A distillate hydrofining catalyst, its preparation method and application

Abstract

The application discloses a distillate oil hydrofining catalyst and a preparation method and application thereof. The distillate oil hydrofining catalyst comprises a catalyst carrier and an active component. The catalyst carrier comprises phosphorus-modified SBA-15 molecular sieve and / or titanium-modified SBA-15 molecular sieve. The active component comprises Group 6B metal oxide and / or Group 8 metal oxide. The catalyst is suitable for the hydrofining of petroleum distillate oil at 150 DEG C to 400 DEG C, and is particularly suitable for the hydrofining of catalytic cracking hydrogen circulation oil with high contents of sulfur, nitrogen and aromatic hydrocarbons and low cetane number. The catalyst can reduce the contents of sulfur, nitrogen and aromatic hydrocarbons under relatively mild hydrofining conditions, and greatly improves the cetane number of products.

Description

Technical Field

[0001] This invention relates to a catalyst for hydrorefining distillate oil, its preparation method and application, which is applicable to the hydrorefining of inferior gasoline and diesel fractions into clean oil products in the petroleum refining field. Background Technology

[0002] In the petroleum refining industry, the development of catalytic cracking and delayed coking technologies has led to an increase in the proportion of secondary processed distillate fuels, such as catalytic and coking gasoline and diesel, in the total gasoline and diesel volume. However, catalytic and coking gasoline and diesel have high levels of impurities such as sulfur and nitrogen, and in particular, they have high aromatic content, poor stability, and low cetane numbers. As refining technology moves towards deeper processing, the quality of catalytic and coking gasoline and diesel will continue to decline. Furthermore, new clean fuel standards and environmental regulations place increasingly stringent requirements on distillate fuel quality. Therefore, how to further improve the quality of secondary processed distillate fuels, especially secondary processed diesel, is an important issue of concern.

[0003] Due to the scarcity of petroleum resources, catalytic diesel in my country is mainly used for blending after hydrorefining to produce automotive diesel. Currently, my country's catalytic cracking units have an annual processing capacity exceeding 100 million tons. In the composition of gasoline and diesel products, catalytic cracked gasoline accounts for approximately 80%, and catalytic diesel accounts for approximately 30%. In recent years, with the increasing quality of crude oil processed domestically, the feedstock for catalytic cracking has also become increasingly heavier and of lower quality. Furthermore, many enterprises have modified or increased the operational stringency of catalytic cracking units to improve gasoline quality or increase propylene production, leading to a further deterioration in the quality of catalytic cracking products, especially catalytic diesel. This is mainly reflected in the high density and low cetane number of catalytic cracked diesel, making it difficult to meet increasingly stringent environmental regulations using conventional hydrorefining technology. Catalytic diesel has become a constraint on product quality upgrades and profit growth for enterprises.

[0004] Because catalytic diesel has a high aromatic content, it has a high density and low cetane number, making it the worst-performing diesel blending component and the most difficult to process in quality upgrades. Typically, the aromatic content ranges from 64.5% to 78.3%, with bicyclic and tricyclic aromatics accounting for over 60%, and cyclic aromatics making up over 50% of the total. For diesel fractions, a high aromatic content is detrimental. To achieve deep desulfurization, denitrification, and dearomatization of inferior diesel fractions and produce clean diesel, various unique processes and catalysts have been developed both domestically and internationally. For example, USP5114562 describes a two-stage hydrotreating technology: in the first stage, a non-precious metal catalyst is used to remove most of the sulfur, while in the second stage, a platinum catalyst with strong hydrosaturation capacity is used for deep hydrotreating to improve the oil's properties. However, this hydrotreating process is relatively complex, requires partial modification of existing equipment, and uses a precious metal catalyst, resulting in relatively high processing costs. Summary of the Invention

[0005] The main objective of this invention is to provide a catalyst for the hydrorefining of distillate oil, its preparation method, and its application, so as to overcome the problems in the prior art where the hydrorefining catalyst for distillate oil is difficult to meet the hydrogenation requirements, has high catalyst cost, or has harsh process conditions for the hydrorefining of distillate oil.

[0006] To achieve the above objectives, the present invention provides a catalyst for hydrorefining distillate oil, comprising a catalyst support and an active component, wherein the catalyst support comprises phosphorus-modified SBA-15 molecular sieve and / or titanium-modified SBA-15 molecular sieve, and the active component comprises Group VIB metal oxides and / or Group VIII metal oxides.

[0007] The distillate oil hydrorefining catalyst of the present invention, wherein, based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the phosphorus-modified SBA-15 molecular sieve is 5% to 40%, and the mass content of the titanium-modified SBA-15 molecular sieve is 5% to 40%; in the phosphorus-modified SBA-15 molecular sieve, the P2O5 / SiO2 molar ratio is 0.1 to 0.5; in the titanium-modified SBA-15 molecular sieve, the TiO2 / SiO2 molar ratio is 0.1 to 0.5.

