A hydrodenitrification catalyst and its preparation method

Abstract

This invention discloses a hydrodenitrogenation catalyst and its preparation method. The hydrodenitrogenation catalyst is a sulfide-state catalyst, comprising a support and active metals Mo and Ni, and also including Ga. Characterized by TEM-EDS, the Ga content distributed in the Ni-Mo-S active phase region accounts for 60%-95% of the total Ga content. The catalyst of this invention exhibits strong hydrodenitrogenation selectivity while maintaining a certain degree of hydrosaturation capacity, especially showing stronger hydrodenitrogenation activity and long-term stability for heavy oil products with high residual carbon content.

Description

Technical Field

[0001] This invention relates to a method for preparing a hydrogenation catalyst, and more particularly to a Ga-modified hydrogenation denitrification catalyst and its preparation method. Background Technology

[0002] Hydrodenitrification has always been a challenge in the hydrotreating process of residual oil molecules. One important reason is that the CN bond of nitrides is more stable than the bond formed between other heteroatoms and carbon atoms. In addition, the substituents of residual oil molecules hinder the effective adsorption of nitride molecules on the hydrotreating active phase, which further complicates the removal of CN bonds by hydrotreating. To promote the breaking of CN bonds, the interaction between the hydrotreating active phase and nitride molecules can be strengthened, especially the interaction between the active phase and nitrogen atoms.

[0003] CN103212432A discloses a catalyst for hydrodenitrogenation of inferior heavy distillate oil, its preparation method, and its application. This method uses a composite of alumina and HY molecular sieve as a support for hydrodenitrogenation. This strongly acidic support significantly improves the hydrodenitrogenation effect. However, increasing the acidity of the support often results in poor catalyst stability and a shorter catalyst lifespan when processing heavy oil products.

[0004] CN109718750A discloses a support, catalyst, and preparation method for hydrodenitrogenation. The support is a silica-alumina support containing rod-shaped silica-alumina clusters. The rod-shaped silica-alumina clusters are 1-4 μm long and 100-300 nm in diameter, with an outer diameter of 5-18 μm. The rod-shaped silica-alumina clusters constitute 5%-15% of the weight of the silica-alumina support. This hydrodenitrogenation catalyst support, being a silica-alumina support, has strong acidity, which can lead to poor catalyst stability and a shortened catalyst lifespan. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a hydrodenitrogenation catalyst and its preparation method. The catalyst of this invention exhibits strong hydrodenitrogenation selectivity while maintaining a certain level of hydrogenation saturation capacity, and demonstrates particularly enhanced hydrodenitrogenation activity and long-term stability for heavy oil products with high residual carbon content.

[0006] The first aspect of the present invention provides a hydrodenitrification catalyst, wherein the hydrodenitrification catalyst is a sulfide-state catalyst, comprising a support and active metals Mo and Ni, and further comprising Ga, wherein, characterized by TEM-EDS, the Ga content distributed in the Ni-Mo-S active phase region accounts for 60%-95% of the total Ga content, preferably 75%-90%.

[0007] Furthermore, in the hydrodenitrification catalyst, the sulfur content at the corner sites of the Ni-Mo-S active phase, characterized by TEM-EDS, is less than 4.0% of the total sulfur content in the Ni-Mo-S active phase, and further is 0.5%-3.0%.

[0008] Furthermore, the hydrodenitrogenation catalyst, based on its mass, contains 10%-20% molybdenum (Mo), preferably 13%-18%, and 1.5%-6.5% nickel (Ni), preferably 2.0%-6%.

[0009] Furthermore, the hydrodenitrogenation catalyst, based on its mass, contains 0.4%-4.0% Ga, preferably 0.8%-3.0% Ga.

[0010] Furthermore, the hydrodenitrogenation catalyst, based on its mass, has a sulfur content of 8%-16%, preferably 9%-15%, calculated as S.

[0011] Furthermore, the hydrodenitrification catalyst, based on its mass, has a support content of 55%-75%, preferably 60%-70%.

