Hydrofining catalyst carrier, preparation method thereof and hydrofining catalyst

Abstract

The invention belongs to the field of petrochemical engineering and fine chemical engineering, and particularly relates to a hydrofining catalyst carrier, a preparation method thereof and a hydrofining catalyst. The preparation method comprises the following steps: mixing, kneading, forming, drying and roasting pseudo-boehmite containing boron and silicon and a forming aid to obtain a hydrofining catalyst carrier; active metal is introduced to the prepared hydrofining catalyst carrier, and the final hydrofining catalyst is prepared after drying and roasting. The hydrofining catalyst prepared by using the hydrofining catalyst carrier has high hydrodesulfurization activity, hydrodenitrification activity and excellent stability, and is especially suitable for the hydrofining process of diesel oil and heavy distillate oil.

Description

Technical Field

[0001] The invention belongs to the field of petrochemical industry and fine chemical industry, and specifically relates to a hydrorefining catalyst carrier and a preparation method thereof and a hydrorefining catalyst. Background Art

[0002] Hydrofining technology is one of the key technologies used to improve the quality of petroleum fractions or chemical raw materials in petrochemical and fine chemical production. It removes impurities such as sulfur, nitrogen, oxygen, and unsaturated hydrocarbons and improves product performance by contacting hydrogen with raw materials at high temperature and high pressure. Its core is the creation of highly active and highly stable hydrofining catalysts.

[0003] Hydrofining catalysts play a vital role in the oil refining industry. Their core task is to deeply remove impurities such as sulfur, nitrogen, and oxygen from crude oil during the hydrofining process, and to hydrogenate saturated and unsaturated hydrocarbons to improve the quality and stability of petroleum products. The composition of the catalyst directly affects its performance and efficiency. Generally speaking, the composition of hydrofining catalysts includes active components, carriers, and additives. The active component is the core of the hydrofining catalyst. Common active components are: metal sulfides: such as molybdenum, tungsten, cobalt, and nickel sulfides. MoS2 and WS2 are typical examples. They have high catalytic activity for hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation reactions. Precious metals: platinum, palladium, etc., are used in high-end hydrofining catalysts with extremely high activity and stability. The role of the carrier is to provide structural support, increase the surface area and porosity of the catalyst, make the active components evenly dispersed, and improve the catalytic efficiency. Alumina is the most commonly used carrier for hydrofining catalysts in the world due to its good stability and high surface area. The function of the additive is to optimize the performance of the active component and improve the stability, activity, and selectivity of the catalyst. Common additives include: elements such as calcium, magnesium, rhenium, barium, and lanthanum: they can improve the dispersion of the catalyst, increase active sites, promote the reaction, and help improve the hydrophobicity and stability of the catalyst.

[0004] CN 108452844 B discloses a diesel hydrorefining catalyst and its preparation method and application. The catalyst comprises 6% NiO2, 15-30% MoO3, and the rest is a carrier Al2O3-(ETS-10)-TiO2-La2O3 graphene composite oxide, based on 100% by weight of the catalyst; the specific surface area of ​​the catalyst is 250-500m 2 / g, pore volume is 0.6~0.8mL / g. The catalyst uses Ni and Mo as active metals and Al2O3-(ETS-10)-TiO2-La2O3-graphene composite oxide as carrier, so that the carrier is properly modified, the activity of the catalyst is significantly improved, and the purpose of improving the hydrodesulfurization activity and extending the operation cycle of the device is achieved. Although the catalyst has a specific pore size, a large pore volume, and a high diesel hydrodesulfurization activity, the carrier introduces graphene composite oxide, and the raw material and production costs are higher than traditional alumina.

[0005] CN 113019425 B discloses a hydroprocessing catalyst carrier, a hydroprocessing catalyst, and a preparation method and application thereof. The hydroprocessing catalyst carrier comprises Al-SBA-15 molecular sieve and alumina, and the pore distribution of the molecular sieve comprises: the pore volume occupied by pores with a pore diameter of <4nm is less than 20% of the total pore volume; in the molecular sieve, the ratio of B acid to L acid is less than 1. The preparation method of the Al-SBA-15 mesoporous molecular sieve used in the carrier is to synthesize the Al-SBA-15 molecular sieve using amorphous silica-alumina dry glue as raw material and P123 triblock copolymer as template. The hydroprocessing catalyst prepared by using the hydroprocessing catalyst carrier of the present invention is suitable for the hydroprocessing process of heavy distillate oil. Although it has good activity and stability, the raw material cost is high and the preparation process is cumbersome.

