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

Abstract

The present application relates to a kind of desulfurization catalyst, the catalyst includes active component and carrier, active component is Cu x B y O m ;B is selected from at least one of alkali earth metal, group VIII metal, group IIB metal, group IVB metal and rare earth metal;X=0.2-2;Y=0-1.8;M is the oxygen atom mole number required to meet the valence of each element in catalyst;Copper has Cu (I) and Cu (II) two valence states, Cu (I) content is 20wt%-60wt% based on the total mass of copper.The desulfurization catalyst in the present application has multiple valence state metals in metal oxide, active metal is highly dispersed, can more effectively utilize active component, does not need to be passivated again when used for reaction, can greatly improve desulfurization rate, according to a preferred embodiment of the present application, metal oxide in the catalyst can maintain regular lattice structure of the catalyst.The catalyst is used for hydrocracking diesel desulfurization, and has the advantages of high desulfurization rate.

Description

Technical Field

[0001] This invention relates to a desulfurization catalyst, its preparation method, and its application. Background Technology

[0002] SO2 is generated after the combustion of sulfur compounds in diesel fuel. x Not only does it contribute to acid rain formation, but it also promotes particulate matter emissions. Current desulfurization technologies are mainly divided into hydrodesulfurization and adsorption desulfurization. Hydrodesulfurization removes organic sulfur by adding hydrogen, offering high yields, but the entire process is lengthy, energy-intensive, and results in significant octane number loss. Adsorption desulfurization, on the other hand, removes organic sulfur through complexation, van der Waals forces, or chemical reactions between the organic sulfur and the adsorbent. It boasts advantages such as high desulfurization depth, easy regeneration, low cost, and high operational activity, but it also faces challenges in adsorption performance and regeneration.

[0003] Materials with a large specific surface area alone often have insufficient adsorption effects. Therefore, researchers often use transition metal ions to modify them, which can improve the desulfurization effect to varying degrees.

[0004] CN102430412B discloses two processes for preparing desulfurizing agents. The first process uses a direct preparation method, which requires hydrothermal treatment under high temperature conditions. The second process uses an impregnation method, using molecular sieves as a carrier to impregnate active metals, followed by high-temperature steam treatment. Both processes are cumbersome and require high-temperature treatment, which can also cause the active metals to agglomerate.

[0005] CN102430412B employs ionic liquid-supported molecular sieves for sulfur removal from gasoline. While ionic liquids can improve the dispersion of acidic sites, the initial preparation process is lengthy and requires both an oxidant (H₂O₂) and an extractant (acetonitrile), making the operation relatively cumbersome and costly. Metal oxides, on the other hand, possess advantages such as high specific surface area, large pore size, and regular pore structure, showing broad application prospects in adsorption and catalysis. Their relatively concentrated and uniform pore size can facilitate the removal of some difficult-to-remove organic sulfur compounds, such as thiols and thioethers. Summary of the Invention

[0006] The purpose of this invention is to overcome the problems of cumbersome catalyst preparation steps and low desulfurization efficiency in actual use in the existing technology, and to provide a desulfurization catalyst, its preparation method and application. The desulfurization catalyst is simple to prepare, the active components are uniformly dispersed, and it is used for desulfurization of hydrocracking diesel with a high desulfurization rate.

[0007] To achieve the above objectives, a first aspect of the present invention provides a desulfurization catalyst, the catalyst comprising an active component and a support, wherein the active component is Cu. x B y O mB is selected from at least one of alkaline earth metals, Group VIII metals, Group IIB metals, Group IVB metals, and rare earth metals; x = 0.2-2; y = 0-1.8; m is the number of moles of oxygen atoms required to satisfy the oxidation states of each element in the catalyst;

[0008] Copper has two valence states, Cu(I) and Cu(II), and the Cu(I) content is 20wt%-60wt% based on the total mass of copper.

[0009] A second aspect of the present invention provides a method for preparing the desulfurization catalyst of the present invention, the method comprising: loading Cu... x B y The (OH)3Cl carrier precursor was calcined.

[0010] A third aspect of the present invention provides the application of the desulfurization catalyst described herein in the desulfurization of hydrocracking diesel.

[0011] Through the above technical solution, the desulfurization catalyst provided by the present invention contains multiple valence states of metal oxides, and the active metals are highly dispersed, enabling more efficient utilization of the active components. During the reaction, no further reduction and passivation are required, significantly improving the desulfurization rate. According to a preferred embodiment of the present invention, the metal oxides in the catalyst maintain a regular crystal lattice structure. This catalyst is used for desulfurization of hydrocracking diesel fuel and has the advantage of a high desulfurization rate.

