Hydrotreatment method of inferior oil

Abstract

The invention provides a hydrotreating method of inferior oil. According to the method, a fixed bed hydrogenation process is adopted, in the presence of hydrogen, the inferior oil is sequentially contacted with at least one hydrodesulfurization catalyst and at least one hydrodenitrification catalyst for hydrogenation reaction, and hydrogenated oil is obtained; the hydrodesulfurization catalyst comprises a carrier and an active component, preferably an auxiliary agent, the carrier comprises a silicon modified nickel-aluminum alloy, the active component is organic molybdenum, preferably molybdenum alkyl dithiophosphate and / or molybdenum alkyl dithiocarbamate, and the auxiliary agent is organic zinc; the hydrodenitrification catalyst comprises a carrier and an active component, the carrier comprises a silicon modified nickel-aluminum alloy, the active component comprises organic molybdenum, and the organic molybdenum is preferably molybdenum alkyl dithiophosphate and / or molybdenum alkyl dithiocarbamate; preferably, the hydrodenitrogenation catalyst comprises an auxiliary agent organic gallium. The hydrotreating method has very strong desulfurization and denitrification effects on inferior secondary processing oil.

Description

Technical Field

[0001] The invention belongs to the field of petrochemical industry and relates to a hydrogenation treatment method for inferior secondary processed oil. Background Art

[0002] Delayed coking, ebullating bed hydrogenation, catalytic cracking and other processing technologies produce a large amount of low-quality secondary processed oil with high aromatic content, high sulfur and nitrogen content. These oils need further hydrogenation treatment to meet the use standards. For the processing of low-quality secondary processed raw materials, certain catalyst grading technology is required. The basic principle of grading is that the catalyst particles are from large to small, the average pore size is from large to small, and the catalyst activity is from low to high along the direction of the reaction liquid phase flow.

[0003] CN113862027A discloses a heavy oil hydroprocessing catalyst grading method, wherein the total amount of hydroxyl groups in the carriers of each loaded catalyst gradually increases, and the content ratio of acidic hydroxyl groups to basic hydroxyl groups gradually increases; the grading method enables the heavy oil hydroprocessing catalyst used in the aforementioned heavy oil hydroprocessing catalyst grading to have excellent reaction activity and reaction stability, and can effectively extend the operation cycle of the heavy oil hydroprocessing unit. However, the catalyst with excessively strong acidity at the rear of the grading causes a relatively serious coking and carbon deposition phenomenon when treating inferior oil products, especially inferior oil products with a high aromatic content.

[0004] CN111196935A discloses a hydroprocessing catalyst grading method, wherein the MoS2 in the hydrodemetallization catalyst after sulfidation is mainly dispersed in single layer and double layer, and the MoS2 in the hydrodesulfurization catalyst after sulfidation is mainly dispersed in multiple layers. The catalyst grading combination obtained by this method has high demetallization, carbon residue removal, desulfurization, and denitrogenation activity and stability, and a long service life. However, during grading, the metal utilization rate of the multi-layer molybdenum disulfide is low, which has certain difficulties in deep hydrodenitrogenation and aromatic saturation of inferior oil products. Summary of the invention

[0005] The invention provides a hydrogenation treatment method for inferior oil, which has strong desulfurization and denitrification effects on inferior secondary processed oil.

[0006] The present invention provides a method for hydrogenating inferior oil, which adopts a fixed bed hydrogenation process, wherein the inferior oil is contacted with at least one hydrodesulfurization catalyst and at least one hydrodenitrogenation catalyst in sequence in the presence of hydrogen to carry out a hydrogenation reaction, thereby obtaining hydrogenated oil;

[0007] The hydrodesulfurization catalyst comprises a carrier and an active component, preferably a promoter, wherein the carrier comprises a silicon-modified nickel-aluminum alloy, the active component is an organic molybdenum, preferably an alkyl dithiophosphate molybdenum and / or an alkyl dithiocarbamate molybdenum, and the promoter is an organic zinc, preferably an alkyl dithiophosphate zinc and / or an alkyl dithiocarbamate zinc;

[0008] The hydrodenitrogenation catalyst comprises a carrier and an active component, wherein the carrier comprises a silicon-modified nickel-aluminum alloy, and the active component comprises organic molybdenum, wherein the organic molybdenum is preferably alkyl dithiophosphate molybdenum and / or alkyl dithiocarbamate molybdenum; preferably, the hydrodenitrogenation catalyst comprises an auxiliary agent organic gallium.

[0009] Further, in the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst, the alkyl dithiophosphate molybdenum is independently selected from one or more of diisopropyl dithiophosphate molybdenum, dibutyl dithiophosphate molybdenum oxysulfide, and diisooctyl dithiophosphate molybdenum. The alkyl dithiocarbamate molybdenum is independently selected from one or more of dibutyl dithiocarbamate molybdenum and diisopropyl dithiocarbamate molybdenum.

[0010] Furthermore, in the hydrodesulfurization catalyst, the alkyl zinc dithiophosphate is selected from one or more of dibutyl zinc dithiophosphate, isodecyl zinc dithiophosphate, diisooctyl zinc dithiophosphate, and di(tetradecyl) zinc dithiophosphate. The alkyl zinc dithiocarbamate is selected from one or more of diethyl zinc dithiocarbamate, ethylphenyl zinc dithiocarbamate, and dibutyl zinc dithiocarbamate.

[0011] Furthermore, when a metallic zinc organic compound is used in the hydrodesulfurization catalyst, since the metallic zinc organic compound and the sulfur-containing organic molybdenum compound have similar physical and chemical properties, their distribution patterns and distribution positions on the surface of the nickel-aluminum alloy carrier are similar, which avoids the phase separation of zinc and molybdenum, making the hydrogenation effect, especially the hydrodesulfurization effect, more obvious.

[0012] Furthermore, in the hydrodenitrogenation catalyst, the organic gallium is one or more of triethyl gallium, triisopropyl gallium, tri-tert-butyl gallium, gallium acetylacetonate, ethoxy gallium, and gallium isopropoxide. With an organic gallium compound as an auxiliary agent, since gallium and aluminum belong to the same group of elements, they can also be combined with nickel and interact with the loaded organic molybdenum species, which is beneficial to the improvement of hydrogenation activity. At the same time, organic gallium and nitrogen can form a strong Ga-N triple bond, which has a very strong interaction with the nitride in the oil product, which is very beneficial to the improvement of hydrodenitrogenation activity.

