Modified hydrogenation catalyst carrier, preparation method thereof and hydrogenation catalyst

Abstract

The invention provides a modified hydrogenation catalyst carrier and a preparation method thereof, and a hydrogenation catalyst, the preparation method of the modified hydrogenation catalyst carrier comprises the following steps: fully dipping alumina in an ammonium fluoborate solution, adding into a polytetrafluoroethylene lined autoclave, carrying out a hydrothermal reaction at 50-90 DEG C, washing the obtained solid with water, and drying to obtain the modified hydrogenation catalyst carrier. And roasting to obtain the modified hydrogenation catalyst carrier. Wherein the mass ratio of the aluminum oxide to the ammonium fluoborate is (9: 1)-(1: 1). According to the preparation method of the modified hydrogenation catalyst carrier, the ammonium fluoborate solution is adopted as the modifier and the hydrothermal medium, and the temperature of the hydrothermal reaction and the concentration of the ammonium fluoborate solution are controlled, so that the surface property of the carrier can be effectively improved, the distribution of active metals is promoted, and the activity of the catalyst is improved; the method is suitable for preparing the diesel oil hydrofining catalyst.

Description

Technical Field

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

[0002] With the continuous upgrading of oil quality, increasingly stringent environmental regulations, and the increasingly inferior and heavy crude oil, hydrogenation technology has been widely valued and applied worldwide. The implementation of the National VI diesel standard has increased the severity of diesel hydrogenation units and shortened the unit operation cycle; in order not to affect the unit's operation cycle, higher requirements are placed on the activity of the catalyst. At present, the general method is to improve the carrier, change the type and number of hydroxyl groups on the carrier surface, enhance the surface acidity, and then improve the activity and stability of the catalyst.

[0003] At present, the carrier of diesel hydrofining catalyst is generally based on alumina, and most of them are modified to adjust the acidity, specific surface area and pore volume of the carrier to improve the utilization rate of active metals, thereby achieving the effect of improving catalyst activity. As disclosed in Chinese patent document CN201610333041.1, a preparation method of boron-modified alumina is used, and boron is added to the alumina carrier by a hydrothermal treatment method. This method can not only make the auxiliary agent boron better distributed on the surface of the alumina carrier, improve the dispersion of active components, but also adjust the B acid (protonic acid) and L acid (Lewisacid) ratio of the alumina carrier, and improve the pore structure of the alumina carrier. However, due to the use of boric acid as a modifier, the medium-strong acid amount of the carrier is large, and the carrier cracking performance is strong.

[0004] Chinese patent document CN201110188433.0 discloses a method for preparing a double-pore structure alumina carrier. In this method, a certain amount of ammonium bicarbonate is added during the carrier preparation process to extrude a plastic body, perform hydrothermal synthesis, and then calcine. The obtained alumina carrier has a double pore distribution and good mechanical strength, and is suitable for the preparation of heavy and residual oil hydrodemetallization catalysts. However, the specific surface area of ​​the alumina carrier obtained by this method is 150 to 200 m 2 / g, which has limitations and is not conducive to the dispersion of high-content active metal components. The alumina material can only be used as a hydrogenation catalyst carrier for heavy oil and residual oil.

[0005] Chinese patent document CN201910907712.4 discloses a modified alumina carrier and a preparation method thereof, wherein the aluminum source and the precipitant are first added to the aqueous solution containing the modifier A precursor in parallel to perform a precipitation reaction, and after the precipitation is completed, the aluminum source and the precipitant are aged, filtered, and washed with deionized water, and then the washed pseudo-boehmite is added to the aqueous solution containing the modifier B precursor and urea for hydrothermal treatment, and then filtered and dried to obtain the modified pseudo-boehmite; then the modified pseudo-boehmite is mixed with the peptizing agent and the extrusion aid to form a strip, and the alumina carrier is obtained by drying and calcining; finally, the metal containing Group VIII is loaded on the alumina carrier, and the alumina carrier is subjected to a sulfidation treatment to obtain the modified alumina carrier. However, the preparation process of the carrier modification method is cumbersome and the preparation process is relatively complicated.

