A modified hydrogenation catalyst carrier and a method for preparing the same, and a hydrogenation catalyst

Abstract

The application provides a modified hydrogenation catalyst carrier, a preparation method of the modified hydrogenation catalyst carrier and a hydrogenation catalyst, and the preparation method of the modified hydrogenation catalyst carrier comprises the following steps: after alumina is sufficiently immersed in an ammonium fluoroborate solution, the alumina is added into a polytetrafluoroethylene-lined autoclave, and a hydrothermal reaction is carried out at 50-90 DEG C, and then the obtained solid is washed with water, dried, and calcined to obtain the modified hydrogenation catalyst carrier; wherein the mass ratio of the alumina to the ammonium fluoroborate is 9:1-1:1. The preparation method of the modified hydrogenation catalyst carrier provided by the application can effectively improve the surface properties of the carrier by using an ammonium fluoroborate solution as a modifier and a hydrothermal medium, and by combining the control of the temperature of the hydrothermal reaction and the concentration of the ammonium fluoroborate solution, thereby promoting the distribution of active metals and improving the catalyst activity; and the method is suitable for preparing diesel hydrofining catalysts.

Description

Technical Field

[0001] This invention relates to the field of petroleum refining hydrogenation, and particularly to modified hydrogenation catalyst supports and their preparation methods, as well as hydrogenation catalysts. Background Technology

[0002] Currently, the supports for diesel hydrorefining catalysts are generally alumina. Most methods involve modifying the support to adjust its acidity, specific surface area, and pore volume to improve the utilization rate of active metals, thereby enhancing catalyst activity. For example, Chinese patent document CN201610333041.1 discloses a method for preparing boron-modified alumina, which uses a hydrothermal treatment method to add boron to the alumina support. This method not only allows the boron additive to be better distributed on the surface of the alumina support, improving the dispersion of the active components, but also adjusts the ratio of Brønsted acid (protic acid) to Lewis acid in the alumina support and improves the pore structure of the alumina support. However, because boric acid is used as a modifier, the support has a high content of moderately strong acids, resulting in strong cracking performance.

[0003] Chinese patent document CN201110188433.0 discloses a method for preparing a dual-pore structured alumina support. This method involves adding a certain amount of ammonium bicarbonate during the support preparation process, extruding it into a plastic body, performing hydrothermal synthesis, and then calcining. The resulting alumina support exhibits a dual-pore distribution and good mechanical strength, making it suitable for preparing catalysts for the hydrodemetallization of heavy and residual oils. However, the specific surface area of ​​the alumina support obtained by this method is only 150–200 m² / g. 2 The alumina material has limitations, such as its low concentration ( / g), which hinders the dispersion of high-content active metal components. Therefore, this alumina material can only be used as a hydrogenation catalyst support for heavy oil and residual oil.

[0004] Chinese patent document CN201910907712.4 discloses a modified alumina carrier and its preparation method. The method involves first adding an aluminum source and a precipitant in a co-current stream to an aqueous solution containing a precursor of modifier A for precipitation. After precipitation, the mixture is aged, filtered, and washed with deionized water. Then, the washed boehmite is added to an aqueous solution containing a precursor of modifier B and urea for hydrothermal treatment, followed by filtration and drying to obtain modified boehmite. Next, the modified boehmite is mixed uniformly with a binder and an extrusion aid, extruded into strips, dried, and calcined to obtain the alumina carrier. Finally, a metal containing Group VIII is loaded onto the alumina carrier and subjected to sulfidation treatment to obtain the modified alumina carrier. However, this method for modifying the carrier involves a cumbersome and complex preparation process.

[0005] Chinese patent document CN201510055751.8 discloses a hydrogenation catalyst with high denitrification performance and its preparation method, using silicon- and phosphorus-containing alumina as a support and group VIB and / or VIII metal oxides as active components; the acidity of the support surface is: acid content of 0.2-0.7 mmol / g, and Brønsted acid of 0.1-0.3 mmol / g. Excessive total acidity of the support affects the stability of the catalyst. Chinese patent document CN200410050716.9 discloses a silicon- and titanium-containing alumina support and its preparation method. The method employs a co-precipitation process to add Si and Ti additives to alumina in different steps. The prepared support features large pore volume, large pore size, concentrated pore distribution, and high Brønsted acid content. The infrared acid content at ≥350℃ is 0.05~0.10 mmol / g, with Brønsted acid accounting for 40%~60% of the total acid. This support exhibits strong acidity, and cracking reactions occur during the high-temperature hydrogenation reaction.

