Hydrodenitrogenation catalyst and method for making same

Abstract

The application provides a hydrodenitrogenation catalyst and a preparation method thereof. The hydrodenitrogenation catalyst comprises a carrier and an active component, the carrier comprises a modified nickel-aluminum alloy, and the active component comprises organic molybdenum, preferably molybdenum alkyl dithiophosphate and / or molybdenum alkyl dithiocarbamate; preferably, the hydrodenitrogenation catalyst comprises an auxiliary organic gallium. The hydrodenitrogenation catalyst has strong hydro-saturation capacity and hydrodenitrogenation capacity for poor raw materials with high nitrogen content and high aromatic content.

Description

Technical Field

[0001] This invention relates to a hydrogenation catalyst, specifically to a hydrogenation denitrification catalyst and its preparation method. Background Technology

[0002] Traditional alumina-nickel-molybdenum hydrogenation catalysts have a limited nickel content, which restricts their hydrogenation activity and makes them unsuitable for processing feedstocks with high aromatic content. Furthermore, traditional hydrogenation catalysts not only require high temperatures and pressures but are also prone to problems such as coking and carbon buildup.

[0003] CN103861596A discloses a method for preparing a nickel-based hydrogenation catalyst. The method involves dissolving a soluble salt of the active component nickel and a soluble salt of an additive in water to prepare a mixed aqueous solution of nickel and the additive. This solution is then added to a reactor in a co-current flow with a soluble salt of a precipitant. Once the reactor temperature reaches a certain level, a support is added, and the reaction is maintained for a period of time. After washing, drying, and reduction, the nickel-based catalyst is obtained. This catalyst has advantages such as mild reaction conditions, high catalyst activity, and high selectivity for the target product, making it widely applicable in practical industrial production. However, this hydrogenation catalyst is not suitable for processing heavy and low-quality oil products.

[0004] CN113019371A discloses a skeletal nickel catalyst precursor, a skeletal nickel catalyst, and a method for preparing the same. The catalyst is prepared by adding a dispersant and water to three alloy particles of different sizes and compositions to form a homogeneous slurry, followed by activation and post-treatment. The catalyst exhibits a wide particle size distribution, and particles of different sizes show magnetic synergistic effects. However, this catalyst is also difficult to effectively remove heteroatoms from oil products, limiting its applications. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a hydrodenitrogenation catalyst and its preparation method. This hydrodenitrogenation catalyst exhibits strong hydrogenation saturation and hydrodenitrogenation capabilities for low-quality feedstocks with high nitrogen and aromatic hydrocarbon content.

[0006] The first aspect of the present invention provides a hydrodenitrification catalyst, the hydrodenitrification catalyst comprising a support and an active component, the support comprising a modified nickel-aluminum alloy, and the active component comprising an organomolybdenum, wherein the organomolybdenum is preferably alkyl dithiophosphate molybdenum and / or alkyl dithiocarbamate molybdenum; preferably, the hydrodenitrification catalyst comprises an auxiliary organogallium.

[0007] Further, the alkyl dithiophosphate molybdenum is selected from one or more of diisopropyl molybdenum dithiophosphate, dibutyl molybdenum dithiophosphate oxysulfide, and diisooctyl molybdenum dithiophosphate. The alkyl dithiocarbamate molybdenum is selected from one or more of dibutyl molybdenum dithiophosphate and diisopropyl molybdenum dithiophosphate.

[0008] Furthermore, the organic gallium is one or more of triethyl gallium, triisopropyl gallium, tritert-butyl gallium, gallium acetylacetonate, gallium ethoxylate, and gallium isopropoxide.

[0009] Furthermore, in this invention, the range of choices for the nickel-aluminum alloy is quite wide. The nickel-aluminum alloy has its conventional meaning in the art, and its source is not particularly limited; it can be commercially purchased or self-made, and self-making can be carried out using any feasible method.

[0010] Furthermore, in this invention, the range of nickel and aluminum content in the nickel-aluminum alloy is relatively wide. Preferably, based on the total amount of the nickel-aluminum alloy, the aluminum content (based on elemental concentration) is 50 wt% to 95 wt%, and the nickel content (based on elemental concentration) is 5 wt% to 50 wt%. More preferably, based on the total amount of the nickel-aluminum alloy, the aluminum content (based on elemental concentration) is 70 wt% to 90 wt%, and the nickel content (based on elemental concentration) is 10 wt% to 30 wt%. This preferred embodiment not only allows nickel to effectively combine with organomolybdenum to improve the hydrogenation performance of the catalyst, but also prevents the nickel content in the nickel-aluminum alloy from becoming too high.

