Hydrodesulfurization catalyst, method for preparing the same, and use thereof

Abstract

The present application relates to the technical field of diesel hydrofining, and discloses a hydrodesulfurization catalyst and a preparation method and application thereof.The catalyst comprises cobalt elements and optionally at least one of other metal elements of group VIII, at least one metal element of group VIB, a phosphorus element, a carrier, and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound; wherein the catalyst comprises at least two CO2 release spectrum peaks in a temperature programmed oxidation process, the first release spectrum peak temperature is 200-300 DEG C, the second release spectrum peak temperature is 300-400 DEG C, and the spectrum peak peak height ratio range is 1-5:1.The catalyst has the advantages of high activity and low hydrogen consumption, is especially suitable for distillate oil with low secondary processing diesel content, and can meet the demand of clean diesel production.

Description

Technical Field

[0001] This invention relates to the technical field of diesel hydrorefining, specifically to a hydrodesulfurization catalyst, its preparation method, and its application. Background Technology

[0002] Driven by the "dual-carbon" strategy, traditional oil refining technologies are facing immense pressure. As a core unit in clean diesel production, the low-carbon and high-efficiency operation of diesel hydrotreating units is of paramount importance. Ultra-deep hydrodesulfurization of diesel requires stringent operating conditions and involves a significant amount of hydrogen consumption due to aromatic saturation reactions. Typically, diesel hydrotreating units operate at pressures of 5-8 MPa, requiring substantial hydrogen circulation and resulting in high energy consumption to maintain operation. Therefore, it is necessary to further reduce energy and hydrogen consumption during the reaction process to meet the demands of low-carbon and high-efficiency production. The core technological challenge lies in developing catalyst technologies capable of efficient hydrodesulfurization in a low-energy-consumption mode, thereby fulfilling the requirements for reduced energy and hydrogen consumption.

[0003] The active metals in diesel hydrodesulfurization catalysts are mainly composed of Group VIB metals (Mo and / or W) and Group VIII metals (Co and / or Ni). Patent application No. 202010395989.6 discloses a hydrorefining catalyst and its preparation method and application. This catalyst comprises 50-80 wt% of a support and 20-50 wt% of an active metal component. The support uses a composite oxide to regulate the interaction force between the active metal and the support, thereby increasing the concentration of active hydrogen species on the active metal surface and improving the hydrodesulfurization performance of the catalyst. Patent application No. 201610388357.0 discloses a hydrodesulfurization catalyst comprising a composite support of NiO, MoO3, WO3, and AlOOH and TiO2. This catalyst is a highly reactive and stable slurry catalyst synthesized via a completely liquid-phase method, which can meet the requirements of ultra-deep hydrodesulfurization of diesel fuel.

[0004] As can be seen from existing technologies, there is still a lack of diesel hydrogenation catalysts specifically designed for low hydrogen consumption. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor activity and high hydrogen consumption of existing hydrodesulfurization catalysts, and to provide a hydrodesulfurization catalyst, its preparation method and application. This catalyst has the advantages of high activity and low hydrogen consumption, and is especially suitable for distillate oils with low secondary diesel content, which can meet the needs of clean diesel production.

[0006] To achieve the above objectives, the first aspect of the present invention provides a hydrodesulfurization catalyst, wherein the catalyst comprises cobalt and optionally at least one of other group VIII metals, at least one group VIB metal, phosphorus, a support, and at least two of organic alcohols, carboxylic acids, and organic amines.

[0007] The catalyst contains at least two CO2 release peaks during the programmed temperature oxidation process. The temperature of the first release peak is between 200-300℃, and the temperature of the second release peak is between 300-400℃. The peak height ratio is between 1 and 5:1.

[0008] Preferably, the atomic ratio of cobalt to the total amount of cobalt and optionally other Group VIII metals is not less than 0.8, and more preferably 0.85-1.

[0009] Preferably, the phosphorus content in the catalyst is 3-10% by weight, calculated as P2O5.

[0010] Preferably, the temperature of the first release peak is between 220-280℃, the temperature of the second release peak is between 320-380℃, and the ratio of peak height to peak height is between 1.5 and 3:1.

[0011] Preferably, the molar ratio of the organic alcohol compound to the Group VIB metal element is 0.2-4:1.

[0012] Preferably, the molar ratio of carboxylic acid compounds and / or organic amine compounds to cobalt and optionally other Group VIII metals is 0.1-4:1.

[0013] A second aspect of the present invention provides a method for preparing the hydrodesulfurization catalyst described in the first aspect, the method comprising:

[0014] The carrier is introduced into a substrate by impregnation using a method that includes a Group VIII metal precursor, a Group VIB metal precursor, a phosphorus-containing compound, and at least two compounds selected from organic alcohols, carboxylic acids, and organic amines, followed by drying.

[0015] The third aspect of this invention provides the application of the hydrodesulfurization catalyst described in the first aspect in the hydrorefining of distillate oils.

[0016] Preferably, the proportion of secondary processed diesel in the distillate oil to be treated does not exceed 15% by weight.

[0017] The catalyst provided by this invention contains at least two CO2 release peaks during programmed temperature oxidation. This catalyst has excellent activity and low hydrogen consumption, and is particularly suitable for processing distillate oils in which the proportion of secondary processed diesel does not exceed 15% by weight.

[0018] The inventors discovered that introducing two or more different types of organic compounds into the catalyst, in conjunction with cobalt and phosphorus, can significantly enhance the catalyst's activity. Preferably, when the atomic ratio of cobalt to the total amount of cobalt and optionally other Group VIII metals is not less than 0.8, the catalyst exhibits lower hydrogen consumption. Simultaneously, introducing some phosphorus into the support can further improve the dispersion of the active metal components, significantly enhancing the catalyst's activity. Attached Figure Description

[0019] Figure 1 This is the CO2 release spectrum of the catalyst in Example 1. Detailed Implementation

[0020] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0021] In this invention, it is understood that "optionally" means that it may or may not be included.