[0012] It is speculated that the desulfurization catalyst preparation process described in this invention involves loading Cu... x B y The calcination of the (OH)3Cl carrier precursor enables the active metal components of the desulfurization catalyst of the present invention to be highly dispersed, and multiple valence states of metals to exist simultaneously. It also enables the metal oxides in the desulfurization catalyst to maintain a regular lattice structure, thereby further improving the desulfurization rate. Attached Figure Description

[0013] Figure 1 These are the XRD spectra of the desulfurization catalyst precursor A1 and desulfurization catalyst B1 synthesized in Example 1;

[0014] Figure 2 This is a TEM image of the desulfurization catalyst synthesized in Example 1;

[0015] Figure 3 This is the XPS spectrum of Cu in the desulfurization catalyst synthesized in Example 1. Detailed Implementation

[0016] 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.

[0017] In this invention, Cu(II) refers to divalent copper; Cu(I) refers to monovalent copper.

[0018] The first aspect of this invention provides a desulfurization catalyst, which includes an active component and a support, wherein the active component is Cu. x B y O m B is selected from at least one of alkaline earth metals, Group VIII metals, Group IIB metals, Group IVB metals, and rare earth metals; x = 0.2-2; y = 0-1.8; m is the number of moles of oxygen atoms required to satisfy the oxidation states of each element in the catalyst;

[0019] Copper has two valence states, Cu(I) and Cu(II), and the Cu(I) content is 20wt%-60wt% based on the total mass of copper. The desulfurization catalyst provided by this invention has copper in both Cu(I) and Cu(II) valence states, and the active metal is highly dispersed, which can more effectively utilize the active components. It does not require further reduction and passivation during the reaction, and can greatly improve the desulfurization rate.

[0020] To further improve the desulfurization rate, based on the total mass of copper, the Cu(I) content can be 53wt%, 50wt%, 45wt%, 43wt%, 40wt%, 38wt%, or 35wt%. According to a preferred embodiment of the present invention, the Cu(I) content is 35wt%-55wt%.

[0021] According to a preferred embodiment of the present invention, the ratio of x to y is 0.1-8, preferably 1-5, and more preferably 1.5-3.

[0022] According to a preferred embodiment of the present invention, x = 1-1.5; y = 0.5-1.

[0023] According to a preferred embodiment of the present invention, the active component has an octahedral cubic structure, and the metal oxide can maintain a regular lattice structure, which is beneficial to improving the desulfurization rate.

[0024] According to a preferred embodiment of the present invention, B is selected from at least one of magnesium, nickel, cobalt, zinc, cadmium, titanium and cerium, preferably at least one of nickel, cobalt and zinc, and more preferably nickel and cobalt.

[0025] In this invention, the content of active components and support can be selected within a wide range. Preferably, in the desulfurization catalyst, the active component is calculated as oxide, the support content is 45wt%-70wt%, and the active component content is 30wt%-55wt%.

[0026] In this invention, there are no special requirements for the carrier. Any carrier conventional in the art can be used as the carrier of this invention. Preferably, the carrier is selected from at least one of Al2O3, MoO3, MnO2, MgO and Fe2O3.

[0027] In this embodiment of the invention, Al2O3 is selected as the carrier to illustrate the advantages of the invention, but the invention is not limited thereto.

[0028] In this invention, any catalyst possessing the characteristics described herein can achieve the objective of this invention. Preferably, a second aspect of this invention provides a method for preparing the desulfurization catalyst described herein, the method comprising: loading Cu... x B y The (OH)3Cl support precursor is calcined. Using the aforementioned method, the active metal components of the desulfurization catalyst of the present invention are highly dispersed, containing multiple valence states of metal, and the metal oxides in the desulfurization catalyst maintain a regular crystal lattice structure, thereby further improving the desulfurization rate.

[0029] The present invention relates to the Cu x B y There are no special requirements for the preparation method of (OH)3Cl. Any material with the above composition and elements can achieve the purpose of this invention. For example, it can be obtained by co-precipitation of elemental ratios, but this does not limit the scope of this invention.

[0030] In this invention, the Cu x B y The XRD pattern of (OH)3Cl shows characteristic peaks at 2θ positions of 16.1°, 17.5°, 32.2°, 39.7°, 49.9°, 53.4°, and 67.4°.

