A method for preparing a high-performance hydrogenation catalyst

Abstract

This invention discloses a method for preparing a high-performance hydrotreating catalyst, comprising the following steps: (1) preparing alumina dry adhesive powder; the alumina dry adhesive powder, based on its dry weight, has an alkali metal content of 0.1wt%~2.0wt%, preferably 0.2wt%~1.2wt%, and more preferably 0.4wt%~1.0wt%; (2) the alumina dry adhesive powder in step (1) is shaped to prepare an alumina support; (3) the alumina support obtained in step (2) is introduced with alkali metal compounds, acidic organic additives, and active metal components, and then dried or dried and calcined to obtain a hydrotreating catalyst. This 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] This invention relates to a method for preparing a high-performance hydrotreating catalyst, and more particularly to a method for improving the activity and stability of a hydrotreating catalyst. Background Technology

[0002] Currently, carbon buildup is the main cause of deactivation of hydrogenation catalysts during industrial operation. Reducing the rate and amount of carbon buildup is a major direction in the research and development of hydrogenation catalysts. Most hydrogenation catalysts are prepared using the impregnation method, and alumina is a commonly used support material for these catalysts. To improve the activity and stability of hydrogenation catalysts, the alumina support needs to be chemically modified, such as by adding additives like silicon, phosphorus, fluorine, boron, zirconium, titanium, magnesium, gallium, vanadium, manganese, copper, and zinc. This modification serves two purposes: firstly, it modulates the acidity of alumina; secondly, it alters the interaction between the active component and alumina, thereby improving the thermal stability of alumina.

[0003] CN00110018.1 discloses a hydrogenation catalyst and its preparation method. The catalyst uses Group VIB and Group VIII metals as the active hydrogenation components, fluorine as the promoter, and simultaneously supports one or a mixture of boron, silicon, phosphorus, magnesium, titanium, zirconium, and gallium as promoters. This patent uses a co-precipitation method to prepare the hydrogenation catalyst. During the co-precipitation and extrusion processes, some active metals may enter the bulk phase or be covered by alumina particles, reducing the utilization rate of the active metals.

[0004] CN202011188999.9 discloses a catalyst and a method for heavy oil hydrotreating. The catalyst contains an alumina support and at least one metal component selected from Group VIII and at least one metal component selected from Group VIB supported on the support. The alumina support is prepared from a highly crystalline, large-grained boehmite. The boehmite has a relative crystallinity higher than 65%, 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 boehmite and calculated as oxides.

[0005] CN202011458545.9 discloses a phosphorus- and / or magnesium-containing heavy oil hydrotreating catalyst and a heavy oil hydrotreating method. The catalyst contains an alumina support and at least one metal component selected from Group VIII and at least one metal component selected from Group VIB supported on the support. The alumina support is prepared from a highly crystalline, large-grained phosphorus- and / or magnesium-containing boehmite. The boehmite has a relative crystallinity higher than 55%, a grain size of 2-5 nm, and a sodium content of no more than 0.08% by weight based on the dry weight of the boehmite and calculated as oxides.

[0006] The aforementioned existing technologies have extremely stringent requirements for the sodium content in the alumina dry gel used in hydrotreating catalysts, with a general requirement of less than 0.08 wt.% sodium oxide content. Furthermore, the anti-carbon deposition performance and long-term activity stability of the hydrotreating catalysts need to be further improved. Summary of the Invention

[0007] To address the problems existing in the prior art, the present invention provides a method for preparing a high-performance 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.

[0008] The first aspect of this invention provides a method for preparing a high-performance hydrogenation catalyst, comprising the following steps:

[0009] (1) Preparation of alumina dry adhesive powder; the alumina dry adhesive powder, based on its dry weight, has an alkali metal content of 0.1wt%~2.0wt% calculated as oxides, preferably 0.2wt%~1.2wt%, more preferably 0.4wt%~1.0wt%;

[0010] (2) The alumina dry adhesive powder in step (1) is molded to prepare an alumina carrier;

[0011] (3) The alumina support obtained in step (2) is introduced with alkali metal compounds, acidic organic additives and active metal components, and then dried or dried and calcined to obtain a hydrogenation catalyst.