[0022] The first aspect of the present invention provides a hydrodesulfurization catalyst, wherein the catalyst comprises cobalt and optionally at least one of other group VIII metals, at least one group VIB metal, phosphorus, a support, and at least two of organic alcohols, carboxylic acids, and organic amines.

[0023] The catalyst contains at least two CO2 release peaks during the programmed temperature oxidation process. The temperature of the first release peak is between 200-300℃, and the temperature of the second release peak is between 300-400℃. The ratio of the peak height to the peak height is between 1 and 5:1.

[0024] In this invention, the first release peak temperature of 200-300℃ refers to a specific temperature value where the peak value of the first release peak appears between 200-300℃, and the second release peak temperature of 300-400℃ refers to a specific temperature value where the peak value of the second release peak appears between 300-400℃.

[0025] In this invention, it is understood that the CO2 emission peak temperature has an error of ±2℃.

[0026] In this invention, "peak height ratio" refers to the ratio of the peak height of the first release peak to the peak height of the second release peak, that is, peak height ratio = peak height of the first release peak / peak height of the second release peak.

[0027] In this invention, the CO2 emission peaks were analyzed on a NETZSCH STA 409PC / PG instrument. The catalyst to be tested was heated in an air atmosphere (heating rate of 10℃ / min), and the gas outlet of the instrument was monitored by a mass spectrometer to obtain the curve of CO2 produced by catalyst decomposition as a function of temperature.

[0028] This invention provides a hydrodesulfurization catalyst with the specific structure and composition described above. By introducing two or more different types of organic compounds, the activity of the catalyst is significantly improved. This catalyst is particularly suitable for distillate oils in which the proportion of secondary processed diesel does not exceed 15% by weight. The catalyst has good activity and low hydrogen consumption.

[0029] In this invention, preferably, based on the total weight of the catalyst and calculated as oxides, the content of cobalt and optionally other Group VIII metals is 1-15% by weight, preferably 2-12% by weight, more preferably 3-7% by weight; the content of Group VIB metals is 12-50% by weight, and the content of Group VIB metals is 15-45% by weight, more preferably 18-40% by weight. The advantage of this preferred embodiment is that the catalyst exhibits higher hydrodesulfurization activity and stability.

[0030] In a preferred embodiment, the atomic ratio of cobalt to the total amount of cobalt and optionally other Group VIII metals is not less than 0.8, more preferably 0.85-1, and even more preferably 0.9-1. The advantage of this preferred embodiment is improved catalyst activity and reduced hydrogen consumption in the reaction.

[0031] In a preferred embodiment, the phosphorus content in the catalyst, calculated as P2O5, is 3-10% by weight, more preferably 3.5-9% by weight, and even more preferably 4-8% by weight. The advantage of this preferred embodiment is that it allows the catalyst to have higher activity.

[0032] In a preferred embodiment, the catalyst exhibits at least two CO2 release peaks during the temperature-programmed oxidation process, with the first peak temperature between 220-280°C and the second peak temperature between 320-380°C, and the peak height ratio ranging from 1.5 to 3:1. The advantage of this preferred embodiment is that the catalyst maintains higher activity and stability.

[0033] In this invention, preferably, the other metal elements of Group VIII are selected from at least one of iron, ruthenium, rhodium, nickel and palladium, and more preferably nickel.

[0034] In this invention, the selection range of Group VIB metal elements is relatively wide. Preferably, the Group VIB metal element is selected from at least one of chromium, molybdenum, and tungsten, and more preferably molybdenum.

[0035] In this invention, there are no specific limitations on the amount of cobalt and optionally other Group VIII and Group VIB metals, as long as the performance of the hydrodesulfurization catalyst is satisfactory. Preferably, the atomic ratio of cobalt and optionally other Group VIII metals to the total amount of cobalt and optionally other Group VIII and Group VIB metals is 0.1-0.5:1, more preferably 0.2-0.35:1. The advantage of this preferred embodiment is that the Group VIII and Group VIB metals maintain a good synergistic effect to achieve higher catalytic performance.

[0036] In this invention, a wide range of carrier types can be selected, and conventional carriers in the art are all suitable for this invention. Preferably, the carrier is an alumina carrier.

[0037] In this invention, preferably, the phosphorus element in the catalyst comprises two parts: one part is introduced into the alumina support, and the other part is introduced during the preparation of the active metal component impregnation solution.

[0038] In a preferred embodiment, the alumina support contains phosphorus, hereinafter referred to as phosphorus-containing alumina. The advantage of this preferred embodiment is that the presence of a specific amount of phosphorus in the alumina support significantly promotes catalyst activity.

[0039] In a preferred embodiment, the phosphorus content in the alumina support, calculated as P2O5, accounts for 10-40% by weight of the total phosphorus content in the catalyst, preferably 20-30% by weight. The advantage of this preferred embodiment is that by rationally controlling the phosphorus content in the alumina support, the loading degree of the active metal component on the alumina support can be further improved, and the dispersion of the active metal component can be enhanced.

[0040] In this invention, phosphorus can be introduced into the formed alumina support, during the alumina support forming process, or during the preparation of the alumina support precursor. Preferably, it is introduced during the preparation of the alumina support precursor. When introduced during the preparation of the alumina precursor, phosphorus can be introduced by adding a phosphorus-containing compound during the preparation of the alumina precursor using the aluminum sulfate-sodium aluminate method. Specifically, phosphoric acid or phosphate can be introduced as a raw material or at any step in the preparation of the alumina precursor. By introducing phosphorus into the alumina precursor, the structural properties of the alumina support are improved, and the dispersion ability of the active metal components is promoted.

[0041] In this invention, the phosphorus element in the phosphorus-containing alumina support is preferably provided by the alumina support precursor. In a preferred embodiment, the precursor of the alumina support is boehmite, and the boehmite contains phosphorus.

