Diesel oil hydrofining catalyst and preparation method thereof

Abstract

The invention provides a diesel oil hydrofining catalyst. The diesel oil hydrofining catalyst comprises a modified alumina carrier and an active component, the active component is an oxide of active metal, and the active metal comprises at least one of Co, Mo, Ni and W; the modified alumina carrier is alumina hydrothermally modified by ammonium fluoborate; the B / L acid value of the modified alumina carrier is 0.07 to 0.15; the specific surface area is 240-400 m < 2 > / g, and the pore volume is 0.55-0.80 mL / g. The diesel oil hydrofining catalyst containing the B acid can promote removal of sulfides with steric hindrance in distillate oil through a direct desulfurization reaction path and a hydroisomerization-direct desulfurization reaction path, promote adsorption and removal of nitrides, and reduce mutual inhibition effect in the removal process of the sulfides and the nitrides; and the diesel oil hydrofining catalyst has excellent hydrogenation activity.

Description

Technical Field

[0001] The invention relates to the field of petroleum refining and hydrogenation, and in particular to a diesel hydrorefining catalyst and a preparation method thereof. Background Art

[0002] Crude oil and gasoline and diesel fractions derived from crude oil contain impurities such as sulfur, nitrogen, oxygen and metals. The presence of these impurities not only affects the stability of the oil, but also emits SO during use. X 、NO X and other toxic and harmful gases, thus polluting the environment. With increasingly stringent environmental regulations, the quality requirements for oil products are getting higher and higher. From the end of 2014 to the beginning of 2019, my country's diesel quality standards were upgraded from National IV to National VI, achieving a triple jump in diesel quality in four years. In recent years, the inferior and heavy quality of crude oil has put forward higher requirements on the activity and stability of catalysts.

[0003] The implementation of the National VI diesel standard has increased the severity of diesel hydrotreating units and shortened the unit operation cycle. In order not to affect the unit's operation cycle, the hydrotreating technology has put forward higher requirements on the activity of the hydrotreating catalyst. Studies have found that by introducing B acid centers in the catalyst and changing the sulfide hydrogenation reaction path, the hydrogenation reaction efficiency can be improved, thereby reducing the reaction temperature, and promoting the simultaneous removal of sulfur, nitrogen, and aromatics, while effectively extending the catalyst life.

[0004] At present, most of the methods for introducing B acid into the catalyst are mainly based on introducing molecular sieves containing B acid, or adding elements such as F, B, and Zr during the preparation of the carrier to increase the B acid content of the carrier. However, the B acid centers formed by these modification methods are random, and the acid amount and acid strength are uncontrollable. The acid strength requirement of the diesel hydrofining catalyst for the carrier is that the acid cannot be too strong, and weak acid is mainly used, so as to avoid cracking during the hydrogenation process, thereby affecting the yield of refined diesel. In addition, due to the presence of acid centers in the hydrogenation catalyst, the precursor compounds of carbon deposition will be strongly adsorbed on the acid centers of the catalyst, thereby covering the active centers and gradually blocking the pores, so that the reactants cannot approach the active centers, and ultimately greatly reduce the surface utilization of the catalyst, causing the catalyst to be deactivated by carbon deposition.

[0005] The deactivation rate of diesel hydrodesulfurization catalyst is related to the catalyst's carbon deposition deactivation, and the carbon deposition reaction is closely related to the catalyst's medium-strong acid strength. At the same time, the interaction between Lewis acid and basic nitrogen compounds is the main carbon formation pathway. Lewis acid centers are the starting point for the formation of coke layers. Basic nitrides have the strongest affinity for protons and the strongest ability to contribute unpaired electrons. Due to the structural similarities between nitrogen-containing heterocyclic compounds and sulfur-containing and aromatic compounds, all of these compounds interact with the active center in a more or less similar form, which can easily cause catalyst carbon deposition poisoning on the Lewis acid center. Catalysts with high acid content not only have high hydrodenitrogenation activity, but also reduce the amount of carbon deposits on the catalyst.

[0006] In summary, to ensure that the diesel hydrogenation catalyst has a low carbon deposition deactivation rate (to ensure the catalyst activity and the stability of the catalyst activity), the strength of the hydrogenation catalyst is required to be appropriate, and The amount of B acid should be high and the amount of Lewis acid should be low, that is, a high B acid / L acid ratio.

[0007] For example, Chinese patent document CN201510055751.8 discloses a high denitrification performance hydrogenation catalyst and its preparation method, which uses silicon and phosphorus-containing alumina as a carrier and metal oxides of Group VIB and / or Group VIII as active components; the surface acid properties of the carrier are: the acid content is 0.2-0.7 mmol / g, and the B acid content is 0.1-0.3 mmol / g. However, this catalyst is mainly used for residual oil hydrodenitrogenation.

[0008] Chinese patent document CN200810055455.8 discloses an alumina carrier and a preparation method thereof, wherein zirconium, titanium, silicon, alkali metals, alkaline earth metals, rare earth metals and carbon black are added to the alumina carrier by a kneading method, and the prepared alumina carrier has the characteristics of large pore size and high B acid content. However, the volume fraction of macropores (>100nm) of the carrier is>90%, the pore size of the carrier is too large, the specific surface area loss is large, and the pore confinement effect is lost, which is not conducive to the hydrodesulfurization reaction.