[0013] Further, in the hydrodesulfurization catalyst or the hydrodenitrogenation catalyst, the silicon-modified nickel-aluminum alloy is an organosilicon-modified nickel-aluminum alloy, and the organosilicon is specifically an alkoxysilane. Further preferably, the alkoxysilane is selected from at least one of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane and octyltriethoxysilane. With this preferred embodiment, the catalyst uses a silicon-modified nickel-aluminum alloy as a catalytic substrate to provide a large amount of activated hydrogen, which can provide conditions for hydrogen transfer, and cooperates with organic molybdenum, especially dialkyl dithiophosphate molybdenum and / or alkyl dithiocarbamate molybdenum as an active component, and the sulfur-containing molybdenum species is combined with nickel to form more Ni-Mo-S active sites, providing hydrogenation centers, and further improving the utilization rate of molybdenum and the hydrogenation activity of the catalyst.

[0014] Furthermore, in the present invention, the nickel-aluminum alloy has a wide selection range. The nickel-aluminum alloy has a conventional definition in the art, and its source is not particularly limited. It can be purchased commercially or made by itself, and any feasible method can be used to make it by itself.

[0015] Further, in the present invention, the amount of nickel and aluminum in the nickel-aluminum alloy is selected in a wide range. Preferably, based on the total amount of the nickel-aluminum alloy, the aluminum content is 50wt% to 95wt% and the nickel content is 5wt% to 50wt%. More preferably, based on the total amount of the nickel-aluminum alloy, the aluminum content is 70wt% to 90wt% and the nickel content is 10wt% to 30wt%. By adopting this preferred embodiment, not only can nickel and sulfur-containing organic molybdenum compounds be effectively combined to improve the hydrogenation performance of the catalyst, but the nickel content in the nickel-aluminum alloy is not too high.

[0016] Furthermore, based on the total dry weight of the hydrodenitrogenation catalyst or the hydrodesulfurization catalyst, the content of Al calculated as aluminum oxide is 62% to 84%, preferably 68% to 80%, the content of Ni calculated as nickel oxide is 8% to 18%, preferably 9% to 15%, the content of molybdenum calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, the content of silicon calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%, and the content of the additive calculated as metal oxide is 1.5% to 7%, preferably 2% to 5.5%.

[0017] Furthermore, in the present invention, the dry basis measurement method of the hydrodenitrogenation catalyst or the hydrodesulfurization catalyst is as follows: in an air atmosphere, the catalyst is heated from 120°C at 3.0°C per minute to 420°C, and then roasted for 4.0 hours, then heated at 3.0°C per minute and roasted at 550°C for 2.0 hours, and the obtained object is analyzed in a dry environment.

[0018] Furthermore, the content of each component in the dry basis can be analyzed by atomic emission spectrometry (ICP-AES), specifically, the equipment is OPTIMA 7000DV atomic emission spectrometer produced by PE. In a typical solution preparation process, 0.1g of sample is dissolved in a mixed solution with a volume ratio of 3HCl:1HNO3:0.5HF, and then the mixed solution is diluted to a certain volume with deionized water, so that the content of the element to be measured in the solution is between 1-10ppm, so as to increase the accuracy of the measurement data.

[0019] Furthermore, the analysis method of the metal organic compound in the catalyst can be used to analyze the product by XPS, and the test conditions of the XPS include: light source: Mg Kα, energy step: 0.05eV, scanning range: 200-250eV (molybdenum), 280-300eV (carbon). When analyzing the valence state of molybdenum, it is considered that the binding energy of the 3d5 / 2 orbit of molybdenum is 227-228eV for 0-valence molybdenum species, the binding energy of the 3d5 / 2 orbit of molybdenum is between 228-229eV for +2-valence molybdenum species, the binding energy of the 3d5 / 2 orbit of molybdenum is between 229-231eV for +4-valence molybdenum species, and the binding energy of the 3d5 / 2 orbit of molybdenum greater than 231eV for +5 or +6-valence molybdenum;

[0020] Among them, the 3d5 / 2 orbital of organic metal molybdenum is between 227-229eV, which belongs to the molybdenum species with valence between 0 and +2. The test method of other metal organic compounds, such as Ga, is similar to that of molybdenum. The analysis shows that the valence state of the above metal additives belongs to organic species with valence between 0 and +1, proving the existence of organic molybdenum compounds.

[0021] Furthermore, the present invention has a wide range of pore volume selection for the hydrodesulfurization catalyst or the hydrodenitrogenation catalyst. Preferably, the pore volume of the hydrodenitrogenation catalyst or the hydrodenitrogenation catalyst is independently 0.1 to 1 cm 3 / g, preferably 0.15 to 0.6 cm 3 / g.

[0022] Further, according to a preferred embodiment of the present invention, the average pore diameter of the hydrodesulfurization catalyst or the hydrodenitrogenation catalyst is independently 4 to 15 nm, preferably 6 to 12 nm.

[0023] Further, according to a preferred embodiment of the present invention, in the hydrodesulfurization catalyst or hydrodenitrogenation catalyst, the pore volume of 0-3 nm pores accounts for 1%-10% of the total pore volume, preferably 2%-5%. The catalyst in the preferred embodiment is more conducive to mass transfer and diffusion of reactant molecules.

[0024] Further, according to some embodiments of the present invention, the pore volume of 0-3 nm pores and the total pore volume of the catalyst are determined by nitrogen isothermal adsorption-desorption method.

[0025] Furthermore, the preparation method of the hydrodesulfurization catalyst comprises:

[0026] An impregnation solution containing organic molybdenum and optional organic zinc is prepared and then impregnated onto a silicon-modified nickel-aluminum alloy carrier, and then dried to obtain a hydrodesulfurization catalyst.

[0027] Furthermore, the silicon-modified nickel-aluminum alloy carrier is an organosilicon-modified nickel-aluminum alloy carrier, and the method for modifying the nickel-aluminum alloy carrier with organosilicon includes: contacting the nickel-aluminum alloy with alkoxysilane gas for silicon modification. Preferably, the method also includes vacuum treatment of the nickel-aluminum alloy before the organosilicon modification and replacement treatment after the silicon modification. This method is more conducive to the deposition of alkoxysilane on the small pores of the nickel-aluminum alloy carrier.