[0012] Furthermore, in the hydrodenitrification catalyst, the support can be an inorganic refractory oxide, such as at least one of alumina, silicon oxide, or amorphous aluminum silicate. The specific surface area of ​​the support is 200-500 m². 2 / g, preferably 250-400m 2 / g, pore volume 0.4-1.0cm 3 / g, preferably 0.6-0.8cm 3 / g. The carrier may also be doped with one or more modifying elements such as phosphorus, silicon, boron, fluorine, and sodium. The amount of the modifying element added is a conventional amount, preferably 0.5%-6.0% of the carrier mass.

[0013] A second aspect of the present invention provides a method for preparing a hydrodenitrification catalyst, the method comprising:

[0014] (1) The oxidized hydrogenation catalyst is subjected to primary sulfidation to obtain the sulfidized hydrogenation catalyst;

[0015] (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment;

[0016] (3) An organic solution containing Ga and a stabilizer is introduced into the catalyst treated in step (2) to carry out the reaction and obtain a hydrodenitrification catalyst.

[0017] Further, in step (1), the oxidized hydrogenation catalyst comprises: a support, active metal components molybdenum and nickel. Based on the weight of the oxidized hydrogenation catalyst, the content of the support is 50%-80%, the content of molybdenum as oxide is 15%-40%, and the content of nickel as oxide is 3%-10%.

[0018] Further, in step (1), the support in the oxidized hydrogenation catalyst is at least one of alumina, silicon oxide, or amorphous silica-alumina. The specific surface area of ​​the support is 200-500 m². 2 / g, preferably 250-400m 2 / g. The pore volume of the carrier is 0.4-1.0 cm³. 3 / g, preferably 0.6-0.8cm 3 / g. The carrier may be doped with one or more modifying elements such as phosphorus, silicon, boron, fluorine, and sodium. The amount of the modifying element added is a conventional amount, preferably 0.5%-6.0% of the carrier mass.

[0019] Furthermore, in step (1), the oxidized hydrogenation catalyst is a catalyst with heavy oil hydrogenation function, which can be prepared by conventional methods in the art or a commercially available catalyst can be purchased.

[0020] Furthermore, in step (1), the initial sulfidation is a full sulfidation, meaning that the active metal in the oxidized hydrogenation catalyst reaches the degree of complete sulfidation, which can be achieved using a known sulfidation method. For example, the conditions for the initial sulfidation are as follows: temperature of 240-400℃, preferably 280-380℃, sulfidation time of 3-8h, hydrogen pressure of 2.0-12.0MPa, preferably 3.0-10.0MPa, and hydrogen flow rate of 2.0-15.0mL·min during sulfidation. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3.0-10.0 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

[0021] Further, in step (1), the vulcanizing liquid used for the initial vulcanization includes a sulfur-containing compound and an organic solvent. The sulfur-containing compound is at least one selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethanethiol, n-butanethiol, di-tert-methyl polysulfide, and dimethyl sulfoxide. The organic solvent is at least one selected from cyclohexane, n-heptane, aviation kerosene, and diesel oil. The mass fraction of the sulfur-containing compound in the vulcanizing liquid is 2%-6%, preferably 4%-6%. The flow rate of the vulcanizing liquid is 0.5-4.0 mL·h. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 1.0-4.0 mL·h -1 ·g-1 Oxidized hydrogenation catalyst.

[0022] Furthermore, in step (2), the desulfurization treatment is a mild desulfurization treatment, carried out in at least one of the following ways:

[0023] (a) The sulfided hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment using hydrogen gas containing hydrogen sulfide;

[0024] (b) In the presence of hydrogen, the sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment with a sulfurized liquid.

[0025] Further, in step (2), the temperature of the desulfurization treatment is 180-370℃, preferably 200-300℃. The treatment time is 4-24 hours, preferably 6-16 hours, and the total pressure is 2.0-18.0MPa, preferably 4.0-15.0MPa.