[0009] Chinese patent document CN200410050713.5 discloses a hydroprocessing catalyst, which uses one or more metals from Group VIB and Group VIII as active metal components. The catalyst uses silicon and titanium modified alumina as a carrier, and the specific surface area is 310m 2 / g~380m 2 / g, pore volume is 0.8cm 3 / g~1.2cm 3 / g, the pore volume with a pore size of 8nm to 15nm accounts for 75% to 85% of the total pore volume, and the infrared acid content at ≥350℃ is 0.04mmol / g to 0.10mmol / g, of which B acid accounts for 40% to 60% of the total acid. However, the infrared acid content of the catalyst at ≥350℃ is 0.04mmol / g to 0.10mmol / g, which is a strong acid. When used in the hydrofining process, it will cause cracking reactions to occur to varying degrees, affecting the yield of refined oil products.

[0010] Chinese patent document CN201711400168.1 discloses a method for preparing a deep hydrodesulfurization catalyst, wherein pseudo-boehmite, solid aluminum sol, active α-alumina powder, binder, and pore expander are mixed evenly in a mixer, and then a mixed aqueous solution of phosphoric acid and acetic acid is added to knead the powder into mud, and then the catalyst carrier is obtained by kneading, extrusion molding, drying, breaking and roasting; then the metal W, Mo, Co, Ni and P are loaded by impregnation method, and the deep hydrodesulfurization catalyst is obtained after drying and roasting. The infrared acid content of the catalyst is 0.4-0.8 mmol / g; the ratio of B acid / L acid is 1.6-1.9. However, the document only gives the acid content and the ratio of B acid / L acid in the claims and the specification, and does not explain the specific acid strength. If the acid strength is strong acid, liquid recovery may be lost during diesel hydrogenation.

[0011] Chinese patent document CN201911353949.9 discloses a hydrorefining catalyst carrier, a hydrorefining catalyst and a preparation method thereof. The carrier includes: Beta / Al-SBA-15 composite molecular sieve and alumina, wherein the medium-strong acid amount of the Beta / Al-SBA-15 composite molecular sieve is 0.6-1.2mL / g, and the ratio of B acid to L acid is less than 0.80. The preparation method of the Beta / Al-SBA-15 composite molecular sieve used in the carrier includes: using amorphous silica-alumina dry glue as a raw material, using P123 triblock copolymer as a template to crystallize and synthesize Al-SBA-15 molecular sieve, and then adding Beta molecular sieve slurry, and crystallizing to obtain Beta / Al-SBA-15 composite molecular sieve. The method of introducing B's acid into the catalyst is to add a molecular sieve into the carrier (introducing a Beta / Al-SBA-15 composite molecular sieve containing B's acid into the carrier), but the synthesis cost of the molecular sieve is relatively high, and the strength of the composite molecular sieve is medium-strong acid, which easily causes mild cracking of the reactants, thereby reducing the distillate oil yield.

[0012] In the document "Preparation of B-acid-Rich Alumina and Hydrodesulfurization Reaction Performance of Using it as a Carrier Catalyst", a B-acid-rich alumina carrier was prepared by modifying pseudo-boehmite with ammonium fluoroborate. By adjusting the F / Al ratio, an alumina carrier with a B / L ratio of 0.17-1.06 was prepared for hydrogenation of 4,6-DMDBT, which can improve the direct desulfurization path of 4,6-DMDBT via the isomerization-direct desulfurization path. However, the carrier surface area and pore structure were significantly destroyed during the carrier modification process. When the B / L value was 1.06, the specific surface area lost 17.3% and the pore volume lost 7.9%. Such a carrier is not conducive to the dispersion of active metals and the diffusion of reactants.

[0013] In Ji Bingjie's master's thesis "Preparation of modified alumina carrier and its ultra-deep hydrodesulfurization performance of diesel", alumina modified with ammonium fluoroborate was used as a carrier, and then the catalyst sample was prepared by equal volume impregnation method. This method is the same as the preparation method of the literature "Preparation of B-acid-rich alumina and hydrodesulfurization reaction performance of catalyst with it as a carrier".

[0014] In summary, in order to improve the activity of the existing diesel hydrogenation catalyst, most of them introduce B acid into the catalyst. However, how to make the strength of the hydrogenation catalyst appropriate, increase the B acid / L acid ratio, increase the selectivity of sterically hindered sulfides through the direct desulfurization reaction path and the hydrogenation isomerization-direct desulfurization reaction path, and then improve the hydrogenation activity, reduce the severity of the reaction without affecting the refined diesel liquid yield is a technical problem that needs to be solved urgently. Summary of the invention

[0015] In view of the problems existing in the prior art and the directions for improvement, the present invention provides a diesel hydrorefining catalyst and a preparation method thereof. The diesel hydrorefining catalyst containing B acid can promote the removal of sterically hindered sulfides in distillate oil through a direct desulfurization reaction pathway and a hydroisomerization-direct desulfurization reaction pathway, and promote the adsorption and removal of nitrides, thereby reducing the mutual inhibition during the removal of sulfides and nitrides. Moreover, the diesel hydrorefining catalyst has excellent hydrogenation activity, can reduce the severity of the reaction, and thus prolong the life of the catalyst.

[0016] To achieve the above object, the present invention provides a diesel hydrofining catalyst, comprising a modified alumina carrier and an active component; the active component is an oxide of an active metal, and the active metal comprises at least one of Co, Mo, Ni, and W;

[0017] The modified alumina carrier is alumina hydrothermally modified by ammonium fluoroborate;

[0018] The modified alumina carrier has a B / L acid value of 0.07 to 0.15 and a specific surface area of ​​240 to 400 m 2 / g, and the pore volume is 0.55~0.80mL / g.