[0028] Furthermore, the preferred preparation method of the hydrodesulfurization catalyst of the present invention comprises:

[0029] (a) vacuumizing the nickel-aluminum alloy carrier;

[0030] (b) introducing alkoxysilane gas into the carrier treated in step (a) to perform modification treatment;

[0031] (c) replacing the alkoxysilane gas described in step (b) with nitrogen and / or inert gas to obtain a modified nickel-aluminum alloy carrier;

[0032] (d) preparing an impregnation solution containing organic molybdenum and organic zinc, and then impregnating the solution onto the modified nickel-aluminum alloy carrier obtained in step (c), and drying the solution to obtain a hydrodesulfurization catalyst.

[0033] Furthermore, in step (a), the pore volume of the nickel-aluminum alloy carrier is 0.4 to 1.0 cm 3 / g, preferably with a pore volume of 0.5 to 0.9 cm 3 / g, the average pore diameter is 4-12nm, preferably 6-10nm, wherein the volume proportion of small pores smaller than 3.0nm is not higher than 20%, preferably 5-10%. .

[0034] Furthermore, the present invention has a wide selection range for the particle size of the nickel-aluminum alloy carrier, and can be adaptively selected according to the actual application environment. Preferably, the average particle size of the nickel-aluminum alloy carrier is 1 to 8 mm, preferably 2 to 5 mm.

[0035] Furthermore, in step (a), the vacuum treatment conditions are: vacuum degree of 0.05-1.0 torr, preferably 0.1-0.5 torr, treatment time of 2-10 hours, preferably 4-8 hours, temperature of 50-140°C, preferably 60-120°C.

[0036] Furthermore, in step (b), before the alkoxysilane gas is introduced, the temperature is first raised according to the boiling point of the alkoxysilane used to make the alkoxysilane in a gaseous state. The alkoxysilane gas is preferably one or more of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, isobutyltriethoxysilane, and n-octyltriethoxysilane.

[0037] Furthermore, in step (b), at least one of nitrogen and / or an inert gas is introduced as a carrier gas while the alkoxysilane gas is introduced. The partial pressure of the alkoxysilane gas is 0.02-1.0 MPa, preferably 0.05-0.5 MPa, the temperature of the modification treatment is 150-400°C, preferably 180-350°C, the time is 1.0-10.0 hours, preferably 2.0-8.0 hours, and the flow rate of the alkoxysilane gas is 1.0-20.0 mL / min·g -1 Nickel aluminum alloy carrier, preferably 3.0-15mL / min·g -1 Nickel aluminum alloy carrier.

[0038] Furthermore, in step (b), the inert gas is preferably argon, neon or a mixture of several of them.

[0039] Furthermore, in step (c), the replacement conditions include: the inert gas introduction rate is 0.5-5 mL / min·g -1 Nickel aluminum alloy carrier, preferably 1-4 mL / min·g -1 For the nickel-aluminum alloy carrier, the replacement time is 0.5-8.0 hours, preferably 1.0-4.0 hours, and the temperature is 100-400°C, preferably 150-350°C.

[0040] Furthermore, in step (d), an organic molybdenum source and an organic zinc source are mixed with a solvent to prepare an impregnation solution. The organic molybdenum source is one or more of alkyl dithiophosphate molybdenum and / or alkyl dithiocarbamate molybdenum. The organic zinc source is one or more of alkyl dithiophosphate zinc and / or alkyl dithiocarbamate molybdenum. The solvent is one or more of n-hexane, n-heptane, n-octane or n-nonane. In the impregnation solution, the concentrations of organic molybdenum and organic zinc are independently 0.1 to 3 mol / L.

[0041] Furthermore, in step (d), the impregnation may be performed by at least one of equal volume impregnation, supersaturated impregnation, etc. conventionally used in the art.

[0042] Furthermore, in step (d), the drying is vacuum drying, the vacuum degree is 0.5-5.0 torr, preferably 1.0-3.0 torr, the drying temperature is 60-150° C., preferably 70-120° C., and the drying time is 2.0-12.0 h, preferably 4.0-8.0 h.

[0043] Furthermore, the method for preparing the hydrodenitrogenation catalyst comprises the following steps:

[0044] (1) preparing a silicon-modified nickel-aluminum alloy carrier;

[0045] (2) preparing an impregnation solution containing an organic molybdenum compound and an optional organic gallium compound, impregnating the solution onto the silicon-modified nickel-aluminum alloy carrier obtained in step (1), and drying the solution to obtain a hydrodenitrogenation catalyst;

[0046] Wherein, when preparing the impregnation solution in step (2), the organic molybdenum compound used is preferably alkyl molybdenum dithiophosphate and / or alkyl molybdenum dithiocarbamate.

[0047] Furthermore, in step (1), the silicon-modified nickel-aluminum alloy carrier is an organosilicon-modified nickel-aluminum alloy carrier, and the method for modifying the nickel-aluminum alloy carrier with organosilicon includes: contacting the nickel-aluminum alloy with a silicon-containing compound in the gas phase for silicon modification. Preferably, the method also includes vacuum treatment of the nickel-aluminum alloy before the organosilicon modification and replacement treatment after the silicon modification. This method is more conducive to the deposition of alkoxysilane on the pores of the nickel-aluminum alloy carrier.

[0048] Furthermore, the preferred method for modifying the nickel-aluminum alloy carrier with organic silicon includes: vacuuming the nickel-aluminum alloy carrier, then introducing a gaseous silicon-containing compound to perform organic silicon modification, and then introducing nitrogen and / or an inert gas for replacement to obtain a modified nickel-aluminum alloy carrier.

[0049] Furthermore, in step (1), the pore volume of the nickel-aluminum alloy carrier is 0.4 to 1.0 cm 3 / g, preferably with a pore volume of 0.5 to 0.9 cm 3 / g, the average pore diameter is 4-12nm, preferably 6-10nm, wherein the volume proportion of small pores smaller than 3.0nm is not higher than 20%, preferably 5-10%.