[0026] Furthermore, in step (2), the temperature of the desulfurization treatment is 50-100°C lower than the temperature of the sulfurization treatment in step (1).

[0027] Further, in method (a), the volume ratio of hydrogen sulfide to hydrogen is 200:1-800:1, preferably 300:1-600:1, and the total gas flow rate is 5-30 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-20 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

[0028] Further, in method (b), the sulfiding liquid comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethanethiol, n-butanethiol, di-tert-methyl polysulfide, and dimethyl sulfoxide; and the organic solvent is at least one selected from cyclohexane, n-heptane, aviation kerosene, and diesel oil. The mass fraction of the sulfur-containing compound in the sulfiding liquid is 0.1%-0.6%. During the desulfurization process, the flow rate of the sulfiding liquid is 0.2-2.0 mL·h. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 0.4-1.5 mL·h -1 ·g -1 Oxidized hydrogenation catalyst. Hydrogen flow rate: 5-30 mL / min. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-20 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

[0029] Further, in step (3), the organic solution containing Ga and a stabilizer contains one or more of the following solvents: toluene, cyclohexane, decahydronaphthalene, tetrahydronaphthalene, and n-heptane; the Ga-containing compound is one or more of gallium acetylacetonate and triethylgallium; and the stabilizer is one or more of triethanolamine, diethanolamine, monoethanolamine, and aniline. Specifically, the mass content of the Ga-containing compound in the organic solution containing Ga and a stabilizer is 0.5%-5%, preferably 1.5%-4%, and the mass content of the stabilizer is 2%-8%, preferably 3%-6%.

[0030] Further, in step (3), the reaction temperature is 80-200℃, preferably 100-160℃, the pressure is 0.2-4.0MPa, preferably 0.5-2.0MPa, and the reaction time is 2-12 hours, preferably 4-10 hours. The hydrogen flow rate is 2-20mL·min. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 5-15 mL·min -1 ·g -1 Oxidized hydrogenation catalyst. The flow rate of the organic solution containing Ga and a stabilizer is 2-10 mL / h. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3-8 mL·h -1 ·g -1 Oxidized hydrogenation catalyst.

[0031] A third aspect of the present invention also provides the application of the above-mentioned hydrodenitrogenation catalyst in the hydrodenitrogenation of heavy oil.

[0032] Further, the application is that the hydrodenitrification catalyst is used to treat heavy oil products with a nitrogen content of 1000 μg / g or higher, more specifically 1500-3000 μg / g, and a residual carbon content of 10 wt% or higher, more specifically 12 wt%-15 wt%. The total nickel and vanadium content (Ni+V) of the heavy oil product is less than 100 μg / g, more specifically 20-60 μg / g. The heavy oil product may be, for example, deasphalted oil.

[0033] Furthermore, the operating conditions for the application are as follows: reaction temperature of 300-420℃, preferably 350-400℃; hydrogen pressure of 10.0-25.0 MPa, preferably 15.0-22.0 MPa; and liquid hourly space velocity of 0.1-1.0 h⁻¹. -1 Preferably 0.15-0.5h -1 The hydrogen-to-oil volume ratio is 600:1-1500:1, preferably 800:1-1200:1.

[0034] Compared with the prior art, the present invention has the following advantages:

[0035] 1. The catalyst provided by this invention has high hydrogenation denitrification capacity and selectivity, appropriate hydrogenation decarbonization capacity, and good long-term stability.

[0036] 2. The preparation method of the catalyst of the present invention is to first perform initial sulfidation and desulfurization on the oxidized hydrogenation catalyst, so that the metal active phase to be modified is in a specific desulfurized high-activity state, and the outer layer of the active phase edge is exposed active metal. At the same time, the three-coordinated sulfur atoms and the stable Ni-Mo-S crystal structure inside the hydrogenation active phase can be effectively retained. The modified Ga element can more effectively contact the outer metal phase of the active phase, so that in the obtained hydrogenation denitrification catalyst, Ga, Ni, Mo and S form a Ga-Ni-Mo-S combined mixed active phase, thereby achieving the purpose of modification. Detailed Implementation

[0037] The present invention will be further described below with reference to embodiments, but it should be understood that the scope of protection of the present invention is not limited to the embodiments. In the present invention, unless otherwise expressly stated, percentages and contents are all expressed by mass.