[0006] Chinese patent document CN201310597191.X discloses a hydrogenation catalyst support, comprising, by weight percentage: 10-70 wt% molecular sieve, 10-40 wt% alumina, 5-30 wt% silica, with the remainder being a binder; the specific surface area of ​​the hydrogenation catalyst support is 380-573 m². 2 The pore volume is 0.63–0.94 cc / g, the infrared acidity is 0.10–0.45 mmol / g, and the ratio of Brønsted acid to Lewis acid is 2.3–0.9:1; the molecular sieve is a multi-level porous composite molecular sieve of mesoporous amorphous silica-alumina coated microporous Beta molecular sieve, the sodium oxide content is ≤0.05 wt%, and the infrared acidity is 0.23–0.58 mmol / g. Chinese patent document CN201611263141.8 discloses a hydrogenation catalyst support comprising a solid acid component and an amorphous heat-resistant oxide, wherein the specific surface area of ​​the hydrogenation catalyst support is 220–450 m² / g. 2 The total pore volume is 0.35–0.70 ml / g, the infrared acid content is 0.50–1.0 mmol / g, the ratio of Brønsted acid to Lewis acid is 0.2–1.0, and the radial crushing resistance is greater than 130 N / cm. Based on the total weight of the carrier, the solid acid component content is 10–80%, and the amorphous heat-resistant oxide content is 20–90%. The solid acid component is a mixture of MCM-22 molecular sieve and ZSM-5 molecular sieve in a mixing ratio of 1:10 to 10:1. The MCM-22 molecular sieve has a silica-to-alumina ratio of 10–60 and a specific surface area of ​​400–600 m². 2 / g, with a pore volume of 0.35–0.75 ml / g; the ZSM-5 molecular sieve has a silica-to-alumina ratio of 10–60, a specific surface area of ​​300–500 m² / g, and a pore volume of 0.15–0.65 ml / g. Both of these hydrogenation catalyst supports containing Brønsted acid incorporate solid acid component molecular sieves, making them suitable for hydrocracking catalyst supports.

[0007] Chinese patent document CN201510056153.2 discloses a hydrogenation catalyst support, using silicon- and phosphorus-containing alumina as the hydrogenation catalyst support, with a pore volume of 0.7–1.5 mL / g and a specific surface area of ​​250–450 m². 2 The catalyst support is 20-30 nm in size, with a porosity exceeding 20%. The surface acidity of the support is 0.2-0.7 mmol / g, and Brønsted acid (B acid) is 0.1-0.3 mmol / g. Chinese patent document CN201910907712.4 discloses a boron, phosphorus, fluorine, and magnesium-modified alumina support prepared by co-precipitation. This material exhibits an infrared acidity of 0.18-0.55 mmol / g at 250-450℃, with Brønsted acid at 0.08-0.150 mmol / g and Lewis acid at 0.10-0.40 mmol / g. This support is more suitable for preparing hydrogenation catalysts for residual oil or heavy oil.

[0008] Therefore, it can be seen that the existing hydrogenation catalyst supports containing Brønsted acid have random acid strength, making them more suitable for hydrocracking, mild hydrocracking, or hydrogenation of heavy distillate oils. When used for hydrogenation of light distillate oils such as diesel, they will be accompanied by mild cracking and are not suitable for hydrorefining. In addition, there are problems such as complicated preparation methods or limited specific surface area of ​​the support. Summary of the Invention

[0009] To address the aforementioned problems and improvement needs of existing technologies, this invention provides a method for preparing a modified hydrogenation catalyst support. This method utilizes ammonium fluoroborate solution as a modifier and hydrothermal medium, and by controlling the temperature of the hydrothermal reaction and the amount of ammonium fluoroborate, it can effectively improve the surface properties of the support, thereby promoting the distribution of active metals and enhancing the hydrogenation activity of the catalyst. Furthermore, the modified support has a pore size suitable for diffusion in light distillate oils and a moderate specific surface area, making it suitable for preparing non-precious metal catalysts with high active metal content. The method for preparing the modified hydrogenation catalyst support provided by this invention is simple and convenient to operate, and is suitable for preparing catalysts for the hydrorefining of light distillate oils.