[0012] In the above-mentioned method for preparing high-performance hydrogenation catalyst, alkali metal is introduced in step (1) through alumina dry gel powder, and alkali metal is introduced in step (3) through alkali metal compound. Based on alkali metal oxide, the mass ratio of alkali metal introduced in step (1) to alkali metal introduced in step (3) is 0.5~20, preferably 1~10, and more preferably 1~5.

[0013] In the above-mentioned method for preparing high-performance hydrogenation catalyst, the alkali metal in step (1) is one or more of lithium, sodium, potassium, rubidium and cesium, preferably potassium and / or sodium, and more preferably sodium.

[0014] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the dry basis content of the alumina dry adhesive powder in step (1) is 60wt%~80wt%, preferably 65wt%~75wt%.

[0015] In the above-mentioned method for preparing high-performance hydrogenation catalysts, the method for preparing alumina dry adhesive powder in step (1) is as follows:

[0016] S1. An aluminum-containing acidic solution and an alkaline solution undergo a gelation reaction to obtain an alumina dry adhesive powder precursor.

[0017] S2. The alumina dry adhesive powder precursor obtained in step S1 is subjected to aging, washing, filtration and drying to obtain the final alumina dry adhesive powder.

[0018] Further, in step S1, the concentration of the aluminum-containing acidic solution is 0.5g~10g / 100mL, preferably 2g~6g / 100mL; and the concentration of the alkaline solution is 5g~30g / 100mL, preferably 10g~25g / 100mL.

[0019] Furthermore, in step S1, the gelation temperature is 30℃~95℃, preferably 50℃~80℃; by adjusting the volume ratio of the aluminum-containing acidic solution to the alkaline solution, the gelation pH value is made to be 4.5~10.0, preferably 5.5~9.0.

[0020] Furthermore, the aluminum-containing acidic solution mentioned in step S1 includes one or more of aluminum sulfate solution, aluminum nitrate solution, and aluminum chloride solution.

[0021] Furthermore, the alkaline solution mentioned in step S1 is a soluble solution containing alkali metals, such as one or more of sodium aluminate solution, potassium aluminate, sodium hydroxide, and potassium hydroxide.

[0022] Further, the alkaline solution mentioned in step S1 is a soluble solution that does not contain alkali metals, including but not limited to one or more of ammonia, ammonium carbonate, and ammonium bicarbonate; the alkali metal element is introduced in step S2, specifically by introducing an alkali metal-containing substance during the aging and / or washing process mentioned in step S2; the alkali metal-containing substance includes but is not limited to one or more of sodium carbonate, sodium bicarbonate, sodium acetate, and sodium citrate.

[0023] Furthermore, the specific operation process of introducing alkali metal substances during the aging process described in step S2 is as follows: alkali metal substances are added during the aging period of 0.3h to 3h, and then aging continues for another 0.3h to 5h, followed by the washing process; alkali metal substances can be added in solid or liquid form, preferably in liquid form, and the addition time is 1min to 10min.

[0024] Furthermore, the specific operation process for introducing alkali metal substances during the washing process described in step S2 is as follows: For intermittent washing processes, alkali metal substances can be added at any point during the washing process; for continuous washing processes, alkali metal substances can be added at any point during the washing process; alkali metal substances can be added in solid or liquid form, preferably in liquid form, and the addition time is 1 min to 5 min.

[0025] Further, the operating conditions for the aging process in step S2 are as follows: the aging temperature is 30℃~95℃, preferably 50℃~90℃; the aging control pH value is 5.5~10.0, preferably 5.5~9.5; the aging time is controlled at 0.5h~8h, preferably 1.5h~4.5h.

[0026] Furthermore, the drying conditions described in step S2 are as follows: it can be static drying or dynamic drying, etc., ensuring that the dry basis of the alumina dry adhesive powder is 60wt%~80wt%, the drying temperature is 60℃~200℃, and the drying time is 0.5h~10.0h.