[0008] The distillate oil hydrorefining catalyst of the present invention further includes alumina as the catalyst support and a modifier oxide as the catalyst. The modifier oxide is at least one of silicon, phosphorus, fluorine, titanium, zirconium, and gallium oxides. Based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the modifier oxide is 0.5% to 5%.

[0009] The distillate oil hydrorefining catalyst of the present invention comprises, wherein the Group VIB metal oxide is an oxide of molybdenum and / or an oxide of tungsten, and the Group VIII metal oxide is at least one of oxides of iron, nickel, and cobalt; based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the Group VIB metal oxide is 15-30%, and the mass content of the Group VIII metal oxide is 2-10 wt%.

[0010] To achieve the above objectives, the present invention also provides a method for preparing a catalyst for hydrorefining distillate oil, comprising the following steps:

[0011] Step 1: Extrude phosphorus-modified SBA-15 molecular sieve and / or titanium-modified SBA-15 molecular sieve to obtain catalyst support;

[0012] Step 2: Prepare an impregnation solution containing compounds of Group VIB metals and / or Group VIII metals, impregnate the catalyst support obtained in Step 1, and dry and calcine to obtain a distillate oil hydrorefining catalyst.

[0013] The preparation method of the distillate oil hydrorefining catalyst of the present invention includes the addition of alumina in step 1 and the addition of a modifier compound in step 1 or step 2. The modifier compound is at least one of silicon-containing compounds, phosphorus-containing compounds, fluorine-containing compounds, titanium-containing compounds, zirconium-containing compounds, and gallium-containing compounds. The compound of the Group VIB metal is an ammonium salt of molybdenum and / or an ammonium salt of tungsten. The compound of the Group VIII metal is at least one of nitrates, carbonates, or acetates of iron, cobalt, and nickel.

[0014] The method for preparing the distillate oil hydrorefining catalyst of the present invention comprises, based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the phosphorus-modified SBA-15 molecular sieve is 5% to 40%, the mass content of the titanium-modified SBA-15 molecular sieve is 5% to 40%, the mass content of the Group VIB metal compound (calculated as oxide) is 15% to 30%, and the mass content of the Group VIII metal compound (calculated as oxide) is 2% to 10%.

[0015] The preparation method of the distillate oil hydrorefining catalyst of the present invention, wherein the impregnation in step 2 is a single-component impregnation or a two-component impregnation, and the impregnation method is excess impregnation or equal volume impregnation.

[0016] The preparation method of the distillate oil hydrorefining catalyst of the present invention includes the following steps: the preparation method of the phosphorus-modified SBA-15 molecular sieve is as follows: mixing SBA-15 molecular sieve with a phosphorus-containing compound, ultrasonically treating, and drying and calcining to obtain phosphorus-modified SBA-15 molecular sieve; the preparation method of the titanium-modified SBA-15 molecular sieve is as follows: mixing SBA-15 molecular sieve with a titanium-containing compound, ultrasonically treating, and drying and calcining to obtain titanium-modified SBA-15 molecular sieve.

[0017] To achieve the above objectives, the present invention also provides the application of the above-mentioned distillate oil hydrorefining catalyst in distillate oil hydrorefining.

[0018] The beneficial effects of this invention are:

[0019] The catalyst of this invention uses titanium-modified SBA-15 molecular sieve and / or phosphorus-modified SBA-15 molecular sieve as a support, which can improve the dispersibility of active components and enhance the hydrodesulfurization performance of the catalyst. Furthermore, through the synergistic effect of the two molecular sieves, the hydrorefining performance of the catalyst can be improved, enabling it to process inferior gasoline and diesel under relatively mild process conditions, achieving deep desulfurization, denitrification, and reduction of olefins and aromatics. Detailed Implementation

[0020] The following provides a detailed description of the embodiments of the present invention. These embodiments are implemented based on the technical solution of the present invention and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0021] This invention provides a hydrorefining catalyst for distillate oils, suitable for hydrorefining petroleum distillate oils at temperatures ranging from 150°C to 400°C. It is applicable to the hydrorefining of low-quality gasoline and diesel fractions (such as catalytic gasoline and diesel, coking gasoline and diesel) in the petroleum refining industry, and is particularly suitable for the hydrorefining of catalytic cracking light cycle oils with high sulfur, nitrogen, and aromatic content and low cetane numbers. The catalyst of this invention can reduce the content of sulfur, nitrogen, and aromatics under relatively mild hydrorefining conditions, and significantly increase the cetane number of the product. The distillate oil hydrorefining catalyst of this invention comprises a catalyst support and an active component. The catalyst support comprises phosphorus-modified SBA-15 molecular sieves and / or titanium-modified SBA-15 molecular sieves, and the active component comprises Group VIB metal oxides and / or Group VIII metal oxides.