[0042] Generally, sodium-containing precursors are used in the preparation of boehmite, and such substances remain in the boehmite. In a preferred embodiment, the sodium oxide content in the boehmite does not exceed 0.08% by weight, preferably not more than 0.05% by weight. The advantage of this preferred embodiment is that it controls the sodium oxide content in the boehmite, further reduces the basicity centers, and thus gives the catalyst good activity, promoting the hydrodesulfurization effect of the catalyst.

[0043] In this invention, there are no specific limitations on the preparation method of the phosphorus-containing alumina support; conventional preparation methods in the art are applicable to this invention. Preferably, the phosphorus-containing alumina support is prepared by extrusion molding; the specific operation method will not be described in detail here.

[0044] In this invention, to further improve the performance of the catalyst, a support with a specific composition and structure is selected as the support for the hydrodesulfurization catalyst. Preferably, the alumina support has a water absorption rate greater than 0.9 mL / g, more preferably 0.95-1.3 mL / g, and a specific surface area greater than 260 m². 2 / g, further preferably 270-320m 2 / g, with an average pore size greater than 8nm, more preferably 9-15nm. The advantage of this preferred embodiment is that a support with a porous structure is used, in which the reactants can come into contact with the active sites of the catalyst and react, thereby improving the activity of the catalyst.

[0045] In a preferred embodiment, the volume of pores with a pore size distribution of 2-6 nm in the alumina carrier accounts for no more than 10% of the total pore volume of the alumina carrier, preferably no more than 8%, and more preferably 3-6%.

[0046] In a preferred embodiment, the volume of pores with a pore size distribution of 2-4 nm in the alumina carrier accounts for no more than 4% of the total pore volume of the alumina carrier, preferably no more than 2%, and more preferably 0-1%.

[0047] By using the aforementioned support with specific composition and structure (preferably alumina support), the proportion of small-sized pores in the support is relatively small, which allows reactants to better approach the active center, ensuring that the catalyst has a relatively unobstructed pore structure, promoting the diffusion of reaction molecules to the active center under low pressure, and thus improving the activity of the catalyst.

[0048] In this invention, the specific surface area, pore volume, pore size, and pore distribution of the carrier were determined using the low-temperature nitrogen adsorption method (BET) (see *Analytical Methods in Petrochemical Industry (RIPP Test Method)*, edited by Yang Cuiding et al., Science Press, 1990). The pore volume in the 2-100 nm range was calculated based on the BET results.

[0049] In a preferred embodiment, the catalyst comprises an organic alcohol compound, a carboxylic acid compound, and / or an organic amine compound. An advantage of this preferred embodiment is that selecting two or more organic compounds can significantly improve the catalyst's activity.

[0050] In this invention, there are no specific limitations on the amount of organic alcohol compounds, carboxylic acid compounds, and organic amine compounds used, as long as the performance requirements of the hydrodesulfurization catalyst are met. Preferably, the molar ratio of organic alcohol compounds to Group VIB metal elements is 0.2-4:1, more preferably 0.3-3.5:1, and even more preferably 0.8-2.5:1. The molar ratio of carboxylic acid compounds and / or organic amine compounds to cobalt and optionally other Group VIII metal elements is 0.1-4:1, more preferably 0.2-3.5:1, and even more preferably 0.5-3:1. The advantage of this preferred embodiment is that it maintains a high degree of metal dispersion in the catalyst, thereby improving the catalyst's activity and stability.

[0051] In this invention, the range of organic alcohol compounds selected is relatively broad, and conventional organic alcohol compounds in the art are all applicable to this invention. Preferably, the organic alcohol compound is selected from at least one of monohydric alcohols, dihydric alcohols, and polyhydric alcohols. More preferably, the organic alcohol compound is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentaethanol, heptanol, ethylene glycol, glycerol, butanetetrol, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol, and trimethylolethane, and even more preferably, at least one of butanol, glycerol, propanol, and ethylene glycol.

[0052] In this invention, there is no specific limitation on the types of carboxylic acid compounds. Preferably, the carboxylic acid compound is selected from at least one of formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, hexanoic acid, decanoic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, stearic acid, and tartaric acid, and more preferably at least one of formic acid, citric acid, and acetic acid.

[0053] In this invention, there is no specific limitation on the type of organic amine compound. Preferably, the organic amine compound is selected from at least one of ethylenediamine, ethylenediaminetetraacetic acid, ethanolamine, triethanolamine, and cyclohexanediaminetetraacetic acid, and more preferably triethanolamine and / or cyclohexanediaminetetraacetic acid.

[0054] In this invention, there is no specific limitation on the size of the catalyst. Preferably, the equivalent diameter of the catalyst is 0.5-1.8 mm, and more preferably 0.8-1.6 mm.

[0055] In this invention, there is no specific limitation on the shape of the catalyst; conventional catalyst shapes in the art are applicable to this invention. Preferably, the catalyst is cylindrical, cloverleaf, four-leaf clover, disc, honeycomb, or other irregular shapes, and more preferably butterfly-shaped.

[0056] The second aspect of the present invention provides a method for preparing a hydrodesulfurization catalyst, the method comprising: introducing a cobalt precursor and optionally other Group VIII metal precursors, Group VIB metal precursors, phosphorus-containing compounds, and at least two compounds selected from organic alcohol compounds, carboxylic acid compounds, and organic amine compounds into a support by impregnation, and then drying.

[0057] In this invention, the types of carriers, other metals of Group VIII, metals of Group VIB, organic alcohol compounds, carboxylic acid compounds, and organic amine compounds have been described in the first aspect and will not be repeated here.

[0058] In a preferred embodiment, the Group VIB metal precursor is selected from at least one of ammonium heptamolybdate, ammonium molybdate, ammonium phosphomolybdate, ammonium metatungstate, and ethyl metatungstate.

[0059] In a preferred embodiment, the cobalt precursor is selected from at least one of cobalt nitrate, basic cobalt carbonate, and cobalt acetate.

[0060] In this invention, the precursors of other Group VIII metal elements are selected from soluble salts of each metal element. Preferably, the precursor of nickel is selected from at least one of nickel nitrate, basic nickel carbonate, and nickel acetate.