[0006] The comprehensive performance of the hydrorefining catalyst is closely related to the type and content of the active metal used and the corresponding preparation method, as well as the pore structure of the catalyst. For example, the hydrorefining catalyst prepared by the above-mentioned prior art either introduces a highly acidic molecular sieve or introduces a high-cost mesoporous material to adjust and optimize the pore structure of the catalyst to improve the activity and stability of the catalyst, but ignores the regulation of the pore structure of the cheap alumina carrier to improve the activity and stability of the catalyst. Summary of the invention

[0007] In view of the deficiencies in the prior art, the present invention provides a hydrorefining catalyst carrier and a preparation method thereof and a hydrorefining catalyst. The hydrorefining catalyst prepared by using the hydrorefining catalyst carrier of the present invention has high hydrodesulfurization activity, hydrodenitrogenation activity and excellent stability, and is particularly suitable for use in the hydrorefining process of diesel and heavy distillate oil.

[0008] In order to achieve the above object, the technical solution of the present invention is as follows:

[0009] One aspect of the present invention provides a method for preparing a hydrotreating catalyst carrier, the method comprising the following steps:

[0010] (1) placing a sodium aluminate solution in a colloid-forming reactor, adding a mixed solution containing boron and silicon precursors and mixing them evenly, introducing a mixed gas of air and CO2, controlling the pH value of the slurry, and stopping the introduction of the mixed gas when the pH value of the slurry reaches the end pH value, filtering the slurry, washing, and drying, to obtain pseudo-boehmite containing boron and silicon;

[0011] (2) The boron-silicon-containing pseudo-boehmite and a molding aid are kneaded and molded, dried in an alkaline gas atmosphere, the pH value is controlled to be 7-12, and then calcined to obtain a hydrogenation refining catalyst carrier.

[0012] In the above technical solution, further, in step (1), the mixed solution containing boron and silicon precursors is a mixed solution of a boron-based surfactant and a silicon surfactant;

[0013] The boron-based surfactant is one or more of a glycerol ester borate surfactant, a boric acid alkyl alcohol amide ester surfactant, and a borate ester amphoteric surfactant;

[0014] The silicon surfactant is one or more of a siloxane surfactant, a polysiloxane or carbosilane surfactant and a polysilane surfactant;

[0015] In the mixed solution containing boron and silicon precursors, the concentration of boron in terms of B2O3 is 10 to 40 g / L, preferably 10 to 20 g / L, and the concentration of silicon in terms of SiO2 is 20 to 180 g / L, preferably 50 to 170 g / L;

[0016] The sodium aluminate solution has a concentration of 80 to 150 g / L, preferably 85 to 140 g / L, in terms of Al2O3, and a caustic ratio of 1.10 to 1.40. The sodium aluminate solution is prepared by a conventional method, and the preferred preparation process is as follows: aluminum hydroxide and sodium hydroxide are prepared by high temperature reaction;

[0017] The volume of the mixed solution containing boron and silicon precursors is 1 / 10 to 2 / 5 of the volume of the sodium aluminate solution.

[0018] In the above technical solution, further, in step (1), the mixing process is stirred by introducing air from the lower part of the reactor, wherein the flow rate of the introduced air is 1.0 to 2.0 m / s. 3 / h;

[0019] The endpoint pH of the slurry is 9.5 to 11.5;

[0020] In the mixed gas of air and CO2, the volume fraction of CO2 is 30% to 60%;

[0021] The flow rate of the mixed gas introduced into each cubic meter of sodium aluminate solution is 1.5-2.5 m 3 / h, preferably 1.7 to 2.3 m 3 / h.

[0022] In the above technical solution, further, in step (1), washing is performed with deionized water until neutral; the drying conditions are as follows: the drying temperature is 100-130°C, preferably 110-120°C, and the drying time is 2-8 hours, preferably 4-6 hours.

[0023] The pseudo-boehmite obtained in step (1) of the present invention has the following properties: pore volume 0.95-1.20 mL / g, specific surface area 330-450 m 2 / g, the pore volume of pores with a pore diameter of less than 6nm accounts for less than 6% of the total pore volume, and the pore volume of pores with a pore diameter of 6-15nm accounts for 45%-65% of the total pore volume. Based on the properties of the dry basis, the boron content is 1.0%-5.0% in terms of B2O3, and the silicon content is 1.0%-20.0% in terms of SiO2.

[0024] In the above technical solution, further, in step (2), the alkaline gas is one or a combination of ammonia, phosphine, and hydrazine. If ammonia is used, it can be derived from thermal decomposition of ammonia water, urea, ammonium bicarbonate, etc.