[0050] Furthermore, the present invention has a wide selection range for the particle size of the nickel-aluminum alloy carrier, and can be adaptively selected according to the actual application environment. Preferably, the average particle size of the nickel-aluminum alloy carrier is 1 to 8 mm, preferably 2 to 5 mm.

[0051] Furthermore, in step (1), the temperature of the vacuum treatment is 50-200° C., preferably 80-150° C.; the vacuum degree is 0.05-1.0 torr, preferably 0.1-0.5 torr; and the treatment time is 2-10 hours, preferably 4-8 hours.

[0052] Furthermore, in step (1), before the silicon-containing compound in the gas phase is introduced, the temperature is first raised according to the boiling point of the silicon-containing compound in the gas phase, and the specific temperature is adjusted according to the corresponding boiling point. The silicon-containing compound in the gas phase is an alkoxysilane in the gas phase, and the alkoxysilane in the gas phase is preferably one or more of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, isobutyltriethoxysilane, and n-octyltriethoxysilane.

[0053] Furthermore, in step (1), when the silicon-containing compound in the gas phase is introduced, at least one of nitrogen and / or an inert gas is introduced as a carrier gas. The partial pressure of the silicon-containing compound in the gas phase is 0.02-1.0 MPa, preferably 0.05-0.5 MPa, the temperature of the modification treatment is 200-450°C, preferably 250-400°C, the time is 1.0-10.0 hours, preferably 2.0-8.0 hours, and the flow rate of the silicon-containing compound introduced into the gas phase is 1.0-20.0 mL / min·g -1 Nickel aluminum alloy carrier, preferably 3.0-15.0 mL / min·g -1 Nickel aluminum alloy carrier.

[0054] Furthermore, in step (1), the inert gas is preferably argon, neon or a mixture of several of them.

[0055] Furthermore, in step (1), the replacement conditions include: the introduction rate of nitrogen and / or inert gas is 0.5-5 mL / min·g -1 Nickel aluminum alloy carrier, preferably 1-4 mL / min·g -1 For the nickel-aluminum alloy carrier, the replacement time is 0.5-8.0 hours, preferably 1.0-4.0 hours, and the temperature is 100-400°C, preferably 150-350°C.

[0056] Furthermore, in step (2), the organic molybdenum source and the organic gallium source are mixed with a solvent to prepare an impregnation solution. The solvent is one or a mixture of n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethanol, methanol, and isopropanol. In the impregnation solution, the concentrations of organic molybdenum and organic gallium are independently 0.1 to 3 mol / L.

[0057] Further, the alkyl dithiophosphate molybdenum is selected from one or more of diisopropyl dithiophosphate molybdenum, dibutyl dithiophosphate sulfide molybdenum oxide, and diisooctyl dithiophosphate molybdenum. The alkyl dithiocarbamate molybdenum is selected from one or more of dibutyl dithiocarbamate molybdenum and diisopropyl dithiocarbamate molybdenum. The organic gallium source is one or more of triethyl gallium, triisopropyl gallium, tri-tert-butyl gallium, gallium acetylacetonate, ethoxy gallium, and gallium isopropoxide.

[0058] Furthermore, in step (2), the impregnation may be performed by at least one of equal volume impregnation, supersaturated impregnation, etc. conventionally used in the art.

[0059] Furthermore, in step (2), the drying is vacuum drying, the vacuum degree is 0.5-5.0 torr, preferably 1.0-3.0 torr, the drying temperature is 60-150° C., preferably 70-120° C., and the drying time is 2.0-12.0 h, preferably 4.0-8.0 h.

[0060] Furthermore, the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst need to be activated before use. The treatment conditions include: hydrogen pressure of 0.1-1.0 MPa, preferably 0.2-0.8 MPa, treatment temperature of 80-250°C, preferably 120-200°C, treatment time of 0.5-5.0 h, preferably 1.0-3.0 h, hydrogen flow rate of 3.0-15.0 mL / h·g -1 Hydrodenitrogenation catalyst, preferably 5.0-10.0 mL / h·g -1 Hydrodenitrogenation catalysts.

[0061] Furthermore, the operating conditions of the fixed bed hydrogenation process are as follows: the reaction hydrogen pressure is 2.0-20.0 MPa, preferably 6.0-16.0 MPa, the hydrogen-oil volume ratio is 200:1-1500:1, preferably 500:1-1200:1, and the volume space velocity is 0.2-3.0 h -1 , preferably 0.5-2.0h -1 , Reaction temperature: the desulfurization catalyst bed is 280-380°C, preferably 300-360°C, and the denitrification catalyst bed is 300-400°C, preferably 320-380°C.

[0062] Furthermore, the loading volume ratio of the hydrodesulfurization catalyst to the hydrodenitrogenation catalyst can be selected in a wide range, for example, it can be 10 to 90:10 to 90. Furthermore, the inferior oil is a secondary processing oil, and the properties are as follows: nitrogen mass content is 300-3000 μg / g, sulfur mass content is 2000-30000 μg / g, aromatics content is 15wt%-80wt%, preferably 30wt%-70wt%.

[0063] Compared with the prior art, the present invention has the following advantages:

[0064] 1. The hydrodenitrogenation catalyst and hydrodesulfurization catalyst used in the present invention use an alkoxysilane-vapor phase deposition method to ensure that alkoxysilane is preferentially blocked in the small pores of the catalyst, thereby optimizing the pore structure of the nickel-aluminum alloy catalyst and preventing subsequent deposition of molybdenum metal in the small pores. At the same time, the organic silicon on the surface of the nickel-aluminum alloy can effectively segment the nickel surface and prevent the aggregation of molybdenum species on the nickel surface.

[0065] 2. The hydrodesulfurization catalyst used in the present invention uses alkyl dithiophosphate molybdenum (and / or alkyl dithiocarbamate molybdenum) as a molybdenum source. This molybdenum species is on the surface of the nickel-aluminum alloy, and due to the steric hindrance effect of the alkyl substitution, the sulfide molybdenum species is in a highly dispersed state. After the mild hydrogen treatment, the Ni-Mo-S active phase obtained has more active centers than the molybdenum species obtained from the oxidation state after sulfurization and the non-loaded MoS2 particles, which improves the utilization rate of molybdenum and the hydrogenation activity of the catalyst. At the same time, alkyl dithiophosphate zinc and / or alkyl dithiocarbamate zinc are used as auxiliary agents. Since alkyl dithiophosphate zinc and / or alkyl dithiocarbamate zinc are similar to specific active component physical and chemical properties, the distribution pattern on the surface of the modified nickel-aluminum alloy carrier is similar, and the distribution position is close, which avoids the phase separation of zinc and molybdenum, making the effect of the auxiliary agent more obvious, and is conducive to deep desulfurization.