[0010] To achieve the above objectives, the present invention provides a method for preparing a modified hydrogenation catalyst support, comprising the following steps:

[0011] After mixing alumina with ammonium fluoroborate solution, the mixture is added to a high-pressure reactor lined with polytetrafluoroethylene and subjected to a hydrothermal reaction at 50–90°C. The resulting solid is washed with water, dried, and calcined to obtain the modified hydrogenation catalyst support.

[0012] The mass ratio of the alumina to the ammonium fluoroborate in the ammonium fluoroborate solution is 9:1 to 1:1.

[0013] Optionally, in the preparation method of the modified hydrogenation catalyst support provided by the present invention, the hydrothermal reaction temperature is 50-70°C and the time is 4-10 hours, preferably 5-7 hours.

[0014] Optionally, in the preparation method of the modified hydrogenation catalyst support provided by the present invention, the mass ratio of the alumina to the ammonium fluoroborate solution is 3:1 to 3:2.

[0015] Optionally, in the preparation method of the modified hydrogenation catalyst support provided by the present invention, the alumina has a specific surface area of ​​290–450 m². 2 / g, pore volume 0.5~0.8mL / g, strength 150~245N / cm.

[0016] Optionally, in the preparation method of the modified hydrogenation catalyst support provided by the present invention, the drying temperature is 80-100℃ and the time is 4-6h.

[0017] Optionally, in the preparation method of the modified hydrogenation catalyst support provided by the present invention, the calcination temperature is 450-600℃, preferably 450-500℃; and the calcination time is 4-6h.

[0018] Optionally, in the preparation method of the modified hydrogenation catalyst support provided by the present invention, the concentration of the ammonium fluoroborate solution is not specifically limited, as long as it can completely dissolve the ammonium fluoroborate. The concentration of the ammonium fluoroborate solution recommended by the present invention is 4wt%-12wt%.

[0019] The present invention also provides a modified hydrogenation catalyst support prepared by the above-described method, wherein the modified hydrogenation catalyst support has a specific surface area of ​​240–380 m². 2 / g, with a pore volume of 0.55~0.80mL / g.

[0020] Optionally, in the modified hydrogenation catalyst support provided by the present invention, the specific surface area of ​​the modified hydrogenation catalyst support is 300-380 m². 2 / g, with a pore volume of 0.55~0.73mL / g.

[0021] Optionally, in the modified hydrogenation catalyst support provided by the present invention, the Brønsted acid / L acid value of the modified hydrogenation catalyst support is 0.02 to 0.3, and the strength is 120 to 224 N / cm; preferably, the Brønsted acid / L acid value of the modified hydrogenation catalyst support is 0.07 to 0.15, and the strength is 145 to 200 N / cm.

[0022] The present invention also provides a hydrogenation catalyst, comprising a support and an active component, wherein the support is selected from the modified hydrogenation catalyst support prepared by the above-described method.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] Beneficial Effect 1: The preparation method of the modified hydrogenation catalyst support provided by this invention can effectively improve the surface properties of the support, thereby promoting the distribution of active metals and improving catalyst activity. The modified support is suitable for preparing catalysts for the hydrorefining of light distillate oils. Specifically, the preparation method provided by this invention uses ammonium fluoroborate as a modifier and ammonium fluoroborate solution as a hydrothermal medium, combined with limiting the temperature of the hydrothermal reaction to modify the alumina support. The specific surface area of ​​the modified support is somewhat reduced, but the degree of specific surface area loss of the modified alumina support can be controlled by adjusting the content of the hydrothermal medium (the ratio of alumina to ammonium fluoroborate). At the same time, the pore structure of the alumina support is changed, generating more angular sites in the pores of the alumina support, which is beneficial to metal dispersion and improving the utilization rate of active metals. Compared with other modification methods, the preparation method provided by this invention is simple and convenient.