[0006] Chinese patent document CN201510055751.8 discloses a hydrogenation catalyst with high denitrification performance and a preparation method thereof, which uses silicon and phosphorus-containing alumina as a carrier and metal oxides of groups VIB and / or VIII as active components; the surface acid properties of the carrier are: the acid content is 0.2-0.7 mmol / g, and the B acid content is 0.1-0.3 mmol / g. Too much total acid content of the carrier affects the stability of the catalyst. Chinese patent document CN200410050716.9 discloses a silicon- and titanium-containing alumina carrier and a preparation method thereof. The Si additive and the Ti additive are added to the alumina in different steps by a coprecipitation method. The prepared carrier has the characteristics of large pore volume, large pore size, concentrated pore distribution and high Br content. The infrared acid content at ≥350°C is 0.05-0.10 mmol / g, and the Br content accounts for 40%-60% of the total acid. The infrared acid content of the carrier at ≥350°C is 0.05-0.10 mmol / g, the acidity is strong, and cracking reaction will occur during the high-temperature hydrogenation reaction.

[0007] Chinese patent document CN201310597191.X discloses a hydrogenation catalyst carrier, which is composed of 10-70wt% molecular sieve, 10-40wt% alumina, 5-30wt% silicon dioxide, and the rest is a binder. The specific surface area of ​​the hydrogenation catalyst carrier is 380-573m 2 / g, pore volume of 0.63 ~ 0.94cc / g, infrared acid content of 0.10 ~ 0.45mmol / g, B acid and L acid ratio of 2.3 ~ 0.9: 1; molecular sieve is a multi-level pore composite molecular sieve of mesoporous amorphous silicon aluminum coated microporous Beta molecular sieve, the content of sodium oxide is ≤ 0.05wt%, and the infrared acid content is 0.23 ~ 0.58mmol / g. Chinese patent document CN201611263141.8 discloses a hydrogenation catalyst carrier, including a solid acid component and an amorphous heat-resistant oxide, the specific surface area of ​​the hydrogenation catalyst carrier is 220 ~ 450m 2 / g, total pore volume 0.35-0.70ml / g, infrared acid content 0.50-1.0mmol / g, ratio of B acid to L acid 0.2-1.0, radial crushing resistance greater than 130N / 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%; wherein the solid acid component is a mixture of MCM-22 molecular sieve and ZSM-5 molecular sieve, and the mixing ratio is 1:10-10:1; the silicon-aluminum ratio of the MCM-22 molecular sieve is 10-60, and the specific surface area is 400-600m 2 / g, pore volume of 0.35-0.75ml / g; the silicon-aluminum ratio of the ZSM-5 molecular sieve is 10-60, the specific surface area is 300-500m2 / g, and the pore volume is 0.15-0.65ml / g. Both of these hydrogenation catalyst supports containing B acid introduce solid acid component molecular sieves, which are suitable for hydrocracking catalyst supports.

[0008] Chinese patent document CN201510056153.2 discloses a hydrogenation catalyst carrier, which uses silicon- and phosphorus-containing alumina as a hydrogenation catalyst carrier, with a carrier pore volume of 0.7 to 1.5 mL / g and a specific surface area of ​​250 to 450 m 2 / g, catalyst carrier 20-30nm, pore ratio reaches more than 20%, carrier surface acid properties are: acid amount is 0.2-0.7mmol / g, B acid is 0.1-0.3mmol / g. Chinese patent document CN201910907712.4 discloses a boron, phosphorus, fluorine, magnesium and other element modified alumina carrier prepared by coprecipitation method. The infrared acid amount of the material at 250-450℃ is 0.18-0.55mmol / g, of which the B acid amount is 0.08-0.150mmol / g, and the L acid amount is 0.10-0.40mmol / g. This carrier is more suitable for the preparation of residual oil or heavy oil hydrogenation catalyst.