[0061] In a preferred embodiment, the phosphorus-containing compound is selected from at least one of phosphoric acid, hypophosphoric acid, ammonium phosphate, and ammonium dihydrogen phosphate.

[0062] According to the present invention, there is no specific limitation on the impregnation method, and conventional impregnation methods in the art are applicable to the present invention. For example, it can be one of co-impregnation, stepwise impregnation, saturated impregnation, and supersaturated impregnation. In a preferred embodiment, the present invention uses co-impregnation to prepare the hydrodesulfurization catalyst. In a more preferred embodiment, the impregnation method includes: impregnating the support (preferably alumina) with an impregnation solution containing a cobalt precursor and optionally other Group VIII metal precursors, Group VIB metal precursors, phosphorus-containing compounds, and at least two of organic alcohol compounds, carboxylic acid compounds, and organic amine compounds.

[0063] In this invention, the order of addition of the cobalt precursor and optionally other Group VIII metal precursors, Group VIB metal precursors, phosphorus-containing compounds, organic alcohol compounds, carboxylic acid compounds, and organic amine compounds is not specifically limited, as long as it facilitates uniform mixing of the components. In a preferred embodiment, at least two of the organic alcohol compounds, carboxylic acid compounds, and organic amine compounds (preferably organic alcohol compounds and carboxylic acid compounds and / or organic amine compounds), the cobalt precursor, and optionally other Group VIII metal precursors and Group VIB metal precursors are added to an aqueous solution of the phosphorus-containing compound to provide the impregnation solution. In this invention, the order of addition of the organic alcohol compounds, carboxylic acid compounds and / or organic amine compounds, phosphorus-containing compounds, and metal precursors can also be interchanged.

[0064] In this invention, the hydrodesulfurization catalyst can be prepared by the following method: First, a phosphorus-containing compound is dissolved in water to obtain a phosphorus-containing aqueous solution. Then, at least two of the following are added: an organic alcohol compound, a carboxylic acid compound, and an organic amine compound (preferably an organic alcohol compound, a carboxylic acid compound, and / or an organic amine compound), a Group VIB metal precursor, a cobalt precursor, and optionally other Group VIII metal precursors. The mixture is heated and stirred until completely dissolved, and kept at a constant temperature to obtain an impregnation solution. The water absorption rate of alumina is measured, and the liquid absorption rate of the alumina support is calculated according to the formula: alumina support water absorption rate - 0.1. According to the liquid absorption rate of the alumina support, the impregnation solution is adjusted to the corresponding volume (alumina liquid absorption rate × support mass), and the impregnation solution is mixed evenly with the corresponding mass of alumina and allowed to stand. Then, the mixture is dried to prepare the hydrodesulfurization catalyst.

[0065] In this invention, there are no specific limitations on the stirring conditions. Preferably, the stirring temperature is 40-100℃ and the stirring time is 1-8 hours.

[0066] In this invention, there are no specific limitations on the selection of drying conditions. Preferably, the drying conditions include: a temperature of 60-200℃ and a time of 2-10 hours.

[0067] In this invention, calcination is preferably not performed. The advantage of this preferred embodiment is that organic matter is retained in the catalyst, which promotes the generation of more active centers and keeps the catalyst at a high initial activity.

[0068] The third aspect of this invention provides the application of the hydrodesulfurization catalyst described in the first aspect in the hydrorefining of distillate oils.

[0069] In a preferred embodiment, the proportion of secondary hydrotreated diesel in the distillate oil to be treated does not exceed 15% by weight. This preferred embodiment can better utilize the hydrodesulfurization activity and stability of the catalyst, ensuring that the sulfur and aromatic hydrocarbon content in the product meets the China VI clean diesel quality standard.

[0070] In a preferred embodiment, the specific composition of the distillate oil to be treated is: straight-run diesel oil content of 90-100% by weight, catalytic diesel oil content of 0-10% by weight, and sulfur content of 5000-18000 ppm.

[0071] In this invention, the secondary hydrogenated diesel refers to catalytic diesel.

[0072] In a preferred embodiment, the hydrodesulfurization catalyst needs to be converted from an oxidized state catalyst to a sulfidized state catalyst before use. In this invention, there is no specific limitation on the sulfidation method; conventional sulfidation methods in the art are applicable. Preferably, for example, it can be either dry sulfidation or wet sulfidation. There is no particular limitation on the type of sulfiding agent; it can be selected according to conventional methods in the art.

[0073] In this invention, preferably, the vulcanization conditions include: a heating rate of 5-60℃ / h, a vulcanization temperature of 280-420℃, a vulcanization time of 8-48h, a vulcanization pressure of 0.1-15MPa, and a volume hourly space velocity of 0.5-20h. -1 The hydrogen-to-oil volume ratio is 100-2000:1.

[0074] In this invention, preferably, the catalyst is used at a temperature of 320-400°C, a reaction pressure of 3-8 MPa, and a volume hourly space velocity of 0.5-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-500:1.

[0075] The present invention will be described in detail below through embodiments.

[0076] In the following examples, the hydrodesulfurization performance of the catalyst was tested in a high-throughput hydrodesulfurization reactor. First, the oxidized catalyst was converted to a sulfidized catalyst using a temperature-programmed sulfidation method. The sulfidation conditions were: sulfidation pressure of 3.2 MPa, kerosene containing 2% by weight of CS2, and volume hourly space velocity of 2 h⁻¹. -1 The hydrogen-to-oil volume ratio was 300 v / v. The mixture was first kept at 230℃ for 6 hours, then heated to 360℃ for 8 hours of sulfidation, with a heating rate of 10℃ / h for each stage. After sulfidation, the feedstock was switched for hydrodesulfurization activity testing. The distillate oil to be treated contained 100% by weight straight-run diesel, 0% by weight catalytic diesel, and 17,000 ppm sulfur. The test conditions were: pressure 3.2 MPa, volume hourly space velocity (VHSV) 0.8 h⁻¹. -1The hydrogen-to-oil volume ratio was 150 v / v, and the reaction temperature was 370℃. The properties of the products were analyzed after the reaction stabilized for 15 days.