[0025] The drying temperature is 50 to 160°C, preferably 85 to 120°C, and the drying time is 1 to 15 hours;

[0026] The drying process is as follows: 80% to 90% of the time before drying, the alkaline gas concentration is adjusted to control the pH range of the alkaline gas atmosphere to 7 to 8, and 10% to 20% of the time after drying, the alkaline gas concentration is adjusted to control the pH range of the alkaline gas atmosphere to 9 to 12, preferably 9 to 10;

[0027] The calcination temperature is 450-650° C., preferably 500-580° C., and the calcination time is 1-10 hours.

[0028] In the above technical solution, further, in step (2), the molding aid is selected from at least one of peptizing acid, extrusion aid, and adhesive;

[0029] The peptizing acid is one of citric acid and nitric acid or a mixture of both, preferably a mixture of citric acid and nitric acid;

[0030] The adhesive is small pore alumina;

[0031] The extrusion aid is one or more of starch, polyvinyl alcohol, polyacrylamide, methyl cellulose and sesbania powder.

[0032] Another aspect of the present invention provides a hydrorefining catalyst carrier prepared by the above preparation method, wherein the carrier has the following properties: pore volume 0.70-1.0 mL / g, specific surface area 250-350 m 2 / g, the pore volume of pores with a pore diameter of less than 6nm accounts for less than 7% of the total pore volume, and the pore volume of pores with a pore diameter of 6-15nm accounts for 45%-65% of the total pore volume;

[0033] Based on the properties of the dry basis, the carrier contains 1.0% to 5.0% boron in terms of B2O3, and 1.0% to 20.0% silicon in terms of SiO2.

[0034] The shape of the hydrotreating catalyst carrier can be formed according to a common forming method in the art, and according to technical requirements, can be a toothed ball shape, a three-leaf clover shape, a four-leaf clover shape, a cylindrical strip shape, etc.

[0035] The present invention also provides a hydrorefining catalyst, which is obtained by impregnating the hydrorefining catalyst carrier with a solution containing active metals, followed by drying and calcining.

[0036] In the above technical solution, further, the active metal is a metal of Group VIII B and Group VIB, wherein the metal of Group VIII B is one or two of Co and Ni, and the metal of Group VIB is one or two of W and Mo;

[0037] Based on the weight of the catalyst, the content of the Group VIB metal in terms of oxide is 2wt% to 16wt%, preferably 5wt% to 11wt%, the content of the Group VIB metal in terms of oxide is 10wt% to 35wt%, preferably 15wt% to 30wt%, and the content of the hydrorefining catalyst carrier is 50wt% to 80wt%, preferably 65wt% to 75wt%.

[0038] In the above technical solution, further, the impregnation method is selected from one of equal volume impregnation, supersaturated impregnation, step impregnation, and co-impregnation, and the equal volume co-impregnation method is preferably adopted;

[0039] The drying temperature is 50 to 200° C., preferably 90 to 160° C., and the drying time is 1 to 10 hours, preferably 1 hour to 5 hours;

[0040] The calcination temperature is 350-600° C., preferably 380-500° C., and the calcination time is 1-10 hours, preferably 1-5 hours.

[0041] In the above technical solution, further, the catalyst also includes an auxiliary agent, which is one or more of P, B, Ti, and Zr oxides. The content of the auxiliary agent is less than 6% of the weight of the hydrorefining catalyst, preferably 0.1% to 5.0%, based on the weight of the catalyst.

[0042] The beneficial effects of the present invention are:

[0043] (1) The preparation method of boron- and silicon-containing pseudo-boehmite of the present invention utilizes the hydrophilic group of the surfactant to couple with the crystals formed in the reaction, thereby overcoming the problem that the boron in the traditional boron auxiliary source (such as boric acid, borax, etc.) is adsorbed on the crystals, and the boron is easily lost in the subsequent water washing process, causing environmental pollution and crop poisoning. At the same time, it also overcomes the bottleneck that the traditional silicon auxiliary source (such as sodium silicate, silica gel, etc.) exists in the slurry in the form of micelles, resulting in uneven dispersion of silicon in the pseudo-boehmite dry glue;

[0044] (2) Since surfactants can reduce the surface tension of the solution, in the liquid, the molecules move slowly and are closer to each other, so the attraction between molecules dominates the surface tension. When surfactants are added to the dilute sodium aluminate solution, the surface area increases while the molecular volume remains unchanged, which will result in an increase in the distance between molecules and a decrease in the interaction between molecules. Therefore, the pseudo-boehmite dry glue prepared by the present invention has a large pore volume and pore size. At the same time, since surfactants have dispersing and solubilizing effects, the present invention can still prepare boron- and silicon-containing pseudo-boehmite with large pore volume and large pore size under the condition of higher raw material concentration, thereby improving production efficiency.