[0025] Beneficial effect 2: The modified hydrogenation catalyst support provided by this invention also increases Brønsted acid sites, which is more conducive to the removal of sterically hindered sulfides. Attached Figure Description

[0026] Figure 1 This is a SEM image of the alumina SR-00 used in Example 5 of the present invention;

[0027] Figure 2 This is a SEM image of the modified hydrogenation catalyst support prepared in Example 5 of the present invention;

[0028] Figure 3 This is a SEM image of the alumina SR-01 used in Example 15 of the present invention;

[0029] Figure 4 This is a SEM image of the modified hydrogenation catalyst support prepared in Example 15 of the present invention;

[0030] Figure 5 This is a SEM image of the modified hydrogenation catalyst support prepared in Comparative Example 1 of the present invention.

[0031] Figure 6 This is a SEM image of the modified hydrogenation catalyst support prepared in Comparative Example 2 of the present invention. Detailed Implementation

[0032] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0033] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0034] Example 1

[0035] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0036] Weigh 1g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0037] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes and place in a PTFE-lined autoclave. Seal the autoclave and place it in a 60°C forced-air drying oven for 6 hours. Then allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100°C forced-air drying oven for 6 hours. Then place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C, and maintain the temperature at 500°C for 4 hours to obtain the modified hydrogenation catalyst support SR-1.

[0038] Example 2

[0039] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0040] Weigh 2g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0041] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven and keep it for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter it again. Place the obtained solid in a 100℃ forced-air drying oven and dry it for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and calcine it at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-2.

[0042] Example 3

[0043] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0044] Weigh 3g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0045] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-3.

[0046] Example 4

[0047] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0048] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0049] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-4.

[0050] Example 5

[0051] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0052] Weigh 4.5g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0053] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-5.

[0054] Example 6

[0055] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0056] Weigh 6.0 g of ammonium fluoroborate and place it in a beaker. Add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0057] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-6.

[0058] Example 7

[0059] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0060] Weigh 9g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0061] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-7.

[0062] Example 8

[0063] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0064] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0065] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-8.

[0066] Example 9

[0067] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0068] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0069] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, put the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 50℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-9.

[0070] Example 10

[0071] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0072] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0073] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL high-pressure reactor with a polytetrafluoroethylene liner. After sealing the high-pressure reactor, place it in a 70℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the reactor, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-10.

[0074] Example 11

[0075] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0076] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0077] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL high-pressure reactor lined with polytetrafluoroethylene. After sealing the high-pressure reactor, place it in a 90℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the reactor, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 500℃, and maintain the temperature at 500℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-11.

[0078] Example 12

[0079] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0080] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0081] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450℃, and maintain the temperature at 450℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-12.

[0082] Example 13

[0083] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0084] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0085] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, put the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 3 hours, raise the temperature from room temperature to 550℃, and maintain the temperature at 550℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-13.

[0086] Example 14

[0087] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0088] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0089] Weigh 9g of alumina support SR-01 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, put the mixture into a 100mL high-pressure reactor lined with polytetrafluoroethylene. After sealing the high-pressure reactor, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the reactor, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in an 80℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450℃, and maintain the temperature at 450℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-14.

[0090] Example 15

[0091] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0092] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0093] Weigh 9g of alumina support SR-01 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450℃, and maintain the temperature at 450℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-15.

[0094] Example 16

[0095] This embodiment provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0096] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0097] Weigh 9g of alumina support SR-02 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 60℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450℃, and maintain the temperature at 450℃ for 4 hours to obtain the modified hydrogenation catalyst support SR-16.

[0098] Comparative Example 1

[0099] This comparative example provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0100] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0101] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Cover with a silicone cap that matches the beaker, heat in a water bath to 60℃, maintain the temperature for 6 hours, and then allow it to cool naturally to room temperature. Filter the material in the beaker, wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven and dry for 6 hours. Then place it in a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450℃, and maintain the temperature at 450℃ for 4 hours to obtain the modified hydrogenation catalyst support CR-1.