[0022] Titanium-modified SBA-15 molecular sieves involve the reaction of titanium metal chlorides or organometallic compounds with the silanol bonds (Si-OH) on the SBA-15 surface to form Ti-O covalent bonds. This fixes metallic Ti onto the SBA-15 framework, introducing a large number of metal ions or other active centers into the pores, resulting in better dispersibility and catalytic activity of active metal species such as Ni, W, Co, and Mo in the catalyst. The titanium loading in the titanium-modified SBA-15 molecular sieve is 2%–10 wt%, with a preferred loading of 4%–8 wt%.

[0023] SBA-15 molecular sieves were modified with phosphoric acid or phosphotungstic acid. The phosphorus-modified SBA-15 molecular sieves exhibited certain acid strength, and the BET specific surface area of ​​the unmodified SBA-15 molecular sieves reached 649 m². 2 / g, pore volume 1.05cm³ 3 / g, average pore size 6.5nm, phosphorus-modified BET specific surface area can reach 900m² 2 / g, pore volume 1.15cm³ 3 With an average pore size of 8.1 nm, the catalyst prepared using phosphorus-modified SBA-15 molecular sieve exhibits better hydrodesulfurization performance for macromolecular sulfides such as dibenzothiophene and dimethyldibenzothiophene.

[0024] The catalyst of this invention uses titanium-modified SBA-15 molecular sieve and / or phosphorus-modified SBA-15 molecular sieve as a support. By adding modified SBA-15 molecular sieve, the synergistic effect of the two molecular sieves can be further utilized to improve the hydrorefining performance of the catalyst, enabling it to process inferior gasoline and diesel under milder process conditions, and achieve deep desulfurization, denitrification, olefin and aromatic hydrocarbon reduction.

[0025] In one embodiment, the catalyst support of the present invention further includes alumina, i.e., the catalyst support is composed of phosphorus-modified SBA-15 molecular sieve and / or titanium-modified SBA-15 molecular sieve, and alumina. In another embodiment, the active component is at least one Group VIII metal oxide and at least one Group VIB metal oxide. In yet another embodiment, the Group VIB metal oxide is an oxide of molybdenum and / or tungsten, i.e., an oxide of molybdenum and / or an oxide of tungsten; the Group VIII metal oxide is an oxide of at least one of iron, nickel, and cobalt, i.e., an oxide of iron, an oxide of nickel, and an oxide of cobalt.

[0026] In one embodiment, the distillate oil hydrorefining catalyst of the present invention further includes a modifier oxide, wherein the modifier oxide is an oxide of at least one selected from silicon, phosphorus, fluorine, titanium, zirconium, and gallium, specifically, the modifier oxide is at least one selected from silicon oxide, phosphorus oxide, fluorine oxide, titanium oxide, zirconium oxide, and gallium oxide. In another embodiment, the distillate oil hydrorefining catalyst of the present invention further includes a binder, extrusion aid, etc., but the present invention is not particularly limited thereto. Generally, the modifier can alter the acidity of the catalyst, facilitating the adsorption of large, complex heteroatom compounds onto the catalyst.

[0027] In one embodiment, based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the catalyst contains 0.5% to 40% phosphorus-modified SBA-15 molecular sieve, preferably 5% to 30% by mass; and 0.5% to 40% titanium-modified SBA-15 molecular sieve, preferably 5% to 30% by mass. In another embodiment, based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the catalyst further includes 20% to 90% alumina by mass, preferably 30% to 80%; 0.5% to 5% modifier oxide by mass; 0% to 30% binder by mass, preferably 0% to 20%; and 0% to 10% extrusion aid by mass, most preferably 3% to 8%.

[0028] In one embodiment, based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the mass content of Group VIB metal oxides in the catalyst of the present invention is 10-30%, preferably 15-25%; and the mass content of Group VIII metal oxides is 1-10%, preferably 3-8%.

[0029] In one embodiment, the distillate oil hydrorefining catalyst of the present invention uses alumina, phosphorus-modified SBA-15 molecular sieve and titanium-modified SBA-15 molecular sieve as supports, wherein alumina is the main support component of the catalyst, with good thermal stability and suitable pore size distribution; the two different molecular sieves are the main acidic components of the catalyst, and through appropriate modification treatment, the acidity can be adjusted and the specific surface area of ​​the support can be increased.

[0030] The specific surface area of ​​the distillate oil hydrorefining catalyst of this invention is 180 m². 2 / g~240m 2 / g, with a pore volume of 0.30ml / g to 0.35ml / g, of which pores with a diameter of 4nm to 10nm account for 70% to 90% of the total pore volume.