[0027] In the above-mentioned method for preparing high-performance hydrogenation catalyst, the molding process in step (2) can be any of the molding methods in the prior art. Specifically, in this invention, the specific operation steps are as follows: alumina dry adhesive powder is mixed evenly with adhesive solvent and / or binder, and then kneaded and / or rolled, shaped, dried and calcined to obtain an alumina support.

[0028] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the colloidal solvent in step (2) is one or more of organic acids, inorganic acids and compounds that can ionize H+, such as nitric acid, oxalic acid, acetic acid and propionic acid.

[0029] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the binder in step (2) is generated by the reaction of aluminum hydroxide and / or silicon oxide with nitric acid.

[0030] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, in step (2), an extrusion aid can be added during molding to improve fluidity; the extrusion aid is not particularly limited and can be at least one of the extrusion aids known in the art, such as alcohol, cellulose and guar gum powder.

[0031] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the drying and calcination in step (2) adopt the operating conditions of existing technology: the drying temperature is 50℃~200℃, preferably 110℃~160℃; the drying time is 0.5h~20h, preferably 1h~6h; the calcination temperature is 400℃~1000℃, preferably 450℃~800℃; and the calcination time is 0.5h~20h, preferably 1h~6h.

[0032] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the alkali metal compound in step (3) includes one or more of lithium-containing compounds, sodium-containing compounds, and potassium-containing compounds, preferably sodium-containing compounds; 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 this 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.

[0033] In the above-mentioned method for preparing high-performance hydrogenation catalysts, the acidic organic auxiliaries in step (3) refer to those that can ionize H+ in aqueous solution. + The ionic compound, wherein the acidic organic auxiliary agent is one or more of nitrogen-containing organic compounds, sulfur-containing organic compounds, and oxygen-containing organic compounds; the nitrogen-containing organic compound is an organic compound containing at least one covalent nitrogen atom, such as at least one of ethylenediaminetetraacetic acid (EDTA), nitric acid triacetic acid (NTA), and cycloethylenediaminetetraacetic acid; the sulfur-containing organic compound is an organic compound containing at least one covalent sulfur atom, such as mercaptoacetic 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.

[0034] In the above-mentioned method for preparing high-performance hydrogenation 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.

[0035] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, there is no restriction on the order in which the alkali metal compound, the acidic organic promoter, and the active metal component are introduced into the alumina support in step (3); the alkali metal compound is introduced before or after the active metal component, or simultaneously, preferably simultaneously with the active metal component; the acidic organic promoter is introduced before or after the active metal component, or simultaneously, preferably simultaneously with the active metal component; the alkali metal compound and the acidic organic promoter can be introduced in one step or in several steps. Specifically, in this invention, the following order can be adopted: first introduce the alkali metal compound, then introduce the acidic organic promoter, and finally introduce the active metal component; or first introduce the acidic organic promoter, then introduce the alkali metal compound, and finally introduce the active metal component; or first introduce the alkali metal compound and the acidic organic promoter simultaneously, then introduce the active metal component; or first introduce the alkali metal compound, then simultaneously introduce the acidic organic promoter and the active metal component.

[0036] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the introduction method in step (3) is impregnation, which is well known to those skilled in the art. Impregnation can be equal volume impregnation or excessive impregnation, stepwise impregnation or co-impregnation, with equal volume co-impregnation being preferred.

[0037] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, in step (3), based on the final catalyst mass, the content of active metal components is as follows: based on oxides, 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%.

[0038] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the molar ratio of the acidic organic auxiliary agent 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.

[0039] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, step (3) also introduces organic matter. The organic matter can be alcohols, such as ethylene glycol, propylene glycol, butanediol, glycerol, trimethylolethane, etc.; ethers, such as diethylene glycol, dipropylene glycol, triethylene glycol, tributylene glycol, tetraethylene glycol, polyethylene glycol, etc.; sugars, such as glucose, fructose, lactose, maltose, sucrose, etc.; or ketones, phenols, aldehydes and lipids. The organic matter can be introduced in the following ways: the organic matter can be pre-impregnated on the catalyst support, dried, and then the active metal component can be introduced; the organic matter can also be added to the impregnation solution of the active metal component and introduced together with it on the catalyst support; or the active metal component can be introduced, dried first, and then the organic matter can be introduced. The drying temperature is generally 60-150℃, and the treatment time is generally 0.5-10 hours.