[0011] Further, the modified nickel-aluminum alloy is an organosilicon-modified nickel-aluminum alloy, specifically an alkoxysilane. More preferably, the alkoxysilane is selected from at least one of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, butyltriethoxysilane, and octyltriethoxysilane. Preferably, based on the dry weight of the hydrodenitrogenation catalyst, the content of organosilicon compounds in the hydrogenation catalyst, calculated as SiO2, is 0.2%–3%, more preferably 0.5%–2%. Using this preferred embodiment, the modified nickel-aluminum alloy as the catalytic substrate in the catalyst can provide a large amount of activated hydrogen, providing conditions for hydrogen transfer. Combined with organomolybdenum compounds, especially dialkyldithiophosphate molybdenum and / or alkyldithiocarbamate molybdenum, as active components, the sulfur-containing molybdenum species combine 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.

[0012] Furthermore, based on the dry weight of the hydrodenitrification catalyst, the content of Al (calculated as aluminum oxide) is 62%–84%, preferably 68%–80%; the content of Ni (calculated as nickel oxide) is 8%–18%, preferably 9%–15%; the content of molybdenum (calculated as molybdenum trioxide) is 6%–18%, preferably 8%–17%; the content of silicon (calculated as silicon dioxide) is 0.2%–3%, preferably 0.5%–2%; and the content of additives (calculated as metal oxides) is 1.5%–7%, preferably 2%–5.5%.

[0013] Furthermore, in this invention, the dry basis measurement method of the hydrodenitrification catalyst is as follows: In an air atmosphere, the catalyst is heated from 120°C to 420°C at a rate of 3.0°C per minute, and then calcined for 4.0 hours at 550°C for 2.0 hours at a rate of 3.0°C per minute. The resulting material is analyzed in a dry environment.

[0014] Furthermore, the content of each component in the dry basis can be determined using atomic emission spectrometry (ICP-AES), specifically using an OPTIMA 7000DV atomic emission spectrometer manufactured by PE Corporation. In a typical solution preparation process, 0.1 g of sample is dissolved in a mixed solution with a volume ratio of 3HCl:1HNO3:0.5HF. The mixed solution is then diluted with deionized water to a certain volume, ensuring that the content of the analyte element in the solution is between 1 and 10 ppm, thereby increasing the accuracy of the measurement data.

[0015] Furthermore, the analysis of organometallic compounds in the catalyst can be performed using XPS. The XPS testing conditions include: light source: Mg Kα, energy step: 0.05 eV, scan range: 200-250 eV (molybdenum), 280-300 eV (carbon). When analyzing the valence state of molybdenum, molybdenum species with a 3d5 / 2 orbital binding energy of 227-228 eV are considered to have a valence of 0; those with a valence between 228-229 eV are considered to have a valence of +2; those with a valence between 229-231 eV are considered to have a valence of +4; and those with a valence greater than 231 eV are considered to have a valence of +5 or +6.

[0016] Among them, the 3d5 / 2 orbital of the organometallic molybdenum is between 227 and 229 eV, belonging to molybdenum species with valences between 0 and +2. Other organometallic compounds, such as Ga, were tested using methods similar to those for molybdenum. Analysis revealed that the valence states of these metal additives belonged to organic species with valences between 0 and +1, proving the existence of organomolybdenum compounds.

[0017] Furthermore, in the hydrodenitrogenation catalyst provided by this invention, organogallium is used as an auxiliary agent. Since gallium and aluminum belong to the same group, gallium can also combine with nickel and interact with the supported organomolybdenum species, which is beneficial to improving the hydrodenitrogenation activity. At the same time, organogallium can form a strong Ga-N triple bond with nitrogen, which has a very strong interaction with nitrides in oil products, and is very beneficial to improving the hydrodenitrogenation activity.

[0018] Furthermore, the present invention allows for a wide range of pore volumes for the hydrodenitrogenation catalyst; preferably, the pore volume of the hydrodenitrogenation catalyst is 0.1–1 cm³. 3 / g, preferably 0.15~0.6cm 3 / g.

[0019] Furthermore, according to a preferred embodiment of the present invention, the average pore size of the hydrodenitrification catalyst is 4-15 nm, preferably 6-12 nm.

[0020] Furthermore, according to a preferred embodiment of the present invention, in the hydrodenitrification catalyst, the pore volume of 0-3 nm pores accounts for 1%-10% of the total pore volume, preferably 2%-5%. The catalyst used in the preferred embodiment is more conducive to the mass transfer and diffusion of reactant molecules.