[0031] This invention also discloses a method for preparing the above-mentioned distillate oil hydrorefining catalyst, comprising the following steps:

[0032] Step 1: Extrude phosphorus-modified SBA-15 molecular sieve and / or titanium-modified SBA-15 molecular sieve to obtain catalyst support;

[0033] Step 2: Prepare an impregnation solution containing compounds of Group VIB metals and / or Group VIII metals, impregnate the catalyst support obtained in Step 1, and dry and calcine to obtain a distillate oil hydrorefining catalyst.

[0034] In one embodiment, the preparation method of the phosphorus-modified SBA-15 molecular sieve of the present invention is as follows: SBA-15 molecular sieve is mixed with a phosphorus-containing compound, ultrasonically treated, and dried and calcined to obtain phosphorus-modified SBA-15 molecular sieve. The phosphorus-containing compound is, for example, phosphoric acid or a phosphate solution. In another embodiment, the preparation method of the phosphorus-modified SBA-15 molecular sieve of the present invention is as follows: phosphoric acid or a phosphate solution is added to an ultrasonic reactor, then SBA-15 molecular sieve is added and stirred evenly; the reaction product is subjected to solid-liquid separation, then washed, dried (drying temperature is 100-120℃, drying time is 4-8h), and calcined (calcination temperature is 500-600℃, calcination time is 4-6h) to obtain phosphorus-modified SBA-15 molecular sieve.

[0035] In one embodiment, the preparation method of the titanium-modified SBA-15 molecular sieve of the present invention is as follows: SBA-15 molecular sieve is mixed with a titanium-containing compound, ultrasonically treated, and dried and calcined to obtain the titanium-modified SBA-15 molecular sieve. The titanium-containing compound can be a titanate ester or an inorganic titanium salt, such as Ti(OR)4, TiCl3, or C. 10 H 10 Cl2Ti, etc., wherein R is, for example, a hydrocarbon group having 1-6 carbons, or more specifically, an alkyl group having 1-6 carbons. In another embodiment, the preparation method of the titanium-modified SBA-15 molecular sieve of the present invention is as follows: a titanium-containing compound and an SBA-15 molecular sieve are fully contacted and reacted in an ultrasonic reactor in an organic solvent (such as toluene, cyclohexane, chloroform, etc.), and the reaction product after contact is subjected to solid-liquid separation, followed by washing, drying (drying temperature is 100-120℃, drying time is 4-8 hours), and calcination (calcination temperature is 500-600℃, calcination time is 4-6 hours) to obtain the titanium-modified SBA-15 molecular sieve.

[0036] In one embodiment, the phosphorus-modified SBA-15 molecular sieve of the present invention has the following properties: a P2O5 / SiO2 molar ratio of 0.1 to 0.5, preferably 0.2 to 0.3, and a Na2O weight content of <0.2%, most preferably <0.15%. Based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the mass content of phosphorus-modified SBA-15 molecular sieve in the catalyst of the present invention is 0.5% to 40%, preferably 5% to 30%.

[0037] In another embodiment, the titanium-modified SBA-15 molecular sieve of the present invention has the following properties: a TiO2 / SiO2 molar ratio of 0.1 to 0.5, preferably 0.2 to 0.3, and a Na2O weight content of <0.2%, most preferably <0.15%. Based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the mass content of the titanium-modified SBA-15 molecular sieve is 0.5% to 40%, preferably 5% to 30%.

[0038] In one embodiment, step 1 further includes the addition of alumina; the alumina may be commercially available boehmite or a commercially available alumina support with a porous distribution. Based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the mass content of alumina is 20% to 90%, preferably 30% to 80%.

[0039] In another embodiment, step 1 or step 2 further includes the addition of a modifier compound, which may be at least one of a silicon-containing compound, a phosphorus-containing compound, a fluorine-containing compound, a titanium-containing compound, a zirconium-containing compound, and a gallium-containing compound. Based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the mass content of the modifier oxide is 0.5% to 5%.

[0040] In one embodiment, a binder is also added in step 1. This binder can be one or more of the following: refractory inorganic oxides: clay, silicon dioxide, aluminum oxide, silicon aluminum, zirconium oxide, and titanium oxide. The weight content of the binder in the final catalyst is 0-40%. Alternatively, the catalyst support of the present invention can be prepared without adding a binder, by directly adding silica sol and kneading and extruding it into strips.

[0041] In one embodiment, a squeezing aid is also added in step 1 of the present invention. Commonly used squeezing aids can be one or more of guar gum powder, citric acid, oxalic acid, cellulose, starch, and polymeric surfactants, with guar gum powder and citric acid being preferred. Based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the mass content of the squeezing aid is 0-10%, preferably 3-8%.

[0042] In one embodiment, the Group VIB metals most commonly used in the distillate oil hydrorefining catalyst of the present invention are Mo and / or W, and the Group VIII metals most commonly used are one or more of Fe, Ni, and Co. The compounds of the Group VIB metals can be soluble salts of Group VIB metals, such as ammonium salts of molybdenum or tungsten, and the compounds of the Group VIII metals can be soluble salts of Group VIII metals, such as nitrates, carbonates, or acetates of iron, cobalt, or nickel, i.e., nitrates, carbonates, or acetates of iron, nitrates, carbonates, or acetates of cobalt, or at least one of nitrates, carbonates, or acetates of nickel.

