Catalyst grading method and hydrofining method of catalyst in distillate oil

Abstract

The present application relates to the technical field of catalyst, and discloses a catalyst grading method and a hydrofining method of the catalyst in distillate oil.The method comprises: a first catalyst and a second catalyst which are sequentially filled along the flow direction;the first catalyst comprises at least one group VIB metal element, an auxiliary active component, a phosphorus element, a first carrier and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound;the auxiliary active component comprises nickel and optionally at least one of iron, ruthenium and osmium elements;the second catalyst comprises a cobalt element and optionally one of other group VIII metal elements, at least one group VIB metal element, a phosphorus element, a second carrier and at least two of an organic alcohol compound, a carboxylic acid compound and an organic amine compound;the volume ratio of the first catalyst and the second catalyst is 1:2-5:1.The method can treat distillate oil with a secondary hydrocracking diesel ratio of 10-30 wt%.

Description

Technical Field

[0001] This invention relates to the technical field of catalysts, specifically to a catalyst gradation method and a method for hydrorefining catalysts in distillate oils. Background Technology

[0002] In recent years, my country's diesel quality standards have been rapidly upgraded. The China VI diesel quality standard requires sulfur content and polycyclic aromatic hydrocarbons (PAHs) in diesel to be reduced to 10 mg / kg and 7%, respectively. On the other hand, the energy consumption of diesel hydrotreating units has been further reduced. Under low-carbon and low-energy operating conditions, higher requirements are placed on the activity, stability, and hydrogen consumption of diesel hydrotreating catalysts. However, a single catalyst is unlikely to simultaneously meet the needs of low-carbon and long-cycle stable production; therefore, selecting a suitable catalyst gradation system has become a crucial solution. Existing diesel hydrotreating catalyst gradation systems either have low performance or are too complex, making it difficult to meet the requirements of low-carbon and high-efficiency diesel hydrotreating.

[0003] Patent application number 201811650785.1 discloses a three-reaction-zone catalyst system. The first reaction zone is filled with a hydroprotective catalyst for the removal of impurities such as metals and colloids; the second reaction zone is filled with a highly active type I hydrodenitrification catalyst; and the third reaction zone is filled with a highly active type II hydrodenitrification catalyst. Through the gradation of different functional hydrocatalysts, nitrides of nitrogen-substituted heterocyclic compounds from polycyclic aromatic hydrocarbons are deeply removed, providing low-nitrogen feedstock for hydrocracking and catalytic cracking. Patent application number 201210409647.0 invented a hydrodesulfurization method for distillate oils, employing at least two graded catalysts. The catalysts use Mo and Ni and / or Co as active metal components, P as an additive, and contain alkali metal salts of heteropoly acids. The content of alkali metal salts of heteropoly acids in the graded catalysts increases sequentially along the fluid flow direction. Patent application number 201010221051.9 discloses a method for hydrodesulfurization of diesel fuel using a catalyst-graded loading system. This method involves setting up two or more catalyst beds, with a mixed catalyst bed composed of Mo-Co and Mo-Ni catalysts, the proportion of Mo-Ni catalyst gradually increasing within the mixed bed. Patent application number 201110192780.0 divides the reactor into four reaction zones, respectively loaded with a first type of catalyst, a mixture of the first and second types of catalysts, a second type of catalyst, and a first type of catalyst. The first type of catalyst is a Mo-Co catalyst, and the second type of catalyst is a W-Mo-Ni catalyst or a W-Ni catalyst. This process treats high-sulfur, high-nitrogen, low-quality diesel fuel through the gradation of different catalysts.

[0004] Research and invention of diesel hydrodesulfurization catalysts have improved the properties of catalysts from many perspectives. However, existing technologies still cannot solve the problem of low-carbon and high-efficiency operation of diesel hydrotreating units. Furthermore, the preparation process or gradation system is relatively complex, and its implementation cost and convenience are still somewhat insufficient, making it difficult to meet the future needs of diesel hydrotreating units. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor desulfurization activity, poor stability, and high hydrogen consumption in the prior art, and to provide a catalyst gradation method and a method for hydrorefining catalysts in distillate oils. This gradation method combines a first catalyst and a second catalyst, and the reaction system has good activity and stability, good desulfurization and dearomatics performance, and low hydrogen consumption.

[0006] To achieve the above objectives, a first aspect of the present invention provides a catalyst gradation method, the method comprising: sequentially loading a first catalyst and a second catalyst along the flow direction;

[0007] The first catalyst comprises at least one Group VIB metal element, a co-active component, phosphorus element, a first support, and at least two of organic alcohol compounds, carboxylic acid compounds, and organic amine compounds; the co-active component includes nickel and at least one of iron, ruthenium, and osmium elements; the pore size distribution of the first catalyst in the 100-300 nm range accounts for no more than 20% of the catalyst pore volume; wherein, during temperature-programmed oxidation, the first catalyst contains at least two CO2 release peaks, the first release peak temperature is in the range of 210-280 °C, the second release peak temperature is in the range of 320-380 °C, and the peak height ratio ranges from 0.5 to 4:1;

[0008] The second catalyst comprises cobalt and optionally one of other Group VIII metals, at least one Group VIB metal, phosphorus, a second support, and at least two of organic alcohols, carboxylic acids, and organic amines; wherein, during temperature-programmed oxidation, the second catalyst contains at least two CO2 release peaks, the third release peak is at a temperature of 200-300℃, the fourth release peak is at a temperature of 300-400℃, and the peak height ratio is in the range of 1-5:1;

[0009] The loading volume ratio of the first catalyst to the second catalyst is 1:2-5:1.

[0010] Preferably, the volume ratio of the first catalyst to the second catalyst is 1:1 to 4:1.

[0011] Preferably, in the first catalyst and the second catalyst, the molar ratio of the organic alcohol compound to the group VIB metal element is independently 0.2-4:1.

[0012] Preferably, in the first catalyst, the molar ratio of carboxylic acid compounds and / or organic amine compounds to co-activating components is 0.3-1.5:1.

[0013] Preferably, in the second catalyst, 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.

[0014] The second aspect of the present invention provides a method for hydrorefining a catalyst in a distillate oil, wherein the method includes: under hydrorefining conditions, loading a first catalyst and a second catalyst into a hydrorefining apparatus according to the gradation method described in the first aspect, and injecting the distillate oil to be treated into the hydrorefining apparatus for reaction;

[0015] Preferably, the proportion of secondary hydrotreated diesel in the distillate oil to be treated is 10-30% by weight.