[0021] Furthermore, according to some embodiments of the present invention, the pore volume of the catalyst in the 0-3 nm range and the total pore volume are determined by nitrogen isothermal adsorption-desorption method.

[0022] A second aspect of the present invention provides a method for preparing the above-mentioned hydrodenitrification catalyst, comprising the following steps:

[0023] (1) Preparation of modified nickel-aluminum alloy carrier;

[0024] (2) Prepare an impregnation solution containing an organomolybdenum compound and an optional organogallium compound, impregnate it onto the modified nickel-aluminum alloy support obtained in step (1), and dry it to obtain a hydrodenitrogenation catalyst.

[0025] In step (2), when preparing the impregnation solution, the organic molybdenum compound used is preferably alkyl dithiophosphate molybdenum and / or alkyl dithiocarbamate molybdenum.

[0026] Further, in step (1), the modified nickel-aluminum alloy carrier is an organosilicon-modified nickel-aluminum alloy carrier. The method for modifying the organosilicon-modified nickel-aluminum alloy carrier includes: contacting the nickel-aluminum alloy with a gaseous silicon-containing compound to perform silicon modification. Preferably, the method further includes a vacuum treatment of the nickel-aluminum alloy before the organosilicon modification and a displacement treatment after the silicon modification. This approach is more conducive to the deposition of alkoxysilanes on the pores of the nickel-aluminum alloy carrier.

[0027] Furthermore, a preferred method for obtaining the organosilicon-modified nickel-aluminum alloy carrier includes: subjecting the nickel-aluminum alloy carrier to vacuum treatment, then introducing a gaseous silicon-containing compound for organosilicon modification treatment, and then introducing nitrogen and / or an inert gas for replacement to obtain the modified nickel-aluminum alloy carrier.

[0028] Furthermore, the pore volume of the nickel-aluminum alloy is 0.4–1.0 cm³. 3 / g, preferably with a pore volume of 0.5–0.9 cm³. 3 / g, with an average pore size of 4-12nm, preferably 6-10nm, wherein the volume ratio of pores smaller than 3.0nm is not higher than 20%, preferably 5-10%.

[0029] Furthermore, the present invention has a wide range of particle size selection for the nickel-aluminum alloy, which can be adapted to the actual application environment. Preferably, the average particle size of the nickel-aluminum alloy carrier is 1-8 mm, and more preferably 2-5 mm.

[0030] Further, in step (1), the temperature of the vacuuming process 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 processing time is 2-10 hours, preferably 4-8 hours.

[0031] Further, in step (1), before introducing the gaseous silicon-containing compound, a heating operation is performed according to the boiling point of the gaseous silicon-containing compound used. The specific temperature can be adjusted according to the corresponding boiling point. The gaseous silicon-containing compound is a gaseous alkoxysilane, preferably one or more of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, isobutyltriethoxysilane, and n-octyltriethoxysilane.

[0032] Further, in step (1), at least one of nitrogen and / or an inert gas is introduced as a carrier gas simultaneously with the introduction of the silicon-containing compound into the gas phase. 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 modification treatment temperature is 160–400 °C, preferably 180–350 °C; the treatment 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.

[0033] Furthermore, in this invention, the inert gas is preferably one or a mixture of several of argon and neon.

[0034] Further, in step (1), the conditions for the replacement include: the rate of introduction 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 The nickel-aluminum alloy carrier has a replacement time of 0.5 to 8.0 hours, preferably 1.0 to 4.0 hours, and a temperature of 100 to 400°C, preferably 150 to 350°C.

[0035] Further, in step (2), the organomolybdenum compound and optionally the organogallium compound are mixed with a solvent to prepare an impregnation solution. The solvent is one or a mixture of several of the following: n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethanol, methanol, and isopropanol. In the impregnation solution, the concentrations of the organomolybdenum compound and the organogallium compound are each independently 0.1–3 mol / L.

[0036] Further, the alkyl dithiophosphate molybdenum is selected from one or more of diisopropyl molybdenum dithiophosphate, dibutyl molybdenum dithiophosphate oxysulfide, and diisooctyl molybdenum dithiophosphate. The alkyl dithiocarbamate molybdenum is selected from one or more of dibutyl molybdenum dithiophosphate and diisopropyl molybdenum dithiophosphate.