[0031] According to a preferred embodiment of the present invention, Cu x B y (OH)3Cl has an octagonal cubic structure.

[0032] According to a preferred embodiment of the present invention, the loaded Cu x B y The preparation methods of the (OH)3Cl support precursor include:

[0033] (1) Prepare a chlorine-containing solution containing Cu source and B source in the presence of chlorine;

[0034] (2) Prepare an alkaline solution;

[0035] (3) Mix the alkaline solution, the chlorine-containing solution and the carrier to obtain a mixed slurry with a pH of 6 to 8;

[0036] (4) Crystallize, wash and dry the mixed slurry.

[0037] The present invention does not require the order of steps (1) and (2), and is only used to differentiate the preparation of chlorine-containing solutions or alkaline solutions.

[0038] In step (3) of this invention, there are no particular limitations on the mixing method of the alkaline solution, the chlorine-containing solution and the carrier. For example, the alkaline solution and the chlorine-containing solution can be mixed with the carrier in a parallel flow and the pH can be controlled at 6-8. Alternatively, the alkaline solution can be added to the mixture of the chlorine-containing solution and the carrier and the pH can be controlled at 6-8.

[0039] In this invention, there is no particular limitation on the source of chlorine in step (1). For example, it can come from a chlorine-containing copper source and / or a B source, or from an additional chlorine-containing substance, such as sodium chloride.

[0040] In this invention, the range of metal ions that can be selected for the chlorine-containing solution is relatively wide. Preferably, the concentration of metal ions in the chlorine-containing solution is 0.3-0.7 mol / L.

[0041] According to a preferred embodiment of the present invention, in the chlorine-containing solution, the molar ratio of copper ions to B metal ions is 0.2-8, preferably 1-5, and more preferably 1.5-3.

[0042] In this invention, the range of alkaline solutions is relatively wide. Preferably, the concentration of the alkaline solution is 0.4-2 mol / L.

[0043] In this invention, the type of copper source is not particularly limited and can be a conventional soluble metal salt in the art. For example, the copper source can be at least one of copper nitrate, copper chloride, and copper sulfate.

[0044] In this invention, the type of source B is not particularly limited and can be a conventional soluble metal salt in the art. Preferably, the source B is selected from at least one of soluble metal salts of alkaline earth metals, Group VIII metals, Group IIB metals, Group IVB metals and rare earth metals.

[0045] According to a preferred embodiment of the present invention, the soluble metal salt is selected from at least one of nitrate metal salts, chloride metal salts and sulfate metal salts; for example, the nickel salt may be at least one of nickel nitrate and nickel sulfate.

[0046] According to a preferred embodiment of the present invention, the copper source or B source contains at least one metal chloride salt.

[0047] In this invention, there is no particular limitation on the type of alkali. Any alkali conventional in the art can be used in this invention. According to a preferred embodiment of this invention, the alkali is selected from at least one of sodium hydroxide, anhydrous sodium carbonate, urea, and potassium hydroxide.

[0048] The present invention does not have any particular limitation on the crystallization conditions. Conventional crystallization conditions in the art are applicable to the present invention. Preferably, in step (4), the crystallization conditions include: static hydrothermal crystallization.

[0049] According to a preferred embodiment of the present invention, in step (4), the crystallization conditions include: a crystallization temperature of 60 to 120°C; the crystallization time can be reasonably adjusted as needed, preferably, the crystallization time is 10 to 36 hours.

[0050] In this invention, there are no special requirements for the roasting conditions, which are determined according to specific needs. According to a preferred embodiment of this invention, the roasting conditions include: a roasting temperature of 300-600°C and a roasting time of 2-6 hours.

[0051] In this invention, calcination can be carried out in an oxygen-containing atmosphere, such as an air atmosphere.

[0052] A third aspect of the present invention provides the application of the desulfurization catalyst described herein in the desulfurization of hydrocracking diesel.

[0053] In this invention, XRD testing was performed using a Rigaku Ultima IV X-ray powder diffractometer (Japan), with Cu Kα lines as the X-ray source. A nickel filter was used to obtain XRD patterns by using a 2θ scanning range of 5–70°, an operating voltage of 40 kV, a current of 40 mA, and a scanning rate of 10° / min.

[0054] In this invention, ICP testing was performed using a Varian 725-ES plasma-coupled atomic absorption spectrometer from Varian Instruments, Inc. All samples were dissolved in 10% HNO3 solution before testing.