[0019] Optionally, the diesel hydrotreating catalyst provided by the present invention comprises 67% to 85% of the modified alumina carrier and 15% to 33% of the active component, based on the total weight of the diesel hydrotreating catalyst being 100%.

[0020] Optionally, in the diesel hydrotreating catalyst provided by the present invention, the active metals are Ni and W, and the molar ratio of Ni / (Ni+W) is 0.25-0.50; preferably, based on the total weight of the diesel hydrotreating catalyst as 100%, the content of the active component is 24%-33%.

[0021] Optionally, in the diesel hydrotreating catalyst provided by the present invention, the active metals are Ni and Mo, and the molar ratio of Ni / (Ni+Mo) is 0.20-0.30; preferably, based on the total weight of the diesel hydrotreating catalyst as 100%, the content of the active component is 18%-28%.

[0022] Optionally, in the diesel hydrotreating catalyst provided by the present invention, the active metals are Co and Mo, and the molar ratio of Co / (Co+Mo) is 0.20-0.50; preferably, based on the total weight of the diesel hydrotreating catalyst as 100%, the content of the active component is 15%-22%.

[0023] Optionally, the diesel hydrorefining catalyst provided by the present invention has a B / L acid value of 0.1-0.3.

[0024] The present invention also provides a method for preparing the above diesel hydrorefining catalyst, comprising the following steps:

[0025] The modified alumina carrier is immersed in an equal volume of the precursor solution of the active component, dried and calcined to obtain the diesel hydrofining catalyst.

[0026] Optionally, in the preparation method of the diesel hydrotreating catalyst provided by the present invention, the precursor of the active component is a water-soluble salt of the active metal; preferably, the water-soluble salt of the active metal is selected from any one of nitrates, carbonates, ammonium salts, etc., such as cobalt nitrate hexahydrate, basic cobalt carbonate, ammonium heptamolybdate, ammonium tetramolybdate, nickel nitrate hexahydrate, basic nickel carbonate, ammonium metatungstate, etc.

[0027] Optionally, in the preparation method of the diesel hydrofining catalyst provided by the present invention, ultrasonic treatment can be performed before drying if necessary, the purpose of ultrasonic treatment is to make the carrier impregnated more fully, which is conducive to the uniform dispersion of active metals; the parameters of roasting and drying are not specifically limited, and the conventional parameters in the industry can be adopted. The present invention recommends that the roasting temperature is 450-500°C and the time is 4-6h; the drying temperature is 100-120°C and the time is 4-6h. It can be adjusted according to actual conditions and needs.

[0028] Optionally, the preparation of the modified alumina carrier comprises the following steps:

[0029] After mixing alumina and ammonium fluoroborate solution, a hydrothermal reaction is carried out at 50-90° C., and the obtained solid is washed with water, dried, and calcined to obtain the modified alumina carrier;

[0030] The mass ratio of the aluminum oxide to the ammonium fluoroborate in the ammonium fluoroborate solution is 9:1 to 1:1.

[0031] Optionally, in the method for preparing a modified alumina carrier provided by the present invention, the temperature of the hydrothermal reaction is 50 to 70° C., and the time is 4 to 10 hours, preferably 5 to 7 hours.

[0032] Optionally, in the method for preparing a modified alumina carrier provided by the present invention, the mass ratio of the alumina to the ammonium fluoroborate in the ammonium fluoroborate solution is 3:1 to 3:2.

[0033] Optionally, in the method for preparing the modified alumina carrier provided by the present invention, the specific surface area of ​​the alumina is 290 to 450 m 2 / g, and the pore volume is 0.5~0.8mL / g.

[0034] Optionally, in the method for preparing a modified alumina carrier provided by the present invention, the drying temperature is 80 to 100° C. and the drying time is 4 to 6 hours.

[0035] Optionally, in the method for preparing a modified alumina carrier provided by the present invention, the calcination temperature is 450 to 600° C., preferably 450 to 500° C.; and the calcination time is 4 to 6 hours.

[0036] Optionally, in the method for preparing the modified alumina carrier provided by the present invention, the concentration of the ammonium fluoroborate solution is not specifically limited, as long as the ammonium fluoroborate can be completely dissolved. The concentration of the ammonium fluoroborate solution recommended by the present invention is 4wt%-12wt%.

[0037] Compared with the prior art, the present invention has the following advantages:

[0038] Beneficial effect 1: The diesel hydrorefining catalyst provided by the present invention uses alumina hydrothermally modified by ammonium fluoroborate as a carrier, which can appropriately increase the amount of B acid on the surface of the diesel hydrorefining catalyst; at the same time, the acid amount and acid strength of the diesel hydrorefining catalyst are adjusted according to different metal active components. The acid amount and acid strength of the diesel hydrorefining catalyst are controllable, which can effectively improve the selectivity of the direct desulfurization reaction path and the hydroisomerization-direct desulfurization reaction path during the catalyst reaction process to reduce hydrogen consumption. However, the B / L value of the alumina carrier reported in the document "Preparation of Br_Acid-Rich Alumina and Hydrodesulfurization Reaction Performance of Catalyst Using It as a Carrier" is 0.17-1.06. The alumina carrier prepared by repeated experiments according to this method has a high content of strong acid, and the initial activity of the catalyst is high but slight cracking will occur, which will affect the liquid yield of the product; therefore, compared with the catalyst prepared by ammonium fluoroborate-modified pseudo-alumina reported in the literature, the alumina carrier prepared by hydrothermal modification of ammonium fluoroborate in the present invention has a controllable amount of Br_acid and is a weak acid, which improves the selectivity of the catalyst direct desulfurization path while ensuring the liquid yield.