[0009] It can be seen from this that the acid strength of the existing hydrogenation catalyst carrier containing B acid is random, and it is more suitable for hydrocracking, mild hydrocracking or heavy distillate oil hydrogenation. When used for light distillate oil such as diesel hydrogenation, it will be accompanied by mild cracking and is not suitable for hydrorefining; and the preparation method is complicated or the specific surface area of ​​the carrier is limited. Summary of the invention

[0010] In view of the above problems and improvement needs in the prior art, the present invention provides a method for preparing a modified hydrogenation catalyst carrier. The method adopts ammonium fluoroborate solution as a modifier and a hydrothermal medium, and controls the temperature of the hydrothermal reaction and the amount of ammonium fluoroborate, so as to effectively improve the surface properties of the carrier, thereby promoting the distribution of active metals and improving the hydrogenation activity of the catalyst; and the pore volume of the modified carrier is suitable for the diffusion of light distillate oil, and the specific surface area is moderate, which is suitable for preparing non-precious metal catalysts with high active metal content. The preparation method of the modified hydrogenation catalyst carrier provided by the present invention is simple and convenient to operate, and is suitable for preparing light distillate oil hydrorefining catalysts.

[0011] To achieve the above object, the present invention provides a method for preparing a modified hydrogenation catalyst carrier, comprising the following steps:

[0012] After mixing the aluminum oxide and the ammonium fluoroborate solution, the mixture is added into a polytetrafluoroethylene-lined autoclave, and a hydrothermal reaction is carried out at 50 to 90° C. The obtained solid is washed with water, dried, and calcined to obtain the modified hydrogenation catalyst carrier;

[0013] Wherein, the mass ratio of the aluminum oxide to the ammonium fluoroborate in the ammonium fluoroborate solution is 9:1 to 1:1.

[0014] Optionally, in the method for preparing a modified hydrogenation catalyst carrier provided by the present invention, the temperature of the hydrothermal reaction is 50 to 70° C., and the time is 4 to 10 hours, preferably 5 to 7 hours.

[0015] Optionally, in the method for preparing a modified hydrogenation catalyst carrier provided by the present invention, the mass ratio of the aluminum oxide to the ammonium fluoroborate in the ammonium fluoroborate solution is 3:1 to 3:2.

[0016] Optionally, in the method for preparing a modified hydrogenation catalyst carrier provided by the present invention, the specific surface area of ​​the alumina is 290 to 450 m 2 / g, pore volume 0.5~0.8mL / g, strength 150~245N / cm.

[0017] Optionally, in the method for preparing a modified hydrogenation catalyst carrier provided by the present invention, the drying temperature is 80 to 100° C. and the drying time is 4 to 6 hours.

[0018] Optionally, in the method for preparing a modified hydrogenation catalyst carrier provided by the present invention, the calcination temperature is 450 to 600° C., preferably 450 to 500° C.; and the calcination time is 4 to 6 hours.

[0019] Optionally, in the method for preparing a modified hydrogenation catalyst carrier provided by the present invention, the concentration of the ammonium fluoroborate solution is not specifically limited, as long as the ammonium fluoroborate can be completely dissolved. The concentration of the ammonium fluoroborate solution recommended by the present invention is 4wt%-12wt%.

[0020] The present invention also provides a modified hydrogenation catalyst carrier prepared by the preparation method of the modified hydrogenation catalyst carrier, wherein the specific surface area of ​​the modified hydrogenation catalyst carrier is 240 to 380 m 2 / g, and the pore volume is 0.55~0.80mL / g.

[0021] Optionally, in the modified hydrogenation catalyst carrier provided by the present invention, the specific surface area of ​​the modified hydrogenation catalyst carrier is 300 to 380 m 2 / g, and the pore volume is 0.55~0.73mL / g.

[0022] Optionally, in the modified hydrogenation catalyst carrier provided by the present invention, the B acid / L acid value of the modified hydrogenation catalyst carrier is 0.02-0.3, and the strength is 120-224 N / cm; preferably, the B acid / L acid value of the modified hydrogenation catalyst carrier is 0.07-0.15, and the strength is 145-200 N / cm.