[0040] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, other auxiliary agents may be introduced in step (3) before or during the introduction of the active metal component. The auxiliary agents are phosphorus-containing compounds, such as one or more of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

[0041] In the preparation method of the above-mentioned high-performance hydrogenation catalyst, the calcination in step (3) is a single calcination or a double calcination; the single calcination is a low-temperature treatment process with a temperature of 70℃~290℃, preferably 100℃~280℃, and a time of 0.5h~20h, preferably 1h~6h; the double calcination is a high-temperature treatment after the above-mentioned low-temperature calcination, with a temperature of 350℃~650℃, preferably 400℃~500℃, and a time of 0.5h~8h, preferably 1h~4h. The calcination atmosphere is one or more of the following: air atmosphere, inert atmosphere (such as nitrogen), reducing atmosphere (such as hydrogen), water vapor atmosphere, and vacuum atmosphere.

[0042] A second aspect of the present invention provides a hydrogenation catalyst obtained by the above-described preparation method. The catalyst comprises an active metal component, alumina, and an alkali metal oxide; the active metal component content, calculated as oxide, is 7 wt.% to 52 wt.%, the alumina content is 40 wt.% to 90 wt.%, and the alkali metal oxide content, calculated as oxide, is 0.1 wt.% to 2.0 wt.%; preferably, the active metal component content, calculated as oxide, is 14 wt.% to 38 wt.%, the alumina content is 55 wt.% to 85 wt.%, and the alkali metal oxide content, calculated as oxide, is 0.2 wt.% to 1.4 wt.%.

[0043] A third aspect of the present invention provides a hydrotreating method in which heavy oil and hydrogen-containing gas react in contact under the presence of the above-mentioned hydrotreating catalyst.

[0044] In the above-mentioned hydrotreating method, the heavy oil is one or more of VGO, CGO, DAO and LCO.

[0045] In the above hydrogenation treatment method, the hydrogen-containing gas is hydrogen or a mixture of hydrogen and other gases, wherein the volume content of hydrogen in the mixture is not less than 80%, preferably not less than 85%.

[0046] In the above-mentioned hydrogenation treatment method, the reaction conditions are as follows: total reaction pressure 6.0 MPa ~ 20.0 MPa, volume hourly space velocity 0.3 h⁻¹. -1 ~3.0 h -1 The hydrogen-to-oil ratio is 400:1 to 1800:1, and the reaction temperature is 300℃ to 420℃.

[0047] Compared with the prior art, the present invention has the following advantages:

[0048] The alkali metal content in the alumina dry gel used in the preparation of the hydrotreating catalyst is 0.1 wt.%~1.5 wt.% as oxides, which is far higher than the sodium content in the alumina dry gel used in the existing hydrotreating catalyst (generally less than 0.08 wt.%), thus reducing the number of washing cycles and the amount of washing water used.

[0049] In the preparation of hydrotreating catalysts, alkali metal elements are introduced stepwise. First, an appropriate amount of alkali metal element is introduced through alumina dry adhesive powder. Then, alkali metal compounds and acidic organic additives are introduced further during catalyst preparation. The synergistic effect of these two agents can adjust the acidity and alkalinity of the support and the metal solution, reduce the viscosity of the active metal solution, and thus improve the surface properties of the catalyst. This not only effectively prevents catalyst carbon deposition but also significantly improves catalyst activity, slows down the deactivation rate of the catalyst during heavy oil hydrotreating, and greatly enhances stability. Implementation

[0050] The technical features of the present invention are further described below through embodiments, but it should not be considered that the present invention is limited to these embodiments. The percentages mentioned are weight percentages.