[0039] Beneficial effect 2: The diesel hydrofining catalyst provided by the present invention contains a certain amount of B acid, which improves the selectivity of the direct desulfurization path, thereby reducing the severity of the reaction. The reason or mechanism for this effect is: 4,6-DMDBT has a large steric hindrance, and the hydrogenation active center is difficult to contact the sulfur atom, resulting in a low reaction rate and desulfurization rate during the direct hydrodesulfurization reaction. The presence of the B acid center in the diesel hydrofining catalyst promotes the 4-6 methyl transfer of 4,6-DMDBT, thereby improving the direct desulfurization and isomerization-direct desulfurization reaction paths, greatly improving the desulfurization efficiency and desulfurization activity; at the same time, the diesel hydrofining catalyst can control the acid amount and acid strength according to actual needs. When the B acid center of the diesel hydrofining catalyst is controlled to be a weak acid and a small amount of medium-strong acid, it promotes the activity of the hydrogenation reaction without causing the occurrence of cracking reaction.

[0040] Beneficial effect 3: The diesel hydrorefining catalyst provided by the present invention has suitable acidity and pore structure, and the active metal is more likely to form highly active angular positions and active neutrality, thereby improving the hydrogenation activity of the catalyst. Among them, the carrier can effectively improve the surface properties of the carrier by using ammonium fluoroborate solution as a modifier and hydrothermal medium, combined with controlling the temperature of the hydrothermal reaction and the amount of ammonium fluoroborate, and the formed sheet carrier can promote the distribution of active metals, thereby making it easier to form angular active centers and improve the hydrogenation activity of the catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 Schematic diagram of the hydrodesulfurization reaction of 4,6-DMDBT. DETAILED DESCRIPTION

[0042] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention.

[0043] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0044] In the process of preparing diesel hydrotreating catalyst, the conventional drying and calcination parameters in the industry can meet the implementation of the technical solution of the present invention. However, for the convenience of comparison, the following embodiments and comparative examples are dried at 110°C for 4 hours and then calcined at 480°C in an air atmosphere for 4 hours.

[0045] Example 1

[0046] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0047] Preparation of modified alumina support

[0048] 1) Weigh 30 g of ammonium fluoroborate into a beaker, add 700 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0049] 2) Weigh 90g of alumina carrier SR-00 and put it into a 1L hydrothermal autoclave, and add the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified alumina carrier SRF-1.

[0050] Preparation of Diesel Hydrotreating Catalyst

[0051] 1) 220 g of nickel nitrate and 352 g of ammonium metatungstate were dissolved in 500 mL of deionized water to prepare a mixed impregnation solution;

[0052] 2) Using the equal volume impregnation method, 50 g of the above-mentioned carrier SRF-1 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110°C for 4 hours, and then calcined at 480°C in an air atmosphere for 4 hours to obtain a W-Ni diesel hydrotreating catalyst CAT1-1.

[0053] Example 2

[0054] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0055] Preparation of modified alumina support

[0056] 1) Weigh 38 g of ammonium fluoroborate into a beaker, add 700 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0057] 2) Weigh 90g of alumina carrier SR-00 and put it into a 1L hydrothermal autoclave and add the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature. After opening the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified alumina carrier SRF-2.

[0058] Preparation of diesel hydrofining catalyst: Similar to Example 1, the only difference is that a different carrier is used. In this example, the carrier SRF-2 is used to finally prepare diesel hydrofining catalyst CAT1-2.

[0059] Example 3

[0060] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0061] Preparation of modified alumina support

[0062] 1) Weigh 45 g of ammonium fluoroborate into a beaker, add 700 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0063] 2) Weigh 90g of alumina carrier SR-00 and put it into a 1L hydrothermal autoclave, add the above-mentioned ammonium fluoroborate solution, stir for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified alumina carrier SRF-3.

[0064] Preparation of diesel hydrofining catalyst: Similar to Example 1, the only difference is that a different carrier is used. In this example, the carrier SRF-3 is used to finally prepare diesel hydrofining catalyst CAT1-3.

[0065] Example 4

[0066] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0067] Preparation of modified alumina support

[0068] 1) Weigh 60 g of ammonium fluoroborate into a beaker, add 700 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0069] 2) Weigh 90g of alumina carrier SR-00 and put it into a 1L hydrothermal autoclave, add the above-mentioned ammonium fluoroborate solution, stir for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SRF-4.

[0070] Preparation of diesel hydrofining catalyst: Similar to Example 1, the only difference is the carrier used. In this example, the carrier SRF-4 is used to finally prepare diesel hydrofining catalyst CAT1-4.

[0071] Comparative Example 1

[0072] This comparative example provides a diesel hydrorefining catalyst, and its preparation method is as follows:

[0073] 1) 220 g of nickel nitrate and 352 g of ammonium metatungstate were dissolved in 500 mL of deionized water to prepare a mixed impregnation solution;

[0074] 2) Using the equal volume impregnation method, 50 g of alumina carrier SR-00 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a W-Ni diesel hydrorefining catalyst CATC-1.