[0045] (3) The boron and silicon pseudo-boehmite of the present invention is formed into gel by carbonization, which does not require too high a gel environment (such as temperature). After the gel is formed, no aging is required, which shortens the production process. The preparation method of the hydrorefining catalyst has a short process, simple process, easy operation and low cost.

[0046] (4) The hydrotreating catalyst of the present invention has the characteristic of a high proportion of macropores, and the catalyst pore structure has been optimized as a whole, which is more conducive to the dispersion of active metals and improves the utilization rate of active metals; the increase in macropore content is conducive to the diffusion of macromolecular reactants and the deposition of impurities during the hydrotreating process, thereby improving the catalyst's ability to resist carbon deposition, thereby improving the activity stability of the catalyst and extending the operating cycle of the device. DETAILED DESCRIPTION

[0047] The technical features of the present invention are further described below by way of examples, but are not limited to the examples. Unless otherwise specified, the materials used in the examples of the present invention can be obtained through commercial channels or prepared according to conventional methods well known to those skilled in the art.

[0048] The following pore volume and surface area were analyzed using low-temperature nitrogen adsorption method.

[0049] Example 1

[0050] Preparation of Hydrotreating Catalyst Carrier:

[0051] Take industrial grade one aluminum hydroxide powder and industrial grade one sodium hydroxide to prepare a concentrated sodium metaaluminate solution with a caustic ratio of 1.15 and a concentration of 351 g / L in terms of Al2O3;

[0052] 285L of the solution was added to a gelling reactor, diluted to 1000L with deionized water to prepare a dilute sodium aluminate solution with a concentration of 100g / L in terms of Al2O3, and 140L of a mixed solution of boric acid alkyl alcohol amide ester and trimethylsiloxane was added, wherein the boron concentration in terms of B2O3 was 20g / L and the silicon concentration in terms of SiO2 was 68g / L.

[0053] Air is introduced from the bottom of the reactor for stirring, and the air flow rate is controlled at 1.8m 3 / h, after stirring evenly, introduce a mixed gas of air and CO2, and control the mixed gas flow rate to 1.85m 3 / h, wherein the volume fraction of CO2 is 55%, when the pH value of the slurry in the reactor drops to 10.5, the mixed gas is turned off, the reaction is stopped, the slurry is filtered to obtain a filter cake, which is washed with deionized water at 65°C to neutrality, and dried at 120°C for 3 hours to obtain boron-silicon pseudo-boehmite;

[0054] 95 g of prepared boron- and silicon-containing pseudo-boehmite and 5 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was dry-mixed by rolling in a rolling mill. After rolling for 15 minutes, an aqueous solution containing 8.25g of nitric acid and 4g of citric acid was added for kneading and extrusion. Then, it was dried at 120°C in an alkaline atmosphere containing ammonia for 3 hours. By adjusting the concentration of alkaline gas ammonia, the pH range was controlled to 7.5 for the first 2.4 hours and to 9.0 for the next 0.6 hours. Thereafter, the carrier DUT1 was obtained by air roasting at 550°C for 3 hours.

[0055] Example 2

[0056] Preparation of Hydrotreating Catalyst Carrier:

[0057] The preparation method of boron- and silicon-containing pseudo-boehmite is the same as that of Example 1, except that: 251 L of a mixed solution of boric acid alkyl alcohol amide ester and trimethylsiloxane is added to a dilute sodium metaaluminate solution to obtain boron- and silicon-containing pseudo-boehmite;

[0058] 90 g of prepared boron- and silicon-containing pseudo-boehmite and 10 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was dry-mixed by rolling in a rolling mill. After rolling for 15 minutes, an aqueous solution containing 8.55g of nitric acid and 4.25g of citric acid was added for kneading and extrusion. Then, it was dried at 120°C in an alkaline atmosphere containing ammonia for 3 hours. By adjusting the concentration of alkaline gas ammonia, the pH range was controlled to 7.5 for the first 2.4 hours and the pH value was controlled to 9.0 for the next 0.6 hours. Thereafter, the carrier DUT2 was calcined at 550°C for 3 hours.