[0016] In this invention, a first catalyst and a second catalyst with specific compositions are packed in a graded manner according to a specific volume ratio, enabling them to work synergistically. The first catalyst contains nickel and phosphorus elements combined with two or more different types of organic compounds to enhance its activity. Simultaneously, a portion of phosphorus is introduced into the support to improve the dispersion of the active metal components, thereby increasing the activity of the first catalyst. Furthermore, the proportion of the pore size distribution of the first catalyst in the 100-300 nm range to the catalyst pore volume does not exceed 20%, which is more conducive to improving the activity and stability of the hydrogenation catalyst. The second catalyst incorporates two or more different types of organic compounds combined with cobalt and phosphorus elements. Preferably, the atomic ratio of cobalt to the total amount of cobalt and optionally other Group VIII metal elements is not less than 0.8, resulting in a lower hydrogen consumption for the second catalyst. When applied to clean diesel production, this gradation method gives the reaction system good activity and stability, especially suitable for distillate oils with a secondary diesel proportion of 10-30% by weight. It fully utilizes the gradation effect of the two catalysts, effectively removing sulfur and aromatics from the distillate oil, and also has low hydrogen consumption, demonstrating potential industrial value. Attached Figure Description

[0017] Figure 1 This is the CO2 release spectrum of the first bed catalyst in Example 1 under programmed temperature rise;

[0018] Figure 2 This is the CO2 release spectrum of the second bed catalyst in Example 1 under programmed temperature rise. Detailed Implementation

[0019] 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.

[0020] In this invention, it is understood that "optionally" means that it may or may not be included.

[0021] The first aspect of the present invention provides a catalyst gradation method, the method comprising: sequentially loading a first catalyst and a second catalyst along the flow direction;

[0022] The first catalyst comprises at least one Group VIB metal element, a co-active component, phosphorus element, a first support, and at least two of organic alcohol compounds, carboxylic acid compounds, and organic amine compounds; the co-active component includes nickel and at least one of iron, ruthenium, and osmium elements; the pore size distribution of the first catalyst in the 100-300 nm range accounts for no more than 20% of the catalyst pore volume; wherein, during temperature-programmed oxidation, the first catalyst contains at least two CO2 release peaks, the first release peak temperature is in the range of 210-280 °C, the second release peak temperature is in the range of 320-380 °C, and the peak height ratio ranges from 0.5 to 4:1;

[0023] The second catalyst comprises cobalt and optionally one of other Group VIII metals, at least one Group VIB metal, phosphorus, a second support, and at least two of organic alcohols, carboxylic acids, and organic amines; wherein, during temperature-programmed oxidation, the second catalyst contains at least two CO2 release peaks, the third release peak is at a temperature of 200-300℃, the fourth release peak is at a temperature of 300-400℃, and the peak height ratio is in the range of 1-5:1;

[0024] The loading volume ratio of the first catalyst to the second catalyst is 1:2-5:1.

[0025] In this invention, the first release peak temperature of 210-280℃ refers to a specific temperature value where the peak value of the first release peak appears between 210-280℃, and the second release peak temperature of 320-380℃ refers to a specific temperature value where the peak value of the second release peak appears between 320-380℃; the temperatures of the third and fourth release peaks have the same meaning as the first and second release peak temperatures, and will not be described again here.

[0026] In this invention, in the first catalyst, "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, i.e., peak height ratio = peak height of the first release peak / peak height of the second release peak. The "peak height ratio" in the second catalyst has the same meaning as in the first catalyst.

[0027] In this invention, it is understood that the CO2 emission peak temperature has an error of ±2℃.

[0028] In this invention, the CO2 release peaks of the first and second catalysts were analyzed on a NETZSCH STA 409PC / PG instrument. The catalysts to be tested were 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 production from catalyst decomposition as a function of temperature.

[0029] In this invention, the first catalyst has a specific pore structure, and the activity of the catalyst is significantly improved by introducing two or more different types of organic compounds into the first catalyst. The catalyst has good activity and stability.

[0030] In this invention, two or more different types of organic compounds are also introduced into the second catalyst, which significantly improves the activity of the catalyst. This catalyst has good activity and low hydrogen consumption.

[0031] In this invention, the first catalyst and the second catalyst are loaded in a specific volume ratio so that the two catalysts work synergistically. When used to treat secondary processed diesel in the distillate oil to be treated, the proportion of the catalyst is 10-30% by weight. It has good activity and low hydrogen consumption, and has excellent industrial value.

[0032] In this invention, preferably, the volume ratio of the first catalyst to the second catalyst is 1:1 to 4:1. This preferred embodiment results in a catalyst system with high desulfurization activity, aromatic saturation activity, and low hydrogen consumption.

[0033] In this invention, preferably, based on the total amount of the first catalyst and calculated as oxides, the content of the co-activating component is 1-15% by weight, more preferably 2-12% by weight, and even more preferably 3-8% by weight; the content of the Group VIB metal element is 12-50% by weight, and the content of the Group VIB metal element is 15-40% by weight, more preferably 20-35% by weight. The advantage of this preferred embodiment is that the first catalyst has higher activity and stability.

[0034] According to a preferred embodiment of the present invention, the atomic ratio of nickel to the total amount of the co-active component is not less than 0.8, preferably 0.85-1. The advantage of this preferred embodiment is that it improves catalyst activity and reduces hydrogen consumption in the reaction.

[0035] According to a preferred embodiment of the present invention, the phosphorus content in the first 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 the first catalyst has higher activity.

[0036] According to a preferred embodiment of the present invention, the first catalyst contains at least two CO2 release peaks during the temperature-programmed oxidation process, with the first release peak temperature at 230-260°C and the second release peak temperature at 320-360°C, and the peak height ratio ranging from 0.7 to 3.5:1. The advantage of this preferred embodiment is that the catalyst can maintain higher activity and stability.

[0037] According to a preferred embodiment of the present invention, the pore size distribution of the first catalyst in the range of 100-300 nm accounts for 5-20% of the catalyst pore volume, more preferably 8-15%. The larger pore size during the reaction process, achieved through the above preferred embodiment, promotes the diffusion of larger reactant molecules, reduces the formation of carbon deposits on the catalyst surface, and enhances catalyst stability.

[0038] In this invention, by limiting the amounts of the co-active component and the Group VIB metal element, the synergistic effect of the two is utilized to improve the catalytic performance of the catalyst. Preferably, the atomic ratio of the co-active component to the total amount of the co-active component and the Group VIB metal element is 0.1-0.5, more preferably 0.2-0.35.

[0039] In this invention, the selection range of Group VIB metal elements in the first and second catalysts is relatively wide. Preferably, the Group VIB metal elements in the first and second catalysts are each independently selected from at least one of chromium, molybdenum, and tungsten, and more preferably molybdenum.

[0040] In this invention, preferably, based on the total amount of the second catalyst and calculated as oxides, the content of cobalt and optionally other Group VIII metals is 1-15% by weight, more preferably 2-12% by weight, and even more preferably 3-7% by weight; the content of Group VIB metals is 12-50% by weight, preferably 15-45% by weight, and even more preferably 18-40% by weight. The advantage of this preferred embodiment is that the catalyst exhibits higher hydrodesulfurization activity and stability.