[0077] The composition of the catalyst was calculated based on the feed amount. The pore distribution, pore size, and pore volume of the catalyst and support in the 2-100 nm range were determined by low-temperature nitrogen adsorption method (see "Analytical Methods in Petrochemical Industry (RIPP Test Methods)", edited by Yang Cuiding et al., Science Press, 1990). The sulfur mass fraction in the product was analyzed using a sulfur-nitrogen analyzer (Thermo Fisher Scientific, model TN / TS3000), and the hydrogen and hydrogen mass fraction were determined by an elemental analyzer (Elementar, model Vario EL cube).

[0078] CO2 emission peaks were measured using a temperature-programmed oxidation method. Analysis was performed on a NETZSCH STA 409PC / PG instrument. The sample was heated in air (heating rate 10 °C / min), and the temperature was monitored at the instrument's gas outlet using a mass spectrometer to obtain a curve showing the change in CO2 production from sample decomposition with temperature.

[0079] The formula for calculating the hydrogen consumption of the reaction is: C f / C p ×H p -H f +16×(S f -C f / C p ×S p )×10 -6 +5.67×(N f -C f / C p ×N p )×10 -6 C f C p The carbon content (H) of raw materials and products are respectively. f H p The H content and S content of raw materials and products are respectively. f S p The sulfur content and nitrogen content of the raw materials and products are respectively. f N p These are the nitrogen contents of the raw materials and the products, respectively.

[0080] Example 1

[0081] A certain amount of MoO3, basic cobalt carbonate, ethylene glycol, and citric acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 85°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with the support and allowed to stand for 3 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared.

[0082] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.02 mL / g and a specific surface area of ​​275 m². 2 The alumina support has an average pore size of 12.5 nm, with pores of 2-6 nm accounting for 6.0% of the total pore volume and pores of 2-4 nm accounting for 2%. The sodium oxide content in the support is 0.05% by weight. The alumina support used to prepare the catalyst contains phosphorus, which comes from the boehmite powder used in its preparation. The phosphorus-containing boehmite powder is obtained by introducing a certain amount of phosphoric acid during the boehmite powder preparation process. The phosphorus-containing boehmite powder is shaped and calcined at 600℃ for 3 hours to obtain the phosphorus-containing alumina support.

[0083] The catalyst contained 28.0 wt% MoO3, 4.9 wt% CoO, with an atomic ratio of Co / (Co+Mo) of 0.25, and 5.0 wt% P2O5, of which 30 wt% of the P2O5 came from the support. The molar ratio of ethylene glycol to Group VIB metals was 1:1, and the molar ratio of citric acid to cobalt was 0.8:1. The catalyst was tested using temperature-programmed oxidation. Figure 1 As shown, CO2 emission peaks appeared at 255℃ and 340℃, respectively, and the ratio of their peak heights was 2.2.

[0084] After sulfidation and reaction testing, the product contained 6.5 ppm of sulfur. By measuring the carbon, hydrogen, sulfur, and nitrogen content in the product and raw materials, and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption for the reaction was calculated to be 0.60%.

[0085] Example 2

[0086] A certain amount of MoO3, basic cobalt carbonate, glycerol, and acetic acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 90°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with a support and allowed to stand for 5 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared. Example 2 used the same support as Example 1.

[0087] The catalyst contained 15.0 wt% MoO3, 3.8 wt% CoO, with an atomic ratio of Co / (Co+Mo) of 0.33, and 8.0 wt% P2O5, of which 30 wt% of the P2O5 was derived from the support. The molar ratio of glycerol to Group VIB metal was 2:1, and the molar ratio of acetic acid to cobalt was 3:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 245℃ and 325℃, with a peak height ratio of 3.5.

[0088] After sulfidation and reaction testing, the product contained 5.8 ppm of sulfur. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.63%.

[0089] Example 3

[0090] A certain amount of MoO3, basic cobalt carbonate, butanol, and acetic acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 95°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with a support and allowed to stand for 5 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared. Example 3 used the same support as Example 1.

[0091] The catalyst contained 24.0 wt% MoO3, 6.0 wt% CoO, with an atomic ratio of Co / (Co+Mo) of 0.32, and 5.0 wt% P2O5, of which 10 wt% of the P2O5 came from the support. The molar ratio of butanol to Group VIB metals was 1:1, and the molar ratio of acetic acid to cobalt was 1.6:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 230℃ and 325℃, with a peak height ratio of 4.2.

[0092] After sulfidation and reaction testing, the product was found to have a sulfur content of 7.0 ppm. By measuring the carbon, hydrogen, sulfur, and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.58%.

[0093] Example 4

[0094] A certain amount of MoO3, basic cobalt carbonate, butanol, and triethanolamine were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 85°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with a support and allowed to stand for 4 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared. Example 4 used the same support as in Example 1.

[0095] The catalyst contained 24.0 wt% MoO3, 6.0 wt% CoO, with an atomic ratio of Co / (Co+Mo) of 0.32, and 7.0 wt% P2O5, of which 10 wt% of the P2O5 came from the support. The molar ratio of butanol to Group VIB metal was 2:1, and the molar ratio of triethanolamine to cobalt was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 245℃ and 335℃, with a peak height ratio of 4.5.

[0096] After sulfidation and reaction testing, the product was found to contain 7.9 ppm of sulfur. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.64%.

[0097] Example 5

[0098] A certain amount of MoO3, basic cobalt carbonate, butanol, and acetic acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 90°C for 4 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with the support and allowed to stand for 5 hours. After drying at 120°C for 3 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared.