[0059] Example 3

[0060] Preparation of Hydrotreating Catalyst Carrier:

[0061] The preparation method of boron- and silicon-containing pseudo-boehmite is the same as that of Example 1, except that: 384.6 L of concentrated sodium aluminate solution is added to a colloid reaction kettle, diluted to 1000 L with deionized water to prepare a dilute sodium aluminate solution having a concentration of 135 g / L in terms of Al2O3, and 339.4 L of a mixed solution of boric acid alkyl alcohol amide ester and trimethylsiloxane silicate is added to the dilute sodium aluminate solution to obtain boron- and silicon-containing pseudo-boehmite;

[0062] 92 g of boron- and silicon-containing pseudo-boehmite and 8 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was rolled and dry mixed in a rolling mill. After rolling for 20 minutes, an aqueous solution containing 9.15g of nitric acid and 3.85g of citric acid was added for kneading and extrusion. Then, it was dried at 120°C in an alkaline atmosphere containing ammonia for 3 hours. By adjusting the concentration of alkaline gas ammonia, the pH range was controlled to 7.5 for the first 2.2 hours and the pH value was controlled to 9.0 for the next 0.8 hour. Thereafter, the carrier DUT3 was obtained by calcining at 550°C for 3 hours.

[0063] Example 4

[0064] Preparation of Hydrotreating Catalyst Carrier:

[0065] The preparation method of boron- and silicon-containing pseudo-boehmite is the same as that of Example 1, except that: a mixed solution of succinimidyl borate and polyvinyl alcohol silicate is added to a dilute sodium metaaluminate solution to obtain boron- and silicon-containing pseudo-boehmite;

[0066] 88 g of boron- and silicon-containing pseudo-boehmite and 12 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was rolled and dry mixed in a rolling mill. After rolling for 20 minutes, an aqueous solution containing 9.23g of nitric acid and 4.25g of citric acid was added for kneading and extrusion. Then, it was dried at 120°C in an alkaline atmosphere containing ammonia for 3 hours. By adjusting the concentration of alkaline gas ammonia, the pH range was controlled to 7.5 for the first 2.6 hours and the pH value was controlled to 9.0 for the next 0.4 hour. Thereafter, the carrier DUT4 was calcined at 570°C for 3 hours.

[0067] Example 5

[0068] Preparation of Hydrotreating Catalyst Carrier:

[0069] Take industrial grade one aluminum hydroxide powder and industrial grade one sodium hydroxide to prepare a concentrated sodium metaaluminate solution with a caustic ratio of 1.35 and a concentration of 320 g / L in terms of Al2O3;

[0070] 266L of the solution was added to a gelling reactor, diluted to 1000L with deionized water to prepare a dilute sodium aluminate solution with a concentration of 85g / L in terms of Al2O3, and 116.5L of a mixed solution of boric acid alkyl alcohol amide ester and trimethylsiloxane was added, wherein the boron concentration in terms of B2O3 was 15g / L and the silicon concentration in terms of SiO2 was 170g / L;

[0071] Air is introduced from the bottom of the reactor for stirring, and the air flow rate is controlled at 1.3m 3 / h, after stirring evenly, introduce a mixed gas of air and CO2, and control the mixed gas flow rate to 2.2m 3 / h, wherein the volume fraction of CO2 is 43%, when the pH value of the slurry in the reactor drops to 9.8, the mixed gas is turned off, the reaction is stopped, the slurry is filtered to obtain a filter cake, washed with deionized water at 65°C to neutrality, and dried at 120°C for 3 hours to obtain the boron- and silicon-containing pseudo-boehmite of the present invention;

[0072] 95 g of prepared boron- and silicon-containing pseudo-boehmite and 5 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was dry-mixed by rolling in a rolling mill. After rolling for 15 minutes, an aqueous solution containing 8.5g of nitric acid and 4.5g of citric acid was added for kneading and extrusion. Then, it was dried at 120°C in an alkaline atmosphere containing ammonia for 3 hours. By adjusting the concentration of alkaline gas ammonia, the pH range was controlled to 8.0 in the first 2.4 hours and to 9.5 in the next 0.6 hours. Then, the carrier DUT5 was calcined at 560°C for 3 hours.

[0073] Example 6

[0074] Preparation of Hydrotreating Catalyst Carrier:

[0075] The preparation method of boron- and silicon-containing pseudo-boehmite is the same as that of Example 5, except that the reaction is stopped when the pH value of the gelation end point is 11.3, thereby obtaining the boron- and silicon-containing pseudo-boehmite of the present invention;

[0076] 92 g of boron- and silicon-containing pseudo-boehmite and 7 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was dry-mixed by rolling in a rolling mill. After rolling for 15 minutes, an aqueous solution containing 8.8g of nitric acid and 4.35g of citric acid was added for kneading and extrusion. Then, it was dried at 120°C in an alkaline atmosphere containing ammonia for 3 hours. By adjusting the concentration of alkaline gas ammonia, the pH range was controlled to 8.0 in the first 2.4 hours and to 9.5 in the next 0.6 hour. Then, the carrier DUT6 was obtained by calcining at 550°C for 3 hours.