[0023] The present invention also provides a hydrogenation catalyst, comprising a carrier and an active component, wherein the carrier is selected from the modified hydrogenation catalyst carrier prepared by the preparation method of the modified hydrogenation catalyst carrier.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] Beneficial effect 1: The preparation method of the modified hydrogenation catalyst carrier provided by the present invention can effectively improve the surface properties of the carrier, thereby promoting the distribution of active metals and improving the activity of the catalyst. The modified carrier is suitable for preparing a light distillate oil hydrorefining catalyst. Specifically, the preparation method provided by the present invention uses ammonium fluoroborate as a modifier and an ammonium fluoroborate solution as a hydrothermal medium, and combines the temperature of the hydrothermal reaction to modify the alumina carrier. The modified carrier has a certain loss in specific surface area, but by adjusting the content of the hydrothermal medium (the ratio of alumina to ammonium fluoroborate), the specific surface loss degree of the modified alumina carrier can be controlled, and at the same time, the pore structure of the alumina carrier is changed, so that more angular positions are generated in the pores of the alumina carrier, which is conducive to metal dispersion and improving the utilization rate of active metals. Compared with other modification methods, the preparation method provided by the present invention is simple and convenient.

[0026] Beneficial effect 2: The modified hydrogenation catalyst carrier provided by the present invention also increases the B acid site, which is more conducive to the removal of sterically hindered sulfides. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is a SEM image of alumina SR-00 used in Example 5 of the present invention;

[0028] Figure 2 This is a SEM image of the modified hydrogenation catalyst carrier prepared in Example 5 of the present invention;

[0029] Figure 3 is a SEM image of alumina SR-01 used in Example 15 of the present invention;

[0030] Figure 4 is a SEM image of the modified hydrogenation catalyst support prepared in Example 15 of the present invention;

[0031] Figure 5 This is a SEM image of the modified hydrogenation catalyst carrier prepared in Comparative Example 1 of the present invention;

[0032] Figure 6 This is a SEM image of the modified hydrogenation catalyst carrier prepared in Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0033] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention.

[0034] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0035] Example 1

[0036] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0037] Weigh 1 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0038] Weigh 9g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution, stir for 10 minutes, put it into a tetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid with deionized water twice and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-1.

[0039] Example 2

[0040] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0041] Weigh 2 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0042] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-2.

[0043] Example 3

[0044] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0045] Weigh 3 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0046] Weigh 9g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-3.

[0047] Example 4

[0048] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0049] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0050] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-4.

[0051] Example 5

[0052] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0053] Weigh 4.5 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0054] Weigh 9g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-5.

[0055] Example 6

[0056] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0057] Weigh 6.0 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0058] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-6.

[0059] Example 7

[0060] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0061] Weigh 9 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0062] Weigh 9g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-7.

[0063] Example 8

[0064] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0065] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0066] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-8.

[0067] Example 9

[0068] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0069] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0070] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 50°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-9.

[0071] Example 10

[0072] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0073] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0074] Weigh 9g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 70°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-10.

[0075] Embodiment 11

[0076] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0077] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0078] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 90°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 500°C and keep it at 500°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-11.

[0079] Example 12

[0080] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0081] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0082] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-12.

[0083] Embodiment 13

[0084] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0085] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0086] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature. After opening the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 3 hours, raise the temperature from room temperature to 550°C and keep it at 550°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-13.

[0087] Embodiment 14

[0088] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0089] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0090] Weigh 9 g of alumina carrier SR-01 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature. After opening the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into an 80°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-14.

[0091] Embodiment 15

[0092] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0093] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0094] Weigh 9 g of alumina carrier SR-01 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-15.

[0095] Example 16

[0096] This embodiment provides a modified hydrogenation catalyst carrier, and the preparation method thereof is as follows:

[0097] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0098] Weigh 9 g of alumina carrier SR-02 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 60°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid twice with deionized water and filter it, and then put the obtained solid into a 100°C forced air drying oven to dry for 6 hours, then put it into a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier SR-16.