[0037] Furthermore, the organic gallium source is one or more of triethylgallium, triisopropylgallium, tritert-butylgallium, gallium acetylacetonate, gallium ethoxylate, and gallium isopropoxide.

[0038] Furthermore, in step (2), the impregnation can be performed using at least one of the conventional methods in the art, such as equal volume impregnation or supersaturated impregnation.

[0039] Further, in step (2), the drying is vacuum drying, with a vacuum degree of 0.5 to 5.0 torr, preferably 1.0 to 3.0 torr, a drying temperature of 60 to 150°C, preferably 70 to 120°C, and a drying time of 2.0 to 12.0 h, preferably 4.0 to 8.0 h.

[0040] Furthermore, the hydrodenitrification catalyst needs to be activated before use. The activation conditions include: hydrogen pressure of 0.1–1.0 MPa, preferably 0.2–0.8 MPa; activation temperature of 80–250 °C, preferably 120–200 °C; activation time of 0.5–5.0 h, preferably 1.0–3.0 h; and hydrogen flow rate of 3.0–15.0 mL / h·g. -1 The preferred hydrodenitrogenation catalyst is 5.0-10.0 mL / h·g. -1 Hydrogenation denitrification catalyst.

[0041] A third aspect of the present invention provides the application of the hydrodenitrogenation catalyst in the hydrodenitrogenation of secondary processed oil.

[0042] Furthermore, the application conditions include: a reaction temperature of 300–420°C, preferably 340–400°C; a hydrogen pressure of 2.0–20.0 MPa, preferably 6.0–12.0 MPa; a hydrogen-to-oil volume ratio of 200:1–1500:1, preferably 500:1–1200:1; and a volume hourly space velocity of 0.2–3.0 h⁻¹. -1 Preferably 0.5–2.0 h -1 .

[0043] Furthermore, the properties of the secondary processed oil are as follows: aromatic content of 30wt% to 80wt%, more specifically 50wt% to 70wt%, and sulfur content of 2000 to 12000 μg·g. -1 The nitrogen content is 800–3000 μg·g -1 。

[0044] Compared with the prior art, the catalyst of the present invention has the following advantages:

[0045] This invention relates to a hydrodenitrogenation catalyst that uses a modified nickel-aluminum alloy as the catalytic substrate, providing a large amount of activated hydrogen and creating conditions for hydrogen transfer. It incorporates alkyl molybdenum dithiophosphate (and / or alkyl molybdenum dithiocarbamate) as the active component. The sulfur-containing molybdenum species combine with nickel to form Ni-Mo-S active sites, providing hydrogenation centers. Furthermore, organogallium is used as an auxiliary agent to further enhance the hydrodenitrogenation effect. This catalyst is suitable for processing oils with high aromatic and high nitrogen content, especially those that have undergone secondary processing in refineries.

[0046] The present invention relates to a hydrodenitrogenation catalyst that uses organogallium as a denitrification aid. Since gallium and aluminum belong to the same group of elements, gallium can also combine with nickel and interact with supported organomolybdenum species. At the same time, organogallium can form a strong Ga-N triple bond with nitrogen, which has a very strong interaction with nitrides in oil products, which is very beneficial to improving the hydrodenitrogenation activity.

[0047] The present invention provides a method for preparing a hydrodenitrification catalyst using an alkoxysilane-vapor phase deposition method. This method ensures that alkoxysilanes preferentially block the pores of the catalyst, thereby optimizing the pore structure of the nickel-aluminum alloy catalyst and preventing subsequent deposition of molybdenum metal in the pores. At the same time, the organosilicon on the surface of the nickel-aluminum alloy can effectively segment the nickel surface, preventing the accumulation of molybdenum species on the nickel surface.

[0048] This invention relates to a method for preparing a hydrodenitrification catalyst, using alkyl molybdenum dithiophosphate (and / or alkyl molybdenum dithiocarbamate) as the molybdenum source. Due to the steric hindrance effect of alkyl substitution on the surface of a nickel-aluminum alloy, this molybdenum species are highly dispersed. After mild hydrogen treatment, a highly dispersed Ni-Mo-S active phase can be obtained. Compared to molybdenum species obtained from the oxidized state via sulfidation and unsupported MoS2 particles, this active phase has more active centers, improving molybdenum utilization and the catalyst's hydrogenation activity. Detailed Implementation

[0049] The present invention will be further described below with reference to the embodiments, but the following embodiments do not constitute a limitation of the present invention. Unless otherwise specified, the percentage content of the materials mentioned herein is a mass percentage content.