[0043] In one embodiment, based on the total mass of the distillate oil hydrorefining catalyst of the present invention, the mass content of Group VIB metal oxides in the catalyst of the present invention is 10-30%, preferably 15-25%; and the mass content of Group VIII metal oxides is 1-10%, preferably 3-8%.

[0044] In one embodiment, the preparation steps of the distillate oil hydrorefining catalyst of the present invention specifically include:

[0045] (1) Phosphorus-modified SBA-15 molecular sieve, titanium-modified SBA-15 molecular sieve, and alumina are mixed evenly in a certain proportion.

[0046] (2) Add adhesive to step (1) or directly add adhesive solvent solution and knead into a paste, then extrude into strips;

[0047] (3) The molded material from step (2) is dried at 100-150°C for 1-12 hours and calcined at 450-650°C for 1-12 hours to obtain the catalyst support;

[0048] (4) Prepare impregnation solutions containing compounds of Group VIB metals and / or Group VIII metals;

[0049] (5) After impregnating the catalyst support obtained in step (3) with the impregnation solution prepared in step (4), dry it at 100-150℃ for 1-12 hours and calcine it at 450-650℃ for 1-12 hours to obtain the finished catalyst product.

[0050] In steps (3) and (5), the drying temperature is preferably 100-120℃ and the drying time is preferably 4-8h; in steps (3) and (5), the roasting temperature is preferably 500-600℃ and the roasting time is preferably 4-8h.

[0051] The impregnation can be either excessive impregnation or equal volume impregnation; it can be single-component impregnation or multi-component impregnation. Single-component impregnation involves preparing the active components into impregnation solutions separately and impregnating the catalyst support separately. Multi-component impregnation involves preparing the active components together in one impregnation solution and impregnating the catalyst support simultaneously.

[0052] The catalyst of this invention can be in the shape of flakes, spheres, cylindrical strips, or irregularly shaped strips (clover, four-leaf clover), preferably cylindrical strips and irregularly shaped strips (clover, four-leaf clover). The diameter of the catalyst can be a thin strip of 0.8 mm to 2.0 mm or a thick strip of >2.5 mm, preferably a thin strip of 1.0 mm to 1.8 mm.

[0053] Therefore, the present invention provides a catalyst for hydrorefining distillate oil, characterized by the addition of phosphorus-modified SBA-15 molecular sieve and / or titanium-modified SBA-15 molecular sieve to the catalyst support, which significantly improves the hydrodesulfurization rate and hydrodenitrification rate of the catalyst. Under relatively mild hydrorefining conditions, it can effectively reduce the content of sulfur, nitrogen and aromatics, and greatly improve the cetane number of the product.

[0054] The catalyst of this invention can be used at reaction temperatures of 240°C to 400°C, hydrogen partial pressures of 2.0 MPa to 10.0 MPa, and liquid hourly space velocity of 0.1 h⁻¹. -1 ~3.5h -1 Under process conditions with a hydrogen-to-oil volume ratio of 200–1000:1, processing inferior gasoline can reduce sulfur content to below 50 μg / g, nitrogen content to below 50 μg / g, and olefin content to below 30 v% with a product octane number loss of less than 3 units; processing inferior diesel can reduce sulfur content to below 50 μg / g, nitrogen content to below 350 μg / g, and aromatics content to below 30 v% with a product cetane number increase of more than 3 units and diesel yield greater than 98.0%.

[0055] The following examples further illustrate the distillate oil hydrorefining catalyst of the present invention, but do not limit the present invention.

[0056] Example 1

[0057] Preparation of the distillate oil hydrorefining catalyst CAT-1 of the present invention:

[0058] 200g of boehmite (produced by Shanxi Aluminum Co., Ltd.), 25g of P-SBA-15 molecular sieve with a phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with a titanium loading of 4wt%, and 10g of guar gum powder were mixed evenly. A mixed solution consisting of 15g of nitric acid, 10g of citric acid, and 200g of deionized water was added dropwise and kneaded. The mixture was then extruded into 1.5mm clover-shaped strips, dried at 110℃ for 2 hours, and then calcined at 550℃ for 4 hours to prepare a support. This support was then impregnated with an impregnation solution prepared from nickel nitrate and ammonium metatungstate, dried at 120℃ for 4 hours, and calcined at 550℃ for 4 hours to obtain catalyst CAT-1.