[0055] In this invention, TEM testing was performed using a Tecnai 20S-TWIN transmission electron microscope from FEI Corporation of the United States to obtain TEM images.

[0056] In this invention, XPS testing was performed using a Thermo Fisher Scientific photoelectron spectroscopy instrument with MgKα as the X-ray source. The surface charge effect on the binding energy was corrected using the contamination carbon peak (EC1S = -284.8 eV). Peak fitting was performed using XPS PEAK software, and the monovalent copper content was calculated based on area ratio.

[0057] In this invention, the desulfurization performance of the desulfurization catalyst is evaluated as follows:

[0058] A fixed-bed reactor was charged with 5 g of catalyst. The experimental feedstock was a compound of products from the third stage of catalytic cracking at Jinling Petrochemical, with a density of 0.747 g / ml and a sulfur content of 74 ppm. The fixed-bed reactor piping was purged with nitrogen three times, followed by hydrogen three times, at a pressure of 1.6 MPa, 170 °C, and a space velocity of 8.0 h⁻¹. -1 Desulfurization experiments were conducted under the specified conditions. The sulfur content in the oil before and after the reaction was analyzed using GB380-77 standard for the determination of sulfur content in petroleum products. The desulfurization rate was calculated using the following formula:

[0059] Desulfurization rate = (S 原料 -S 产品油 ) / S 原料 ×100%

[0060] S 原料 —Sulfur content in raw materials;

[0061] S 产品油 —The sulfur content in exported oil products.

[0062] The present invention will be described in detail below through embodiments.

[0063] Example 1

[0064] (1) Dissolve 0.0445 mol of copper chloride dihydrate and 0.0225 mol of nickel chloride hexahydrate in 100 ml of deionized water to prepare a mixed salt solution;

[0065] (2) Dissolve 0.12 mol of sodium hydroxide in 100 ml of deionized water to prepare an alkaline solution;

[0066] (3) The two solutions were slowly added dropwise to 4.75g of Al2O3 carrier under vigorous stirring. After the addition was completed, stirring was continued for 0.5h to obtain a mixed slurry with a pH of 7.

[0067] (4) The mixed slurry was allowed to stand at 80°C for 24 hours to crystallize. The resulting precipitate was then filtered, washed until neutral, and dried to obtain catalyst precursor A1. Catalyst precursor A1 was then calcined at 450°C for 4 hours to obtain desulfurization catalyst B1.

[0068] The XRD patterns of catalyst precursor A1 and desulfurization catalyst B1 are as follows: Figure 1 As shown in the XRD spectrum, A1 exhibits characteristic peaks belonging to the target intermediate at 2θ positions of 16.1°, 17.5°, 32.2°, 39.7°, 49.9°, 53.4°, and 67.4°.

[0069] The ICP test results for desulfurization catalyst B1 showed a Cu / Ni molar ratio of 1.97.

[0070] The TEM spectrum of desulfurization catalyst B1 is as follows: Figure 2 As shown, the active components with an octagonal cubic structure aggregate on the surface of the carrier.

[0071] XPS spectra of Cu and Ni metals in desulfurization catalyst B1 are as follows: Figure 3 As shown, the Cu(I) content was calculated to be 51.4% by XPS PEAK peak fitting, indicating that the content of Cu(I) in the active center can be increased by using the intermediate.

[0072] The catalyst composition and desulfurization evaluation results are shown in Table 1.

[0073] Example 2

[0074] (1) Weigh 0.034 mol of copper chloride dihydrate and 0.034 mol of nickel nitrate hexahydrate and dissolve them in 100 ml of deionized water to prepare a mixed salt solution;

[0075] (2) Dissolve 0.2 mol NaOH in 100 ml of deionized water to prepare an alkaline solution;

[0076] (3) The two solutions were slowly added dropwise to 4.75g of Al2O3 carrier under vigorous stirring. After the addition was completed, stirring was continued for 0.5h to obtain a mixed slurry with a pH of 6.

[0077] (4) The mixed slurry was allowed to stand at 120°C for 12 hours to crystallize. The resulting precipitate was then filtered, washed until neutral, and dried to obtain catalyst precursor A2. Catalyst precursor A2 was then calcined at 400°C for 5 hours to obtain desulfurization catalyst B2.