[0066] 3. The hydrodenitrogenation catalyst used in the present invention uses a modified nickel-aluminum alloy as a carrier material for the catalytic substrate, which can provide a large amount of activated hydrogen and provide conditions for hydrogen transfer. It is combined with alkyl dithiophosphate molybdenum (and / or alkyl dithiocarbamate molybdenum) as an active component. The sulfur-containing molybdenum species combines with nickel to form Ni-Mo-S active sites, providing hydrogenation centers. At the same time, organic gallium is used as an auxiliary agent to further improve the hydrodenitrogenation effect.

[0067] 4. The present invention adopts specific hydrodesulfurization and hydrodenitrogenation catalysts for combination, and still has strong desulfurization and denitrification effects on inferior secondary processed oil. DETAILED DESCRIPTION

[0068] The present invention will be further described below in conjunction with the examples, but the following examples do not constitute a limitation of the present invention, wherein the percentages of the materials described are by mass percentage unless otherwise specified.

[0069] The present invention selects two types of nickel-aluminum alloys as matrix carriers of hydrodesulfurization catalyst and hydrodenitrogenation catalyst respectively, wherein the matrix carrier of hydrodesulfurization catalyst is denoted as nickel-aluminum alloy-I, and the matrix carrier of hydrodenitrogenation catalyst is denoted as nickel-aluminum alloy-II.

[0070] The properties of nickel aluminum alloy-I are: average particle size 4.1mm, pore volume 0.72cm 3 / g, the average pore diameter of the carrier is 8.3nm, the volume of small pores less than 3nm is 7.6%, the mass fraction of Al is 83.6%, and the mass fraction of Ni is 16.4%.

[0071] The properties of NiAl-II are: average particle size 3.2 mm, pore volume 0.68 cm 3 / g, the average pore size of the carrier is 7.5nm, the volume of small pores less than 3nm is 8.1%, the mass fraction of Al is 80.1%, and the mass fraction of Ni is 19.9%.

[0072] Example 1

[0073] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.2 torr, the temperature was 80° C., and the treatment time was 4.0 hours.

[0074] The temperature of the vacuum drying oven was raised to 220° C., and nitrogen and methyltrimethoxysilane gas were introduced therein. The partial pressure of the methyltrimethoxysilane gas was 0.1 MPa, the gas flow rate was 400 mL / min, and the gas introduction time was 3.0 hours.

[0075] The temperature of the drying box was adjusted to 160° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min. The replacement time was 1.0 hour, and the modified nickel-aluminum alloy carrier obtained was recorded as L-1.

[0076] Take 20.0 g of diisopropyl molybdenum dithiophosphate, 6.0 g of dibutyl zinc dithiophosphate, and 70.0 g of n-heptane to prepare an impregnation solution Q-1.

[0077] L-1 was impregnated with Q-1, and then vacuum dried at 70°C with a vacuum degree of 1.0 torr for 4 hours. The obtained catalyst was designated Cat-1.

[0078] Example 2

[0079] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.4 torr, the temperature was 100° C., and the treatment time was 5.0 hours.

[0080] The temperature of the vacuum drying oven was raised to 240° C., and nitrogen and triethoxysilane were introduced therein. The gas partial pressure of triethoxysilane was 0.1 MPa, the gas flow rate was 450 mL / min·, and the gas introduction time was 4.0 hours.

[0081] The temperature of the drying box was adjusted to 170° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min. The replacement time was 1.5 hours, and the modified nickel-aluminum alloy carrier was obtained and recorded as L-2.

[0082] Take 25.0 g of dibutyl dithiophosphorothioate molybdenum oxide sulfide, 8.0 g of diisooctyl zinc dithiophosphate, and 70.0 g of n-octane to prepare the impregnation solution Q-2.

[0083] L-2 was impregnated with Q-2, and then vacuum dried at 90°C with the vacuum degree controlled at 1.0 torr for 4 hours. The obtained catalyst was designated as Cat-2.

[0084] Example 3

[0085] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours.

[0086] The temperature of the vacuum drying oven was raised to 270° C., and nitrogen and isobutyltriethoxysilane were introduced therein. The gas partial pressure of isobutyltriethoxysilane was 0.1 MPa, the gas flow rate was 500 mL / min·, and the gas introduction time was 5.0 hours.

[0087] The temperature of the drying box was adjusted to 200° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min. The replacement time was 2.0 hours, and the modified nickel-aluminum alloy carrier obtained was recorded as L-3.

[0088] 20.0 g of molybdenum diisopropyldithiocarbamate, 4.0 g of zinc diethyldithiocarbamate, and 70.0 g of n-nonane were used to prepare an impregnation solution Q-3.

[0089] L-3 was impregnated with Q-3, and then vacuum dried at 120°C with the vacuum degree controlled at 1.0 torr for 4 hours. The obtained catalyst was designated as Cat-3.

[0090] Example 4

[0091] 100.0 g of nickel-aluminum alloy-II carrier particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.4 torr, the temperature was 100° C., and the treatment time was 5.0 hours.

[0092] The temperature of the vacuum drying oven was raised to 240° C., and nitrogen and triethoxysilane gas were introduced therein. The partial pressure of the triethoxysilane gas was 0.1 MPa, the gas flow rate was 450 mL / min, and the gas introduction time was 4.0 hours.

[0093] The temperature of the drying box was adjusted to 170° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min. The replacement time was 1.5 hours, and the obtained modified nickel-aluminum alloy carrier was recorded as L-4.

[0094] 25.0 g of dibutyl dithiophosphorosulfide molybdenum oxide, 8.0 g of gallium acetylacetonate, 40.0 g of n-heptane and 30.0 g of ethanol were prepared into an impregnation solution Q-4.

[0095] L-4 was impregnated with Q-4, and then vacuum dried at 90°C with the vacuum degree controlled at 1.0 torr for 4.0 hours. The obtained catalyst was designated as Cat-4.