[0099] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.08 mL / g and a specific surface area of ​​282 m². 2 The catalyst has an average pore size of 11.9 nm, with pores of 2-6 nm accounting for 4.9% of the total pore volume and pores of 2-4 nm accounting for 1.5% of the total pore volume. The sodium oxide content in the support is 0.05%. The support used to prepare the catalyst is a phosphorus-containing alumina support. The phosphorus element in the support is introduced by modifying the alumina with a certain amount of phosphoric acid and then calcining it at 600℃ for 3 hours.

[0100] The catalyst contained 24.0 wt% MoO3, 6.0 wt% CoO, with an atomic ratio of Co / (Co+Mo) of 0.32, and 5.0 wt% P2O5, of which 10 wt% of the P2O5 came from the support. The molar ratio of butanol to Group VIB metal was 1:1, and the molar ratio of acetic acid to cobalt was 3:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 230℃ and 325℃, with a peak height ratio of 2.6.

[0101] After sulfidation and reaction testing, the product was found to have a sulfur content of 8.9 ppm. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.60%.

[0102] Example 6

[0103] A certain amount of MoO3, basic cobalt carbonate, butanol, and acetic acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 95°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with the support and allowed to stand for 5 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared.

[0104] The catalyst was prepared using a γ-alumina support with a water absorption rate of 0.97 mL / g and a specific surface area of ​​280 m². 2 The alumina support has an average pore size of 11.7 nm, with pores of 2-6 nm accounting for 7.2% of the total pore volume and pores of 2-4 nm accounting for 2.5% of the total pore volume. The sodium oxide content in the support is 0.05%. The alumina support used to prepare the catalyst does not contain phosphorus.

[0105] The catalyst contained 24.0 wt% MoO3, 6.0 wt% CoO, an atomic ratio of Co / (Co+Mo) of 0.32, and 5.0 wt% P2O5. The molar ratio of butanol to Group VIB metals was 1:1, and the molar ratio of acetic acid to cobalt was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 230℃ and 325℃, with a peak height ratio of 2.1.

[0106] After the catalyst was sulfided and the reaction was tested, the sulfur content in the product was 9.5 ppm. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.56%.

[0107] Example 7

[0108] A certain amount of MoO3, basic cobalt carbonate, basic nickel carbonate, ethylene glycol, and citric acid were added to an aqueous solution containing phosphoric acid. The solution was heated and stirred at 85°C for 3 hours until completely dissolved, obtaining an impregnation solution containing active metals. The impregnation solution was mixed evenly with a support and allowed to stand for 3 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared.

[0109] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.02 mL / g and a specific surface area of ​​275 m². 2 The alumina support has an average pore size of 12.5 nm, with pores of 2-6 nm accounting for 6.0% of the total pore volume and pores of 2-4 nm accounting for 2%. The sodium oxide content in the support is 0.05% by weight. The alumina support used to prepare the catalyst contains phosphorus, which comes from the boehmite powder used in its preparation. The phosphorus-containing boehmite powder is obtained by introducing a certain amount of phosphoric acid during the boehmite powder preparation process. The phosphorus-containing boehmite powder is shaped and calcined at 600℃ for 3 hours to obtain the phosphorus-containing alumina support.

[0110] The catalyst contained 28.0 wt% MoO3, 3 wt% CoO, and 2 wt% NiO. The atomic ratio of (Co+Ni) / (Co+Ni+Mo) was 0.256, the atomic ratio of Co / (Co+Ni) was 0.6, and the P2O5 content was 5.0 wt%, of which 30 wt% of the P2O5 came from the support. The molar ratio of ethylene glycol to Group VIB metals was 1.5:1, and the molar ratio of citric acid to the sum of cobalt and nickel was 0.8:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks were observed at 255℃ and 340℃, with a peak height ratio of 4.3.

[0111] After sulfidation and reaction testing, the product contained 14.5 ppm of sulfur. By measuring the carbon, hydrogen, sulfur, and nitrogen content in the product and raw materials, and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption for the reaction was calculated to be 0.65%.

[0112] Example 8

[0113] A certain amount of MoO3, basic cobalt carbonate, butanol, and acetic acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 95°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with the support and allowed to stand for 5 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared.

[0114] The catalyst was prepared using a γ-alumina support with a water absorption rate of 0.97 mL / g and a specific surface area of ​​280 m². 2 The alumina support has an average pore size of 11.7 nm, with pores of 2-6 nm accounting for 7.2% of the total pore volume and pores of 2-4 nm accounting for 2.5% of the total pore volume. The sodium oxide content in the support is 0.05%. The alumina support used to prepare the catalyst does not contain phosphorus.

[0115] The catalyst contained 23.5 wt% MoO3, 4.5 wt% CoO, an atomic ratio of Co / (Co+Mo) of 0.27, 12.0 wt% P2O5, and had a molar ratio of butanol to Group VIB metals of 1:1 and a molar ratio of acetic acid to cobalt of 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks were observed at 230℃ and 325℃, with a peak height ratio of 1.5.

[0116] After sulfidation and reaction testing, the product was found to have a sulfur content of 16.0 ppm. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.59%.

[0117] Example 9

[0118] A certain amount of MoO3, basic cobalt carbonate, glycerol, and acetic acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 90°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with the support and allowed to stand for 5 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared.

[0119] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.02 mL / g and a specific surface area of ​​275 m². 2 The alumina support has an average pore size of 12.5 nm, with pores of 2-6 nm accounting for 6% of the total pore volume and pores of 2-4 nm accounting for 2%. The sodium oxide content in the support is 0.05% by weight. The alumina support used to prepare the catalyst contains phosphorus, which comes from the boehmite powder used in its preparation. The phosphorus-containing boehmite powder is obtained by introducing a certain amount of phosphoric acid during the boehmite powder preparation process. The phosphorus-containing boehmite powder is shaped and calcined at 600℃ for 3 hours to obtain the phosphorus-containing alumina support.

[0120] The catalyst contained 25.0 wt% MoO3, 2.0 wt% CoO, and an atomic ratio of Co / (Co+Mo) of 0.13. It also contained 6.0 wt% P2O5, of which 30 wt% of the P2O5 was derived from the support. The molar ratio of glycerol to Group VIB metal was 0.8:1, and the molar ratio of acetic acid to cobalt was 3:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks were observed at 245 °C and 325 °C, with a peak height ratio of 3.6.