[0059] Example 2

[0060] Preparation of CAT-2, the hydrorefining catalyst for distillate oils of the present invention:

[0061] Take 200g of boehmite (produced by Shanxi Aluminum Co., Ltd.), 25g of P-SBA-15 molecular sieve with a phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with a titanium loading of 4wt%, and 10g of guar gum powder, mix them evenly, and add dropwise a mixed solution composed of 15g nitric acid, 10g citric acid, 20g silica sol, and 200g deionized water. Knead the mixture, extrude it into 1.5mm clover-shaped strips, dry them at 110℃ for 2 hours, and then calcine them at 550℃ for 4 hours to prepare a support. Impregnate the support with an impregnation solution prepared with ammonium fluoride, dry it at 120℃ for 4 hours, calcine it at 350℃ for 4 hours, and then impregnate it with an impregnation solution prepared with nickel nitrate and ammonium metatungstate, dry it at 120℃ for 4 hours, and calcine it at 550℃ for 4 hours to obtain catalyst CAT-2.

[0062] Example 3

[0063] Preparation of CAT-3, the hydrorefining catalyst for distillate oils of the present invention:

[0064] Take 200g of boehmite (produced by Shanxi Aluminum Co., Ltd.), 40g of P-SBA-15 molecular sieve with a phosphorus loading of 6wt%, and 10g of guar gum powder, mix them evenly, add dropwise a mixed solution composed of 15g nitric acid, 10g citric acid, and 200g deionized water, knead, extrude into 1.5mm clover-shaped strips, dry at 110℃ for 2h, and then calcine at 550℃ for 4h to prepare a support. Impregnate with an impregnation solution prepared from nickel nitrate and ammonium metatungstate, dry at 120℃ for 4h, and calcine at 550℃ for 4h to obtain catalyst CAT-3.

[0065] Example 4

[0066] Preparation of CAT-4, the hydrorefining catalyst for distillate oils of the present invention:

[0067] 200g of boehmite (produced by Shanxi Aluminum Co., Ltd.), 40g of Ti-SBA-15 molecular sieve with a titanium loading of 4wt%, and 10g of guar gum powder were mixed evenly. A mixed solution consisting of 15g nitric acid, 10g citric acid, and 200g deionized water was added dropwise and kneaded. The mixture was then extruded into 1.5mm clover-shaped strips, dried at 110℃ for 2 hours, and then calcined at 550℃ for 4 hours to prepare a support. This support was then impregnated with an impregnation solution prepared from nickel nitrate and ammonium metatungstate, dried at 120℃ for 4 hours, and calcined at 550℃ for 4 hours to obtain catalyst CAT-4.

[0068] Example 5

[0069] Preparation of CAT-5, the hydrorefining catalyst for distillate oils of the present invention:

[0070] 200g of boehmite (produced by Shanxi Aluminum Co., Ltd.), 25g of P-SBA-15 molecular sieve with a phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with a titanium loading of 4wt%, and 10g of guar gum powder were mixed evenly. A mixed solution consisting of 15g of nitric acid, 10g of citric acid, and 200g of deionized water was added dropwise and kneaded. The mixture was then extruded into 1.5mm clover-shaped strips, dried at 110℃ for 2 hours, and then calcined at 550℃ for 4 hours to prepare a support. This support was then impregnated with an impregnation solution prepared from basic nickel carbonate and ammonium molybdate, dried at 120℃ for 4 hours, and calcined at 550℃ for 4 hours to obtain catalyst CAT-5.

[0071] Example 6

[0072] Preparation of CAT-6, the hydrorefining catalyst for distillate oils of the present invention:

[0073] 200g of boehmite (produced by Shanxi Aluminum Co., Ltd.), 25g of P-SBA-15 molecular sieve with a phosphorus loading of 6wt%, 25g of Ti-SBA-15 molecular sieve with a titanium loading of 4wt%, and 10g of guar gum powder were mixed evenly. A mixed solution consisting of 15g of nitric acid, 10g of citric acid, and 200g of deionized water was added dropwise and kneaded. The mixture was then extruded into 1.5mm clover-shaped strips, dried at 110℃ for 2 hours, and then calcined at 550℃ for 4 hours to prepare a support. This support was then impregnated with an impregnation solution prepared from nickel nitrate and ammonium metatungstate, dried at 120℃ for 4 hours, and calcined at 550℃ for 4 hours to obtain catalyst CAT-6.

[0074] Example 7

[0075] Preparation of CAT-7, the hydrorefining catalyst for distillate oils of the present invention:

[0076] 200g of boehmite (produced by Shanxi Aluminum Co., Ltd.), 15g of P-SBA-15 molecular sieve with a phosphorus loading of 6wt%, 15g of Ti-SBA-15 molecular sieve with a titanium loading of 4wt%, and 10g of guar gum powder were mixed evenly. A mixed solution consisting of 15g of nitric acid, 10g of citric acid, and 200g of deionized water was added dropwise and kneaded. The mixture was extruded into 1.5mm clover-shaped strips, dried at 110℃ for 2 hours, and then calcined at 550℃ for 4 hours to prepare a support. The support was then impregnated with an impregnation solution prepared from nickel nitrate and ammonium metatungstate, dried at 120℃ for 4 hours, and calcined at 550℃ for 4 hours to obtain catalyst CAT-7.