[0038] In this invention, the hydrodenitrification catalyst was characterized by TEM-EDS (transmission electron microscopy-energy dispersive X-ray spectroscopy) using an instrument of model JY / T 011-1996, JEM-1400Flash. The determination process is as follows: the catalyst particles were ground and the sample was prepared by suspension method. 0.1g of the catalyst sample was placed in a 2mL container and ultrasonically dispersed with anhydrous ethanol. The supernatant was collected, and two to three drops were taken with a dropper and dropped onto a 3mm diameter sample grid. After drying, the sample to be tested was obtained. Then, the sample to be tested was observed and analyzed by TEM. Combined with EDS, the Ga content distribution was statistically analyzed. The ratio of Ga content distributed in the Ni-Mo-S active phase region to the total Ga content (Ga-Ni-Mo-S / Ga) was obtained based on the corresponding peak area of ​​Ga. 总 (This means that) the present invention selects 20 TEM images and combines them with the average value obtained by EDS analysis.

[0039] In this invention, the sulfur content at the corner sites of the Ni-Mo-S active phase relative to the total sulfur content in the Ni-Mo-S active phase is characterized using the TEM-EDS method. The instrument used is JY / T 011-1996, JEM-1400Flash. The determination process is as follows: The catalyst particles are ground and the sample is prepared using the suspension method. 0.1g of the catalyst sample is placed in a 2mL container and ultrasonically dispersed with anhydrous ethanol. The supernatant is collected, and two to three drops are taken with a dropper and dropped onto a 3mm diameter sample mesh. After drying, the sample to be tested is obtained. Then, the sample to be tested is observed and analyzed using TEM. Any active phase observed under a TEM microscope is selected, and combined with EDS, the sulfur content at the edge of the active phase (which can be considered the corner sites of the active phase) and the sulfur content in the active phase are statistically analyzed. The sulfur content at the corner sites of the Ni-Mo-S active phase relative to the total sulfur content in the Ni-Mo-S active phase is obtained based on the corresponding peak area of ​​sulfur. (Using S...) 边角位 / S 总 (Represented). This invention uses the average value obtained from 20 TEM images combined with EDS analysis.

[0040] The oxidized hydrogenation catalysts used in the following embodiments and comparative examples of this invention were all prepared by the following methods:

[0041] Weigh 1000.0g of alumina dry adhesive powder, add 30.0g of citric acid and 10.0g of guar gum powder, mix well, then add 900.0g of an aqueous solution containing 2.0% nitric acid. After rolling for 30.0min, extrude the mixture using a 1.6mm diameter clover-shaped perforated plate. Dry at 120℃ for 6.0h, then calcine at 600℃ for 6.0h. The calcined carrier is designated S-0 (the specific surface area of ​​the carrier is 304m²). 2 / g, pore volume 0.75cm 3 Weigh 120.0 g ammonium heptamolybdate tetrahydrate, 80.0 g nickel nitrate hexahydrate, and 120.0 g deionized water. Stir thoroughly at 80 °C for 30 min, cool to room temperature, and then dilute to 180.0 mL with deionized water. The resulting solution is denoted as Q-0.

[0042] Take 200g of support S-0, impregnate it with Q-0, air dry it naturally for 24 hours, then dry it at 120℃ for 4 hours, and then calcine it at 420℃ for 4.0 hours. The resulting oxidized hydrogenation catalyst is denoted as CT-0 (by weight of catalyst, the content of support is 68.4%, the content of molybdenum as oxide is 26.5%, and the content of nickel as oxide is 5.1%).