[0078] XRD analysis showed that the catalyst precursor A2 exhibited characteristic peaks belonging to the target intermediate. Catalyst composition and desulfurization evaluation results are shown in Table 1.

[0079] Example 3

[0080] (1) Weigh 0.03 mol copper nitrate trihydrate, 0.01 mol nickel chloride hexahydrate and 0.5 g NaCl and dissolve them in 100 ml deionized water to prepare a mixed salt solution;

[0081] (2) Dissolve 0.1 mol NaOH in 100 ml of deionized water to prepare an alkaline solution;

[0082] (3) The two solutions were slowly added dropwise to 6.8g of Al2O3 carrier under vigorous stirring. After the addition was completed, stirring was continued for 0.5h to obtain a mixed slurry with a pH of 8.

[0083] (4) The mixed slurry was allowed to stand at 60°C for 36 hours to crystallize. The resulting precipitate was then filtered, washed until neutral, and dried to obtain catalyst precursor A3. Catalyst precursor A3 was then calcined at 500°C for 3 hours to obtain desulfurization catalyst B3.

[0084] XRD analysis showed that the catalyst precursor A3 exhibited characteristic peaks belonging to the target intermediate. Catalyst composition and desulfurization evaluation results are shown in Table 1.

[0085] Example 4

[0086] Following the method of Example 1, except that only 0.066 mol of copper chloride dihydrate was weighed and dissolved in 100 ml of deionized water to prepare a mixed salt solution. Catalyst precursor A4 was prepared, and the resulting catalyst was designated B4.

[0087] XRD analysis showed that the catalyst precursor A4 exhibited characteristic peaks belonging to the intermediate. Catalyst composition and desulfurization evaluation results are shown in Table 1.

[0088] Example 5

[0089] The difference from Example 1 is that 0.0225 mol of cobalt chloride hexahydrate was used instead of 0.0225 mol of nickel chloride, while the other conditions were the same as in Example 1. Catalyst precursor A5 was prepared, and the resulting catalyst was designated B5.

[0090] XRD analysis showed that the catalyst precursor A5 exhibited characteristic peaks belonging to the target intermediate. Catalyst composition and desulfurization evaluation results are shown in Table 1.

[0091] Example 6

[0092] The difference from Example 1 is that 0.0225 mol zinc chloride was used instead of 0.0225 mol nickel chloride hexahydrate, and the support was 4.6 g Al2O3. All other conditions were the same as in Example 1. Catalyst precursor A6 was prepared, and the resulting catalyst was designated B6.

[0093] XRD analysis showed that the catalyst precursor A6 exhibited characteristic peaks belonging to the target intermediate. Catalyst composition and desulfurization evaluation results are shown in Table 1.

[0094] Example 7

[0095] The difference from Example 1 is that 0.011 mol cobalt chloride hexahydrate and 0.0115 mol nickel chloride hexahydrate were used instead of 0.0225 mol nickel chloride hexahydrate, while the other conditions were the same as in Example 1. Catalyst precursor A5 was prepared, and the resulting catalyst was designated B5.

[0096] XRD analysis showed that the catalyst precursor A5 exhibited characteristic peaks belonging to the target intermediate. Catalyst composition and desulfurization evaluation results are shown in Table 1.

[0097] Comparative Example 1

[0098] The method was followed as in Example 1, except that in step (1), 0.0445 mol copper nitrate trihydrate was used instead of 0.0445 mol copper chloride dihydrate, and 0.0225 mol nickel nitrate hexahydrate was used instead of 0.0225 mol nickel chloride hexahydrate. XRD analysis showed no characteristic peaks of the target intermediate. The prepared catalyst was designated D1.

[0099] The test results are shown in Table 1.

[0100] Comparative Example 2

[0101] The method was followed in Example 1, except that in step (3), the amount of alkali added was adjusted so that the pH of the mixed slurry was 10. XRD testing showed that there were no characteristic peaks of the target intermediate. The prepared catalyst was designated as D2.