[0077] Comparative Example 1

[0078] Preparation of Hydrorefining Catalyst Carrier:

[0079] Take industrial grade one aluminum hydroxide powder and industrial grade one sodium hydroxide to prepare a concentrated sodium aluminate solution with a caustic ratio of 1.15 and a concentration of 351 g / L in terms of Al2O3;

[0080] 285L of the solution was added to a gelling reactor, diluted to 1000L with deionized water to prepare a dilute sodium aluminate solution with a concentration of 100g / L in terms of Al2O3, and 140L of a mixed solution of boric acid and water glass was added, wherein the concentration of boron in terms of B2O3 was 20g / L and the concentration of silicon in terms of SiO2 was 68g / L;

[0081] Air is introduced from the bottom of the reactor for stirring, and the air flow rate is controlled at 1.8m 3 / h, after stirring evenly, introduce a mixed gas of air and CO2, and control the mixed gas flow rate to 1.85m 3 / h, wherein the volume fraction of CO2 is 55%, when the pH value of the slurry in the reactor drops to 10.5, the mixed gas is turned off, the reaction is stopped, the slurry is filtered to obtain a filter cake, and washed with deionized water at 65°C until neutral, to obtain boron-silicon pseudo-boehmite;

[0082] 95 g of prepared boron- and silicon-containing pseudo-boehmite and 5 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was dry-mixed by rolling in a rolling mill. After rolling for 15 minutes, an aqueous solution containing 8.25g of nitric acid and 4g of citric acid was added, kneaded, extruded into strips, and then dried at 120°C for 3 hours and calcined at 550°C for 3 hours to obtain the carrier DUT7.

[0083] Comparative Example 2

[0084] Preparation of Hydrorefining Catalyst Carrier:

[0085] According to the current industrial carbonization method for producing silicon-containing pseudo-boehmite, industrial grade one aluminum hydroxide powder and industrial grade one sodium hydroxide are prepared into a concentrated sodium aluminate solution with a caustic ratio of 1.15 and a concentration of 351 g / L in terms of Al2O3;

[0086] Take 285L of the solution and add it to the gelling reactor, dilute it to 1000L with deionized water to make a dilute sodium aluminate solution with a concentration of 100g / L in terms of Al2O3, and introduce air from the bottom of the reactor for stirring. The air flow rate is controlled at 1.8m / s. 3 / h, after stirring evenly, introduce a mixed gas of air and CO2, and control the mixed gas flow rate to 1.85m 3 / h, wherein the volume fraction of CO2 is 55%, when the pH value of the slurry in the reactor drops to 12.5, add 140L of a mixed solution of boric acid and water glass, wherein the concentration of boron in the mixed solution is 20g / L as B2O3, and the concentration of silicon in the mixed solution is 68g / L as SiO2; continue to introduce a mixed gas of air and CO2, and when the pH value of the slurry in the reactor drops to 10.5, turn off the mixed gas to stop the reaction, filter the slurry to obtain a filter cake, and wash it with deionized water at 65°C until it is neutral to obtain pseudo-boehmite containing boron and silicon;

[0087] 90 g of prepared boron- and silicon-containing pseudo-boehmite and 10 g of small-pore alumina (specific surface area 352 m 2 / g, pore volume 0.5mL / g, average pore diameter 5.5nm) was dry-mixed by rolling in a rolling mill. After rolling for 15 minutes, an aqueous solution containing 8.55g of nitric acid and 4.25g of citric acid was added for kneading and extrusion. Then, it was dried at 120°C in an alkaline atmosphere containing ammonia for 3 hours. By adjusting the concentration of alkaline gas ammonia, the pH range was controlled to 8.0 in the first 2.4 hours and to 9.5 in the next 0.6 hour. Then, the carrier DUT8 was obtained by calcining at 550°C for 3 hours.

[0088] Examples 7-12

[0089] Preparation of hydrotreating catalyst:

[0090] Calculated by catalyst weight: 3.65% is nickel oxide, 23.5% is molybdenum oxide to prepare a molybdenum-nickel metal solution, and an equal volume of the solution is used to impregnate carriers DUT1 to DUT6. After drying at 120°C for 3 hours and calcining at 500°C in air atmosphere for 2 hours, the hydrorefining catalysts Cat1 to Cat6 are obtained.