[0043] Example 1

[0044] Take 1000g of cyclohexane and 50.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as SQ-0.

[0045] Take 1000g of cyclohexane and 2.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as TQ-1.

[0046] Take 1000g toluene, 25.0g gallium acetylacetonate, and 40.0g triethanolamine, and prepare an organic solution containing gallium, denoted as GQ-1.

[0047] 20.0g of CT-0 was loaded into a reaction tube and sulfided using SQ-0. During the sulfidation process, the hydrogen pressure was 6.0MPa, the hydrogen flow rate was 300.0mL / min, the flow rate of the sulfidation liquid SQ-0 was 40.0mL / h, the sulfidation temperature was 350℃, and the sulfidation time was 6 hours. The resulting sulfided hydrogenation catalyst was denoted as SCT-0.

[0048] The reaction tube temperature was lowered to 260℃, the hydrogen pressure was adjusted to 5.0 MPa, and the hydrogen flow rate was 200.0 mL / min. TQ-1 was introduced into the reaction tube at a flow rate of 30.0 mL / h, and the treatment time was 9 hours. The obtained catalyst was designated TCT-1.

[0049] The reaction tube temperature was lowered to 110℃, the hydrogen pressure was adjusted to 0.8 MPa, and the hydrogen flow rate was 120.0 mL / min. GQ-1 was introduced into the reaction tube at a flow rate of 120.0 mL / h, and the treatment time was 8.0 hours. The resulting catalyst was designated ECT-1.

[0050] Example 2

[0051] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0052] Take 1000g of cyclohexane and 3.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as TQ-2.

[0053] Take 1000g toluene, 15.0g triethylgallium, and 50.0g triethanolamine, and prepare an organic solution containing gallium, denoted as GQ-2.

[0054] The reaction tube temperature was lowered to 280℃, the hydrogen pressure was adjusted to 6.0 MPa, and the hydrogen flow rate was 300.0 mL / min. TQ-2 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was 12 hours. The obtained catalyst was designated TCT-2.

[0055] The reaction tube temperature was lowered to 130℃, the pressure adjusted to 1.2 MPa, the hydrogen flow rate was 150.0 mL / min, and GQ-2 was introduced into the reaction tube at a flow rate of 120.0 mL / h for 8.0 hours. The resulting catalyst was designated ECT-2.

[0056] Example 3

[0057] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0058] The preparation processes of support S-0, solution Q-0, oxidized hydrogenation catalyst CT-0, sulfidation liquid SQ-0, and sulfidation catalyst SCT-0 are the same as in Example 1.

[0059] Take 1000g of cyclohexane and 4.0g of dimethyl disulfide, and the resulting sulfidation solution is designated as TQ-3.

[0060] Take 1000g toluene, 10.0g triethylgallium, 20.0g gallium acetylacetonate, and 60.0g triethanolamine, and prepare an organic solution containing gallium, denoted as GQ-3.

[0061] The reaction tube temperature was lowered to 300℃, the hydrogen pressure was adjusted to 10.0 MPa, and the hydrogen flow rate was 400.0 mL / min. TQ-3 was introduced into the reaction tube at a flow rate of 40.0 mL / h, and the treatment time was 12 hours. The obtained catalyst was designated as TCT-3.

[0062] The reaction tube temperature was lowered to 150℃, the pressure adjusted to 1.8 MPa, the hydrogen flow rate was 180.0 mL / min, and GQ-3 was introduced into the reaction tube at a flow rate of 120.0 mL / h for 8.0 hours. The resulting catalyst was designated ECT-3.

[0063] Example 4

[0064] The preparation processes of support S-0, solution Q-0, oxidized hydrogenation catalyst CT-0, sulfidation liquid SQ-0, and sulfidation catalyst SCT-0 are the same as in Example 1.

[0065] The reaction tube temperature was lowered to 280℃, the reaction pressure was adjusted to 6.0 MPa, and a mixture of hydrogen and hydrogen sulfide was introduced into the reaction tube at a volume ratio of 400:1. The total flow rate of the mixed gas was 400 mL / min, and the treatment time was 12 hours. The resulting catalyst was designated TCT-4.

