Preparation method of high-performance hydrotreating catalyst

Abstract

The invention discloses a preparation method of a high-performance hydrotreating catalyst. The preparation method comprises the following steps: (1) preparing alumina dry glue powder; the content of alkali metal in terms of oxide is 0.1 wt%-2.0 wt%, preferably 0.2 wt%-1.2 wt%, and further preferably 0.4 wt%-1.0 wt% on the basis of the dry basis weight of the aluminum oxide dry glue powder; (2) forming the alumina dry glue powder in the step (1) to prepare an alumina carrier; and (3) introducing an alkali metal compound, an acidic organic auxiliary agent and an active metal component into the alumina carrier obtained in the step (2), and drying or drying and roasting to obtain the hydrotreating catalyst. The method can improve the activity and stability of the hydrotreating catalyst, and is suitable for the hydrotreating process of heavy distillate oil.

Description

Technical Field

[0001] The invention relates to a preparation method of a high-performance hydroprocessing catalyst, and in particular to a preparation method for improving the activity and stability of the hydroprocessing catalyst. Background Art

[0002] At present, carbon deposition in industrial operation is the main cause of hydrogenation catalyst deactivation. How to reduce the carbon deposition rate and amount of catalysts is the main direction of hydrogenation catalyst research and development. Most hydrogenation catalysts are prepared by impregnation method, and the commonly used carrier material for this type of catalyst is alumina. In order to improve the activity and stability of hydroprocessing catalysts, it is necessary to chemically modify the alumina carrier, such as adding silicon, phosphorus, fluorine, boron, zirconium, titanium, magnesium, gallium, vanadium, manganese, copper, zinc and other additives. One is to adjust the acidity of alumina, and the other is to change the interaction between active components and alumina, and improve the thermal stability of alumina.

[0003] CN00110018.1 discloses a hydrogenation catalyst and a preparation method thereof, wherein the catalyst uses Group VIB and Group VIII metals as hydrogenation active components, fluorine as an auxiliary agent, and supports one of boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium or a mixture thereof as an auxiliary agent. The patent adopts a coprecipitation method to prepare the hydrogenation catalyst. During the coprecipitation and extrusion process, some active metals may enter the bulk phase or be covered by alumina particles, and the utilization rate of the active metals will be reduced.

[0004] CN202011188999.9 discloses a heavy oil hydroprocessing catalyst and a heavy oil hydroprocessing method, wherein the catalyst contains an alumina carrier and at least one metal component selected from Group VIII and at least one metal component selected from Group VIB loaded on the carrier, wherein the alumina carrier is prepared from a high-crystallinity, large-grained pseudo-boehmite, the relative crystallinity of the pseudo-boehmite is higher than 65%, the grain size is 2-5nm, and the sodium content, based on the dry weight of the pseudo-boehmite and calculated as oxide, is not higher than 0.08wt%.

[0005] CN202011458545.9 discloses a phosphorus and / or magnesium-containing heavy oil hydroprocessing catalyst and a heavy oil hydroprocessing method, wherein the catalyst contains an alumina carrier and at least one metal component selected from Group VIII and at least one metal component selected from Group VIB loaded on the carrier, wherein the alumina carrier is prepared from a high-crystallinity, large-grained pseudo-boehmite containing phosphorus and / or magnesium, the pseudo-boehmite having a relative crystallinity higher than 55%, a grain size of 2-5 nm, and a sodium content of not more than 0.08 wt.% based on the dry weight of the pseudo-boehmite and calculated as oxide.

[0006] The above-mentioned prior art has extremely stringent requirements on the sodium content in the alumina dry gel used in the hydroprocessing catalyst, and the general indicator is that the sodium oxide content is less than 0.08wt.%, and the anti-carbon deposition performance of the hydroprocessing catalyst during use and the activity stability during long-term operation need to be further improved. Summary of the invention

[0007] In view of the problems existing in the prior art, the present invention provides a method for preparing a high-performance hydroprocessing catalyst, which can improve the activity and stability of the hydroprocessing catalyst and is suitable for the hydroprocessing process of heavy distillate oil.