[0102] Comparative Example 2

[0103] This comparative example provides a modified hydrogenation catalyst support, the preparation method of which is as follows:

[0104] Weigh 3.8g of ammonium fluoroborate and place it in a beaker. Add 70mL of water and stir until the ammonium fluoroborate is completely dissolved; thus, an ammonium fluoroborate solution is obtained.

[0105] Weigh 9g of alumina support SR-00 and add it to the above ammonium fluoroborate solution. Stir for 10 minutes to fully impregnate the alumina support in the ammonium fluoroborate solution. Then, place the mixture into a 100mL polytetrafluoroethylene-lined autoclave. After sealing the autoclave, place it in a 110℃ forced-air drying oven for 6 hours. Then, allow it to cool naturally to room temperature. After opening the autoclave, filter the material inside. Wash the obtained solid twice with deionized water and filter again. Place the obtained solid in a 100℃ forced-air drying oven for 6 hours. Then, place it in a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450℃, and maintain the temperature at 450℃ for 4 hours to obtain the modified hydrogenation catalyst support CR-2.

[0106] The modified hydrogenation catalyst supports prepared in each embodiment and comparative example were analyzed for specific surface area (S). BET The pore volume (V), Brønsted acid, Lewis acid, and strength were tested. Specific results are shown in the table below.

[0107] Specific surface area and pore volume were measured using the BET method: an Autosorb-6B physical adsorption analyzer manufactured by CANTA Corporation was used. Adsorption and desorption test points were set according to the pore structure of the alumina support. High-purity nitrogen was used as the adsorption medium and liquid nitrogen was used as the cold trap. The alumina sample was degassed at 300℃ for 8 h before analysis. Based on the characteristics of nitrogen adsorption on the surface of porous materials as a function of relative pressure, the adsorption-desorption curve was tested, and the total pore volume and specific surface area of ​​the support were calculated.

[0108] The B / L ratio of the carrier was determined by measuring the values ​​of Brønsted (B) and Lewis (L) acids using infrared pyridine adsorption, and then the B / L value was calculated. The specific detection method was as follows: An FT-IR spectrometer manufactured by Thermo Nicolet (USA) was used, employing pyridine adsorption infrared spectroscopy to determine the type (Brønsted, L) and amount of acid on the carrier surface; the carrier was dehydrated at 350℃ for 4 h, then cooled and subjected to vacuum adsorption of pyridine in a pyridine desiccator for 24 h. Desorption was then performed in a drying oven at 150℃ for approximately 1 h. A blank sample without pyridine adsorption was used as a background for comparison, and diffuse reflectance infrared scanning was performed in the range of 650–4000 cm⁻¹. -1 .

[0109] Strength was tested according to HG / T 2782.

[0110] Table 1

[0111]

[0112] As shown in the table above, compared with the unmodified support, this invention, by using ammonium fluoroborate as a modifier and ammonium fluoroborate solution as a hydrothermal medium, and by limiting the hydrothermal reaction temperature, effectively improves the surface properties of the alumina support, making the modified support suitable for preparing catalysts for the hydrorefining of light distillate oils. Furthermore, compared with the unmodified support, the modified support also increases Brønsted acid sites. Among these, CR-2 was not tested for Brønsted acid, Lewis acid, and strength due to its poor specific surface area and pore volume.

[0113] The alumina support SR-00 (before modification) used in Example 5 and the modified hydrogenation catalyst support SR-5 prepared in Example 5 were characterized by SEM under the same conditions. The results are shown in [Figure number missing]. Figure 1 and Figure 2 As shown, by Figure 1 and Figure 2 It can be seen that, compared with SR-00, the modified SR-5 carrier has formed intersecting rod-shaped and sheet-like structures on its cross-section. Such a carrier can form more angular corners to achieve active neutrality after loading metal, which can improve the utilization rate of active metal.