[0050] The nickel-aluminum alloy carriers used in the embodiments and comparative examples of this invention have the following properties: average particle size 3.2 mm, pore volume 0.68 cm³. 3 / g, the average pore size of the support is 7.5nm. The volume of pores smaller than 3nm is 8.1%. The mass fraction of Al is 80.1%, and the mass fraction of Ni is 19.9%.

[0051] Example 1

[0052] 100.0g of nickel-aluminum alloy carrier particles were placed in a vacuum drying oven, with the vacuum level controlled at 0.2 torr, the temperature at 80℃, and the processing time at 4.0 hours.

[0053] The temperature of the vacuum drying oven was raised to 220℃, and nitrogen and methyltrimethoxysilane gas were introduced into it. The partial pressure of methyltrimethoxysilane gas was 0.1 MPa, the gas flow rate was 400 mL / min, and the gas was introduced for 3.0 hours.

[0054] The temperature of the drying oven was adjusted to 160℃, and the drying oven was purged with nitrogen at a rate of 200 mL / min for 1 hour. The resulting modified nickel-aluminum alloy carrier was denoted as L-1.

[0055] Prepare impregnation solution Q-1 by taking 22.0g of molybdenum diisopropyl dithiophosphate, 5.0g of tritert-butylgallium, 50.0g of cyclohexane and 20.0g of ethanol.

[0056] L-1 was impregnated with Q-1 and then vacuum dried at 70°C, with the vacuum level controlled at 1.0 torr, for 4.0 hours. The resulting catalyst is designated Cat-1.

[0057] Example 2

[0058] 100.0g of nickel-aluminum alloy carrier particles were placed in a vacuum drying oven, with the vacuum level controlled at 0.4 torr, the temperature at 100℃, and the processing time at 5.0 hours.

[0059] The temperature of the vacuum drying oven was raised to 240℃, and nitrogen and triethoxysilane gas were introduced into it. 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.

[0060] The temperature of the drying oven was adjusted to 170℃, and the drying oven was purged with nitrogen at a rate of 200 mL / min for 1.5 hours. The resulting modified nickel-aluminum alloy carrier was denoted as L-2.

[0061] Prepare impregnation solution Q-2 by taking 25.0g of dibutyl dithiophosphate molybdenum sulfide, 8.0g of gallium acetylacetonate, 40.0g of n-heptane and 30.0g of ethanol.

[0062] L-2 was impregnated with Q-2, and then vacuum dried at 90°C with the vacuum level controlled at 1.0 torr for 4.0 hours. The resulting catalyst is designated Cat-2.

[0063] Example 3

[0064] 100.0g of nickel-aluminum alloy carrier particles were placed in a vacuum drying oven, and the vacuum degree was controlled at 0.5 torr, the temperature at 120℃, and the processing time was 5.0 hours.

[0065] The temperature of the vacuum drying oven was raised to 270℃, and nitrogen and isobutyltriethoxysilane gas were introduced into it. 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.

[0066] The temperature of the drying oven was adjusted to 200℃, and the drying oven was purged with nitrogen at a rate of 200 mL / min for 2.0 hours. The resulting modified nickel-aluminum alloy carrier was designated L-3.

[0067] Prepare impregnation solution Q-3 by taking 20.0g of molybdenum diisopropyl dithiocarbamate, 6.0g of gallium ethoxylate, 40.0g of n-nonane and 30.0g of ethanol.

[0068] L-3 was impregnated with Q-3, and then vacuum dried at 120°C with the vacuum level controlled at 1.0 torr for 4.0 hours. The resulting catalyst is designated Cat-3.

[0069] Example 4

[0070] 100.0g of nickel-aluminum alloy carrier particles were placed in a vacuum drying oven, and the vacuum degree was controlled at 0.5 torr, the temperature at 120℃, and the processing time was 5.0 hours.

[0071] The temperature of the vacuum drying oven was raised to 380℃, and nitrogen and n-octyltriethoxysilane gas were introduced into it. The partial pressure of the n-octyltriethoxysilane gas was 0.1 MPa, the gas flow rate was 600 mL / min, and the gas introduction time was 5.0 hours.

[0072] The temperature of the drying oven was adjusted to 200℃, and the drying oven was purged with nitrogen at a rate of 200 mL / min for 2.0 hours. The resulting modified nickel-aluminum alloy carrier was designated L-4.

[0073] Prepare impregnation solution Q-4 by taking 25.0g of molybdenum dibutyldithiocarbamate, 8.0g of gallium isopropoxide, and 60.0g of n-decane.