[0075] Example 5

[0076] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0077] Preparation of modified alumina support

[0078] 1) Weigh 38 g of ammonium fluoroborate into a beaker, add 700 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0079] 2) Weigh 90g of alumina carrier SR-01 and put it into a 1L hydrothermal autoclave, and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature. After opening the autoclave, filter the material in the autoclave, wash the obtained solid with deionized water twice and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier SRF-5.

[0080] Preparation of Diesel Hydrotreating Catalyst

[0081] 1) 110 g of nickel nitrate and 252 g of ammonium metatungstate were dissolved in 500 mL of deionized water to prepare a mixed impregnation solution;

[0082] 2) Using the equal volume impregnation method, 50 g of the above-mentioned carrier SRF-5 is added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor is placed in an ultrasonic oscillator for 20 minutes, dried at 110°C for 4 hours, and then calcined at 480°C in an air atmosphere for 4 hours to obtain a W-Ni diesel hydrotreating catalyst CAT2-5.

[0083] Example 6

[0084] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0085] Preparation of modified alumina support

[0086] 1) Weigh 38 g of ammonium fluoroborate into a beaker, add 700 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0087] 2) Weigh 90g of alumina carrier SR-02 and put it into a 1L hydrothermal autoclave, and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature. After opening the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, and then put it into a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier SRF-6.

[0088] Preparation of Diesel Hydrotreating Catalyst

[0089] 1) 110 g of nickel nitrate and 252 g of ammonium metatungstate were dissolved in 500 mL of deionized water to prepare a mixed impregnation solution;

[0090] 2) Using the equal volume impregnation method, 50 g of the above-mentioned carrier SRF-6 is added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor is placed in an ultrasonic oscillator for 20 minutes, dried at 110°C for 4 hours, and then calcined at 480°C in an air atmosphere for 4 hours to obtain a W-Ni diesel hydrotreating catalyst CAT2-6.

[0091] Comparative Example 2

[0092] This comparative example provides a diesel hydrorefining catalyst, and its preparation method is as follows:

[0093] 1) 110 g of nickel nitrate and 252 g of ammonium metatungstate were dissolved in 500 mL of deionized water to prepare a mixed impregnation solution;

[0094] 2) Using an equal volume impregnation method, 50 g of alumina carrier SR-01 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a W-Ni diesel hydrorefining catalyst CATC-2.

[0095] Comparative Example 3

[0096] This comparative example provides a diesel hydrorefining catalyst, and its preparation method is as follows:

[0097] 1) 110 g of nickel nitrate and 252 g of ammonium metatungstate were dissolved in 500 mL of deionized water to prepare a mixed impregnation solution;

[0098] 2) Using the equal volume impregnation method, 50 g of alumina carrier SR-02 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a W-Ni diesel hydrorefining catalyst CATC-3.

[0099] Example 7

[0100] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0101] Preparation of modified alumina carrier: same as Example 1.

[0102] Preparation of Diesel Hydrotreating Catalyst

[0103] 1) Weigh 42g of citric acid and dissolve it in 250mL of deionized water. After it is completely dissolved, add 40g of basic cobalt carbonate, stir and heat to above 90°C, continue heating until the mixture is in a paste state, stop heating, add 300mL of ammonia water to the mixture, continue stirring until the paste is completely dissolved, gradually add 142g of ammonium heptamolybdate to the solution, continue adding ammonia water after it is completely dissolved, and use a 500mL volumetric flask to make up the volume to obtain a CoMo impregnation solution;

[0104] 2) Using the equal volume impregnation method, 50 g of the above-mentioned carrier SRF-1 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110°C for 4 hours, and then calcined at 480°C in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrotreating catalyst CAT3-1.

[0105] Example 8

[0106] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0107] Preparation of modified alumina carrier: same as Example 2.

[0108] Preparation of diesel hydrofining catalyst: Similar to Example 7, the only difference is that a different carrier is used. In this example, the carrier SRF-2 is used to finally prepare a diesel hydrofining catalyst CAT3-2.

[0109] Example 9

[0110] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0111] Preparation of modified alumina carrier: same as Example 3.

[0112] Preparation of diesel hydrofining catalyst: Similar to Example 7, the only difference is that a different carrier is used. In this example, the carrier SRF-3 is used, and finally a diesel hydrofining catalyst CAT3-3 is prepared.

[0113] Example 10

[0114] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0115] Preparation of modified alumina carrier: same as Example 4.

[0116] Preparation of diesel hydrofining catalyst: Similar to Example 7, the only difference is that a different carrier is used. In this example, the carrier SRF-4 is used to finally prepare a diesel hydrofining catalyst CAT3-4.

[0117] Comparative Example 4

[0118] This comparative example provides a diesel hydrorefining catalyst, and its preparation method is as follows:

[0119] 1) CoMo impregnation solution: same as in Example 7.

[0120] 2) Using an equal volume impregnation method, 50 g of alumina carrier SR-00 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrorefining catalyst CATC-4.

[0121] Embodiment 11

[0122] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0123] Preparation of modified alumina carrier: same as Example 5.