[0008] The first aspect of the present invention provides a method for preparing a high-performance hydroprocessing catalyst, comprising the following steps: (1) preparing alumina dry glue powder; the alumina dry glue powder has an alkali metal content of 0.1wt% to 2.0wt% in terms of oxide, based on its dry weight, preferably 0.2wt% to 1.2wt%, and more preferably 0.4wt% to 1.0wt%; (2) The alumina dry gel powder in step (1) is molded to prepare an alumina carrier; (3) An alkali metal compound, an acidic organic additive and an active metal component are introduced into the alumina carrier obtained in step (2), and a hydroprocessing catalyst is obtained after drying or drying and calcining.

[0009] In the method for preparing the high-performance hydroprocessing catalyst, the alkali metal is introduced in step (1) by alumina dry rubber powder, and the alkali metal is introduced in step (3) by an alkali metal compound. The mass ratio of the alkali metal introduced in step (1) to the alkali metal introduced in step (3) is 0.5 to 20, preferably 1 to 10, and more preferably 1 to 5, calculated as alkali metal oxide.

[0010] In the method for preparing the high-performance hydroprocessing catalyst, the alkali metal in step (1) is one or more of lithium, sodium, potassium, rubidium and cesium, preferably potassium and / or sodium, more preferably sodium.

[0011] In the above-mentioned method for preparing a high-performance hydroprocessing catalyst, the dry content of the alumina dry rubber powder in step (1) is 60wt% to 80wt%, preferably 65wt% to 75wt%.

[0012] In the above-mentioned method for preparing the high-performance hydroprocessing catalyst, the method for preparing the alumina dry rubber powder in step (1) is: S1, the aluminum-containing acidic solution and the alkaline solution are subjected to a colloid reaction to obtain an aluminum oxide dry glue powder precursor; S2. The alumina dry glue powder precursor obtained in step S1 is aged, washed, filtered and dried to obtain the final alumina dry glue powder.

[0013] Furthermore, the concentration of the aluminum-containing acidic solution in step S1 is 0.5 g ~ 10 g / 100 mL, preferably 2 g ~ 6 g / 100 mL; the concentration of the alkaline solution is 5 g ~ 30 g / 100 mL, preferably 10 g ~ 25 g / 100 mL.

[0014] Furthermore, in step S1, the gelling temperature is 30°C to 95°C, preferably 50°C to 80°C; and by adjusting the volume ratio of the aluminum-containing acidic solution to the alkaline solution, the gelling pH value is 4.5 to 10.0, preferably 5.5 to 9.0.

[0015] Furthermore, the aluminum-containing acidic solution in step S1 includes one or more of aluminum sulfate solution, aluminum nitrate solution and aluminum chloride solution.

[0016] Furthermore, the alkaline solution in step S1 is a soluble solution containing an alkali metal, such as one or more of sodium aluminate solution, potassium aluminate, sodium hydroxide and potassium hydroxide.

[0017] Furthermore, the alkaline solution in step S1 is a soluble solution that does not contain alkali metals, including but not limited to one or more of ammonia water, ammonium carbonate and ammonium bicarbonate; the alkali metal element is introduced in step S2, and the specific operation process is: in the aging and / or washing process in step S2, an alkali metal-containing substance is introduced; the alkali metal-containing substance includes but is not limited to one or more of sodium carbonate, sodium bicarbonate, sodium acetate and sodium citrate.

[0018] Furthermore, the specific operation process of introducing the alkali metal-containing substance during the aging process in step S2 is as follows: adding the alkali metal-containing substance during the aging time of 0.3h~3h, and then continuing the aging for 0.3h~5h, and then entering the washing process; the alkali metal-containing substance can be added in solid or liquid form, preferably in liquid form, and the addition time is 1min~10min.

[0019] Furthermore, the specific operation process of introducing the alkali metal-containing substance in the washing process in step S2 is as follows: for an intermittent washing process, the alkali metal-containing substance can be added at any time in the washing process, and for a continuous washing process, the alkali metal-containing substance can be added at any position in the washing process; the alkali metal-containing substance can be added in solid or liquid form, preferably in liquid form, and the addition time is 1 min to 5 min.

[0020] Furthermore, the operating conditions of the aging process in step S2 are as follows: the aging temperature is 30°C to 95°C, preferably 50°C to 90°C; the aging control pH value is 5.5 to 10.0, preferably 5.5 to 9.5; the aging time is controlled to be 0.5h to 8h, preferably 1.5h to 4.5h.