[0074] L-4 was impregnated with Q-4, and then vacuum dried at 120°C with the vacuum level controlled at 1.0 torr for 4.0 hours. The resulting catalyst is designated Cat-4.

[0075] Comparative Example 1

[0076] 100.0g of nickel-aluminum alloy carrier particles were placed in a vacuum drying oven, with the vacuum level controlled at 0.5 torr, the temperature at 120℃, and the processing time at 5.0 hours. The resulting nickel-aluminum alloy carrier is designated as DL-1.

[0077] Prepare impregnation solution DQ-1 by taking 25.0g of molybdenum dibutyldithiocarbamate, 8.0g of gallium isopropoxide, and 60.0g of n-decane.

[0078] DL-1 was impregnated with DQ-1, and then vacuum dried at 120°C with the vacuum level controlled at 1.0 torr for 4.0 hours. The resulting catalyst was designated DCT-1.

[0079] Comparative Example 2

[0080] The preparation method of the modified nickel-aluminum alloy carrier L-4 is the same as in Example 4.

[0081] Prepare solution DQ-2 by taking 22.0g of molybdenum carbonyl, 6.0g of gallium ethoxylate, 60.0g of cyclohexane and 10.0g of ethanol.

[0082] L-4 was impregnated with DQ-2, and then vacuum dried at 120°C with the vacuum level controlled at 1.0 torr for 4.0 hours. The resulting catalyst was in its oxidized state.

[0083] Weigh 20.0g of the above-mentioned oxidized catalyst and place it in a tubular reactor for conventional sulfidation treatment. The treatment conditions are as follows: the sulfidation solution is a cyclohexane solution containing 5.0% dithiodimethyl, the sulfidation solution volume is 40.0g / h, the hydrogen pressure is 4.0MPa, the hydrogen flow rate is 200mL / min, the sulfidation temperature is 340℃, and the sulfidation time is 6.0 hours. The obtained catalyst is designated as DCT-2.

[0084] Comparative Example 3

[0085] The preparation method of the modified nickel-aluminum alloy carrier L-4 is the same as in Example 4.

[0086] Take 13.0g of molybdenum disulfide powder and 6.0g of gallium ethoxylate, dissolve them in a mixed solution of 30.0g of isopropanol and 40.0g of dimethyl disulfide, and prepare an impregnation solution labeled DQ-3.

[0087] L-4 was impregnated with DQ-3, and then vacuum dried at 120°C with the vacuum level controlled at 1.0 torr for 4.0 hours. The resulting catalyst was designated DCT-3.

[0088] Activation of catalyst

[0089] 20.0g of catalysts Cat-1, Cat-2, Cat-3, Cat-4, DCT-1, DCT-2, and DCT-3 were weighed and placed into a tubular reactor. The activation conditions were: temperature 120℃, hydrogen pressure 0.5MPa, hydrogen flow rate 150.0mL / min, and activation time 2.0 hours.

[0090] Examples 5-8

[0091] The effects of the activated catalysts Cat-1, Cat-2, Cat-3, and Cat-4 in each embodiment were evaluated. The properties of the feed oil are shown in Table 2.

[0092] 20.0 g of each activated catalyst was loaded into a fixed-bed reactor for hydrogenation evaluation experiments under the following conditions:

[0093] The reaction temperature was 370℃, the hydrogen pressure was 12.0 MPa, the hydrogen-to-oil ratio was 800:1, and the volume hourly space velocity (VHSV) was 1.0 h⁻¹. -1 After reacting for 1200 hours, the sample analysis results are shown in Table 3.

[0094] Comparative Examples 4-6

[0095] 20.0g of each of the activated catalysts from Comparative Examples 1-3 were loaded into a fixed-bed reactor for hydrogenation evaluation experiments. The feedstock and reaction conditions were the same as in Example 5.

[0096] Table 1. Catalyst composition and properties

[0097]

[0098] Table 2 Properties of Crude Oil

[0099]

[0100]

[0101] Table 3 Catalyst Evaluation Results

[0102] catalyst Cat-1 Cat-2 Cat-3 Cat-4 DCT-1 DCT-2 DCT-3 <![CDATA[S / μg·g -1 ]]> 251 212 114 85.3 312 496 1029 <![CDATA[N / μg·g -1 ]]> 7.5 4.2 2.8 1.1 26.9 46.1 114 Aromatics, wt% 43.5 37.7 35.7 34.7 43.2 48.1 53.4 Bicyclic and above aromatic hydrocarbons, wt% 3.1 2.6 2.2 1.9 12.6 14.7 16.9

[0103] The evaluation results show that the hydrodenitrification catalyst of this invention has good hydrodesulfurization, hydrodenitrification and aromatic saturation effects when treating inferior heavy secondary processed crude oil.