[0041] According to a preferred embodiment of the present invention, 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 that it improves the activity of the second catalyst and reduces the hydrogen consumption of the reaction.

[0042] According to a preferred embodiment of the present invention, the phosphorus content in the second 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 the second catalyst has higher activity.

[0043] According to a preferred embodiment of the present invention, the catalyst contains at least two CO2 release peaks during the temperature-programmed oxidation process, with the first release peak temperature at 220-280°C and the second release peak temperature at 320-380°C, and the peak height ratio ranging from 1.5 to 3:1. The advantage of this preferred embodiment is that the second catalyst can maintain higher activity and stability.

[0044] 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.

[0045] In this invention, there are no particular restrictions on the amount of cobalt and optionally other Group VIII and Group VIB metals, as long as the catalyst performance 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, more preferably 0.2-0.35. 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.

[0046] In this invention, the range of types of the first carrier is relatively wide, and conventional carriers in the art are all applicable to this invention. Preferably, the first carrier is a first alumina carrier.

[0047] In this invention, the range of types of the second carrier is relatively wide, and conventional carriers in the art are all applicable to this invention. Preferably, the second carrier is a second alumina carrier.

[0048] In this invention, preferably, the phosphorus element in both the first catalyst and the second catalyst originates from two sources. Taking the first catalyst as an example, one part originates from the first alumina support, and the other part is introduced during the preparation of the active component impregnation solution.

[0049] According to a preferred embodiment of the present invention, both the first alumina support and the second alumina support contain phosphorus, hereinafter referred to as the first phosphorus-containing alumina and the second phosphorus-containing alumina, respectively. The advantage of this preferred embodiment is that the presence of specific amounts of phosphorus in both the first and second alumina significantly promotes the activity of the catalyst.

[0050] According to a preferred embodiment of the present invention, based on P2O5, the phosphorus element in the first alumina support and the second alumina support each independently accounts for 10-40% by weight of the total phosphorus content in the first catalyst and the second catalyst, preferably 20-30% by weight. The advantage of this preferred embodiment is that by reasonably controlling the phosphorus content in the first alumina support and the second alumina support, the loading degree of the active component on the alumina support can be further improved, and the dispersion of the active component can be enhanced.

[0051] In this invention, there are no particular limitations on the method and timing of introducing phosphorus into the first and second alumina supports; they can be introduced in the same way. Preferably, taking the first alumina support as an example, phosphorus can be introduced into the formed first alumina support, during the forming process, or during the preparation of the first alumina support precursor. Preferably, it is introduced during the preparation of the first alumina support precursor. When introducing phosphorus during the preparation of the first alumina precursor, it can be introduced by adding a phosphorus-containing compound during the preparation of the first 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 first alumina precursor. Introducing phosphorus into the first alumina precursor improves the structural properties of the first alumina support and promotes the dispersion of the active components.

[0052] In this invention, the phosphorus element in the first phosphorus-containing alumina support and the second phosphorus-containing alumina support is independently provided by the first alumina support precursor and the second alumina support. In a preferred embodiment, the precursor of the first alumina support and the second alumina support is boehmite, and the boehmite contains phosphorus.

[0053] 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 controlling the sodium oxide content in the boehmite further reduces the basicity centers, resulting in good catalyst activity and promoting the hydrogenation effect of the catalyst.

[0054] In this invention, there are no particular limitations on the preparation methods of the first phosphorus-containing alumina carrier and the second phosphorus-containing alumina carrier. Conventional preparation methods in the art are applicable to this invention. For example, the first phosphorus-containing alumina carrier and the second phosphorus-containing alumina carrier can be prepared by extrusion molding. The specific methods will not be described in detail here.

[0055] In this invention, to further improve the performance of the first catalyst, a support with a specific composition and structure is selected as the support for the first catalyst. Preferably, the water absorption rate of the first alumina support is greater than 0.9 mL / g, more preferably 0.95-1.3 mL / g, and the specific surface area is greater than 260 m². 2 / g, further preferably 270-320m 2 / g, with an average pore size greater than 8nm, more preferably 10-15nm. The advantage of this preferred embodiment is that the first alumina support can provide a larger pore size, promoting sufficient contact between reactant molecules and active components, thereby improving the activity and stability of the catalyst.

[0056] According to a preferred embodiment of the present invention, the pore size distribution of the first alumina support in the range of 100-300 nm accounts for 5-15% of the pore volume of the first alumina support, preferably 7-13%.

[0057] In this invention, there are no particular limitations on the structural parameters of the second alumina support. Preferably, the water absorption rate of the second alumina support is greater than 0.9 mL / g, more preferably 0.95-1.3 mL / g, and the specific surface area is 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.

[0058] According to a preferred embodiment of the present invention, in the second alumina carrier, 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 carrier, preferably no more than 8%, and more preferably 3-6%.

[0059] According to a preferred embodiment of the present invention, in the second alumina carrier, 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 carrier, preferably no more than 2%, and more preferably 0-1%.

[0060] In this invention, the specific surface area, pore volume, pore size, and pore distribution of the first and second alumina supports were determined using the low-temperature nitrogen adsorption (BET) method and mercury porosimetry (see *Analytical Methods in Petrochemical Industry (RIPP Test Methods)*, edited by Yang Cuiding et al., Science Press, 1990). Specifically, the pore volume of 2-100 nm was calculated based on the BET results, and the pore volume of 100-300 nm was calculated based on the mercury porosimetry results.

[0061] According to a particularly preferred embodiment of the present invention, both the first catalyst and the second catalyst contain organic alcohol compounds, as well as carboxylic acid compounds and / or organic amine compounds. An advantage of this preferred embodiment is that selecting two or more organic compounds can significantly improve the activity of the catalyst.

[0062] According to a particularly preferred embodiment of the present invention, in the first catalyst and the second catalyst, the molar ratio of the organic alcohol compound to the group VIB metal element is independently 0.2-4:1, preferably 0.5-2.5:1, and more preferably 0.6-2.2:1.

[0063] According to a particularly preferred embodiment of the present invention, in the first catalyst, the molar ratio of carboxylic acid compounds and / or organic amine compounds to co-active components is 0.3-1.5:1, preferably 0.4-1.2:1, and more preferably 0.5-1.1:1. The advantage of this preferred embodiment is that it maintains a high degree of dispersion of the active components in the catalyst, thereby improving the activity and stability of the catalyst.

[0064] According to a preferred embodiment of the present invention, in the second catalyst, 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, preferably 0.2-3.5:1, and more preferably 0.5-3:1.

[0065] In this invention, the range of organic alcohol compounds selected for the first and second catalysts is relatively wide. Preferably, the organic alcohol compounds in the first and second catalysts are selected from at least one of monohydric alcohols, dihydric alcohols, and polyhydric alcohols. More preferably, the organic alcohol compounds in the first and second catalysts are each independently 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.

