims 1-22.

24. The catalyst support material having hierarchical pores according to claim 23, wherein: The pore distribution of the catalyst support material has the following characteristics: pores with a diameter <10 nm account for 10% to 30% of the total pore volume, pores with a diameter of 10 to 50 nm account for 60% to 80% of the total pore volume, and pores with a diameter >50 nm account for ≤10% of the total pore volume.

25. The catalyst support material having hierarchical pores according to claim 23, wherein: The pore distribution of the catalyst support material has the following characteristics: pores with a diameter <10 nm account for 12% to 22% of the total pore volume, pores with a diameter of 10 to 50 nm account for 70% to 80% of the total pore volume, and pores with a diameter >50 nm account for ≤8% of the total pore volume.

26. The catalyst support material having a hierarchy of pores according to claim 23, wherein: The Brønsted acid content of the catalyst support material is 0.18–0.25 mmol / g.

27. The catalyst support material with hierarchical pores according to claim 23, characterized in that: The Brønsted acid content of the catalyst support material is 0.20–0.23 mmol / g.

28. The catalyst support material having a hierarchy of pores according to claim 23, wherein: The pore volume of the catalyst carrier material is not less than 1.0 mL / g; the specific surface area is 330-480 m 2 / g.

29. The catalyst support material having a hierarchy of pores according to claim 23, wherein: The pore volume of the catalyst carrier material is 1.05-1.5 mL / g; the specific surface area is 350-420 m2 / g. 2 / g.

30. The catalyst support material having a hierarchy of pores according to claim 23, wherein: The average pore size of the catalyst support material is 3–15 nm.

31. The catalyst support material having a hierarchy of pores according to claim 23, wherein: The average pore size of the catalyst support material is 8–13 nm.

32. A catalytic material comprising an active component and a catalyst support material as described in any one of claims 23-31.

33. The catalytic material according to claim 32, characterized in that: The active component is an active metal component, selected from at least one metal from Group VIB and Group VIII of the periodic table.

34. A hydrogenation process for hydrocarbon-containing materials, wherein the hydrocarbon-containing material and hydrogen-containing gas are reacted in contact under hydrogenation reaction conditions in the presence of the catalyst material as described in claim 32 or 33.

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