[0066] Take 1000g toluene, 15.0g triethylgallium, 15.0g gallium acetylacetonate, and 60.0g triethanolamine to prepare an organic solution containing gallium, denoted as GQ-4.

[0067] The reaction tube temperature was lowered to 150℃, the pressure adjusted to 0.6 MPa, the hydrogen flow rate was 150.0 mL / min, and GQ-4 was introduced into the reaction tube at a flow rate of 120.0 mL / h for 8.0 hours. The resulting catalyst was designated ECT-4.

[0068] Example 5

[0069] The preparation processes of support S-0, solution Q-0, oxidized hydrogenation catalyst CT-0, sulfidation liquid SQ-0, and sulfidation catalyst SCT-0 are the same as in Example 1.

[0070] The reaction tube temperature was lowered to 280℃, the reaction pressure was adjusted to 6.0 MPa, and a mixture of hydrogen and hydrogen sulfide was introduced into the reaction tube at a volume ratio of 500:1. The total flow rate of the mixed gas was 500 mL / min, and the treatment time was 12 hours. The resulting catalyst was designated TCT-5.

[0071] Take 1000g toluene, 10.0g triethylgallium, 20.0g gallium acetylacetonate, and 60.0g triethanolamine, and prepare an organic solution containing gallium, denoted as GQ-5.

[0072] The reaction tube temperature was lowered to 150℃, the pressure adjusted to 0.6 MPa, the hydrogen flow rate was 150.0 mL / min, and GQ-5 was introduced into the reaction tube at a flow rate of 120.0 mL / h for 8.0 hours. The resulting catalyst was designated ECT-5.

[0073] Example 6

[0074] The method of Example 1 was followed, except that triethanolamine was not added to GQ-1. The resulting catalyst was designated ECT-6.

[0075] Comparative Example 1

[0076] Take 20.0g of CT-0 and put it into a reaction tube. Use SQ-0 for sulfidation. During the sulfidation process, the hydrogen pressure is 6.0MPa, the hydrogen flow rate is 300.0mL / min, the flow rate of the sulfidation liquid SQ-0 is 40.0mL / h, the sulfidation temperature is 350℃, and the sulfidation time is 6 hours. The catalyst after sulfidation is designated as DCT-1.

[0077] Comparative Example 2

[0078] The preparation process of catalyst DCT-1 is the same as that of comparative example 1.

[0079] The reaction tube containing DCT-1 was cooled to 260℃, the hydrogen pressure was adjusted to 5.0 MPa, and the hydrogen flow rate was 200.0 mL / min. TQ-1 was then introduced into the reaction tube at a flow rate of 30.0 mL / h for 9 hours. The resulting catalyst was designated DCT-2.

[0080] Comparative Example 3

[0081] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0082] The reaction tube containing SCT-0 was cooled to 110℃, the pressure was adjusted to 0.8 MPa, the hydrogen flow rate was 120.0 mL / min, and GQ-1 was introduced into the reaction tube at a flow rate of 120 mL / h for 8.0 hours. The resulting catalyst was designated DCT-3.

[0083] Comparative Example 4

[0084] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0085] The reaction tube containing SCT-0 was cooled to 260℃, the hydrogen pressure was adjusted to 5.0 MPa, the hydrogen flow rate was 240.0 mL / min, and the treatment time was 9 hours. The resulting catalyst was designated DTCT-4.

[0086] The reaction tube temperature was lowered to 110℃, the pressure adjusted to 0.8 MPa, the hydrogen flow rate was 120.0 mL / min, and GQ-1 was introduced into the reaction tube at a flow rate of 120 L / h for 8.0 hours. The resulting catalyst was designated DCT-4.