[0099] Comparative Example 1

[0100] This comparative example provides a modified hydrogenation catalyst carrier, and its preparation method is as follows:

[0101] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0102] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, cover it with a silica gel cover that matches the beaker, heat it to 60°C in a water bath, keep the temperature constant for 6 hours, and then naturally cool it to room temperature. Filter the material in the beaker, wash the obtained solid with deionized water twice and filter it. Then, put the obtained solid into a 100°C forced drying oven and dry it for 6 hours, then put it into a muffle furnace for 4.5 hours, raise it from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier CR-1.

[0103] Comparative Example 2

[0104] This comparative example provides a modified hydrogenation catalyst carrier, and its preparation method is as follows:

[0105] Weigh 3.8 g of ammonium fluoroborate into a beaker, add 70 mL of water and stir until the ammonium fluoroborate is completely dissolved; obtain an ammonium fluoroborate solution;

[0106] Weigh 9 g of alumina carrier SR-00 and add it to the above-mentioned ammonium fluoroborate solution. After stirring for 10 minutes to allow the alumina carrier to be fully immersed in the ammonium fluoroborate solution, put the mixture into a 100 mL polytetrafluoroethylene-lined autoclave, seal the autoclave and put it into a 110°C forced air drying oven for 6 hours, then naturally cool to room temperature, open the autoclave, filter the material in the autoclave, wash the obtained solid with deionized water twice and filter it, and then put the obtained solid into a 100°C forced air drying oven for 6 hours, then put it into a muffle furnace for 4.5 hours, raise the temperature from room temperature to 450°C and keep it at 450°C for 4 hours to obtain a modified hydrogenation catalyst carrier CR-2.

[0107] The modified hydrogenation catalyst carriers prepared in each embodiment and comparative example were respectively measured for specific surface area (S BET ), pore volume (V), B acid, L acid and strength test. The specific results are shown in the table below.

[0108] The specific surface area and pore volume were measured by the BET method: the Autosorb-6B physical adsorption analyzer produced by Quantachrome Inc. was used for analysis. The adsorption test points and desorption test points were set according to the pore structure of the alumina carrier. 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°C for 8 hours and then analyzed and tested. The adsorption-desorption curve was tested according to the characteristics of the change of the adsorption amount of nitrogen on the surface of porous materials with relative pressure, and the total pore volume and specific surface area of ​​the carrier were calculated.

[0109] The B / L ratio of the carrier is determined by the infrared pyridine adsorption method to determine the values ​​of B acid and L acid, and then the B / L value is calculated. The specific detection method is: the equipment is an FT-IR infrared spectrometer produced by Thermo Nicolet, USA, and the pyridine adsorption infrared spectroscopy is used to determine the type of acid (B acid, L acid) and the amount of acid on the surface of the carrier; at 350°C, dehydrate for 4 hours, and after cooling, vacuum adsorb pyridine in a pyridine dryer for 24 hours. Desorb in a drying oven at 150°C for about 1 hour. Using a blank sample without pyridine adsorption as the background comparison, a diffuse reflectance infrared scan is performed with a scanning range of 650 to 4000 cm -1 .

[0110] The strength is tested according to HG / T2782.

[0111] Table 1

[0112]

[0113] It can be seen from the data in the above table that, compared with the unmodified carrier, the present invention uses ammonium fluoroborate as a modifier, ammonium fluoroborate solution as a hydrothermal medium, and combines the temperature of the hydrothermal reaction to modify the alumina carrier, which can effectively improve the surface properties of the carrier, so that the modified carrier is suitable for the prepared light distillate oil hydrorefining catalyst. In addition, compared with the unmodified carrier, the modified carrier also increases the B acid site. Among them, CR-2 was not tested for B acid, L acid and strength due to its poor specific surface area and pore volume.

[0114] The alumina carrier SR-00 (before modification) used in Example 5 and the modified hydrogenation catalyst carrier SR-5 prepared in Example 5 were characterized by SEM under the same conditions. The results are shown in FIG. Figure 1 and Figure 2 As shown by Figure 1 and Figure 2 It can be seen that compared with SR-00, the cross-section of the modified SR-5 carrier forms intersecting rod-like and sheet-like structures. After such a carrier is loaded with metal, more edges and corners can be formed as active neutrals, which can improve the utilization rate of active metals.