[0051] The specific surface area and pore volume of the samples were determined using a Micromeritics ASAP2405 physical adsorption instrument, with liquid nitrogen as the adsorbate and an adsorption temperature of -196℃. The Na₂O content in the catalyst was determined using a Thermo Fisher IRIS Advantage instrument. In this invention, the dry basis method involves taking an appropriate amount of sample (m₁), calcining it at 500℃ for 3 hours, and then measuring its mass (m₂). The percentage of the mass of the calcined sample compared to the uncalcined sample is calculated as m₂ / m₁ × 100%, which is the dry basis of the sample.

[0052] The alumina dry adhesive powder was obtained using the preparation method described in the invention summary. Table 1 shows the properties of alumina dry adhesive powders with different sodium oxide contents. F1 was prepared by neutralizing sodium aluminate and aluminum sulfate to form a gel. 1L of deionized water was added to a container, and the temperature was raised to 65℃. Simultaneously, an aluminum sulfate solution containing 4g / 100mL Al2O3 and a sodium aluminate solution containing 18g / 100mL Al2O3 were added, controlling the pH at 7.8, with a feeding time of 60min. After stopping the feeding, the temperature was raised to 75℃, and after aging for 30min, a Na2CO3 solution with a concentration of 12g Na2O / 100mL was added. The temperature was controlled at 75℃, and the pH at 9.0. Aging continued for 3h, followed by filtration. After washing once, the filter cake was dried at 110℃ for 7h, and then pulverized until more than 95% of the particles were smaller than 180 mesh, yielding dry adhesive powder F1.

[0053] F2 is formed by neutralizing aluminum chloride and ammonia water to form a gel. 1L of deionized water is added to a container, and the temperature is raised to 75℃. Simultaneously, an aluminum chloride solution containing 6g / 100mL of Al2O3 and an ammonia solution containing 12% NH3 are added, controlling the pH at 8.5 for 60 minutes. Aging is then carried out under the above temperature and pH conditions. After 60 minutes of aging, a sodium bicarbonate solution with a concentration of 5g Na2O / 100mL is added, calculated based on a sodium oxide content of 2.5wt% in Al2O3, for 5 minutes. After completion, the pH is adjusted to 9.0 with ammonia water, and aging continues for another 60 minutes. After washing once, the mixture is filtered. The filter cake is dried at 120℃ for 6 hours and then pulverized until at least 95% of the particles are smaller than 180 mesh, yielding dry gel powder F2.

[0054] F3 is formed by neutralizing aluminum sulfate and ammonia water to form a gel. 1L of deionized water is added to a container, and the temperature is raised to 60℃. Simultaneously, an aluminum sulfate solution containing 5g / 100mL Al2O3 and an ammonia solution containing 10% NH3 are added, controlling the pH at 8.0 for 60 minutes. The mixture is then aged under the above temperature and pH conditions. After aging for 120 minutes, it is filtered, and the filter cake is pulped and washed. A sodium carbonate solution with a concentration of 10g Na2O / 100mL is added, calculated based on a sodium oxide content of 0.5wt% in Al2O3, for 3 minutes. Stirring and washing are continued for 60 minutes, followed by filtration. The filter cake is dried at 120℃ for 6 hours and then pulverized until at least 95% of the particles are smaller than 180 mesh, yielding dry gel powder F3.

[0055] F4 is prepared by neutralizing aluminum chloride and ammonia water to form a gel. 1L of deionized water is added to a container, and the temperature is raised to 70℃. Simultaneously, an aluminum chloride solution containing 5g / 100mL of Al2O3 and an ammonia solution containing 13% NH3 are added, maintaining the pH at 7.5 for 60 minutes. The mixture is then aged under the above temperature and pH conditions. After 3 hours of aging, it is filtered, washed once, and the filter cake is dried at 120℃ for 6 hours. Finally, it is pulverized until at least 95% of the particles are smaller than 180 mesh, yielding dry gel powder F4.