[0114] The alumina support SR-01 (before modification) used in Example 15 and the modified hydrogenation catalyst support SR-15 prepared in Example 15 were characterized by SEM under the same conditions. The results are shown in the appendix. Figure 3 and Figure 4 As shown, by Figure 3 and Figure 4 It can be seen that, compared to SR-01, the modified SR-15 carrier exhibits intersecting rod-like and sheet-like structures on its cross-section, resulting in a similar appearance to the attached... Figure 1-2Similarly, because the surface properties of SR-00 and SR-01 are not exactly the same, the state exhibited after modification is not exactly the same. This rod-shaped or sheet-like carrier surface state is conducive to forming more angular corners after loading metal, which is active neutral and can improve the utilization rate of active metal.

[0115] Figure 5 The image shows a SEM image of the modified hydrogenation catalyst support CR-1 prepared in Comparative Example 1. Figure 1 and Figure 5 The comparison shows that under non-pressurized water bath heating conditions (i.e. hydrothermal conditions), the surface of the support forms loose particles. As can be seen from the data in Table 1, the specific surface area loss of the modified hydrogenation catalyst support CR-1 prepared in Comparative Example 1 is greater than that of the support under pressurized hydrothermal conditions, and the strength of CR-1 drops to 112 N / cm. Under these conditions, it can no longer meet the requirements of industrial applications.

[0116] Figure 6 The image shows a SEM image of the modified hydrogenation catalyst support CR-2 prepared in Comparative Example 2. Figure 1 and Figure 6 The comparison shows that Comparative Example 2, conducted under pressurized hydrothermal conditions at 110℃, resulted in a significant loss of specific surface area in the modified hydrogenation catalyst support CR-2. Figure 6 The SEM images show that the carrier CR-2 was dissolved into flakes by the hydrothermal medium, indicating that when the hydrothermal temperature was raised to 110℃, the hydrothermal medium decomposed into hydrogen fluoride, which severely corroded the carrier and caused changes in the basic properties of the carrier. When the carrier CR-2 was touched lightly, it turned into powder.

[0117] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing a modified hydrogenation catalyst support, characterized in that, Includes the following steps: After fully impregnating alumina in ammonium fluoroborate solution, it is added to a high-pressure reactor lined with polytetrafluoroethylene and subjected to hydrothermal reaction at 50-90°C. The resulting solid is washed with water, dried, and calcined to obtain the modified hydrogenation catalyst support. The mass ratio of the alumina to the ammonium fluoroborate in the ammonium fluoroborate solution is 9:1 to 1:

1.

2. The preparation method according to claim 1, characterized in that, The hydrothermal reaction is carried out at a temperature of 50–70°C for 4–10 hours.

3. The preparation method according to claim 1, characterized in that, The mass ratio of the alumina to the ammonium fluoroborate solution is 3:1 to 3:

2.

4. The preparation method according to claim 1, characterized in that, The specific surface area of ​​the alumina is 290–450 m². 2 / g, pore volume 0.5~0.8mL / g, strength 150~245N / cm.

5. The preparation method according to claim 1, characterized in that, The drying temperature is 80–100°C, and the time is 4–6 hours.

6. The preparation method according to claim 1, characterized in that, The roasting temperature is 450–600℃; the roasting time is 4–6 hours.

7. A modified hydrogenation catalyst support prepared by the method of any one of claims 1-6, wherein the modified hydrogenation catalyst support has a specific surface area of ​​240-380 m². 2 / g, with a pore volume of 0.55~0.80mL / g.

8. The modified hydrogenation catalyst support as described in claim 7, characterized in that, The specific surface area of ​​the modified hydrogenation catalyst support is 300–380 m². 2 / g, with a pore volume of 0.55~0.73mL / g.

9. The modified hydrogenation catalyst support as described in claim 7, characterized in that, The modified hydrogenation catalyst support has a B-acid / L acid value of 0.02 to 0.3 and a strength of 120 to 224 N / cm.

10. A hydrogenation catalyst, characterized in that, The support for the hydrogenation catalyst is selected from the modified hydrogenation catalyst support prepared by the method described in any one of claims 1-6.

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