[0121] After sulfidation and reaction testing, the product contained 17.6 ppm of sulfur. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.52%.

[0122] Example 10

[0123] A certain amount of MoO3, basic cobalt carbonate, glycerol, and acetic acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 90°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with the support and allowed to stand for 5 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared.

[0124] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.02 mL / g and a specific surface area of ​​275 m². 2The alumina support has an average pore size of 12.5 nm, with pores of 2-6 nm accounting for 6% of the total pore volume and pores of 2-4 nm accounting for 2%. The sodium oxide content in the support is 0.05% by weight. The alumina support used to prepare the catalyst contains phosphorus, which comes from the boehmite powder used in its preparation. The phosphorus-containing boehmite powder is obtained by introducing a certain amount of phosphoric acid during the boehmite powder preparation process. The phosphorus-containing boehmite powder is shaped and calcined at 600℃ for 3 hours to obtain the phosphorus-containing alumina support.

[0125] The catalyst contained 15.0 wt% MoO3, 3.8 wt% CoO, with an atomic ratio of Co / (Co+Mo) of 0.33, and 8.0 wt% P2O5, of which 30 wt% of the P2O5 was derived from the support. The molar ratio of glycerol to Group VIB metal was 2.2:1, and the molar ratio of acetic acid to cobalt was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 245℃ and 325℃, with a peak height ratio of 7.2.

[0126] After sulfidation and reaction testing, the product was found to contain 12.5 ppm of sulfur. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.62%.

[0127] Comparative Example 1

[0128] A certain amount of MoO3, basic cobalt carbonate, basic nickel carbonate, and citric acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 95°C for 2 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with a support and allowed to stand for 3 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared. The phosphorus-containing alumina support used was the same as that in Example 1.

[0129] The catalyst contained 28.0 wt% MoO3, 2.0 wt% CoO, and 4.0 wt% NiO. The atomic ratio of (Co+Ni) / (Co+Ni+Mo) was 0.29, the atomic ratio of Co / (Co+Ni) was 0.33, and the P2O5 content was 5.0 wt%, of which 30 wt% of the P2O5 came from the support. The molar ratio of citric acid to Group VIII metal was 0.8:1. The catalyst was tested using temperature-programmed oxidation, and a CO2 release peak appeared at 375℃.

[0130] After sulfidation and reaction testing, the product was found to contain 20.5 ppm of sulfur. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.73%.

[0131] Comparative Example 2

[0132] A certain amount of MoO3, basic nickel carbonate, and glycerol were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 90°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was mixed evenly with a support and allowed to stand for 2 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared. The phosphorus-containing alumina support used was the same as that in Example 1.

[0133] The catalyst contained 24.0 wt% MoO3, 6.0 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.33, and 8.0 wt% P2O5, of which 15 wt% of the P2O5 came from the support. The molar ratio of glycerol to Group VIB metal was 1:1. The catalyst was tested using temperature-programmed oxidation, and a CO2 release peak appeared at 260 °C.

[0134] After sulfidation and reaction testing, the product was found to contain 19.5 ppm of sulfur. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.75%.

[0135] Comparative Example 3

[0136] A certain amount of MoO3, basic nickel carbonate, and citric acid were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 95°C for 3 hours until completely dissolved to obtain an impregnation solution containing the active metal. The impregnation solution was mixed evenly with a support and allowed to stand for 2 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared. The phosphorus-containing alumina support used was the same as that in Example 1.

[0137] The catalyst contained 28.0 wt% MoO3, 4.9 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.25, and 5.0% P2O5, of which 15 wt% of the P2O5 came from the support. The molar ratio of citric acid to Group VIII metals was 1:1. The catalyst was tested using temperature-programmed oxidation, and a CO2 release peak appeared at 360℃.

[0138] After sulfidation and reaction testing, the product contained 25.6 ppm of sulfur. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.73%.

[0139] Comparative Example 4

[0140] A certain amount of MoO3, basic nickel carbonate, and ethylenediaminetetraacetic acid (EDTA) were added to an aqueous solution containing phosphoric acid, and the solution was heated and stirred at 95°C for 3 hours until completely dissolved to obtain an impregnation solution containing the active metal. The impregnation solution was mixed evenly with a support and allowed to stand for 2 hours. After drying at 120°C for 5 hours, a catalyst with a particle size of 1.6 mm and a butterfly shape was prepared. The prepared catalyst was then impregnated with an EDTA solution and dried at 130°C for 3 hours. The phosphorus-containing alumina support used was the same as that in Example 1.

[0141] The catalyst contained 28.0 wt% MoO3, 4.9 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.25, and 5.0% P2O5, of which 15 wt% of the P2O5 came from the support. The molar ratio of ethylenediaminetetraacetic acid to Group VIII metals was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 285℃ and 380℃, with a peak height ratio of 0.92.

[0142] After sulfidation and reaction testing, the product was found to have a sulfur content of 22.0 ppm. By measuring the carbon, hydrogen, sulfur and nitrogen content in the product and raw materials and using the aforementioned hydrogen consumption calculation formula, the hydrogen consumption of the reaction was calculated to be 0.76%.

[0143] As can be seen from the examples and comparative examples, the present invention has good inventive effects, and the prepared catalyst has high activity and low reaction hydrogen consumption, and has good prospects for industrial application.