[0021] Furthermore, the drying treatment operating conditions in step S2 are as follows: it can be static drying or dynamic drying, etc., to ensure that the dry basis of the alumina dry glue powder is 60wt%~80wt%, the drying temperature is 60℃~200℃, and the drying time is 0.5h~10.0h.

[0022] In the above-mentioned method for preparing a high-performance hydroprocessing catalyst, the molding described in step (2) can adopt any molding method in the prior art. Specifically in the present invention, the specific operation steps are as follows: the aluminum oxide dry glue powder is mixed with a glue solvent and / or a binder, and the aluminum oxide carrier is obtained by kneading and / or rolling, molding, drying and calcining.

[0023] In the preparation method of the above-mentioned high-performance hydroprocessing catalyst, the peptizing agent in step (2) is one or more of an organic acid, an inorganic acid and a compound that can ionize H+, such as nitric acid, oxalic acid, acetic acid and propionic acid.

[0024] In the above-mentioned method for preparing the high-performance hydroprocessing catalyst, the binder in step (2) is produced by the reaction of aluminum hydroxide and / or silicon oxide with nitric acid.

[0025] In the preparation method of the high-performance hydroprocessing catalyst, an extrusion aid may be added during molding in step (2) to improve fluidity; the extrusion aid is not particularly limited and may be any extrusion aid known in the art, such as at least one of alcohol, cellulose and sesbania powder.

[0026] In the preparation method of the above-mentioned high-performance hydroprocessing catalyst, the drying and calcination in step (2) adopt the operating conditions of the prior art: the drying temperature is 50°C to 200°C, preferably 110°C to 160°C; the drying time is 0.5h to 20h, preferably 1h to 6h; the calcination temperature is 400°C to 1000°C, preferably 450°C to 800°C; the calcination time is 0.5h to 20h, preferably 1h to 6h.

[0027] In the preparation method of the above-mentioned high-performance hydroprocessing catalyst, the alkali metal compound in step (3) includes one or more of a lithium-containing compound, a sodium-containing compound and a potassium-containing compound, preferably a sodium-containing compound; the sodium-containing compound is an inorganic sodium-containing compound and / or an organic sodium-containing compound; there is no special limitation on the inorganic sodium-containing compound and the organic sodium-containing compound, and any one of the inorganic sodium-containing compounds and / or organic sodium-containing compounds known in the art can be used; specifically in the present invention, the source of the inorganic sodium-containing compound includes but is not limited to one or more of the following compounds: sodium carbonate, sodium bicarbonate, sodium nitrate, sodium sulfate, sodium borate, sodium chloride, sodium phosphate, sodium polyphosphate and sodium silicate; the source of the organic sodium-containing compound includes but is not limited to one or more of sodium acetate, sodium citrate, sodium oxalate and sodium petroleum sulfonate.

[0028] In the above-mentioned method for preparing a high-performance hydroprocessing catalyst, the acidic organic additive in step (3) refers to an organic additive that can ionize H in aqueous solution. + The acidic organic auxiliary agent is one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound and an oxygen-containing organic compound; the nitrogen-containing organic compound is an organic compound containing at least one covalently bonded nitrogen atom, such as at least one of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid; the sulfur-containing organic compound is an organic compound containing at least one covalently bonded sulfur atom, such as thioglycolic acid and / or mercaptopropionic acid; the oxygen-containing organic compound is an organic compound containing at least one carbon atom and one oxygen atom, such as at least one of acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid and citric acid.

[0029] In the above-mentioned method for preparing a high-performance hydroprocessing catalyst, the active metal component in step (3) is at least one of Group VIB and Group VIII metals; the Group VIB metal is preferably Mo and / or W, and the Group VIII metal is preferably Ni and / or Co.