[0077] Example 8

[0078] Preparation of the distillate oil hydrorefining catalyst CAT-8 of the present invention:

[0079] Take 200g of pseudoboehmite produced by Shanxi Aluminum Co., Ltd., add 10g of guar gum powder, mix evenly, and then add dropwise a mixed solution composed of 10g nitric acid, 10g citric acid and 200g deionized water. Extrude the mixture into 1.5mm clover-shaped strips, dry at 110℃ for 2 hours, and then calcine at 550℃ for 4 hours to prepare a carrier. Impregnate the carrier with an impregnation solution prepared from nickel nitrate and ammonium metatungstate, dry at 120℃ for 4 hours, and calcine at 550℃ for 4 hours to obtain catalyst CAT-8.

[0080] Comparative Example 1

[0081] An industrial diesel hydrorefining agent CAT-A, wherein the carrier is titanium-modified alumina (titanium loading 3-5 wt%), and the active metals for hydrorefining are tungsten, nickel, and fluorine.

[0082] Table 1 Catalyst composition

[0083]

[0084]

[0085] Example 9

[0086] This embodiment describes the microreactor evaluation results of the above catalyst.

[0087] The catalyst used for microreactor evaluation was 1.5 g. A decane solution containing dibenzothiophene (1000 μg / g sulfur) and a decane solution containing indole (500 μg / g nitrogen) were used as evaluation raw materials to conduct comparative tests on hydrodesulfurization and hydrodenitrification performance. The reaction conditions are shown in Table 2, and the results of the catalyst's microreactor hydrogenation evaluation are shown in Table 3.

[0088] Table 2 Evaluation conditions for microreactor hydrogenation

[0089]

[0090] Table 3 Evaluation results of microreactor hydrogenation

[0091]

[0092]

[0093] As shown in Table 3, the hydrodesulfurization and hydronitrogenation activities of catalysts CAT-1 to CAT-7 with added molecular sieves were significantly improved compared to catalyst CAT-8 without added molecular sieves. Furthermore, the simultaneous addition of phosphorus-modified and titanium-modified SBA-15 molecular sieves further enhanced the hydrodesulfurization and hydronitrogenation performance of catalysts CAT-1, CAT-6, and CAT-7 compared to catalysts CAT-3 (with phosphorus-modified SBA-15 molecular sieve alone) and CAT-4 (with titanium-modified SBA-15 molecular sieve alone). The introduction of the fluorine additive slightly reduced the hydrodesulfurization and hydronitrogenation performance of catalyst CAT-2. Catalysts CAT-1, CAT-6, and CAT-7 using tungsten and nickel as active metals exhibited higher hydrodesulfurization and hydronitrogenation performance than catalyst CAT-5 (using molybdenum and nickel as active metals). Additionally, the hydrorefining catalysts incorporating modified SBA-15 molecular sieves showed superior hydrodesulfurization performance compared to the industrial hydrorefining catalyst CAT-A prepared using conventional processes.

[0094] Example 10

[0095] In this embodiment, a 100ml hydrogenation evaluation device was used to evaluate the single-stage, single-agent hydrogenation performance of catalysts CAT-1 and CAT-A using catalytic diesel with high sulfur and nitrogen content and a mixture of catalytic diesel and coking diesel (weight ratio 1:1) as raw materials. The reaction conditions are shown in Table 4, and the hydrogenation evaluation results are shown in Table 5.

[0096] Table 4 Evaluation conditions for the 100ml hydrogenation evaluation device

[0097]

[0098] Table 5. Hydrogenation evaluation results of the catalyst in a 100ml hydrogenation evaluation device.

[0099]

[0100]

[0101] Example 11

[0102] In this embodiment, a 100ml hydrogenation evaluation device was used. A mixture of catalytic gasoline with high sulfur and nitrogen content and straight-run naphtha (weight ratio 6:4) was used as raw material to evaluate the single-stage single-agent hydrogenation performance of catalysts CAT-1 and CAT-A. The reaction conditions are shown in Table 6, and the hydrogenation evaluation results are shown in Table 7.

[0103] Table 6 Evaluation conditions in the 100ml hydrogenation evaluation device

[0104]

[0105] Table 7 Evaluation results of the catalyst in a 100ml hydrogenation evaluation device.

[0106]

[0107] Example 12

[0108] In this embodiment, a 100ml hydrogenation evaluation device was used. Canadian oil sands bitumen with high sulfur and nitrogen content was used as raw material to evaluate the single-stage, single-agent hydrogenation performance of catalysts CAT-1 and CAT-A. The reaction conditions are shown in Table 8, and the hydrogenation evaluation results are shown in Table 9.