[0096] Example 5

[0097] 100.0 g of nickel-aluminum alloy-II particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours.

[0098] The temperature of the vacuum drying oven was raised to 270° C., and nitrogen and isobutyltriethoxysilane gas were introduced therein. The partial pressure of the isobutyltriethoxysilane gas was 0.1 MPa, the gas flow rate was 500 mL / min, and the gas introduction time was 5.0 hours.

[0099] The temperature of the drying box was adjusted to 200° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min. The replacement time was 2.0 hours, and the obtained modified nickel-aluminum alloy carrier was recorded as L-5.

[0100] 20.0 g of molybdenum diisopropyldithiocarbamate, 6.0 g of gallium ethoxide, 40.0 g of n-nonane and 30.0 g of ethanol were prepared into an impregnation solution Q-5.

[0101] L-5 was impregnated with Q-5, and then vacuum dried at 120°C with the vacuum degree controlled at 1.0 torr for 4 hours. The obtained catalyst was designated as Cat-5.

[0102] Example 6

[0103] 100.0 g of nickel-aluminum alloy-II particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours.

[0104] The temperature of the vacuum drying oven was raised to 380° C., and nitrogen and n-octyltriethoxysilane gas were introduced therein. The partial pressure of n-octyltriethoxysilane gas was 0.1 MPa, the gas flow rate was 600 mL / min, and the gas introduction time was 5.0 hours.

[0105] The temperature of the drying box was adjusted to 200° C., and the drying box was replaced with nitrogen at a rate of 200 mL / min. The replacement time was 2.0 hours, and the obtained modified nickel-aluminum alloy carrier was recorded as L-6.

[0106] 25.0 g of dibutyl dithiocarbamate molybdenum, 8.0 g of gallium isopropoxide, and 60.0 g of n-decane were prepared to prepare impregnation solution Q-6.

[0107] L-6 was impregnated with Q-6, and then vacuum dried at 120°C, with the vacuum degree controlled at 1.0 torr and the drying time being 4.0 hours. The obtained catalyst was recorded as Cat-6.

[0108] Comparative Example 1

[0109] 100.0 g of nickel-aluminum alloy-I particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours. The obtained nickel-aluminum alloy carrier was recorded as DL-1.

[0110] 20.0 g of molybdenum diisopropyldithiocarbamate, 4.0 g of zinc diethyldithiocarbamate, and 75.0 g of n-octane were used to prepare an impregnation solution DQ-1.

[0111] DL-1 was impregnated with DQ-1 and then vacuum dried at 120°C with the vacuum degree controlled at 1.0 torr for 4 hours. The obtained catalyst was recorded as DCT-1.

[0112] Comparative Example 2

[0113] The preparation method of the modified nickel-aluminum alloy carrier L-3 is the same as that in Example 3.

[0114] 20.0 g of carbonyl molybdenum, 7.0 g of zinc octoate, and 70.0 g of toluene were prepared into solution DQ-2.

[0115] L-3 was impregnated with DQ-2, and then vacuum dried at 120°C, with the vacuum degree controlled at 1.0 torr and the drying time being 4.0 hours to obtain an oxidized catalyst.

[0116] Weigh 20.0 g of the above-mentioned oxidized catalyst, put it into a tubular reactor, and carry out conventional sulfidation treatment. The treatment conditions are: the sulfiding liquid is a cyclohexane solution containing 5.0% dimethyl disulfide by mass, the amount of sulfiding liquid is 40.0 g / h, the hydrogen pressure is 4.0 MPa, the hydrogen flow rate is 200 mL / min, the sulfidation temperature is 340° C., and the sulfidation time is 6.0 hours. The obtained catalyst is recorded as DCT-2.

[0117] Comparative Example 3

[0118] The preparation method of the modified nickel-aluminum alloy carrier L-3 is the same as that in Example 3.

[0119] 12.0 g of molybdenum disulfide powder and 2.0 g of zinc sulfide powder were dissolved in a mixed solution of 40.0 g of n-octane and 30.0 g of DMDS to prepare an impregnation solution named DQ-3.

[0120] L-3 was impregnated with DQ-3 and then vacuum dried at 120°C with the vacuum degree controlled at 1.0 torr for 4 hours. The obtained catalyst was recorded as DCT-3.

[0121] Comparative Example 4

[0122] 100.0 g of nickel-aluminum alloy-II carrier particles were placed in a vacuum drying oven, the vacuum degree was controlled at 0.5 torr, the temperature was 120° C., and the treatment time was 5.0 hours. The obtained nickel-aluminum alloy carrier was recorded as DL-4.

[0123] 25.0 g of dibutyl dithiocarbamate molybdenum, 8.0 g of gallium isopropoxide, and 60.0 g of n-decane were prepared to prepare an impregnation solution DQ-4.

[0124] DL-4 was impregnated with DQ-4 and then vacuum dried at 120°C with the vacuum degree controlled at 1.0 torr for 4.0 hours. The obtained catalyst was recorded as DCT-4.

[0125] Comparative Example 5

[0126] The preparation method of the modified nickel-aluminum alloy carrier L-6 is the same as that in Example 6.

[0127] 22.0 g of carbonyl molybdenum, 6.0 g of ethoxygallium, 60.0 g of cyclohexane and 10.0 g of ethanol were prepared into solution DQ-5.

[0128] L-6 was impregnated with DQ-5, and then vacuum dried at 120°C, with the vacuum degree controlled at 1.0 torr and the drying time being 4.0 hours to obtain an oxidized catalyst.

[0129] Weigh 20.0 g of the above-mentioned oxidized catalyst, put it into a tubular reactor, and carry out conventional sulfidation treatment. The treatment conditions are: the sulfiding liquid is a cyclohexane solution containing 5.0% dimethyl disulfide by mass, the amount of sulfiding liquid is 40.0 g / h, the hydrogen pressure is 4.0 MPa, the hydrogen flow rate is 200 mL / min, the sulfidation temperature is 340° C., and the sulfidation time is 6.0 hours. The obtained catalyst is recorded as DCT-5.

[0130] Comparative Example 6

[0131] The preparation method of the modified nickel-aluminum alloy carrier L-6 is the same as that in Example 6.