[0030] In the preparation method of the above-mentioned high-performance hydroprocessing catalyst, there is no restriction on the order of introducing the alkali metal compound, the acidic organic auxiliary agent and the active metal component into the alumina carrier in step (3); the alkali metal compound is introduced before or after the active metal component is introduced or at the same time, preferably at the same time as the active metal component; the acidic organic auxiliary agent is introduced before or after the active metal component is introduced or at the same time, preferably at the same time as the active metal component; the alkali metal compound and the acidic organic auxiliary agent can be introduced in one step or in several steps. Specifically in the present invention, the following order can be adopted: first introduce the alkali metal compound, then introduce the acidic organic auxiliary agent, and finally introduce the active metal component; or first introduce the acidic organic auxiliary agent, then introduce the alkali metal compound, and finally introduce the active metal component; or first introduce the alkali metal compound and the acidic organic auxiliary agent at the same time, and then introduce the active metal component; or the alkali metal compound, the acidic organic auxiliary agent and the active metal component are introduced at the same time; or first introduce the alkali metal compound, and then introduce the acidic organic auxiliary agent and the active metal component at the same time.

[0031] In the above-mentioned method for preparing the high-performance hydroprocessing catalyst, the introduction method in step (3) adopts the impregnation method, which is well known to technicians. The impregnation method can be equal volume impregnation, or excess impregnation, or step impregnation, or co-impregnation, preferably equal volume co-impregnation.

[0032] In the method for preparing the high-performance hydroprocessing catalyst, in step (3), based on the final catalyst mass, the content of active metal components is: calculated as oxide, the content of Group VIB metals is 5wt% to 40wt%, preferably 12% to 30%, and the content of Group VIII metals is 2wt% to 12wt%, preferably 2% to 8%.

[0033] In the method for preparing the high-performance hydroprocessing catalyst, the molar ratio of the acidic organic additive to the Group VIII metal element in the active metal component in step (3) is 0.05:1 to 5:1, preferably 0.1:1 to 1:1.

[0034] In the preparation method of the high-performance hydroprocessing catalyst, an organic substance is also introduced in step (3), and the organic substance may be an alcohol, such as ethylene glycol, propylene glycol, butylene glycol, glycerol, trimethylolethane, etc.; an ether, such as diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, polyethylene glycol, etc.; a sugar, such as glucose, fructose, lactose, maltose, sucrose, etc.; or a ketone, phenol, aldehyde, or lipid. The organic substance may be introduced in the following manner: the catalyst carrier may be pre-impregnated with the organic substance, and then the active metal component may be introduced after drying; the organic substance may be added to the impregnation solution of the active metal component and introduced into the catalyst carrier together; or the active metal component may be introduced and then dried before the organic substance is introduced. The drying temperature is generally 60-150°C, and the treatment time is generally 0.5-10 hours.

[0035] In the preparation method of the high-performance hydroprocessing catalyst, other additives may be introduced successively or simultaneously with the introduction of the active metal component in step (3), wherein the additive is a phosphorus-containing compound, such as one or more of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

[0036] In the preparation method of the high-performance hydroprocessing catalyst, the calcination in step (3) is one or two calcinations; the first calcination is a low-temperature treatment process, the temperature is 70°C to 290°C, preferably 100°C to 280°C, the time is 0.5h to 20h, preferably 1h to 6h; the second calcination is a high-temperature treatment after the first calcination low-temperature treatment, the temperature is 350°C to 650°C, preferably 400°C to 500°C, the time is 0.5h to 8h, preferably 1h to 4h. The calcination atmosphere is one or more of air atmosphere, inert atmosphere (such as nitrogen), reducing atmosphere (such as hydrogen), water vapor atmosphere and vacuum atmosphere.

[0037] The second aspect of the present invention provides a hydroprocessing catalyst obtained by the above preparation method. The catalyst comprises an active metal component, aluminum oxide and an alkali metal oxide; the active metal component content is 7wt.%~52wt.% in terms of oxide, the aluminum oxide content is 40wt.%~90wt.%, and the alkali metal oxide content is 0.1wt.%~2.0wt.% in terms of oxide; preferably, the active metal component content is 14wt.%~38wt.% in terms of oxide, the aluminum oxide content is 55wt.%~85wt.%, and the alkali metal oxide content is 0.2wt.%~1.4wt.% in terms of oxide.

[0038] The third aspect of the present invention provides a hydroprocessing method, wherein heavy oil and hydrogen-containing gas are contacted and reacted in the presence of the above-mentioned hydroprocessing catalyst.

[0039] In the above hydroprocessing method, the heavy oil is one or more of VGO, CGO, DAO and LCO.

[0040] In the above-mentioned hydrogenation treatment method, the hydrogen-containing gas is hydrogen, or a mixture of hydrogen and other gases, and the volume content of hydrogen in the mixture is not less than 80%, preferably not less than 85%.