[0102] Table 1

[0103] B1 51.4 <![CDATA[52wt%Cu 1.33 In 0.67 SHE m ,48wt% Al2O3]]> 97.9 B2 41.9 <![CDATA[52wt%Cu1Ni1O m ,48wt%Al2O3]]> 92.5 B3 42.8 <![CDATA[31wt%Cu 1.5 In 0.5 SHE m ,69wt% Al2O3]]> 88.2 B4 30.7 <![CDATA[52wt%CuOm,48wt%Al2O3]]> 80.3 B5 46.0 <![CDATA[52wt%Cu 1.33 Co 0.67 EITHER m ,48wt%Al2O3]]> 96.5 B6 31.8 <![CDATA[52wt%Cu 1.33 Zn 0.67 O m ,48wt%Al2O3]]> 90.5 B7 45.2 <![CDATA[52wt%Cu 1.33 Ni 0.33 Co 0.33 O m , 48 wt% Al2O3]]> 98.4 D1 20.2 <![CDATA[12wt%Cu 1.33 Ni 0.67 O2, 78wt%Al2O3]]> 53.6 D2 22.9 <![CDATA[53wt%Cu 1.33 Ni 0.67 O2, 47wt%Al2O3]]> 44.9

[0104] As can be seen from the results in Table 1, the desulfurization catalyst described in this invention has a high desulfurization rate.

[0105] 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 desulfurization catalyst, characterized in that, The catalyst comprises an active component and a support; the active component is Cu. x B y O m ; Element B is selected from at least one of alkaline earth metals, Group VIII metals, Group IIB metals, Group IVB metals, and rare earth metals; x = 1-1.5; y = 0.5-1; m is the number of moles of oxygen atoms required to satisfy the oxidation states of each element in the catalyst; Copper has two valence states, Cu(I) and Cu(II), and the Cu(I) content is 35-55% based on the total mass of copper; the active component has an octahedral cubic structure.

2. The desulfurization catalyst according to claim 1, wherein, The ratio of x to y is 0.1-8; and / or B is selected from at least one of magnesium, nickel, cobalt, zinc, cadmium, titanium, and cerium; and / or The desulfurization catalyst has a support content of 45wt%-70wt% and an active component content of 30wt%-55wt%.

3. The desulfurization catalyst according to claim 1, wherein, The ratio of x to y is 1-5; and / or B. Nickel and cobalt.

4. The desulfurization catalyst according to claim 1, wherein, The ratio of x to y is 1.5-3.

5. The desulfurization catalyst according to any one of claims 1-4, wherein, The support is selected from at least one of Al2O3, MoO3, MnO2, MgO and Fe2O3.

6. The method for preparing the desulfurization catalyst according to any one of claims 1-5, characterized in that, The method includes: loading Cu x B y The (OH)3Cl support precursor was calcined, and Cu x B y (OH)3Cl has an octahedral cubic structure.

7. The preparation method according to claim 6, wherein, The load is Cu x B y The preparation methods of the (OH)3Cl support precursor include: (1) Prepare a chlorine-containing solution containing copper source and B source in the presence of chlorine; (2) Prepare an alkaline solution; (3) Mix the alkaline solution, the chlorine-containing solution and the carrier to obtain a mixed slurry with a pH of 6 to 8; (4) Crystallize, wash and dry the mixed slurry.

8. The preparation method according to claim 7, wherein, The chlorine-containing solution has a metal ion concentration of 0.3-0.7 mol / L; and / or In the chlorine-containing solution, the molar ratio of copper ions to boron ions is 0.2-8; and / or The concentration of the alkaline solution is 0.4-2 mol / L.

9. The preparation method according to claim 8, wherein, In the chlorine-containing solution, the molar ratio of copper ions to B metal ions is 1-5.

10. The preparation method according to claim 8, wherein, In the chlorine-containing solution, the molar ratio of copper ions to B metal ions is 1.5-3.

11. The preparation method according to claim 7, wherein, The copper source is selected from one of the soluble metal salts of copper; The B source is selected from at least one of the soluble metal salts of alkaline earth metals, Group VIII metals, Group IIB metals, Group IVB metals, and rare earth metals.

12. The preparation method according to claim 11, wherein, The soluble metal salt is selected from at least one of nitrate metal salts, chloride metal salts, and sulfate metal salts; The alkali is selected from at least one of sodium hydroxide, anhydrous sodium carbonate, urea, and potassium hydroxide.

13. The preparation method according to claim 11, wherein, The copper source or B source contains at least one metal chloride salt.

14. The preparation method according to claim 6 or 7, wherein, In step (4), the crystallization conditions include: static hydrothermal crystallization, a crystallization temperature of 60–120°C, and a crystallization time of 10–36 hours; and / or The roasting conditions include: a roasting temperature of 300–600℃ and a roasting time of 2–6 hours.

15. The application of the desulfurization catalyst according to any one of claims 1-5 in the desulfurization of hydrocracking diesel.

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