[0132] 13.0 g of molybdenum disulfide powder and 6.0 g of ethoxygallium were dissolved in a mixed solution of 30.0 g of isopropanol and 40.0 g of dimethyl disulfide to prepare an impregnation solution named DQ-6.

[0133] L-6 was impregnated with DQ-6 and then vacuum dried at 120°C with the vacuum degree controlled at 1.0 torr for 4 hours. The obtained catalyst was recorded as DCT-6.

[0134] Table 1 Composition and properties of the catalysts obtained in each embodiment and comparative example

[0135]

[0136]

[0137] Embodiment 7-9

[0138] The catalysts obtained in Examples 1-6 were graded and loaded (see Table 3), and the properties of the secondary processing oil used are shown in Table 2. A fixed bed process was used, and the loading volume ratio of the hydrodesulfurization catalyst to the hydrodenitrogenation catalyst was 1:1.

[0139] Catalyst activation and evaluation

[0140] Weigh 20.0 g of catalysts Cat-1, Cat-2, Cat-3, Cat-4, Cat-5, and Cat-6 respectively and put them into a tubular reactor. The activation conditions are: temperature 120°C, hydrogen pressure 0.5 MPa, hydrogen flow rate 150.0 ml / min, and activation time 2.0 hours.

[0141] Comparative Examples 7-9

[0142] The catalysts obtained in Comparative Examples 1-3 and 4-6 were graded and loaded (Table 3). The properties of the secondary processing oil used are shown in Table 2. The fixed bed process was used, and the loading volume ratio of the hydrodesulfurization catalyst to the hydrodenitrogenation catalyst was 1:1.

[0143] 20.0 g of catalysts DCT-1, DCT-2, DCT-3, DCT-4, DCT-5 and DCT-6 were weighed respectively and placed in a tubular reactor. The activation conditions were: temperature 120° C., hydrogen pressure 0.5 MPa, hydrogen flow rate 150.0 mL / min and activation time 2.0 hours.

[0144] Table 2 Raw oil properties

[0145]

[0146]

[0147] The evaluation conditions are: hydrogen pressure of 10.0 MPa, hydrogen flow rate of 500 mL / min, oil feed rate of 50.0 g / h, total catalyst volume space velocity of 1.0 h -1 The reaction temperature of the desulfurization catalyst bed is 320°C, and the reaction temperature of the denitrification catalyst bed is 350°C. After 1200 hours of reaction, the sample analysis results are as follows:

[0148] Table 3

[0149]

[0150] It can be seen from the evaluation results that the use of the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst grading process of the present invention has good hydrodesulfurization, hydrodenitrogenation and aromatic saturation effects on the treatment of heavy secondary processed crude oil.

Claims

1. A method for hydrogenating low-quality oil, which adopts a fixed bed hydrogenation process, wherein the low-quality oil is contacted with at least one hydrodesulfurization catalyst and at least one hydrodenitrogenation catalyst in sequence in the presence of hydrogen to carry out a hydrogenation reaction to obtain hydrogenated oil; characterized in that: The hydrodesulfurization catalyst comprises a carrier and an active component, preferably comprises an auxiliary agent, the carrier comprises a silicon-modified nickel-aluminum alloy, the active component is organic molybdenum, preferably alkyl molybdenum dithiophosphate and / or alkyl molybdenum dithiocarbamate, and the auxiliary agent is organic zinc, preferably alkyl zinc dithiophosphate and / or alkyl zinc dithiocarbamate; the hydrodenitrogenation catalyst comprises a carrier and an active component, the carrier comprises a silicon-modified nickel-aluminum alloy, the active component comprises organic molybdenum, preferably alkyl molybdenum dithiophosphate and / or alkyl molybdenum dithiocarbamate; preferably, the hydrodenitrogenation catalyst comprises an auxiliary agent organic gallium.

2. The method according to claim 1, characterized in that In the hydrodesulfurization catalyst and the hydrodenitrogenation catalyst, the alkyl molybdenum dithiophosphate is independently selected from one or more of diisopropyl molybdenum dithiophosphate, dibutyl molybdenum dithiophosphate sulfide, and diisooctyl molybdenum dithiophosphate; the alkyl molybdenum dithiocarbamate is independently selected from one or more of dibutyl molybdenum dithiocarbamate and diisopropyl molybdenum dithiocarbamate.

3. The method according to claim 1, characterized in that: In the hydrodesulfurization catalyst, the alkyl zinc dithiophosphate is selected from one or more of dibutyl zinc dithiophosphate, isodecyl zinc dithiophosphate, diisooctyl zinc dithiophosphate, and di(tetradecyl) zinc dithiophosphate; the alkyl zinc dithiocarbamate is selected from one or more of diethyl zinc dithiocarbamate, ethylphenyl zinc dithiocarbamate, and dibutyl zinc dithiocarbamate.

4. The method according to claim 1, characterized in that In the hydrodenitrogenation catalyst, the organic gallium is one or more of triethyl gallium, triisopropyl gallium, tri-tert-butyl gallium, gallium acetylacetonate, ethoxy gallium, and gallium isopropoxide.

5. The method according to claim 1, characterized in that In the hydrodesulfurization catalyst or the hydrodenitrogenation catalyst, the silicon-modified nickel-aluminum alloy is an organosilicon-modified nickel-aluminum alloy, and the organosilicon is specifically an alkoxysilane; preferably, the alkoxysilane is selected from at least one of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane and octyltriethoxysilane.

6. The method according to claim 1, characterized in that Based on the total dry weight of the hydrodesulfurization catalyst, the content of Al calculated as aluminum oxide is 62% to 84%, preferably 68% to 80%, the content of Ni calculated as nickel oxide is 8% to 18%, preferably 9% to 15%, the content of molybdenum calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, the content of silicon calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%, and the content of the additive calculated as metal oxide is 1.5% to 7%, preferably 2% to 5.5%.

7. The method according to claim 1, characterized in that Based on the total dry weight of the hydrodenitrogenation catalyst, the content of Al calculated as aluminum oxide is 62% to 84%, preferably 68% to 80%, the content of Ni calculated as nickel oxide is 8% to 18%, preferably 9% to 15%, the content of molybdenum calculated as molybdenum trioxide is 6% to 18%, preferably 8% to 17%, the content of silicon calculated as silicon dioxide is 0.2% to 3%, preferably 0.5% to 2%, and the content of the additive calculated as metal oxide is 1.5% to 7%, preferably 2% to 5.5%.