[0056] Table 1 Properties of alumina dry adhesive powder with different sodium contents

[0057]

[0058] Example 1

[0059] Take 300g of dry adhesive powder F1, add 8g of guar gum powder, mix well, and then slowly and evenly add 230g of nitric acid aqueous solution (containing 8.0g of nitric acid) over 8 minutes. Knead for 25 minutes, then extrude using a 1.7mm diameter clover perforated plate. Dry at 110℃ for 4 hours, then calcine at 500℃ for 4 hours. The calcined carrier is designated Z1. Carriers Z2, Z3, and Z4 are prepared using the same method with dry adhesive powders F2, F3, and F4, respectively.

[0060] Example 2

[0061] The calcined carrier strips Z1, Z2 and Z3 were used as carriers in the example. When Z1 was used as carrier, the impregnation solution was prepared using Mo, Ni, P solution, mercaptoacetic acid, propylene glycol and sodium nitrate. The molar ratio of mercaptoacetic acid, propylene glycol and Ni element was 0.3:0.4:1.

[0062] When Z2 is used as a carrier, an impregnation solution is prepared using Mo, Ni, P solution, citric acid and sodium citrate, with a molar ratio of citric acid to Ni element of 0.5:1.

[0063] When Z3 is used as a carrier, an impregnation solution is prepared using Mo, Ni, P solution, nitric acid triacetic acid and sodium bicarbonate, with a molar ratio of nitric acid triacetic acid to Ni element of 0.6:1.

[0064] The catalysts were obtained by using the equal volume impregnation method, impregnating for 3 hours, drying at 120℃ for 6 hours, and calcining at 430℃ for 2 hours, and were denoted as C1, C2, and C3, respectively.

[0065] Comparative Example 1

[0066] The calcined support strip Z4 was used as a comparative support, and the preparation process was the same as that in Example 2 when Z1 was used as the support. The resulting catalyst was denoted as DC1.

[0067] Comparative Example 2

[0068] The calcined support strip Z2 was used as a comparative support. An impregnation solution was prepared using Mo, Ni, and P solutions. The remaining conditions were the same as those in Example 2 when Z2 was used as the support. The resulting catalyst was denoted as DC2.

[0069] Comparative Example 3

[0070] The calcined support strip Z2 was used as a comparative support. An impregnation solution was prepared using Mo, Ni, P solution and citric acid. The remaining conditions were the same as those in Example 2 when Z2 was used as the support. The resulting catalyst was denoted as DC3.

[0071] Comparative Example 4

[0072] The calcined support strip Z2 was used as a comparative support. An impregnation solution was prepared using Mo, Ni, P solution and sodium citrate. The remaining conditions were the same as those in Example 2 when Z2 was used as the support. The resulting catalyst was denoted as DC4.

[0073] Table 2. Metal composition of the prepared Mo and Ni catalysts

[0074]

[0075] Example 3

[0076] This example is an experiment to evaluate the activity of the catalyst.

[0077] Catalyst activity evaluation experiments were conducted on a 100 ml small-scale hydrogenation apparatus. The catalyst was pre-sulfurized prior to the evaluation. The evaluation conditions were a total reaction pressure of 14.5 MPa and a volume hourly space velocity (VHSV) of 1.0 h⁻¹. -1 The hydrogen-to-oil ratio was 800:1, and the reaction temperature was 380℃. The properties of the feedstock oil used in the activity evaluation experiment are shown in Table 3, and the activity evaluation results are shown in Table 4. As can be seen from the data in the tables, the hydrotreating catalyst prepared using this invention exhibits significantly improved hydrodenitrogenation activity and a marked reduction in carbon deposit content, which is beneficial for long-term stable operation.

[0078] Table 3 Properties of Feed Oil

[0079]

[0080] Table 4 Catalyst activity evaluation results

[0081]