[0109] Table 8 Evaluation conditions in the 100ml hydrogenation evaluation device

[0110]

[0111] Table 9 Evaluation results of the catalyst in a 100ml hydrogenation evaluation device.

[0112]

[0113] As shown in the above evaluation results, the distillate oil hydrorefining catalyst of the present invention can process inferior gasoline and diesel under relatively mild process conditions to achieve deep desulfurization, denitrification, reduction of olefins and aromatics, and can also significantly improve the cetane number of diesel.

[0114] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A catalyst for the hydrorefining of distillate oils, characterized in that, It includes a catalyst support and an active component, wherein the catalyst support includes alumina, phosphorus-modified SBA-15 molecular sieve and titanium-modified SBA-15 molecular sieve, and the active component includes Group VIB metal oxide and / or Group VIII metal oxide; The preparation method of the phosphorus-modified SBA-15 molecular sieve is as follows: SBA-15 molecular sieve is mixed with a phosphorus-containing compound, ultrasonically treated, and dried and calcined to obtain phosphorus-modified SBA-15 molecular sieve; the preparation method of the titanium-modified SBA-15 molecular sieve is as follows: SBA-15 molecular sieve is mixed with a titanium-containing compound, ultrasonically treated, and dried and calcined to obtain titanium-modified SBA-15 molecular sieve.

2. The distillate oil hydrorefining catalyst according to claim 1, characterized in that, Based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the phosphorus-modified SBA-15 molecular sieve is 5% to 40%, and the mass content of the titanium-modified SBA-15 molecular sieve is 5% to 40%; in the phosphorus-modified SBA-15 molecular sieve, the molar ratio of P2O5 / SiO2 is 0.1 to 0.5; in the titanium-modified SBA-15 molecular sieve, the molar ratio of TiO2 / SiO2 is 0.1 to 0.

5.

3. The distillate oil hydrorefining catalyst according to claim 2, characterized in that, The distillate oil hydrorefining catalyst further includes a modifier oxide, which is at least one of silicon, phosphorus, fluorine, titanium, zirconium, and gallium oxides. Based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the modifier oxide is 0.5% to 5%.

4. The distillate oil hydrorefining catalyst according to claim 1, characterized in that, The Group VIB metal oxide is an oxide of molybdenum and / or an oxide of tungsten, and the Group VIII metal oxide is at least one of oxides of iron, nickel, and cobalt; based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the Group VIB metal oxide is 15-30%, and the mass content of the Group VIII metal oxide is 2-10 wt%.

5. A method for preparing a catalyst for the hydrorefining of distillate oil, characterized in that, Includes the following steps: Step 1: Extruding alumina, phosphorus-modified SBA-15 molecular sieve and titanium-modified SBA-15 molecular sieve to obtain catalyst support; Step 2: Prepare an impregnation solution containing compounds of Group VIB metals and / or Group VIII metals, impregnate the catalyst support obtained in Step 1, and dry and calcine to obtain a distillate oil hydrorefining catalyst. The preparation method of the phosphorus-modified SBA-15 molecular sieve is as follows: SBA-15 molecular sieve is mixed with a phosphorus-containing compound, ultrasonically treated, and dried and calcined to obtain phosphorus-modified SBA-15 molecular sieve; the preparation method of the titanium-modified SBA-15 molecular sieve is as follows: SBA-15 molecular sieve is mixed with a titanium-containing compound, ultrasonically treated, and dried and calcined to obtain titanium-modified SBA-15 molecular sieve.

6. The method for preparing the distillate oil hydrorefining catalyst according to claim 5, characterized in that, Step 1 or Step 2 may further include the addition of a modifier compound, wherein the modifier compound is at least one of a silicon-containing compound, a phosphorus-containing compound, a fluorine-containing compound, a titanium-containing compound, a zirconium-containing compound, and a gallium-containing compound; the group VIB metal compound is an ammonium salt of molybdenum and / or an ammonium salt of tungsten; and the group VIII metal compound is at least one of an iron, cobalt, or nickel nitrate, carbonate, or acetate.

7. The method for preparing the distillate oil hydrorefining catalyst according to claim 5, characterized in that, Based on the total mass of the distillate oil hydrorefining catalyst, the mass content of the phosphorus-modified SBA-15 molecular sieve is 5% to 40%, the mass content of the titanium-modified SBA-15 molecular sieve is 5% to 40%, the mass content of the Group VIB metal compound (calculated as oxide) is 15% to 30%, and the mass content of the Group VIII metal compound (calculated as oxide) is 2% to 10%.

8. The method for preparing the distillate oil hydrorefining catalyst according to claim 5, characterized in that, The impregnation in step 2 is either single-component impregnation or two-component impregnation, and the impregnation method is either excessive impregnation or equal-volume impregnation.

9. The application of the distillate oil hydrorefining catalyst according to any one of claims 1-4 in distillate oil hydrorefining.

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