[0066] In this invention, there are no specific limitations on the types of carboxylic acid compounds in the first and second catalysts. Preferably, in both the first and second catalysts, the carboxylic acid compounds are each independently 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.

[0067] In this invention, there are no specific limitations on the types of organic amine compounds in the first and second catalysts. Preferably, in the first and second catalysts, the organic amine compounds are each independently selected from at least one of ethylenediamine, ethylenediaminetetraacetic acid, ethanolamine, triethanolamine, and cyclohexanediaminetetraacetic acid, and more preferably triethanolamine and / or cyclohexanediaminetetraacetic acid.

[0068] In this invention, there are no specific limitations on the size of the first catalyst and the second catalyst. Preferably, the equivalent diameter of the first catalyst and the second catalyst is 0.5-1.8 mm, and more preferably 0.8-1.6 mm.

[0069] In this invention, there is no specific limitation on the shape of the first catalyst and the second catalyst; conventional catalyst shapes in the art are applicable to this invention. Preferably, the first catalyst and the second catalyst are each independently cylindrical, cloverleaf, four-leaf clover, disc, honeycomb, or other irregular shapes, and more preferably butterfly-shaped.

[0070] In this invention, the preparation method of the first catalyst is not particularly limited. Preferably, the preparation method of the first catalyst includes: introducing a co-active component precursor, a Group VIB metal precursor, a phosphorus-containing compound, and at least two compounds selected from organic alcohol compounds, carboxylic acid compounds, and organic amine compounds into a first support by impregnation, followed by drying.

[0071] In this invention, the types of the first carrier, the co-active component, the group VIB metal, the organic alcohol compound, the carboxylic acid compound, and the organic amine compound have been described above and will not be repeated here.

[0072] According to a preferred embodiment of the present invention, in the first catalyst, the precursor of the co-active component is selected from its respective soluble salt or chloride.

[0073] In a preferred embodiment, the precursor of the co-active component is selected from at least one of nickel nitrate, basic nickel carbonate, nickel acetate, nickel propionate, ferric nitrate, ferric chloride, ferric acetate, ruthenium nitrate, ruthenium chloride, ruthenium acetate, osmium nitrate, and osmium trichloride.

[0074] 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.

[0075] 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.

[0076] 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 first catalyst is prepared by co-impregnation in the present invention. In a more preferred embodiment, the impregnation method includes: impregnating the first support with an impregnation solution containing at least two of the following: a co-active component precursor, a Group VIB metal precursor, a phosphorus-containing compound, and an organic alcohol compound, a carboxylic acid compound, and an organic amine compound.

[0077] In this invention, there is no specific limitation on the order of adding the co-active component precursor, the Group VIB metal precursor, the phosphorus-containing compound, and the organic alcohol compound, carboxylic acid compound, and organic amine compound, as long as it facilitates uniform mixing of all components. In a preferred embodiment, at least two of the organic alcohol compound, carboxylic acid compound, and organic amine compound (preferably an organic alcohol compound and a carboxylic acid compound and / or an organic amine compound), the co-active component precursor, and the Group VIB metal precursor are added to an aqueous solution of the phosphorus-containing compound to provide the impregnation solution. In this invention, the order of adding the organic alcohol compound, carboxylic acid compound and / or organic amine compound, phosphorus-containing compound, and metal precursor can also be interchanged.

[0078] In this invention, the first 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, and a co-active component precursor. 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 the first alumina support is measured, and the liquid absorption rate of the first alumina support is calculated according to the formula: first alumina support water absorption rate - 0.1. According to the liquid absorption rate of the first alumina support, the impregnation solution is adjusted to a corresponding volume (first alumina support liquid absorption rate × support mass). The impregnation solution is then mixed evenly with the corresponding mass of the first alumina support and allowed to stand. Finally, the mixture is dried to obtain the first catalyst.

[0079] In this invention, the preparation method of the second catalyst is not particularly limited. Preferably, the preparation method of the second catalyst includes: introducing 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 into a second support using the same impregnation method as the first catalyst, followed by drying.

[0080] In this invention, the types of the second carrier, other metals of Group VIII, metals of Group VIB, organic alcohol compounds, carboxylic acid compounds, and organic amine compounds have been described above and will not be repeated here.

[0081] According to a preferred embodiment of the present invention, the cobalt precursor is selected from at least one of cobalt nitrate, basic cobalt carbonate, and cobalt acetate.

[0082] In this invention, the types of precursors for other metals in Group VIII and metals in Group VIB, as well as the types of phosphorus-containing compounds, can be selected from the precursors of the corresponding substances in the first catalyst, and will not be elaborated further here.

[0083] In this invention, the second catalyst and the first catalyst can be prepared using the same method. The specific operation methods and conditions have been described above and will not be repeated here.

[0084] In this invention, there are no specific limitations on the stirring conditions in the preparation methods of the first and second catalysts. Preferably, in the preparation methods of the first and second catalysts, the stirring independently includes: a temperature of 40-100℃ and a time of 1-8 hours.

[0085] In this invention, there are no specific limitations on the selection of drying conditions in the preparation methods of the first and second catalysts. Preferably, in the preparation methods of the first and second catalysts, the drying conditions each independently include: a temperature of 60-200℃ and a time of 2-10h.

[0086] According to a preferred embodiment of the present invention, both the first and second catalysts are prepared without calcination. The advantage of this preferred embodiment is that it retains organic matter within the catalyst, promoting the formation of more active sites and maintaining high initial activity of the catalyst.

[0087] A second aspect of the present invention provides a method for hydrorefining a catalyst in a distillate oil, wherein the method comprises: under hydrorefining conditions, loading a first catalyst and a second catalyst into a hydrorefining apparatus according to the grading method described in the first aspect, and injecting the distillate oil to be treated into the hydrorefining apparatus for reaction.

[0088] In this invention, the catalyst in the hydrorefining apparatus is the first catalyst and the second catalyst described in the first aspect of this invention.

[0089] In this invention, the amounts of the first catalyst and the second catalyst have been described in the first aspect and will not be described again here.

[0090] According to the present invention, the hydrorefining apparatus can be selected from any conventional reactor, as long as it can realize the reaction of the raw material with the first catalyst and the second catalyst in sequence. For example, the following two methods can be used: Method 1: Two hydrorefining reactors are connected in series to form a first reaction zone and a second reaction zone. The first reaction zone is filled with the first catalyst, and the second reaction zone is filled with the second catalyst. The raw material flows through the first reactor and then into the second reactor for reaction; Method 2: The reactor is divided into a first reaction zone and a second reaction zone arranged vertically. The first catalyst and the second catalyst are filled in the two reaction zones respectively. The raw material is injected into the reactor from top to bottom for reaction.