Claims

1. A process for the preparation of a high performance hydroprocessing catalyst characterized by: The method comprises the following steps: (1) preparing an alumina dry gel powder; the alumina dry gel powder has an alkali metal content of 0.1wt%-2.0wt% in terms of oxides based on its dry weight; (2) preparing an alumina carrier by molding the alumina dry gel powder in step (1); (3) introducing an alkali metal compound, an acidic organic additive and an active metal component into the alumina carrier obtained in step (2), and then drying or drying and calcining to obtain a hydroprocessing catalyst; the mass ratio of the alkali metal introduced in step (1) to the alkali metal introduced in step (3) is 0.5-20 in terms of alkali metal oxides; the preparation method of the alumina dry gel powder in step (1) comprises the following steps: S1, performing a gelation reaction on an aluminum-containing acidic solution and a basic solution to obtain an alumina dry gel powder precursor; S2, performing aging, washing, filtering and drying on the alumina dry gel powder precursor obtained in step S1 to obtain the final alumina dry gel powder; the aluminum-containing acidic solution in step S1 comprises one or more of aluminum sulfate solution, aluminum nitrate and aluminum chloride solution; the basic solution in step S1 is a soluble solution containing alkali metal, and the soluble solution containing alkali metal comprises one or more of sodium aluminate solution, potassium aluminate, sodium hydroxide and potassium hydroxide; alternatively, the basic solution in step S1 is a soluble solution not containing alkali metal, and the soluble solution not containing alkali metal comprises one or more of ammonia, ammonium carbonate and ammonium bicarbonate; an alkali metal-containing substance is introduced in the aging process in step S2; the alkali metal-containing substance comprises one or more of sodium carbonate, sodium bicarbonate, sodium acetate and sodium citrate; the specific operation process of introducing the alkali metal-containing substance in the aging process in step S2 is as follows: the alkali metal-containing substance is added within 0.3h-3h of aging, and then the aging is continued for 0.3h-5h, and then the washing process is entered; the alkali metal-containing substance is added in solid or liquid form, and the addition time is 1min-10min; the alkali metal in step (1) is sodium; the alkali metal compound in step (3) is a sodium-containing compound; the active metal component in step (3) is at least one of Group 6B and Group 8 metals; the Group 6B metal is Mo, and the Group 8 metal is Ni; the content of the active metal component in step (3) is as follows: the content of the Group 6B metal is 5wt%-40wt% in terms of oxides, and the content of the Group 8 metal is 2wt%-12wt% in terms of oxides based on the mass of the final catalyst; the active metal component is introduced before or simultaneously with the additive in step (3); the additive is a phosphorus-containing compound.

2. The method of claim 1, wherein: the alkali metal content of the alumina dry gel powder in step (1) is 0.2wt%-1.2wt% in terms of oxides based on its dry weight.

3. The method of claim 1, wherein: the alkali metal content of the alumina dry gel powder in step (1) is 0.4wt%-1.0wt% in terms of oxides based on its dry weight.

4. The method of claim 1, wherein: the mass ratio of the alkali metal introduced in step (1) to the alkali metal introduced in step (3) is 1-10 in terms of alkali metal oxides.

5. The method of claim 4, wherein: The mass ratio of the alkali metal introduced in step (1) to the alkali metal introduced in step (3) is 1-5, based on alkali metal oxides.

6. The method of claim 1, wherein: The dry-basis content of the alumina dry gel powder in step (1) is 60wt%-80wt%.

7. The method of claim 6, wherein: The dry-basis content of the alumina dry gel powder in step (1) is 65wt%-75wt%.

8. The method of claim 1, wherein: The specific operation steps of the shaping in step (2) are as follows: the alumina dry gel powder is uniformly mixed with a peptizing agent and / or a binder, and then is subjected to mixing and kneading, and / or rolling and pressing, shaping, drying, and calcination to obtain an alumina carrier.

9. The method of claim 1, wherein: The sodium-containing compound in step (3) is an inorganic sodium-containing compound and / or an organic sodium-containing compound.

10. The method of claim 9, wherein: The inorganic sodium-containing compound in step (3) includes one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium sulfate, sodium borate, sodium chloride, sodium phosphate, sodium polyphosphate, and sodium silicate.

11. The method of claim 9, wherein: The organic sodium-containing compound in step (3) includes one or more of sodium acetate, sodium citrate, sodium oxalate, and sodium petroleum sulfonate.

12. The method of claim 1, wherein: The acidic organic additive in step (3) is one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound, and an oxygen-containing organic compound.