[0124] Preparation of Diesel Hydrotreating Catalyst

[0125] 1) Weigh 70g of citric acid and dissolve it in 250mL of deionized water. After it is completely dissolved, add 65g of basic cobalt carbonate, stir and heat to above 90°C, continue heating until the mixture is in a paste state, stop heating, add 300mL of ammonia water to the mixture, continue stirring until the paste is completely dissolved, gradually add 142g of ammonium heptamolybdate to the solution, continue adding ammonia water after it is completely dissolved, and use a 500mL volumetric flask to make up the volume to obtain a CoMo impregnation solution;

[0126] 2) Using the equal volume impregnation method, 50 g of the above-mentioned carrier SRF-5 is added to the impregnation solution prepared in step 1) to obtain a catalyst precursor after impregnation. The catalyst precursor is placed in an ultrasonic oscillator for 20 minutes, dried at 110°C for 4 hours, and then calcined at 480°C in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrorefining catalyst CAT4-5.

[0127] Example 12

[0128] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0129] Preparation of modified alumina carrier: same as Example 6.

[0130] Preparation of Diesel Hydrotreating Catalyst

[0131] 1) CoMo impregnation solution: same as in Example 11;

[0132] 2) 50 g of the carrier SRF-6 was added to the impregnation solution prepared in step 1) by an equal volume impregnation method to obtain a catalyst precursor, which was ultrasonicated in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrorefining catalyst CAT4-6.

[0133] Comparative Example 5

[0134] This comparative example provides a diesel hydrorefining catalyst, and its preparation method is as follows:

[0135] 1) CoMo impregnation solution: same as Example 11.

[0136] 2) Using an equal volume impregnation method, 50 g of alumina carrier SR-01 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrorefining catalyst CATC-5.

[0137] Comparative Example 6

[0138] This comparative example provides a diesel hydrorefining catalyst, and its preparation method is as follows:

[0139] 1) CoMo impregnation solution: same as Example 11.

[0140] 2) Using an equal volume impregnation method, 50 g of alumina carrier SR-02 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrorefining catalyst CATC-6.

[0141] Embodiment 13

[0142] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0143] Preparation of modified alumina carrier: same as Example 1.

[0144] Preparation of Diesel Hydrotreating Catalyst

[0145] 1) 70 mL of phosphoric acid (with a concentration of 85%) is added to 800 mL of deionized water to prepare a phosphoric acid solution; the phosphoric acid solution is mixed with 240 g of molybdenum trioxide and stirred, and heated to above 90° C. until most or all of the molybdenum trioxide is dissolved, then cooled to 60-70° C., 92 g of basic nickel carbonate is added thereto and continued to be heated until the solution is dark green and transparent, and the solution is concentrated to a constant volume of 500 mL to obtain a NiMo impregnation solution;

[0146] 2) Using the equal volume impregnation method, 50 g of the above-mentioned carrier SRF-1 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110°C for 4 hours, and then calcined at 480°C in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrotreating catalyst CAT5-1.

[0147] Embodiment 14

[0148] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0149] Preparation of modified alumina carrier: same as Example 2.

[0150] Preparation of diesel hydrotreating catalyst: Similar to Example 13, the only difference is the carrier used. In this example, the carrier SRF-2 is used to finally prepare diesel hydrotreating catalyst CAT5-2.

[0151] Embodiment 15

[0152] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0153] Preparation of modified alumina carrier: same as Example 3.

[0154] Preparation of diesel hydrotreating catalyst: Similar to Example 13, the only difference is the carrier used. In this example, the carrier SRF-3 is used to finally prepare the diesel hydrotreating catalyst CAT5-3.

[0155] Example 16

[0156] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0157] Preparation of modified alumina carrier: same as Example 4.

[0158] Preparation of diesel hydrotreating catalyst: Similar to Example 13, the only difference is the carrier used. In this example, the carrier SRF-4 is used to finally prepare diesel hydrotreating catalyst CAT5-4.

[0159] Comparative Example 7

[0160] This comparative example provides a diesel hydrorefining catalyst, and its preparation method is as follows:

[0161] 1) NiMo impregnation solution: same as Example 13.

[0162] 2) Using an equal volume impregnation method, 50 g of alumina carrier SR-00 was added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor was placed in an ultrasonic oscillator for 20 minutes, dried at 110° C. for 4 hours, and then calcined at 480° C. in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrorefining catalyst CATC-7.

[0163] Embodiment 17

[0164] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0165] Preparation of modified alumina carrier: same as Example 5.

[0166] Preparation of Diesel Hydrotreating Catalyst

[0167] 1) 75 mL of phosphoric acid (with a concentration of 85%) is added to 800 mL of deionized water to prepare a phosphoric acid solution, 160 g of molybdenum trioxide is added to the phosphoric acid solution, mixed and stirred, and heated to above 90° C. until most or all of the molybdenum trioxide is dissolved, then cooled to 60-70° C., and then 92 g of basic nickel carbonate is added and continued to be heated until the solution is dark green and transparent, and the solution is concentrated to 500 mL to obtain a NiMo impregnation solution;

[0168] 2) Using the equal volume impregnation method, 50 g of the above-mentioned carrier SRF-5 is added to the impregnation solution prepared in step 1) to obtain a catalyst precursor. The catalyst precursor is placed in an ultrasonic oscillator for 20 minutes, dried at 110°C for 4 hours, and then calcined at 480°C in an air atmosphere for 4 hours to obtain a Co-Mo diesel hydrotreating catalyst CAT6-5.

[0169] Embodiment 18

[0170] This embodiment provides a diesel hydrorefining catalyst, and the preparation method thereof is as follows:

[0171] Preparation of modified alumina carrier: same as Example 6.