[0041] In the above-mentioned hydrogenation treatment method, the reaction conditions are as follows: total reaction pressure 6.0 MPa ~20.0 MPa, volume space velocity 0.3h -1 ~3.0 h -1 , hydrogen-oil ratio is 400:1~1800:1, and the reaction temperature is 300℃~420℃.

[0042] Compared with the prior art, the present invention has the following advantages: The alkali metal content in the alumina dry gel used in the preparation process of the hydroprocessing catalyst is 0.1wt.%~1.5wt.% in terms of oxide, which is much higher than the sodium content in the alumina dry gel used in the hydroprocessing catalyst in the prior art (generally, the sodium oxide content is less than 0.08wt.%), which can reduce the number of washing times and the amount of washing water used; During the preparation of the hydroprocessing catalyst, alkali metal elements are introduced step by step. First, an appropriate amount of alkali metal elements are introduced through alumina dry rubber powder, and then alkali metal compounds and acidic organic additives are introduced during the catalyst preparation process. The synergistic effect of the two can adjust the acidity and alkalinity of the carrier and the metal solution, reduce the viscosity of the active metal solution, and thus improve the surface properties of the catalyst, which can not only effectively avoid carbon deposition on the catalyst, but also significantly improve the catalyst activity, slow down the deactivation rate of the catalyst during the heavy oil hydroprocessing process, and greatly improve the stability. Implementation

[0043] The technical features of the present invention are further described below by way of examples, but the present invention should not be considered to be limited to these examples. The percentages involved are percentages by weight.

[0044] The specific surface area and pore volume of the samples were determined using the ASAP2405 physical adsorption instrument from Micromeritics, with liquid nitrogen as the adsorbent and an adsorption temperature of -196°C. The Na 2 O content. The dry basis determination method in the present invention is to take an appropriate amount of sample, the mass is m1, roast it at 500°C for 3h, then measure the mass as m2, calculate the mass percentage of the sample after roasting to the sample before roasting, m2 / m1×100%, which is the dry basis of the sample.

[0045] Alumina dry glue powder is obtained by the preparation method described in the invention content. Table 1 shows the properties of alumina dry glue powder with different sodium oxide contents. F1 is prepared by neutralizing sodium metaaluminate and aluminum sulfate into glue. 1L of deionized water is added to the container, the temperature is raised to 65°C, and Al 2 O 3 4g / 100mL aluminum sulfate solution and Al 2 O 3 The sodium aluminate solution was 18g / 100mL, the pH value was controlled at 7.8, and the feeding time was 60min. After stopping the feeding, the temperature was raised to 75℃, and after aging for 30min, Na 2 CO 3 Solution, in which Na 2 CO 3 Solution concentration 12g Na 2 O / 100mL, temperature controlled at 75℃, pH value controlled at 9.0, continue aging for 3h and filter. Wash once, dry the filter cake at 110℃ for 7h, and crush it until the particle size is less than 180 mesh accounting for more than 95%, to obtain dry rubber powder F1.

[0046] F2 is aluminum chloride and ammonia water neutralized into gel. Add 1L of deionized water into the container, heat it to 75℃, and add Al 2 O 3 6g / 100mL aluminum chloride solution and NH 3 The amount of ammonia solution was 12%, the pH value was controlled to 8.5, and the feeding time was 60 minutes. Then, aging was carried out under the above temperature and pH conditions. After aging for 60 minutes, sodium bicarbonate solution with a concentration of 5g Na 2 O / 100mL, the amount added is based on Al 2 O 3The sodium oxide content is 2.5wt%, the addition time is 5min, after completion, the pH value is adjusted to 9.0 with ammonia water, and aging is continued for 60min. After washing once, it is filtered, and the filter cake is dried at 120℃ for 6h, and then crushed to a particle size of less than 180 mesh, accounting for more than 95%, to obtain dry rubber powder F2.