[0091] According to a particularly preferred embodiment of the present invention, the proportion of secondary hydrogenated diesel in the distillate oil to be treated is 10-30% by weight. The advantage of this preferred embodiment is that it can produce clean diesel that meets the China VI emission standard under relatively mild conditions, and also has low hydrogen consumption during the reaction process.

[0092] According to a preferred embodiment of the present invention, the distillate oil to be treated contains 75-85% by weight of straight-run diesel oil, 15-25% by weight of catalytic diesel oil, 2000-18000 ppm of sulfur, and 15-45% by weight of aromatics.

[0093] In this invention, the secondary hydrogenated diesel refers to catalytic diesel.

[0094] In this invention, preferably, the reaction conditions include: a temperature of 300-450℃, a pressure of 3-20 MPa, and a volume hourly space velocity of 0.5-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-2000:1.

[0095] According to the present invention, the first catalyst is packed in a first reaction zone, and the second catalyst is packed in a second reaction zone. Preferably, the conditions of the first reaction zone include: a temperature of 320-420°C, a pressure of 6-20 MPa, and a volume hourly space velocity of 0.5-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-1500:1; preferably, the conditions in the second hydrogenation reaction zone include: a temperature of 320-400℃, a pressure of 3-8 MPa, and a volume hourly space velocity of 0.5-3 h⁻¹. -1The hydrogen-to-oil volume ratio is 100-500:1. The advantage of adopting the above-mentioned preferred embodiment is that it can better utilize the performance of the catalyst in the first and second reaction zones.

[0096] According to a preferred embodiment of the present invention, the first catalyst and the second catalyst need to be converted from oxidized catalyst to sulfidized 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.

[0097] In this invention, preferably, the sulfidation conditions of the first catalyst and the second catalyst include: a heating rate of 5-60℃ / h, a sulfidation temperature of 280-420℃, a sulfidation time of 8-48h, a sulfidation 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.

[0098] The following embodiments will further illustrate the present invention.

[0099] In the following embodiments, the hydrogenation performance of the catalyst was tested in a high-throughput hydrogenation reactor. This reactor consisted of a single reactor divided into upper and lower beds. The first reaction zone was loaded with the first catalyst of this invention, and the second reaction zone was loaded with the second catalyst of this invention. First, the oxidized catalyst was converted to a sulfidized catalyst using a temperature-programmed sulfidation method. The sulfidation conditions were: sulfidation pressure of 6.4 MPa, kerosene containing 2% CS2 by weight as sulfidation oil, and a volumetric hourly space velocity of 2 h⁻¹. -1 The hydrogen-to-oil 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 80% by weight straight-run diesel, 20% by weight catalytic diesel, 10890 ppm sulfur, and 37.4% by weight aromatics. The test conditions were: pressure 6.4 MPa, total volumetric space velocity (VHSV) of the reactor 1.5 h⁻¹. -1 The hydrogen-to-oil ratio was 300 v / v, and the reaction temperature was 360℃. The reaction proceeded stably for 12 days. The change in the reaction rate constant after 12 days was calculated. Specifically, the ratio of the stable rate constant to the initial reaction rate constant is called the activity retention, which expresses the catalyst's stability. The higher the activity retention, the better the catalyst's stability.

[0100] The composition of the catalyst was calculated based on the feed rate. The pore distribution, pore size, and pore volume in the catalyst and support (2-100 nm) were determined using the low-temperature nitrogen adsorption method (see *Analytical Methods in Petrochemicals (RIPP Test Methods)*, edited by Yang Cuiding et al., Science Press, 1990). The pore distribution, pore size, and pore volume in the 100-300 nm range were determined using the mercury porosimetry method. The sulfur mass fraction in the products was analyzed using a sulfur-nitrogen analyzer (Thermo Fisher Scientific, model TN / TS3000), and the aromatic hydrocarbon content was analyzed using near-infrared spectroscopy.

[0101] 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.

[0102] 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.

[0103] The reaction rate constant is calculated using the following formula: LHSV is the reaction space velocity, n is the reaction order (assuming n = 1.2), and S f S p These refer to the sulfur content of the raw materials and the finished products, respectively.

[0104] Example 1

[0105] First-bed catalyst: A certain amount of MoO3, basic nickel carbonate, ethylene glycol, and citric acid were added to an aqueous solution containing phosphoric acid, and heated and stirred at 85°C for 3 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was then mixed evenly with the support and dried at 120°C for 5 hours to prepare a catalyst with a particle size of 1.6 mm and a butterfly shape. The pore size distribution of the catalyst in the 100-300 nm range accounted for 15% of the catalyst pore volume.

[0106] 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 ​​280 m². 2 The alumina support has an average pore size of 14.8 nm, with pores ranging from 100 to 300 nm accounting for 12% of the total pore volume. 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.

[0107] The catalyst contained 30.0 wt% MoO3, 4.5 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.22, and 7.0 wt% P2O5, of which 30 wt% of the P2O5 came from the support. The molar ratio of ethylene glycol to Group VIB metals was 1.5:1, and the molar ratio of citric acid to nickel was 1:1. The catalyst was tested using temperature-programmed oxidation. Figure 1 As shown, CO2 release peaks appeared at 238℃ and 345℃, respectively, and the ratio of their peak heights was 3.5.

[0108] Second bed catalyst:

[0109] 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. After the impregnation solution was mixed evenly with the support, it was dried at 120°C for 5 hours to prepare a catalyst with a particle size of 1.6 mm and a butterfly shape.

[0110] 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 6.0% of the total pore volume and pores of 2-4 nm accounting for 2.0%. The sodium oxide content in the support is 0.05%. 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.

[0111] The catalyst contained 28.0 wt% MoO3, 4.9 wt% CoO, 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 2 As shown, CO2 emission peaks appeared at 255℃ and 340℃, respectively, and the ratio of their peak heights was 2.2.

[0112] Performance testing of the catalyst system:

[0113] The volume ratio of the first catalyst bed to the second catalyst bed was 1:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 8.9 ppm sulfur, 27.0% aromatic hydrocarbons by weight, and 0.97% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 88.5% after 12 days of reaction.

[0114] Example 2

[0115] First-bed catalyst: A certain amount of MoO3, basic nickel carbonate, glycerol, and acetic acid were added to an aqueous solution containing phosphoric acid, and 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. The pore size distribution of the catalyst in the 100-300 nm range accounted for 15% of the catalyst pore volume.

[0116] In Example 2, the first bed catalyst used the same support as the first bed catalyst in Example 1.

[0117] The catalyst contained 24.0 wt% MoO3, 7.0 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.36, and 6.5 wt% P2O5, of which 20 wt% of the P2O5 came from the support. The molar ratio of glycerol to Group VIB metal was 1.2:1, and the molar ratio of acetic acid to nickel was 1.5:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 240℃ and 340℃, with a peak height ratio of 3.3.