[0144] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. The application of a hydrodesulfurization catalyst in the hydrorefining of distillate oils, wherein, The specific composition of the distillate oil is as follows: straight-run diesel oil content is 90-100% by weight, catalytic diesel oil content is 0-10% by weight, and sulfur content is 5000-18000 ppm; The catalyst comprises cobalt and optionally at least one of other Group VIII metals, at least one Group VIB metal, phosphorus, and a support. The catalyst contains at least two CO2 release peaks during the programmed temperature oxidation process, with the first release peak temperature at 220-280℃ and the second release peak temperature at 320-380℃, and the peak height ratio ranges from 1.5 to 3:

1. Based on the total weight of the catalyst, and calculated as oxides, the content of cobalt and optionally other Group VIII metals is 3-7% by weight, and the content of Group VIB metals is 18-28% by weight. The atomic ratio of cobalt to the total amount of cobalt and optionally other metals in Group VIII is not less than 0.8; the atomic ratio of cobalt and optionally other metals in Group VIII to the total amount of cobalt and optionally other metals in Group VIII and Group VIB is 0.2-0.35:

1. The carrier is an alumina carrier; the alumina carrier contains phosphorus. Of which, based on P2O5, phosphorus in the alumina support accounts for 20-30% by weight of the total phosphorus content in the catalyst; The catalyst contains organic alcohol compounds as well as carboxylic acid compounds or organic amine compounds; The molar ratio of organic alcohol compounds to Group VIB metals is 0.2-4:1, and the molar ratio of carboxylic acid compounds or organic amine compounds to cobalt and optionally other Group VIII metals is 0.1-4:

1.

2. The application according to claim 1, wherein, The atomic ratio of cobalt to the total amount of cobalt and optionally other metals in Group VIII is 0.85-1.

3. The application according to claim 1, wherein, The phosphorus content in the catalyst is 3-10% by weight, calculated as P2O5.

4. The application according to any one of claims 1-3, wherein, Group VIB metals are selected from at least one of chromium, molybdenum, and tungsten.

5. The application according to claim 1, wherein, The precursor of the alumina carrier is boehmite, which contains phosphorus.

6. The application according to claim 5, wherein, The sodium oxide content in the pseudoboehmite does not exceed 0.08% by weight.

7. The application according to claim 6, wherein, The sodium oxide content in the pseudoboehmite does not exceed 0.05% by weight.

8. The application according to claim 1, wherein, The alumina carrier has a water absorption rate greater than 0.9 mL / g and a specific surface area greater than 260 m². 2 / g, with an average pore size greater than 8nm.

9. The application according to claim 1, wherein, In the alumina support, the pore volume with a pore size distribution of 2-6 nm accounts for no more than 10% of the total pore volume of the alumina support.

10. The application according to claim 9, wherein, In the alumina support, the pore volume with a pore size distribution of 2-6 nm accounts for no more than 8% of the total pore volume of the alumina support.

11. The application according to claim 1, wherein, In the alumina support, the pore volume with a pore size distribution of 2-4 nm accounts for no more than 4% of the total pore volume of the alumina support.

12. The application according to claim 11, wherein, In the alumina carrier, the pore volume with a pore size distribution of 2-4 nm accounts for no more than 2% of the total pore volume of the alumina carrier.

13. The application according to claim 1, wherein, The organic alcohol compound is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, heptanol, ethylene glycol, glycerol, butanetetraethanolamine, polyethylene glycol, polyglycerol, pentaerythritol, xylitol, sorbitol and trimethylolethane.

14. The application according to claim 13, wherein, The organic alcohol compound is selected from at least one of butanol, glycerol, propanol, and ethylene glycol.

15. The application according to claim 1, wherein, The carboxylic acid compound is selected from at least one of formic acid, acetic acid, propionic acid, citric acid, octanoic acid, adipic acid, malonic acid, succinic acid, maleic acid, valeric acid, hexanoic acid, decanoic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, stearic acid, and tartaric acid.

16. The application according to claim 15, wherein, The carboxylic acid compound is selected from at least one of formic acid, citric acid, and acetic acid.

17. The application according to claim 1, wherein, The organic amine compound is selected from at least one of ethylenediamine, ethylenediaminetetraacetic acid, ethanolamine, triethanolamine, and cyclohexanediaminetetraacetic acid.

18. The application according to any one of claims 1-3, wherein, The equivalent diameter of the catalyst is 0.5-1.8 mm.

19. The application according to claim 18, wherein, The equivalent diameter of the catalyst is 0.8-1.6 mm.

20. The application according to any one of claims 1-3, wherein, The catalyst may be cylindrical, clover-shaped, four-leaf clover-shaped, butterfly-shaped, honeycomb-shaped, or other irregular shapes.

21. The application according to any one of claims 1-3, wherein, The preparation method of the hydrodesulfurization catalyst includes: A cobalt precursor, and optionally other Group VIII metal precursors, Group VIB metal precursors, phosphorus-containing compounds, organic alcohol compounds, carboxylic acid compounds, or organic amine compounds are introduced into a support by impregnation, followed by drying.

22. The application according to claim 21, wherein, The impregnation method includes impregnating the carrier with an impregnation solution containing a cobalt precursor and optionally other Group VIII metal precursors, Group VIB metal precursors, phosphorus-containing compounds, organic alcohol compounds, carboxylic acid compounds, or organic amine compounds.

23. The application according to claim 22, wherein, The organic alcohol compound, carboxylic acid compound or organic amine compound, cobalt precursor and optionally other Group VIII metal precursors and Group VIB metal precursors are respectively added to an aqueous solution containing a phosphorus compound to provide the impregnation solution.

24. The application according to claim 21, wherein, The drying conditions include a temperature of 60-200℃ and a time of 2-10 hours.

25. The application according to claim 1, wherein, The hydrodesulfurization catalyst is converted into a sulfidized state catalyst by sulfidation before use.

26. The application according to claim 25, wherein, The vulcanization conditions include: a heating rate of 5-60℃ / h, a vulcanization temperature of 280-420℃, a vulcanization time of 8-48h, a vulcanization pressure of 0.1-15MPa, and a volume hourly space velocity of 0.5-20h. -1 The hydrogen-to-oil volume ratio is 100-2000:

1.

27. The application according to claim 1, wherein, The catalyst is used at a temperature of 320-400℃, a reaction pressure of 3-8 MPa, and a volume hourly space velocity of 0.5-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-500:1.

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