[0115] The alumina carrier SR-01 (before modification) used in Example 15 and the modified hydrogenation catalyst carrier SR-15 prepared in Example 15 were characterized by SEM under the same conditions. The results are shown in the attached Figure 3 and Figure 4 As shown by Figure 3 and Figure 4 It can be seen that compared with SR-01, the cross-section of the modified SR-15 carrier formed intersecting rod-like and sheet-like structures, and the results were consistent with the attached Figure 1-2 Similarly, because the surface properties of SR-00 and SR-01 are not exactly the same, the states they show after modification are not exactly the same. Similar rod-shaped or sheet-shaped carrier surface states are conducive to forming more active neutral corners after loading metals, which can improve the utilization rate of active metals.

[0116] Figure 5 is a SEM image of the modified hydrogenation catalyst carrier CR-1 prepared in Comparative Example 1. Figure 1 and Figure 5 By comparison, it can be seen that under non-pressurized water bath heating conditions (i.e., hydrothermal conditions), loose particles are formed on the surface of the carrier. From the data in Table 1, it can be seen that the specific surface loss of the modified hydrogenation catalyst carrier CR-1 prepared in Comparative Example 1 is greater than that of the carrier under pressurized hydrothermal conditions, and the strength of CR-1 drops to 112 N / cm, which can no longer meet the needs of industrial applications.

[0117] Figure 6 is a SEM image of the modified hydrogenation catalyst carrier CR-2 prepared in Comparative Example 2. Figure 1 and Figure 6 By comparison, it can be seen that in Comparative Example 2, the reaction was carried out under pressurized hydrothermal conditions at 110°C, and the specific surface area of ​​the modified hydrogenation catalyst carrier CR-2 obtained was seriously lost. Figure 6 It can be seen from the SEM photo that the carrier CR-2 is dissolved into flakes by the hydrothermal medium, indicating that after the hydrothermal temperature is increased to 110°C, the hydrothermal medium decomposes into hydrogen fluoride, which seriously corrodes the carrier and causes changes in the basic properties of the carrier. The carrier CR-2 becomes pulverized when touched lightly by hand.

[0118] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a modified hydrogenation catalyst carrier, characterized in that: The steps include: After fully impregnating alumina in an ammonium fluoroborate solution, adding the alumina into a polytetrafluoroethylene-lined autoclave, and performing a hydrothermal reaction at 50 to 90° C., the obtained solid is washed with water, dried, and calcined to obtain the modified hydrogenation catalyst carrier; Wherein, the mass ratio of the aluminum oxide 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 temperature of the hydrothermal reaction is 50-70° C. and the time is 4-10 hours.

3. The preparation method according to claim 1, characterized in that: The mass ratio of the aluminum oxide to the ammonium fluoroborate in 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 to 450 m 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 drying time is 4-6 hours.

6. The preparation method according to claim 1, characterized in that: The calcination temperature is 450-600° C. and the calcination time is 4-6 hours.

7. A modified hydrogenation catalyst carrier obtained by the method for preparing a modified hydrogenation catalyst carrier according to any one of claims 1 to 6, wherein the specific surface area of ​​the modified hydrogenation catalyst carrier is 240 to 380 m 2 / g, and the pore volume is 0.55~0.80mL / g.

8. The modified hydrogenation catalyst carrier according to claim 7, characterized in that The specific surface area of ​​the modified hydrogenation catalyst carrier is 300 to 380 m 2 / g, and the pore volume is 0.55~0.73mL / g.

9. The modified hydrogenation catalyst carrier according to claim 7, characterized in that The modified hydrogenation catalyst carrier 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 carrier of the hydrogenation catalyst is selected from the modified hydrogenation catalyst carrier prepared by the preparation method of the modified hydrogenation catalyst carrier according to any one of claims 1 to 6.

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