[0118] Second bed catalyst:

[0119] 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 the active metal. The impregnation solution was mixed evenly with the support, allowed to stand for 5 hours, and then dried at 120°C for 5 hours to prepare a catalyst with a particle size of 1.6 mm and a butterfly shape. In Example 2, the second bed catalyst used the same support as the second bed catalyst in Example 1.

[0120] The catalyst contained 15.0 wt% MoO3, 3.8 wt% CoO, 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.

[0121] Performance testing of the catalyst system:

[0122] The volume ratio of the first catalyst bed to the second catalyst bed was 3:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 6.3 ppm sulfur, 25.6% aromatic hydrocarbons by weight, and 1.15% hydrogen consumption by weight. Maintaining stable reaction conditions, the activity retention was 86.6% after 12 days of reaction.

[0123] Example 3

[0124] First-bed catalyst: A certain amount of MoO3, basic nickel carbonate, butanol, and acetic acid were added to an aqueous solution containing phosphoric acid, and 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. The pore size distribution of the catalyst in the 100-300 nm range accounted for 15% of the catalyst pore volume.

[0125] In Example 3, the first bed catalyst used the same support as the first bed catalyst in Example 1.

[0126] The catalyst contained 38.0 wt% MoO3, 6.5 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.25, 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 0.6:1, and the molar ratio of citric acid to nickel was 1.2:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 230℃ and 348℃, with a peak height ratio of 1.9.

[0127] Second bed catalyst:

[0128] 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 the active metal. 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. In Example 3, the second bed catalyst used the same support as the second bed catalyst in Example 1.

[0129] The catalyst contained 24.0 wt% MoO3, 6.0 wt% CoO, and an atomic ratio of Co / (Co+Mo) of 0.32. It also contained 5.0 wt% P2O5, of which 10 wt% of the P2O5 was derived 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 were observed at 230℃ and 325℃, with a peak height ratio of 4.2.

[0130] Performance testing of the catalyst system:

[0131] The volume ratio of the first catalyst bed to the second catalyst bed was 3:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 7.5 ppm sulfur, 25.9% aromatic hydrocarbons by weight, and 1.1% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 83.8% after 12 days of reaction.

[0132] Example 4

[0133] First bed catalyst:

[0134] A certain amount of MoO3, basic nickel 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 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 pore size distribution of the catalyst in the 100-300 nm range accounted for 15% of the catalyst pore volume.

[0135] In Example 4, the first bed catalyst used the same support as the first bed catalyst in Example 1.

[0136] The catalyst contained 26.0 wt% MoO3, 5.5 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.29, and 4.5 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 triethanolamine to nickel was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 230℃ and 332℃, with a peak height ratio of 2.7.

[0137] Second bed catalyst:

[0138] 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. In Example 4, the second bed catalyst used the same support as the second bed catalyst in Example 1.

[0139] The catalyst contained 24.0 wt% MoO3, 6.0 wt% CoO, and an atomic ratio of Co / (Co+Mo) of 0.32. It also contained 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.

[0140] Performance testing of the catalyst system:

[0141] The volume ratio of the first catalyst bed to the second catalyst bed was 2:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 8.5 ppm sulfur, 26.3% aromatic hydrocarbons by weight, and 1.05% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 85% after 12 days of reaction.

[0142] Example 5

[0143] The first and second bed catalysts are the same as those in Example 1.

[0144] Performance testing of the catalyst system:

[0145] The volume ratio of the first catalyst bed to the second catalyst bed was 1:2, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 8.6 ppm sulfur, 27.5% aromatic hydrocarbons by weight, and 0.92% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 88.6% after 12 days of reaction.

[0146] Example 6

[0147] First bed catalyst:

[0148] A certain amount of MoO3, basic nickel carbonate, ethylene glycol, 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 then 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 pore size distribution of the catalyst in the 100-300 nm range accounted for 10% of the catalyst pore volume.

[0149] The catalyst was prepared using a γ-alumina support with a water absorption rate of 1.04 mL / g and a specific surface area of ​​285 m². 2 / g, with an average pore size of 12.6nm, and the volume of pores with a size of 100-300nm accounting for 8% of the total pore volume. The sodium oxide content in the support is 0.03% by weight. The alumina support used to prepare the catalyst does not contain phosphorus.

[0150] The catalyst contained 26.0 wt% MoO3, 5.5 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.29, and 5.9 wt% P2O5. The molar ratio of ethylene glycol to Group VIB metals was 0.8:1, and the molar ratio of citric acid to nickel was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 240℃ and 345℃, with a peak height ratio of 1.2.

[0151] Second bed catalyst:

[0152] 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.

[0153] 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.

[0154] 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.

[0155] Performance testing of the catalyst system:

[0156] The volume ratio of the first catalyst bed to the second catalyst bed was 1:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 7.5 ppm sulfur, 27.6% aromatic hydrocarbons by weight, and 0.95% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 86.5% after 12 days of reaction.

[0157] Example 7

[0158] The first bed catalyst is the same as the first bed catalyst in Example 1.

[0159] Second bed catalyst:

[0160] 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.

[0161] 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.

[0162] 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.

[0163] Performance testing of the catalyst system:

[0164] The volume ratio of the first catalyst bed to the second catalyst bed was 1:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 7.3 ppm sulfur, 26.5% aromatic hydrocarbons by weight, and 1.05% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 84.2% after 12 days of reaction.

[0165] Example 8

[0166] First bed catalyst:

[0167] A certain amount of MoO3, basic nickel 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 the active metal. 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. The pore size distribution of the catalyst in the 100-300 nm range accounted for 15% of the catalyst pore volume. The support was the same as that used in the first bed catalyst in Example 1.

[0168] The catalyst contained 30.0 wt% MoO3, 4.5 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.22, and 7.0 wt% P2O5, of which 30 wt% of the P2O5 came from the support. The molar ratio of ethylene glycol to Group VIB metals was 0.3:1, and the molar ratio of citric acid to nickel was 1:1. The catalyst was tested using temperature-programmed oxidation, and CO2 release peaks appeared at 243℃ and 342℃, with a peak height ratio of 0.73.

[0169] The second bed catalyst is the same as the second bed catalyst in Example 1.

[0170] The volume ratio of the first catalyst bed to the second catalyst bed was 1:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 9.0 ppm sulfur, 28.2% aromatic hydrocarbons by weight, and 0.88% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 85.4% after 12 days of reaction.

[0171] Example 9

[0172] First bed catalyst: The method of the first bed catalyst in Example 1 is the same, except that the molar ratio of citric acid to nickel is 0.2:1.

[0173] The second bed catalyst is the same as the second bed catalyst in Example 1.

[0174] Performance testing of the catalyst system:

[0175] The volume ratio of the first catalyst bed to the second catalyst bed was 1:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 10.5 ppm sulfur, 28.5% aromatic hydrocarbons by weight, and 0.78% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 87.2% after 12 days of reaction.