8. The method according to claim 1, characterized in that: The preparation method of the hydrodesulfurization catalyst comprises: An impregnation solution containing organic molybdenum and optional organic zinc is prepared and then impregnated onto a silicon-modified nickel-aluminum alloy carrier, and then dried to obtain a hydrodesulfurization catalyst.

9. The method according to claim 8, characterized in that The silicon-modified nickel-aluminum alloy carrier is an organosilicon-modified nickel-aluminum alloy carrier, and the method for modifying the nickel-aluminum alloy carrier with organosilicon includes: contacting the nickel-aluminum alloy with alkoxysilane gas for silicon modification; preferably, the method also includes vacuum treatment of the nickel-aluminum alloy before the organosilicon modification and replacement treatment after the silicon modification.

10. The method according to claim 8 or 9, characterized in that: The preparation method of the hydrodesulfurization catalyst comprises: (a) vacuumizing the nickel-aluminum alloy carrier; (b) introducing alkoxysilane gas into the carrier treated in step (a) to perform modification treatment; (c) replacing the alkoxysilane gas described in step (b) with nitrogen and / or inert gas to obtain a modified nickel-aluminum alloy carrier; (d) preparing an impregnation solution containing organic molybdenum and organic zinc, and then impregnating the solution onto the modified nickel-aluminum alloy carrier obtained in step (c), and drying the solution to obtain a hydrodesulfurization catalyst.

11. The method according to claim 10, characterized in that In step (a), based on the total amount of the nickel-aluminum alloy, the content of aluminum as element is 50wt% to 95wt%, and the content of nickel as element is 5wt% to 50wt%; based on the total amount of the nickel-aluminum alloy, the content of aluminum as element is 70wt% to 90wt%, and the content of nickel as element is 10wt% to 30wt%.

12. The method according to claim 10, characterized in that In step (a), the vacuum treatment conditions are: vacuum degree of 0.05-1.0 torr, preferably 0.1-0.5 torr, treatment time of 2-10 hours, preferably 4-8 hours, temperature of 50-140°C, preferably 60-120°C.

13. The method according to claim 10, characterized in that The alkoxysilane gas is selected from one or more of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, isobutyltriethoxysilane and n-octyltriethoxysilane.

14. The method according to claim 10, characterized in that In step (d), an organic molybdenum source and an organic zinc source are mixed with a solvent to prepare an impregnation solution; the solvent is one or a mixture of n-hexane, n-heptane, n-octane or n-nonane; in the impregnation solution, the concentrations of the organic molybdenum and organic zinc are independently 0.1 to 3 mol / L.

15. The method according to claim 1, characterized in that The method for preparing the hydrodenitrification catalyst comprises the following steps: (1) preparing a silicon-modified nickel-aluminum alloy carrier; (2) preparing an impregnation solution containing an organic molybdenum compound and an optional organic gallium compound, impregnating the solution onto the silicon-modified nickel-aluminum alloy carrier obtained in step (1), and drying the solution to obtain a hydrodenitrogenation catalyst; Wherein, when preparing the impregnation solution in step (2), the organic molybdenum compound used is alkyl dithiophosphate molybdenum and / or alkyl dithiocarbamate molybdenum.

16. The method according to claim 15, characterized in that In step (1), the silicon-modified nickel-aluminum alloy carrier is an organosilicon-modified nickel-aluminum alloy carrier, and the method for modifying the nickel-aluminum alloy carrier with organosilicon includes: contacting the nickel-aluminum alloy with a silicon-containing compound in the gas phase for silicon modification; preferably, the method also includes vacuuming the nickel-aluminum alloy before the organosilicon modification and replacing it after the silicon modification.

17. The method according to claim 16, characterized in that The method for modifying a nickel-aluminum alloy carrier with organic silicon comprises: vacuuming the nickel-aluminum alloy carrier, introducing a silicon-containing compound in a gas phase, performing an organic silicon modification treatment, and then introducing nitrogen and / or an inert gas for replacement to obtain a modified nickel-aluminum alloy carrier.

18. The method according to claim 16 or 17, characterized in that Based on the total amount of the nickel-aluminum alloy, the aluminum content as element is 50wt% to 95wt%, and the nickel content as element is 5wt% to 50wt%; preferably, based on the total amount of the nickel-aluminum alloy, the aluminum content as element is 70wt% to 90wt%, and the nickel content as element is 10wt% to 30wt%.

19. The method according to claim 16 or 17, characterized in that The temperature of the vacuum treatment is 50-200° C., preferably 80-150° C.; the vacuum degree is 0.05-1.0 torr, preferably 0.1-0.5 torr; and the treatment time is 2-10 hours, preferably 4-8 hours.

20. The method according to claim 16 or 17, characterized in that The gas phase silicon-containing compound is a gas phase alkoxysilane, and the gas phase alkoxysilane is preferably one or more of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, isobutyltriethoxysilane, and n-octyltriethoxysilane.

21. The method according to claim 15, characterized in that In step (2), an organic molybdenum compound and an optional organic gallium compound are mixed with a solvent to prepare an impregnation solution; the solvent is one or a mixture of n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethanol, methanol, and isopropanol; and in the impregnation solution, the concentrations of organic molybdenum and organic gallium are independently 0.1 to 3 mol / L.

22. The method according to claim 1, characterized in that The operating conditions of the fixed bed hydrogenation process are as follows: the reaction hydrogen pressure is 2.0-20.0 MPa, preferably 6.0-16.0 MPa, the hydrogen-oil volume ratio is 200:1-1500:1, preferably 500:1-1200:1, and the volume space velocity is 0.2-3.0 h -1 , preferably 0.5-2.0h -1 , Reaction temperature: the desulfurization catalyst bed is 280-380°C, preferably 300-360°C, and the denitrification catalyst bed is 300-400°C, preferably 320-380°C.

23. The method according to claim 1, characterized in that The inferior oil is a secondary processed oil with the following properties: nitrogen mass content of 300-3000 μg / g, sulfur mass content of 2000-30000 μg / g, aromatic hydrocarbon content of 15wt%-80wt%, preferably 30wt%-70wt%.

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