[0087] Comparative Example 5

[0088] Weigh 1000.0g of alumina dry adhesive powder, add 30.0g of citric acid and 10.0g of guar gum powder, mix well, then add 900.0g of an aqueous solution containing 2.0% nitric acid by mass. After rolling for 30.0min, extrude the mixture using a 1.6mm diameter clover-shaped perforated plate. Dry at 120℃ for 6.0h, then calcine at 600℃ for 6.0h. The calcined carrier is designated S-0.

[0089] Weigh 120.0g ammonium heptamolybdate tetrahydrate, 80.0g nickel nitrate hexahydrate, 12.0g anhydrous gallium nitrate, and 120.0g deionized water. Stir thoroughly at 80℃ for 30 minutes, cool to room temperature, and then dilute to 180.0mL with deionized water. The resulting solution is denoted as DQ-5.

[0090] Take 200g of carrier S-0, impregnate it with DQ-5, air dry it naturally for 24 hours, then dry it at 120℃ for 4 hours, and then calcine it at 420℃ for 4.0 hours. The resulting oxidized hydrogenation catalyst is denoted as DCT-0.

[0091] 20.0g of DCT-0 was loaded into a reaction tube and sulfided using SQ-0 (same as in Example 1). During the sulfidation process, the hydrogen pressure was 6.0MPa, the hydrogen flow rate was 300.0mL / min, the flow rate of the sulfidation liquid SQ-0 was 40.0mL / h, the sulfidation temperature was 350℃, and the sulfidation time was 6 hours. The resulting sulfided hydrogenation catalyst was designated as DCT-5.

[0092] Table 1 shows the physicochemical composition of the catalysts obtained in each example.

[0093]

[0094]

[0095] The hydrodenitrification catalyst was characterized by TEM-EDS to obtain the percentage of Ga content distributed in the Ni-Mo-S active phase region and the percentage of sulfur content at the corner sites of the Ni-Mo-S active phase. See Table 2 for details.

[0096] Table 2

[0097] Catalyst number ECT-1 ECT-2 ECT-3 ECT-4 ECT-5 ETC-6 DCT-1 DCT-2 DCT-3 DCT-4 DCT-5 <![CDATA[Ga-Ni-Mo-S / Ga 总 ,%]]> 79 80 79 76 83 59 - - 29 43 27 <![CDATA[S 边角位 / S 总 ,%]]> 1.5 1.1 1.3 1.0 1.2 1.3 8.5 1.2 7.2 4.5 7.9

[0098] Examples 7-12

[0099] The activity of the catalysts obtained in Examples 1-6 was evaluated, and the properties of the deasphalted oil are shown in Table 3. A fixed-bed process was used, with a hydrotreating protectant (FZC-100B) loaded before the above catalysts. The volume ratio of the protectant to the hydrodenitrification catalyst obtained in the examples was 1:4. The operating conditions were: reaction temperature 390℃, reaction pressure 20.0 MPa, hydrogen-to-oil volume ratio 1000:1, and liquid hourly space velocity 0.2 h⁻¹. -1 After 2000 hours of reaction evaluation, the residual carbon value, sulfur content, and nitrogen content of the hydrogenated oil fraction at a temperature not lower than 200℃ were analyzed, and the results are shown in Table 4.

[0100] Comparative Examples 6-10

[0101] The activity of the catalysts obtained in Comparative Examples 1-5 was evaluated, and the properties of the deasphalted oil are shown in Table 3. A fixed-bed process was used, with a hydrotreating protectant (FZC-100B) loaded before the above catalysts. The volume ratio of the protectant to the hydrodenitrification catalyst obtained in the comparative examples was 1:4. The operating conditions were: reaction temperature 390℃, reaction pressure 20.0 MPa, hydrogen-to-oil volume ratio 1000:1, and liquid hourly space velocity (LISH) 0.2 h⁻¹. -1 After 1000 hours of reaction evaluation, the residual carbon value, sulfur content, and nitrogen content of the hydrotreated oil fraction at temperatures not lower than 200℃ were analyzed, and the results are shown in Table 4.