[0176] Example 10

[0177] First bed catalyst: The catalyst was prepared according to the method of the first bed catalyst in Example 1, and the proportion of the catalyst pore size distribution in the 100-300 nm range to the catalyst pore volume was 2%.

[0178] The catalyst was prepared using a γ-alumina support with a water absorption rate of 0.99 mL / g and a specific surface area of ​​286 m². 2The alumina support has an average pore size of 11.8 nm, with pores ranging from 100 to 300 nm accounting for 1% of the total pore volume. 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.

[0179] Second bed catalyst: Same as the second bed catalyst in Example 1.

[0180] Performance testing of the catalyst system:

[0181] The volume ratio of the first catalyst bed to the second catalyst bed was 1:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 10.2 ppm sulfur, 27.2% aromatic hydrocarbons by weight, and 0.95% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 82.1% after 12 days of reaction.

[0182] Comparative Example 1

[0183] First bed catalyst:

[0184] 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 2 hours until completely dissolved to obtain an impregnation solution containing the active metal. 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. The pore size distribution of the catalyst in the 100-300 nm range accounted for 15% of the catalyst pore volume. The support was the same as that used in the first bed catalyst of Example 1.

[0185] The catalyst contained 30.0 wt% MoO3, 4.5 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.22, and 7.0 wt% P2O5, of which 30 wt% of the P2O5 came from the support. The molar ratio of citric acid to nickel was 0.8:1. The catalyst was tested using temperature-programmed oxidation, and a CO2 release peak appeared at 360℃.

[0186] Second bed catalyst:

[0187] 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 selected was the same as the support used in the second bed catalyst in Example 1.

[0188] 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℃.

[0189] Performance testing of the catalyst system:

[0190] The volume ratio of the first catalyst bed to the second catalyst bed was 1:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 26.0 ppm sulfur, 29.5% aromatic hydrocarbons by weight, and 0.86% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 77.2% after 12 days of reaction.

[0191] Comparative Example 2

[0192] First bed catalyst:

[0193] 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 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 pore size distribution of the catalyst in the 100-300 nm range accounted for 15% of the catalyst pore volume.

[0194] The support is the same as that of the first bed catalyst in Example 1.

[0195] The catalyst contained 24.0 wt% MoO3, 7 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.36, and 6.5 wt% P2O5, of which 20 wt% of the P2O5 came from the support. The molar ratio of glycerol to nickel was 1.2:1.

[0196] The catalyst was tested using temperature-programmed oxidation, and a CO2 release peak appeared at 235℃.

[0197] Second bed catalyst:

[0198] 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 the active metal. The impregnation solution was mixed evenly with the 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 selected was the same as the support used in the second bed catalyst in Example 1.

[0199] 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℃.

[0200] Performance testing of the catalyst system:

[0201] The volume ratio of the first catalyst bed to the second catalyst bed was 3:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 28.5 ppm sulfur, 29.8% aromatic hydrocarbons by weight, and 0.84% ​​hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 76.0% after 12 days of reaction.

[0202] Comparative Example 3

[0203] First bed catalyst:

[0204] 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 2 hours until completely dissolved to obtain an impregnation solution containing active metals. The impregnation solution was then 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 pore size distribution of the catalyst in the 100-300 nm range accounted for 30% of the catalyst pore volume.

[0205] The support used was prepared using the same process as the first catalyst support in Example 1. The support was γ-alumina, with a water absorption rate of 1.3 mL / g and a specific surface area of ​​270 m². 2 / g, with an average pore size of 16.5nm, and pores with a size of 100-300nm accounting for 25% of the total pore volume. The sodium oxide content in the support is 0.05% by weight.

[0206] The catalyst contained 30.0 wt% MoO3, 4.5 wt% NiO, an atomic ratio of Ni / (Ni+Mo) of 0.22, and 7.0 wt% P2O5, of which 30 wt% of the P2O5 came from the support. The molar ratio of citric acid to nickel was 0.8:1. The catalyst was tested using temperature-programmed oxidation, and a CO2 release peak appeared at 365℃.

[0207] Second bed catalyst:

[0208] 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 the 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 selected was the same as that used in the second catalyst bed in Example 1.

[0209] 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℃.

[0210] Performance testing of the catalyst system:

[0211] The volume ratio of the first catalyst bed to the second catalyst bed was 2:1, and the reaction temperature of both beds was 360℃. After sulfidation and reaction testing, the product contained 35 ppm sulfur, 27.5% aromatic hydrocarbons by weight, and 1.03% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 75.4% after 12 days of reaction.

[0212] Comparative Example 4

[0213] Following the method of Example 1, the first and second bed catalysts were identical to those in Example 1, except that the volume ratio of the first bed catalyst to the second bed catalyst was 1:8. After sulfidation and reaction testing, the product contained 27.0 ppm sulfur, 30.5% aromatic hydrocarbons by weight, and 0.73% hydrogen consumption. Maintaining stable reaction conditions, the activity retention was 79.5% after 12 days of reaction.

[0214] In this invention, by selecting two specific catalysts for graded formulation, good desulfurization and dearomatics removal effects and low reaction hydrogen consumption can be achieved.

[0215] 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. A method for hydrorefining distillate oils using a catalyst, wherein, The method includes: under hydrorefining conditions, loading a first catalyst and a second catalyst into a hydrorefining unit according to a catalyst gradation method, and injecting the distillate oil to be treated into the hydrorefining unit for reaction; The catalyst gradation method includes: sequentially loading a first catalyst and a second catalyst along the material flow direction; The first catalyst comprises at least one Group VIB metal element, a co-active component, phosphorus element, and a first support; the co-active component includes nickel and at least one of iron, ruthenium, and osmium elements; the pore size distribution of the first catalyst in the range of 100-300 nm accounts for no more than 20% of the catalyst pore volume; wherein, during temperature-programmed oxidation, the first catalyst contains at least two CO2 release peaks, the first release peak temperature is in the range of 230-260℃, the second release peak temperature is in the range of 320-360℃, and the peak height ratio ranges from 0.7 to 3.5:1; The second catalyst comprises cobalt and optionally one of other group VIII metals, at least one group VIB metal, phosphorus, and a second support; wherein, during the temperature-programmed oxidation process, the second catalyst contains at least two CO2 release peaks, the third release peak is at a temperature of 200-300℃, the fourth release peak is at a temperature of 300-400℃, and the peak height ratio is in the range of 1-5:

1. The loading volume ratio of the first catalyst and the second catalyst is 1:2-5:1; In the first catalyst, the molar ratio of carboxylic acid compounds and / or organic amine compounds to the co-activating components is 0.3-1.5:1; In the second catalyst, 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; The atomic ratio of cobalt to the total amount of cobalt and optionally other Group VIII metallic elements is not less than 0.8; Both the first catalyst and the second catalyst contain organic alcohol compounds, as well as carboxylic acid compounds and / or organic amine compounds; The distillate oil to be treated contains 75-85% by weight straight-run diesel, 15-25% by weight catalytic diesel, 2000-18000 ppm sulfur, and 15-45% by weight aromatics.