[0091] All prepared hydrotreating catalysts Cat1 to Cat6 were evaluated on a 100mL small-scale hydrogenation unit, using vacuum wax oil as the raw material to evaluate the hydrodesulfurization and hydrodenitrogenation activities of the catalysts. The operating conditions of the evaluation experiment were as follows: reaction temperature of 360°C, reaction hydrogen partial pressure of 8.5MPa, liquid hourly volume space velocity of 1.2h -1 The volume ratio of hydrogen to oil is 800:1. The properties of the raw oil used in the activity evaluation experiment are shown in Table 2, and the activity evaluation results are shown in Table 4.

[0092] Comparative Examples 3-4

[0093] Calculated by catalyst weight: 3.65% is nickel oxide and 23.5% is molybdenum oxide to make a molybdenum-nickel metal solution, and equal volumes of the solutions are used to impregnate carriers DUT7 and DUT8. After drying at 120°C for 3 hours and calcining at 500°C in air atmosphere for 2 hours, the hydrorefining catalysts Cat7 and Cat8 are obtained respectively.

[0094] All prepared hydrotreating catalysts Cat7 and Cat8 were evaluated on a 100mL small-scale hydrogenation unit, using vacuum wax oil as the raw material to evaluate the hydrodesulfurization and hydrodenitrogenation activities of the catalysts. The operating conditions of the evaluation experiment were as follows: reaction temperature of 360°C, reaction hydrogen partial pressure of 8.5MPa, liquid hourly volume space velocity of 1.2h -1 The volume ratio of hydrogen to oil is 800: 1. The properties of the raw oil used in the activity evaluation experiment are shown in Table 2, and the activity evaluation results are shown in Table 4.

[0095] Table 1 Physical and chemical properties of the carriers prepared in Examples 1-6 and Comparative Examples 1-2

[0096]

[0097] Table 2 Raw oil properties

[0098]

[0099]

[0100] Table 3 Physicochemical properties of the catalysts prepared in Examples 7-12 and Comparative Examples 3-4

[0101]

[0102] Table 4 Catalyst performance of Examples 7-12 and Comparative Examples 3-4

[0103]

[0104] *Relative activity is based on the 200h activity of Cat7 in Comparative Example 3.

[0105] Comparative Example 1 adopts a conventional method to prepare pseudo-boehmite, and adopts a conventional drying method to prepare a catalyst carrier. Comparative Example 2 adopts a conventional method to prepare pseudo-boehmite, but adopts the same drying method as the present invention to prepare a catalyst carrier. It can be seen from Table 1 that the preparation method and drying method of the pseudo-boehmite of the present invention can increase the macropore ratio of the carrier. At the same time, the macropore ratio of the carrier in Comparative Example 2 is also improved compared with Comparative Example 1, indicating that the macropore ratio of the carrier can be improved by the drying method of the present invention. It can be seen from Table 4 that the hydrodesulfurization activity and hydrodenitrogenation activity of the catalyst prepared using the carrier of the present invention are improved. With the increase of operating time, the activity only decreases slightly, indicating that the increase in macropore content can improve the catalyst's ability to resist carbon deposition, thereby improving the activity and stability of the catalyst and extending the operating cycle of the device.

[0106] In summary, the hydrotreating catalyst prepared by the present invention has excellent hydrodesulfurization activity and hydrodenitrogenation activity and has good stability.

[0107] The above embodiments are only preferred embodiments of the present invention and are not intended to limit the implementation methods. The protection scope of the present invention shall be subject to the scope defined in the claims. Other different forms of changes or modifications may be made based on the above description. Obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A method for preparing a hydrotreating catalyst carrier, characterized in that: The method comprises the following steps: (1) placing a sodium aluminate solution in a colloid-forming reactor, adding a mixed solution containing boron and silicon precursors and mixing them evenly, introducing a mixed gas of air and CO2, controlling the pH value of the slurry, and stopping the introduction of the mixed gas when the pH value of the slurry reaches the end pH value, filtering the slurry, washing, and drying, to obtain pseudo-boehmite containing boron and silicon; (2) The boron-silicon-containing pseudo-boehmite and a molding aid are kneaded and molded, dried in an alkaline gas atmosphere, the pH value is controlled to be 7-12, and then calcined to obtain a hydrogenation refining catalyst carrier.