[0172] Preparation of diesel hydrotreating catalyst: Similar to Example 17, the only difference is the carrier used. In this example, a modified alumina carrier SRF-6 is used to finally obtain a diesel hydrotreating catalyst CAT6-6.

[0173] Comparative Example 8

[0174] This comparative example provides a diesel hydrotreating catalyst, and its preparation method is similar to that of Example 17, except that a different carrier is used. In this comparative example, an alumina carrier SR-01 is used, and a diesel hydrotreating catalyst CATC-8 is finally obtained.

[0175] Comparative Example 9

[0176] This comparative example provides a diesel hydrotreating catalyst, and its preparation method is similar to that of Example 17, except that a different carrier is used. In this comparative example, an alumina carrier SR-02 is used, and a diesel hydrotreating catalyst CATC-9 is finally obtained.

[0177] Experimental Example 1

[0178] The modified alumina carriers, alumina carriers SR-00, SR-01 and SR-02 prepared in Examples 1-6 were respectively subjected to specific surface area (S BET ), pore volume (V), B acid, and L acid tests. The specific results are shown in Table 1 below.

[0179] The diesel hydrotreating catalysts prepared in the above examples and comparative examples were respectively measured by specific surface area (S BET ), pore volume (V), B acid, and L acid tests. The specific results are shown in Table 2 below.

[0180] Among them, the specific surface area and pore volume are measured by BET method: Autosorb-6B physical adsorption analyzer produced by Quantachrome Corporation of the United States is used for analysis, adsorption test points and desorption test points are set according to the pore structure of the carrier or catalyst, high-purity nitrogen is used as the adsorption medium, liquid nitrogen is used as the cold trap, and the alumina sample is degassed at 300°C for 8 hours before analysis and testing. According to the characteristics of the change of nitrogen adsorption amount on the surface of porous materials with relative pressure, the adsorption-desorption curve is tested, and then the total pore volume and specific surface area of ​​the carrier or catalyst are calculated.

[0181] The B / L ratio uses an infrared pyridine adsorption method to determine the values ​​of B acid and L acid and then calculate the value of B / L. The specific detection method is: the equipment is an FT-IR infrared spectrometer produced by Thermo Nicolet, USA, and the pyridine adsorption infrared spectroscopy is used to determine the acid type (B acid, L acid) and acid amount on the surface of the carrier or catalyst; at 350°C, dehydrate for 4 hours, and after cooling, vacuum adsorb pyridine in a pyridine dryer for 24 hours. Desorb in a drying oven at 150°C for about 1 hour. Using a blank sample without pyridine adsorption as the background comparison, perform a diffuse reflectance infrared scan with a scanning range of 650 to 4000 cm -1 .

[0182] Table 1

[0183]

[0184]

[0185] It can be seen from the data in the above table that, compared with the unmodified carrier, the present invention uses ammonium fluoroborate as a modifier, an ammonium fluoroborate solution as a hydrothermal medium, and combines the temperature of the hydrothermal reaction to modify the alumina carrier, which can effectively improve the surface properties of the carrier, so that the modified carrier is suitable for the prepared light distillate oil hydrorefining catalyst. In addition, compared with the unmodified carrier, the modified carrier has increased B acid sites, and the increased B acid sites are mainly weak acids.

[0186] Table 2

[0187]

[0188]

[0189] It can be seen from the data in the above table that, compared with the unmodified carrier, the specific surface area and pore volume data of the catalyst prepared by using the alumina carrier hydrothermally modified by ammonium fluoroborate in the present invention can meet the needs of industrial production of catalysts, and the B / L value is increased to a certain extent, which is conducive to the removal of sterically hindered sulfides through the direct desulfurization reaction pathway or the isomerization-direct desulfurization reaction pathway; and a suitable catalyst can be selected according to the different properties of the raw materials.

[0190] Experimental Example 2

[0191] The active component contents of the catalysts prepared in the above-mentioned embodiments and comparative examples are shown in Table 3, and the active component contents in the catalysts are theoretically calculated values. The catalysts prepared in the embodiments and comparative examples were evaluated for their effects according to the following method, and the evaluation results are shown in Table 3 below.

[0192] The catalyst was evaluated in a 20mL pilot hydrogenation evaluation device. The amount of catalyst used was 20mL. The raw material was a catalytic diesel coking diesel mixed oil of a refinery. The raw material sulfur content was 1400μg / g, the nitrogen content was 914μg / g, the reaction temperature was 360℃, the hydrogen partial pressure was 6.4MPa, the hydrogen-oil volume ratio was 500:1, and the volume space velocity was 2.0h -1 .

[0193] Desulfurization rate = (raw material sulfur content - product sulfur content) / raw material sulfur content × 100%

[0194] Denitrification rate = (nitrogen content of raw materials - nitrogen content of products) / nitrogen content of raw materials × 100%

[0195] Table 3

[0196]

[0197]

[0198] As can be seen from the data in the above table, the active component and the content of the active component have an effect on the catalyst activity, but in the case of the same metal component and content, the acidity of the carrier and the reasonable matching of the pore volume are also very important. In the case of the same carrier, the CoMo catalyst has a relatively higher denitrification activity, and the W-Ni component has a higher desulfurization activity. For example, when the desulfurization activity of Example 5 is equivalent to that of Example 7, the CoMo catalyst has a higher denitrification activity; In addition, the content of the active metal is also another factor affecting the activity of the catalyst. For the catalysts with the same active metal and the same metal content, as the B / L value increases, the desulfurization activity also increases accordingly, but due to the catalyst specific surface area of ​​the higher B acid value, the B / L has a peak value, that is, the acid properties and the pore structure are reasonably matched to play the best performance of the catalyst. Overall, in the case of the same active component and the same metal content, the modified carrier is compared with the carrier before modification, and the catalyst prepared after modification has a higher desulfurization activity and denitrification activity; It can be seen from the liquid collection data in the table that the modified catalyst has a higher desulfurization and denitrification activity, and the liquid collection is not significantly reduced, indicating that the acid center on the catalyst is a weak acid site, and no obvious cracking reaction occurs.