Claims

1. A hydrodenitrogenation catalyst characterized in that, The hydrogen denitrification catalyst comprises a carrier and an active component, the carrier comprises an organosilicon modified nickel-aluminum alloy, and the active component comprises organomolybdenum, the organomolybdenum is molybdenum alkyl dithiophosphate and / or molybdenum alkyl dithiocarbamate; the hydrogen denitrification catalyst comprises an auxiliary organogallium.

2. The hydrodenitrogenation catalyst of claim 1, wherein, The molybdenum alkyl dithiophosphate is selected from one or more of molybdenum diisopropyl dithiophosphate, molybdenum dibutyl dithiophosphate sulfide oxide, and molybdenum diisooctyl dithiophosphate; the molybdenum alkyl dithiocarbamate is selected from one or more of molybdenum dibutyl dithiocarbamate and molybdenum diisopropyl dithiocarbamate.

3. The hydrodenitrogenation catalyst of claim 1, wherein, The organogallium is one or more of triethyl gallium, triisopropyl gallium, tri-tert-butyl gallium, acetylacetone gallium, ethoxy gallium, and isopropyl alcohol gallium.

4. The hydrodenitrogenation catalyst of claim 1, wherein, The organosilicon is an alkoxysilane.

5. The hydrodenitrogenation catalyst of claim 4, wherein, The alkoxysilane is at least one of methyl trimethoxysilane, triethoxysilane, methyl triethoxysilane, propyl trimethoxysilane, butyl triethoxysilane, and octyl triethoxysilane.

6. The hydrodenitrogenation catalyst of claim 4, wherein, The content of the organosilicon compound, calculated as SiO2, in the hydrogen denitrification catalyst is 0.2% to 3% based on the total dry weight of the hydrogen denitrification catalyst.

7. The hydrodenitrogenation catalyst of claim 6, wherein, The content of the organosilicon compound, calculated as SiO2, in the hydrogen denitrification catalyst is 0.5% to 2% based on the total dry weight of the hydrogen denitrification catalyst.

8. The hydrodenitrogenation catalyst of claim 1, wherein, The content of Al, calculated as Al2O3, is 62% to 84%, the content of Ni, calculated as NiO, is 8% to 18%, the content of Mo, calculated as MoO3, is 6% to 18%, the content of Si, calculated as SiO2, is 0.2% to 3%, and the content of the auxiliary, calculated as metal oxide, is 1.5% to 7% based on the total dry weight of the hydrogen denitrification catalyst.

9. The hydrodenitrogenation catalyst of claim 8, wherein, The content of Al, calculated as Al2O3, is 68% to 80%, the content of Ni, calculated as NiO, is 9% to 15%, the content of Mo, calculated as MoO3, is 8% to 17%, the content of Si, calculated as SiO2, is 0.5% to 2%, and the content of the auxiliary, calculated as metal oxide, is 2% to 5.5% based on the total dry weight of the hydrogen denitrification catalyst.

10. The hydrodenitrogenation catalyst of claim 1, wherein, The properties of the hydrodenitrogenation catalyst include a pore volume of 0.1 to 1 cm 3 / g, an average pore diameter of 4 to 15 nm, and a pore volume of 0 to 3 nm pores of 1 to 10% of the total pore volume.

11. The hydrodenitrogenation catalyst of claim 10, wherein, The properties of the hydrodenitrogenation catalyst include a pore volume of 0.15 to 0.6 cm 3 / g, an average pore diameter of 6 to 12 nm, and a pore volume of 0 to 3 nm pores of 2 to 5% of the total pore volume.

12. The process for preparing a hydrodenitrogenation catalyst according to any one of claims 1 to 11, characterized in that, The method comprises the following steps: (1) preparing an organosilicon modified nickel-aluminum alloy carrier; (2) preparing an impregnation solution containing an organomolybdenum compound and an organogallium compound, impregnating the organosilicon modified nickel-aluminum alloy carrier obtained in step (1), and drying to obtain a hydrogen denitrification catalyst; In step (2), the organomolybdenum compound used for preparing the impregnation solution is molybdenum alkyl dithiophosphate and / or molybdenum alkyl dithiocarbamate.