13. The method of claim 12, wherein: The nitrogen-containing organic compound in step (3) is at least one of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and cyclen; the sulfur-containing organic compound is mercaptoacetic acid and / or mercapto-propanoic acid; and the oxygen-containing organic compound is at least one of acetic acid, oxalic acid, malonic acid, tartaric acid, malic acid, and citric acid.

14. The method of claim 1, wherein: The alkali metal compound in step (3) is introduced before or after the introduction of the active metal component or is introduced simultaneously with the active metal component; the acidic organic additive is introduced before or after the introduction of the active metal component or is introduced simultaneously with the active metal component; and the alkali metal compound and the acidic organic additive are introduced in one step or in several steps.

15. The method of claim 14, wherein: The alkali metal compound in step (3) is introduced simultaneously with the active metal component; and the acidic organic additive is introduced simultaneously with the active metal component.

16. The method of claim 1, wherein: The introduction method in step (3) is an impregnation method, and the impregnation method is one of equal-volume impregnation, excess impregnation, stepwise impregnation, and co-impregnation.

17. The method of claim 16, wherein: The impregnation method in step (3) is equal-volume co-impregnation.

18. The method of claim 1, wherein: In step (3), the content of the active metal component is 12wt%-30wt% of Group 6B metal and 2wt%-8wt% of Group 8 metal, based on oxides, with reference to the mass of the final catalyst.

19. The method of claim 1, wherein: The molar ratio of the acidic organic additive to the Group 8 metal element in the active metal component in step (3) is 0.05:1-5:

1.

20. The method of claim 19, wherein: The molar ratio of the acidic organic additive to the Group 8 metal element in the active metal component in step (3) is 0.1:1-1:

1.

21. The method of claim 1, wherein: 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; and the sugars include one or more of glucose, fructose, lactose, maltose, and sucrose.

22. The method of claim 21, wherein: The organic matter is introduced by any one of the following ways: the organic matter is used to pre-impregnate the catalyst carrier, and after drying treatment, the active metal component is introduced; the organic matter is added to the impregnation solution of the active metal component, and introduced together into the catalyst carrier; After the introduction of the active metal component, the organic matter is introduced after drying treatment.

23. The method of claim 1, wherein: The phosphorus-containing compound in step (3) is one or more of phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.

24. The method of claim 1, wherein: The calcination in step (3) is one-time calcination or two-time calcination; the one-time calcination temperature is 70-290℃, and the time is 0.5-20h; the two-time calcination is after the one-time calcination, and the temperature is 350-650℃, and the time is 0.5-8h; the calcination atmosphere is one or more of air atmosphere, inert atmosphere, reducing atmosphere, water vapor atmosphere and vacuum atmosphere.

25. The method of claim 24, wherein: The one-time calcination temperature in step (3) is 100-280℃, and the time is 1-6h; the two-time calcination is after the one-time calcination, and the temperature is 400-500℃, and the time is 1-4h.

26. A hydroprocessing catalyst prepared by the method of any one of claims 1-25.

27. The hydroprocessing catalyst of claim 26, wherein: The catalyst comprises an active metal component, alumina and alkali metal oxide; the content of the active metal component is 7-52wt.% in terms of oxide, the content of alumina is 40-90wt.%, and the content of alkali metal oxide is 0.1-2.0wt.% in terms of oxide.

28. The hydroprocessing catalyst of claim 27, wherein: The content of the active metal component is 14-38wt.% in terms of oxide, the content of alumina is 55-85wt.%, and the content of alkali metal oxide is 0.2-1.4wt.% in terms of oxide.

29. A hydroprocessing process characterized by: The method is carried out in the presence of the hydroprocessing catalyst of any one of claims 26-28, and heavy oil and hydrogen-containing gas are contacted to react.

30. The hydroprocessing process of claim 29, wherein: The heavy oil is one or more of VGO, CGO, DAO and LCO.

31. The hydroprocessing process of claim 29 wherein: 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%.

32. The hydroprocessing process of claim 31 wherein: The volume content of hydrogen in the mixture is not less than 85%.

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