2. The preparation method according to claim 1, characterized in that: In step (1), the mixed solution containing boron and silicon precursors is a mixed solution of a boron-based surfactant and a silicon surfactant; The boron-based surfactant is one or more of a glyceride borate surfactant, a boric acid alkyl alcohol amide ester surfactant, and a borate ester amphoteric surfactant; The silicon surfactant is one or more of a siloxane surfactant, a polysiloxane or carbosilane surfactant and a polysilane surfactant; In the mixed solution containing boron and silicon precursors, the concentration of boron in terms of B2O3 is 10 to 40 g / L, preferably 10 to 20 g / L, and the concentration of silicon in terms of SiO2 is 20 to 180 g / L, preferably 50 to 170 g / L; The sodium aluminate solution has a concentration of 80 to 150 g / L, preferably 85 to 140 g / L, in terms of Al2O3, and a caustic ratio of 1.10 to 1.40; The volume of the mixed solution containing boron and silicon precursors is 1 / 10 to 2 / 5 of the volume of the sodium aluminate solution.

3. The preparation method according to claim 1, characterized in that: In step (1), the mixing process is stirred by introducing air into the lower part of the reactor, wherein the flow rate of the introduced air is 1.0 to 2.0 m / s. 3 / h; The endpoint pH of the slurry is 9.5 to 11.5; In the mixed gas of air and CO2, the volume fraction of CO2 is 30% to 60%; The flow rate of the mixed gas introduced into each cubic meter of sodium aluminate solution is 1.5-2.5 m 3 / h, preferably 1.7 to 2.3 m 3 / h.

4. The preparation method according to claim 1, characterized in that: In step (2), the alkaline gas is one or a combination of ammonia, phosphine, and hydrazine; The drying temperature is 50 to 160°C, preferably 85 to 120°C, and the drying time is 1 to 15 hours; The drying process is as follows: during 80% to 90% of the time before drying, the pH value of the alkaline gas atmosphere is controlled to be in the range of 7 to 8 by adjusting the concentration of the alkaline gas, and during 10% to 20% of the time after drying, the pH value of the alkaline gas atmosphere is controlled to be in the range of 9 to 12 by adjusting the concentration of the alkaline gas; The calcination temperature is 450-650° C., preferably 500-580° C., and the calcination time is 1-10 hours.

5. The preparation method according to claim 1, characterized in that: In step (2), the molding aid is selected from at least one of a peptizing acid, an extrusion aid, and a binder; The peptizing acid is one of citric acid and nitric acid or a mixture of both, preferably a mixture of citric acid and nitric acid; The adhesive is small pore alumina; The extrusion aid is one or more of starch, polyvinyl alcohol, polyacrylamide, methyl cellulose and sesbania powder.

6. A hydrotreating catalyst carrier prepared by the preparation method according to any one of claims 1 to 5, characterized in that: The carrier has the following properties: pore volume 0.70-1.0 mL / g, specific surface area 250-350 m 2 / g, the pore volume of pores with a pore diameter of less than 6nm accounts for less than 7% of the total pore volume, and the pore volume of pores with a pore diameter of 6-15nm accounts for 45%-65% of the total pore volume; Based on the properties on a dry basis, the carrier contains 1.0% to 5.0% boron in terms of B2O3 and 1.0% to 20.0% silicon in terms of SiO2.

7. A hydrotreating catalyst, characterized in that: The catalyst is obtained by impregnating the hydrorefining catalyst carrier according to claim 6 with a solution containing active metals, followed by drying and calcining.

8. The hydrotreating catalyst according to claim 7, characterized in that: The active metal is a metal of Group VIIIB or Group VIB, wherein the metal of Group VIIIB is one or two of Co and Ni, and the metal of Group VIB is one or two of W and Mo; Based on the weight of the catalyst, the content of the Group VIB metal in terms of oxide is 2wt% to 16wt%, preferably 5wt% to 11wt%, the content of the Group VIB metal in terms of oxide is 10wt% to 35wt%, preferably 15wt% to 30wt%, and the content of the hydrorefining catalyst carrier is 50wt% to 80wt%, preferably 65wt% to 75wt%.

9. The hydrotreating catalyst according to claim 7, characterized in that: The impregnation method is selected from one of equal volume impregnation, supersaturated impregnation, step impregnation, and co-impregnation, preferably the equal volume co-impregnation method; The drying temperature is 50 to 200° C., preferably 90 to 160° C., and the drying time is 1 to 10 hours, preferably 1 to 5 hours; The calcination temperature is 350-600° C., preferably 380-500° C., and the calcination time is 1-10 hours, preferably 1-5 hours.

10. The hydrotreating catalyst according to claim 7, characterized in that: The catalyst also includes an additive, which is one or more oxides of P, B, Ti and Zr. The content of the additive, calculated on the weight of the catalyst, is less than 6% by weight of the hydrorefining catalyst, preferably 0.1% to 5.0%.

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