13. The method of claim 12, wherein, In step (1), the method for preparing the organosilicon modified nickel-aluminum alloy carrier comprises contacting a nickel-aluminum alloy with a gaseous silicon-containing compound for organosilicon modification.

14. The method of claim 13, wherein, The method for preparing the organosilicon modified nickel-aluminum alloy carrier comprises vacuumizing a nickel-aluminum alloy carrier, introducing a gaseous silicon-containing compound for organosilicon modification, introducing nitrogen and / or an inert gas for replacement, and obtaining an organosilicon modified nickel-aluminum alloy carrier.

15. The method according to claim 13 or 14, characterized in that, The content of Al, calculated as an element, is 50wt% to 95wt%, and the content of Ni, calculated as an element, is 5wt% to 50wt% based on the total amount of the nickel-aluminum alloy.

16. The method of claim 15, wherein, The content of aluminum, in terms of element, is 70wt%-90wt% and the content of nickel, in terms of element, is 10wt%-30wt%, based on the total amount of the nickel-aluminum alloy.

17. The method of claim 13 or 14, wherein, The nickel-aluminum alloy has a pore volume of 0.4 to 1.0 cm 3 / g, and an average pore diameter of 4 to 12 nm, wherein the volume ratio of small pores of less than 3.0 nm is not higher than 20%.

18. The method of claim 17, wherein, The nickel-aluminum alloy has a pore volume of 0.5 to 0.9 cm 3 / g, and an average pore diameter of 6 to 10 nm, wherein the volume ratio of small pores of less than 3.0 nm is 5 to 10%.

19. The method of claim 14, wherein, The temperature of the vacuumizing treatment is 50-200℃, the vacuum degree is 0.05-1.0 torr, and the treatment time is 2-10 hours.

20. The method of claim 19, wherein, The temperature of the vacuumizing treatment is 80-150℃, the vacuum degree is 0.1-0.5 torr, and the treatment time is 4-8 hours.

21. The method of claim 13 or 14, wherein, The gaseous silicon-containing compound is a gaseous alkoxysilane.

22. The method of claim 21, wherein, The gaseous alkoxysilane is one or more of methyltrimethoxysilane, triethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, isobutyltriethoxysilane, and n-octyltriethoxysilane.

23. The method of claim 14, wherein, The silicon-containing compound in the gas phase is also supplied together with at least one of nitrogen and an inert gas as a carrier gas; the partial pressure of the silicon-containing compound in the gas phase is 0.02-1.0 MPa, the temperature of the modification treatment is 160-400℃, the time is 1.0-10.0 hours, and the flow rate of the silicon-containing compound in the gas phase is 1.0-20.0 mL / min·g -1 Nickel-aluminum alloy carrier.

24. The method of claim 23, wherein, The partial pressure of the silicon-containing compound in the gas phase is 0.05-0.5 MPa, the temperature of the modification treatment is 180-350℃, the time is 2.0-8.0 hours, and the flow rate of the silicon-containing compound introduced into the gas phase is 3.0-15.0 mL / min·g -1 Nickel-aluminum alloy carrier.

25. The method of claim 14, wherein, The conditions of the substitution include: the nitrogen and / or inert gas flow rate is 0.5-5 mL / min·g -1 Nickel-aluminum alloy carrier, substitution time is 0.5-8.0 hours, temperature is 100-400℃.

26. The method of claim 25, wherein, The conditions of the substitution include: the flow rate of nitrogen and / or inert gas is 1-4 mL / min·g -1 Nickel-aluminum alloy carrier, substitution time is 1.0-4.0 hours, temperature is 150-350℃.

27. The method of claim 12, wherein, In step (2), the organic molybdenum compound and the organic gallium compound are mixed with a solvent to prepare an impregnation solution; the solvent is one or a mixture of several of n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, ethanol, methanol, and isopropanol; the concentration of the organic molybdenum and the organic gallium in the impregnation solution is independently 0.1-3 mol / L.

28. The method of claim 12, wherein, In step (2), the drying is vacuum drying, the vacuum degree is 0.5-5.0 torr, the drying temperature is 60-150℃, and the drying time is 2.0-12.0 h.

29. The method of claim 28, wherein, In step (2), the drying is vacuum drying, the vacuum degree is 1.0-3.0 torr, the drying temperature is 70-120℃, and the drying time is 4.0-8.0 h.

30. Use of the hydrodenitrogenation catalyst of any one of claims 1-11 or the hydrodenitrogenation catalyst prepared according to the method of any one of claims 12-29 in the hydrodenitrogenation of a secondary processing oil.

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