[0047] F3 is aluminum sulfate and ammonia water neutralized into gel. Add 1L of deionized water into the container, heat it to 60℃, and add Al 2 O 3 5g / 100mL aluminum sulfate solution and NH 3 The amount of ammonia solution was 10%, the pH value was controlled to be 8.0, and the feeding time was 60 minutes. Then, the aging was carried out under the above temperature and pH conditions. After aging for 120 minutes, the filter cake was slurried and washed, and sodium carbonate solution was added with a concentration of 10g Na 2 O / 100mL, the amount added is based on Al 2 O 3 The sodium oxide content is 0.5wt%, the addition time is 3min, stirring and washing is continued for 60min, and then the filter cake is filtered. After drying at 120°C for 6h, it is crushed to a particle size of less than 180 mesh, accounting for more than 95%, to obtain dry rubber powder F3.

[0048] F4 is prepared by neutralizing aluminum chloride and ammonia water into colloid. Add 1L of deionized water into the container, heat it to 70℃, and add Al 2 O 3 5g / 100mL aluminum chloride solution and NH 3 The amount of ammonia solution was 13%, the pH value was controlled to be 7.5, and the feeding time was 60 minutes. Then, the aging was carried out under the above temperature and pH conditions. After aging for 3 hours, the filter cake was filtered and washed once. After drying at 120°C for 6 hours, it was crushed to a particle size of less than 180 mesh, accounting for more than 95%, to obtain dry rubber powder F4.

[0049] Table 1 Properties of alumina dry rubber powder with different sodium contents

[0050] Example 1 Take 300g of dry rubber powder F1, add 8g of sesbania powder, mix well, then slowly and evenly add 230g of nitric acid aqueous solution (containing 8.0g of nitric acid) for 8 minutes, then knead for 25 minutes, and squeeze out strips using a clover plate with a diameter of 1.7mm. Dry at 110℃ for 4h and then roast at 500℃ for 4h. The roasted carrier is recorded as Z1. The same method is used to prepare carriers Z2, Z3, and Z4 using F2, F3, and F4 dry rubber powders.

[0051] Example 2 The calcined carrier strips Z1, Z2 and Z3 were used as carriers in the embodiment. When Z1 was used as the carrier, the impregnation solution was prepared using Mo, Ni, P solution, thioglycolic acid, propylene glycol and sodium nitrate, and the molar ratio of thioglycolic acid, propylene glycol and Ni element was 0.3:0.4:1. When Z2 is used as the carrier, the impregnation solution is prepared by using Mo, Ni, P solution, citric acid and sodium citrate, and the molar ratio of citric acid to Ni element is 0.5:1; When Z3 is used as the carrier, the impregnation solution is prepared by using Mo, Ni, P solution, nitrilotriacetic acid and sodium bicarbonate, and the molar ratio of nitrilotriacetic acid to Ni element is 0.6:1; The equal volume impregnation method was adopted. After impregnation for 3 hours, the catalysts were dried at 120°C for 6 hours and calcined at 430°C for 2 hours. The obtained catalysts were marked as C1, C2 and C3 respectively.

[0052] Comparative Example 1 The calcined carrier strip Z4 was taken as a comparative carrier, and the preparation process was the same as the preparation process in Example 2 when Z1 was used as the carrier. The obtained catalyst was recorded as DC1.

[0053] Comparative Example 2 The calcined carrier strip Z2 was taken as a comparative carrier, and the impregnation solution was prepared using Mo, Ni, and P solutions. The remaining conditions were the same as the preparation process in Example 2 when Z2 was used as the carrier. The obtained catalyst was recorded as DC2.

[0054] Comparative Example 3 The calcined carrier strip Z2 was taken as a comparative carrier, and the impregnation solution was prepared using Mo, Ni, P solution and citric acid. The other conditions were the same as the preparation process in Example 2 when Z2 was used as the carrier. The obtained catalyst was recorded as DC3.

[0055] Comparative Example 4 The calcined carrier strip Z2 was taken as a comparative carrier, and the impregnation solution was prepared using Mo, Ni, P solution and sodium citrate. The other conditions were the same as the preparation process in Example 2 when Z2 was used as the carrier. The obtained catalyst was recorded as DC4.

[0056] Table 2 Metal composition of prepared Mo and Ni catalysts

[0057] Example 3 This example is an activity evaluation experiment of the catalyst.