2. The method according to claim 1, wherein, The volume ratio of the first catalyst to the second catalyst is 1:1 to 4:

1.

3. The method according to claim 1, wherein, Based on the total amount of the first catalyst, the content of the co-activating component, calculated as oxides, is 1-15% by weight, and the content of the Group VIB metal element is 12-50% by weight.

4. The method according to claim 1, wherein, The atomic ratio of nickel to the total amount of the auxiliary active components is not less than 0.

8.

5. The method according to claim 4, wherein, The atomic ratio of nickel to the total amount of the active component is 0.85-1.

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

7. The method according to claim 1, wherein, The proportion of the pore size distribution of the first catalyst in the range of 100-300 nm to the pore volume of the first catalyst is 5-20%.

8. The method according to claim 1, wherein, The atomic ratio of the co-active component to the total amount of the co-active component and the Group VIB metal elements is 0.1-0.

5.

9. The method according to claim 8, wherein, The atomic ratio of the co-active component to the total amount of the co-active component and Group VIB metal elements is 0.2-0.

35.

10. The method according to claim 1, wherein, In the first catalyst and the second catalyst, the Group VIB metal element is independently selected from at least one of chromium, molybdenum and tungsten.

11. The method according to claim 1, wherein, Based on the total amount of the second catalyst, the content of cobalt and optionally other Group VIII metals is 1-15% by weight, and the content of Group VIB metals is 12-50% by weight, calculated as oxides.

12. The method 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.

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

14. The method according to claim 1, wherein, The second catalyst contains at least two CO2 release peaks during the programmed temperature oxidation process, with the third release peak at a temperature of 220-280℃ and the fourth release peak at a temperature of 320-380℃, and the peak height ratio ranges from 1.5 to 3:

1.

15. The method according to claim 1, wherein, The atomic ratio of cobalt and optionally other Group VIII metals to the total amount of cobalt and optionally other Group VIII metals and Group VIB metals is 0.1-0.

5.

16. The method according to claim 15, wherein, The atomic ratio of cobalt and optionally other Group VIII metals to the total amount of cobalt and optionally other Group VIII metals and Group VIB metals is 0.2-0.

35.

17. The method according to claim 1, wherein, The first carrier is a first alumina carrier.

18. The method according to claim 17, wherein, The second carrier is a second alumina carrier.

19. The method according to claim 18, wherein, Both the first alumina support and the second alumina support contain phosphorus.

20. The method according to claim 19, wherein, Based on P2O5, the phosphorus element in the first alumina support and the second alumina support each independently accounts for 10-40% of the total phosphorus content in the first catalyst and the second catalyst.

21. The method according to claim 20, wherein, Based on P2O5, the phosphorus element in the first alumina support and the second alumina support each independently accounts for 20-30% of the total phosphorus content in the first catalyst and the second catalyst.

22. The method according to claim 19, wherein, The precursors of the first alumina support and the second alumina support are each independently boehmite, which contains phosphorus.

23. The method according to claim 22, wherein, The sodium oxide content in the pseudoboehmite does not exceed 0.08% by weight.

24. The method according to claim 23, wherein, The sodium oxide content in the pseudoboehmite does not exceed 0.05% by weight.

25. The method according to claim 19, wherein, The first 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.

26. The method according to claim 19, wherein, The pore size distribution of the first alumina support in the range of 100-300 nm accounts for 5-15% of the pore volume of the first alumina support.

27. The method according to claim 19, wherein, The second 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.

28. The method according to claim 19, wherein, In the second 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 second alumina support.

29. The method according to claim 28, wherein, In the second alumina carrier, 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 second alumina carrier.

30. The method according to claim 19, wherein, In the second alumina carrier, 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 second alumina carrier.

31. The method according to claim 30, wherein, In the second 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 second alumina carrier.

32. The method according to claim 1, wherein, In both the first and second catalysts, the molar ratio of the organic alcohol compound to the Group VIB metal element is independently 0.2-4:

1.

33. The method according to claim 1, wherein, In both the first and second catalysts, the organic alcohol compounds are each independently 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.

34. The method according to claim 33, wherein, In both the first and second catalysts, the organic alcohol compounds are each independently selected from at least one of butanol, glycerol, propanol, and ethylene glycol.

35. The method according to claim 1, wherein, In the first catalyst and the second catalyst, the carboxylic acid compounds are each independently 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.

36. The method according to claim 35, wherein, In both the first and second catalysts, the carboxylic acid compounds are each independently selected from at least one of formic acid, citric acid, and acetic acid.

37. The method according to claim 1, wherein, In both the first and second catalysts, the organic amine compounds are each independently selected from at least one of ethylenediamine, ethylenediaminetetraacetic acid, ethanolamine, triethanolamine, and cyclohexanediaminetetraacetic acid.

38. The method according to claim 1, wherein, The equivalent diameters of the first catalyst and the second catalyst are each independently 0.5-1.8 mm.

39. The method according to claim 38, wherein, The equivalent diameters of the first catalyst and the second catalyst are each independently 0.8-1.6 mm.

40. The method according to claim 1, wherein, The first catalyst and the second catalyst are each independently butterfly-shaped, cylindrical, clover-shaped, honeycomb-shaped, or other irregular shapes.

41. The method according to any one of claims 1-40, wherein, The preparation method of the first catalyst includes: introducing a co-active component precursor, a Group VIB metal precursor, a phosphorus-containing compound, an organic alcohol compound, a carboxylic acid compound, and / or an organic amine compound into a first support by impregnation, and then drying.

42. The method according to any one of claims 1-40, wherein, The preparation method of the second catalyst includes: introducing a cobalt precursor and optionally other Group VIII metal precursors, Group VIB metal precursors, phosphorus-containing compounds, organic alcohol compounds, carboxylic acid compounds and / or organic amine compounds into a second support using the same impregnation method as the first catalyst, and then drying.

43. The method according to claim 41, wherein, In the preparation methods of the first catalyst and the second catalyst, the drying conditions each independently include: a temperature of 60-200℃ and a time of 2-10h.

44. The method according to claim 1, wherein, The reaction conditions include: a temperature of 300-450℃, a pressure of 3-20 MPa, and a volume hourly space velocity of 0.5-3 h⁻¹. -1 The hydrogen-to-oil volume ratio is 100-2000:

1.

45. The method according to claim 1, wherein, The sulfidation conditions for the first and second catalysts include: a heating rate of 5-60℃ / h, a sulfidation temperature of 280-420℃, a sulfidation time of 8-48h, a sulfidation 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.

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