[0199] Experimental Example 3

[0200] This experimental example mainly introduces the catalyst hydrodesulfurization reaction path. Using 2% 4,6-DMDBT (4.6-dimethyldibenzothiophene) n-heptane model compound as raw material, the product composition after the reaction is shown in the table below under the reaction conditions of reaction temperature 360°C, hydrogen partial pressure 6.4MPa, hydrogen oil volume ratio 500:1, and volume space velocity 2.0h-1. Figure 1 shown.

[0201] Table 4 Evaluation results

[0202]

[0203] a: HYD: hydrodesulfurization pathway;

[0204] b: DDS: direct desulfurization pathway;

[0205] c: ISO-DDS: isomerization followed by direct desulfurization.

[0206] It is generally believed that 3,3'-DMBCH (3,3'-dimethylbicyclohexane), 3,3'-DMCHB (3,3'-dimethylcyclohexylbenzene), 4,6-THDMDBT and 4,6-HHDMDBT are products of hydrogenation followed by desulfurization; 3,3'-DMBP (3,3'-dimethylbiphenyl) is a direct desulfurization product; and 4,4'-DMBP (4,4'-dimethylbiphenyl) is a product of isomerization followed by direct desulfurization.

[0207] From the data in the above table, it can be seen that direct desulfurization active centers are more easily formed during the preparation of Co-Mo catalysts, so the direct desulfurization activity of CATC-5 catalyst is higher than that of CATC-1 tungsten-nickel catalyst and CATC-8 molybdenum-nickel catalyst. The activity and direct desulfurization activity of the three catalysts CAT1-3, CAT4-5 and CAT6-5 prepared with modified carriers are improved. The evaluation results of these three catalysts also show that the Co-Mo catalyst CAT4-5 exhibits higher direct desulfurization activity.

[0208] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A diesel hydrorefining catalyst, characterized in that: It comprises a modified alumina carrier and an active component; the active component is an oxide of an active metal, and the active metal comprises at least one of Co, Mo, Ni, and W; The modified alumina carrier is alumina hydrothermally modified by ammonium fluoroborate; The modified alumina carrier has a B / L acid value of 0.07 to 0.15 and a specific surface area of ​​240 to 400 m 2 / g, and the pore volume is 0.55~0.80mL / g.

2. The diesel hydrotreating catalyst according to claim 1, characterized in that: Taking the total weight of the diesel hydrofining catalyst as 100%, the catalyst comprises 67% to 85% of the modified alumina carrier and 15% to 33% of the active component.

3. The diesel hydrotreating catalyst according to claim 1, characterized in that: The active metals are Ni and W, and the molar ratio of Ni / (Ni+W) is 0.25-0.50; preferably, based on the total weight of the diesel hydrotreating catalyst being 100%, the content of the active component is 24%-33%.

4. The diesel hydrotreating catalyst according to claim 1, characterized in that: The active metals are Ni and Mo, and the molar ratio of Ni / (Ni+Mo) is 0.20-0.30; preferably, based on the total weight of the diesel hydrotreating catalyst being 100%, the content of the active component is 18%-28%.

5. The diesel hydrotreating catalyst according to claim 1, characterized in that: The active metals are Co and Mo, and the molar ratio of Co / (Co+Mo) is 0.20-0.50; preferably, based on the total weight of the diesel hydrotreating catalyst being 100%, the content of the active component is 15%-22%.

6. The diesel hydrotreating catalyst according to any one of claims 1 to 5, characterized in that: The B / L acid value of the diesel hydrorefining catalyst is 0.1 to 0.

3.

7. A method for preparing a diesel hydrorefining catalyst according to any one of claims 1 to 6, characterized in that: The steps include: The modified alumina carrier is immersed in an equal volume of the precursor solution of the active component, dried and calcined to obtain the diesel hydrofining catalyst.

8. The method for preparing a diesel hydrorefining catalyst according to claim 7, characterized in that: The preparation of the modified alumina carrier comprises the following steps: After mixing alumina and ammonium fluoroborate solution, a hydrothermal reaction is carried out at 50-90° C., and the obtained solid is washed with water, dried, and calcined to obtain the modified alumina carrier; The mass ratio of the aluminum oxide to the ammonium fluoroborate in the ammonium fluoroborate solution is 9:1 to 1:

1.

9. The method for preparing a diesel hydrorefining catalyst according to claim 8, characterized in that: The temperature of the hydrothermal reaction is 50-70° C., and the time is 4-10 hours, preferably 5-7 hours.

10. The method for preparing a diesel hydrorefining catalyst according to claim 8, characterized in that: The specific surface area of ​​the alumina is 290 to 450 m 2 / g, and the pore volume is 0.5~0.8mL / g.

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