[0058] The catalyst activity evaluation experiment was carried out on a 100ml small hydrogenation unit, and the catalyst was presulfurized before the activity evaluation. The catalyst evaluation conditions were a total reaction pressure of 14.5MPa and a volume space velocity of 1.0 h -1, hydrogen-oil ratio 800:1, reaction temperature 380°C. The properties of the raw oil used in the activity evaluation experiment are shown in Table 3, and the activity evaluation results are shown in Table 4. It can be seen from the data in the table that the hydrotreating catalyst prepared by the present invention has a greatly improved catalyst hydrodenitrogenation activity, and the carbon deposit content of the catalyst is significantly reduced, which is conducive to long-term stable operation.

[0059] Table 3 Raw oil properties

[0060] Table 4 Catalyst activity evaluation results

Claims

1. A method for preparing a high performance hydroprocessing catalyst, Features: The steps include: (1) preparing alumina dry glue powder; the alumina dry glue powder has an alkali metal content of 0.1wt% to 2.0wt% in terms of oxide, based on its dry weight, preferably 0.2wt% to 1.2wt%, and more preferably 0.4wt% to 1.0wt%; (2) The alumina dry gel powder in step (1) is molded to prepare an alumina carrier; (3) An alkali metal compound, an acidic organic additive and an active metal component are introduced into the alumina carrier obtained in step (2), and a hydroprocessing catalyst is obtained after drying or drying and calcining.

2. The method according to claim 1, Features: The mass ratio of the alkali metal introduced in step (1) to the alkali metal introduced in step (3) is 0.5 to 20, preferably 1 to 10, and more preferably 1 to 5, calculated as alkali metal oxide.

3. The method according to claim 1, Features: In step (1), the alkali metal is one or more of lithium, sodium, potassium, rubidium and cesium, preferably potassium and / or sodium, more preferably sodium.

4. The method according to claim 1, Features: The alumina dry glue powder in step (1) has a dry basis content of 60wt% to 80wt%, preferably 65wt% to 75wt%.

5. The method according to claim 1, Features: Preparation method of alumina dry glue powder in step (1): S1, the aluminum-containing acidic solution and the alkaline solution are subjected to a colloid reaction to obtain an aluminum oxide dry glue powder precursor; S2. The alumina dry glue powder precursor obtained in step S1 is aged, washed, filtered and dried to obtain the final alumina dry glue powder.

6. The method according to claim 5, Features: The aluminum-containing acidic solution in step S1 includes one or more of aluminum sulfate solution, aluminum nitrate solution and aluminum chloride solution.

7. The method according to claim 5, Features: The alkaline solution in step S1 is a soluble solution containing an alkali metal, including one or more of sodium aluminate solution, potassium aluminate, sodium hydroxide and potassium hydroxide.

8. The method according to claim 5, Features: The alkaline solution in step S1 is a soluble solution that does not contain alkali metals, including one or more of ammonia water, ammonium carbonate and ammonium bicarbonate; in step S2, alkali metal-containing substances are introduced during the aging and / or washing process; the alkali metal-containing substances include one or more of sodium carbonate, sodium bicarbonate, sodium acetate and sodium citrate.

9. The method according to claim 8, Features: The specific operation process of introducing the alkali metal-containing substance during the aging process in step S2 is as follows: adding the alkali metal-containing substance during the aging time of 0.3h~3h, and then continuing the aging for 0.3h~5h, and then entering the washing process; the alkali metal-containing substance is added in solid or liquid form, preferably in liquid form, and the addition time is 1min~10min.

10. The method according to claim 1, Features: The specific operation steps of the molding described in step (2) are as follows: the aluminum oxide dry glue powder is evenly mixed with the glue solvent and / or the adhesive, and the aluminum oxide carrier is obtained by kneading and / or rolling, molding, drying and calcining.

11. The method according to claim 1, Features: The alkali metal compound in step (3) includes one or more of a lithium-containing compound, a sodium-containing compound and a potassium-containing compound, preferably a sodium-containing compound; the sodium-containing compound is an inorganic sodium-containing compound and / or an organic sodium-containing compound; the inorganic sodium-containing compound includes one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium sulfate, sodium borate, sodium chloride, sodium phosphate, sodium polyphosphate and sodium silicate; the organic sodium-containing compound includes one or more of sodium acetate, sodium citrate, sodium oxalate and sodium petroleum sulfonate.

12. The method according to claim 1, Features: The acidic organic auxiliary agent in step (3) is one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound and an oxygen-containing organic compound; the nitrogen-containing organic compound is at least one of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and ethylenediaminetetraacetic acid; the sulfur-containing organic compound is thioglycolic acid and / or mercaptopropionic acid; the oxygen-containing organic compound is at least one of acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid and citric acid.

13. The method according to claim 1, Features: The active metal component in step (3) is at least one of Group VIB and Group VIII metals; the Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co.

14. The method according to claim 1, Features: In step (3), the alkali metal compound is introduced before or after the active metal component is introduced, or simultaneously therewith, preferably simultaneously therewith; the acidic organic auxiliary agent is introduced before or after the active metal component is introduced, or simultaneously therewith, preferably simultaneously therewith; the alkali metal compound and the acidic organic auxiliary agent are both introduced in one step or in several steps.

15. The method according to claim 1, Features: The introduction method in step (3) is an impregnation method, and the impregnation method is one of equal volume impregnation, excess impregnation, step impregnation and co-impregnation, preferably equal volume co-impregnation.

16. The method according to claim 13, Features: In step (3), based on the final catalyst mass, the content of active metal components is: calculated as oxide, the content of Group VIB metal is 5wt% to 40wt%, preferably 12wt% to 30wt%, and the content of Group VIII metal is 2wt% to 12wt%, preferably 2wt% to 8wt%.

17. The method according to claim 1, Features: In step (3), the molar ratio of the acidic organic auxiliary agent to the Group VIII metal element in the active metal component is 0.05:1 to 5:1, preferably 0.1:1 to 1:

1.

18. The method according to claim 1, Features: In step (3), an organic substance is also introduced, and the organic substance is one or more of alcohols, ethers, sugars, ketones, phenols, aldehydes and lipids; the alcohols include one or more of ethylene glycol, propylene glycol, butylene glycol, glycerol and trimethylolethane; the ethers include one or more of diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol and polyethylene glycol; the sugars include one or more of glucose, fructose, lactose, maltose and sucrose.

19. The method according to claim 18, Features: The method of introducing the organic matter is any of the following methods: pre-impregnating the catalyst carrier with the organic matter, and then introducing the active metal component after drying; adding the organic matter to the impregnation solution of the active metal component and introducing it into the catalyst carrier together; After the active metal components are introduced, they are first dried and then the organic matter is introduced.

20. The method according to claim 1, Features: In step (3), other auxiliary agents may be introduced successively or simultaneously with the introduction of the active metal component. The auxiliary agent is a phosphorus-containing compound, such as one or more of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

21. The method according to claim 1, Features: The calcination in step (3) is one or two calcinations; the temperature of the first calcination is 70°C to 290°C, preferably 100°C to 280°C, and the time is 0.5h to 20h, preferably 1h to 6h; the second calcination is performed after the first calcination, the temperature is 350°C to 650°C, preferably 400°C to 500°C, and the time is 0.5h to 8h, preferably 1h to 4h; the calcination atmosphere is one or more of air atmosphere, inert atmosphere (such as nitrogen), reducing atmosphere (such as hydrogen), water vapor atmosphere and vacuum atmosphere.

22. A hydroprocessing catalyst prepared by the method according to any one of claims 1 to 21.

23. The hydroprocessing catalyst according to claim 22, Features: The catalyst comprises an active metal component, aluminum oxide and an alkali metal oxide; the content of the active metal component is 7wt.%~52wt.% in terms of oxide, the content of aluminum oxide is 40wt.%~90wt.%, and the content of alkali metal oxide is 0.1wt.%~2.0wt.% in terms of oxide; preferably, the content of the active metal component is 14wt.%~38wt.% in terms of oxide, the content of aluminum oxide is 55wt.%~85wt.%, and the content of alkali metal oxide is 0.2wt.%~1.4wt.% in terms of oxide.

24. A hydroprocessing method, Features: In the method, heavy oil and hydrogen-containing gas are contacted and reacted in the presence of any hydroprocessing catalyst according to claim 22 or 23.

25. In the hydroprocessing method according to claim 24, Features: The heavy oil is one or more of VGO, CGO, DAO and LCO.

26. In the hydroprocessing method according to claim 24, Features: The hydrogen-containing gas is hydrogen, or a mixture of hydrogen and other gases, and the volume content of hydrogen in the mixture is not less than 80%, preferably not less than 85%.

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