[0102] Table 3 Properties of Deasphalted Oil

[0103] <![CDATA[Density, kg / m 3 > 998 Vanadium + Nickel content, μg / g 24.4 Sulfur content, μg / g 35074 Nitrogen content, μg / g 2958 Saturated fraction, wt% 42.8 Aromatic components, wt% 35.2 Gel, wt% 21.9 Asphalt, wt% 0.1 Carbon residue value, wt% 12.9

[0104] Table 4. Evaluation results of catalyst hydrogenation after 2000 hours.

[0105] Catalyst number Nitrogen content, μg / g Carbon residue value, wt% Saturated fraction, wt% Sulfur content, μg / g Example 7 ECT-1 413 1.2 61.3 1263 Example 8 ECT-2 385 1.3 59.3 1534 Example 9 ECT-3 359 1.1 60.5 1397 Example 10 ECT-4 401 0.9 61.9 1429 Example 11 ECT-5 365 1.0 58.7 1296 Example 12 ECT-6 604 1.8 57.4 1710 Comparative Example 6 DCT-1 1362 4.0 48.9 2436 Comparative Example 7 DCT-2 1638 4.2 51.4 3637 Comparative Example 8 DCT-3 761 2.1 55.8 1937 Comparative Example 9 DCT-4 1068 3.0 50.7 2594 Comparative Example 10 DCT-5 846 2.6 56.8 2193

[0106] As can be seen from the evaluation results in Table 4, the hydrodenitrification catalyst prepared in this invention not only has excellent hydrodenitrification capability, but also good aromatic saturation capability and hydrodesulfurization capability.

Claims

1. A hydrodenitrification catalyst, wherein the hydrodenitrification catalyst is a sulfide-state catalyst, comprising a support and active metals Mo and Ni, and further comprising Ga, wherein, Characterized by TEM-EDS, the Ga content distributed in the Ni-Mo-S active phase region accounts for 60%-95% of the total Ga content; The hydrodenitrogenation catalyst is prepared by the following method, including: (1) The oxidized hydrogenation catalyst is subjected to primary sulfidation to obtain the sulfidated hydrogenation catalyst, wherein the primary sulfidation is full sulfidation; (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment, wherein the desulfurization treatment is a mild desulfurization treatment; (3) Pass an organic solution containing Ga and a stabilizer into the catalyst treated in step (2) to carry out the reaction and obtain a hydrodenitrification catalyst.

2. The hydrodenitrification catalyst according to claim 1, characterized in that: Characterized by TEM-EDS, the Ga content distributed in the Ni-Mo-S active phase region accounts for 75%-90% of the total Ga content.

3. The hydrodenitrification catalyst according to claim 1, characterized in that: Characterized by TEM-EDS, the sulfur content at the corner sites of the Ni-Mo-S active phase accounts for less than 4.0% of the total sulfur content in the Ni-Mo-S active phase. The sulfur content at the corner sites refers to the sulfur content at the edge endpoint of the active phase, which is less than 1 nm away from the edge.

4. The hydrodenitrification catalyst according to claim 3, characterized in that: Characterized by TEM-EDS, the sulfur content at the corner sites of the Ni-Mo-S active phase accounts for 0.5%-3.0% of the total sulfur content in the Ni-Mo-S active phase.

5. The hydrodenitrification catalyst according to claim 1, characterized in that: Based on the mass of the hydrodenitrification catalyst, the content of molybdenum (Mo) is 10%-20%, the content of nickel (Ni) is 1.5%-6.5%, and the content of the support is 55%-75%.

6. The hydrodenitrification catalyst according to claim 5, characterized in that: Based on the mass of the hydrodenitrification catalyst, the molybdenum content (Mo) is 13%-18%, the nickel content (Ni) is 2.0%-6%, and the support content is 60%-70%.

7. The hydrodenitrification catalyst according to claim 1 or 5, characterized in that: Based on the mass of the hydrodenitrification catalyst, the content of Ga (calculated as Ga) is 0.4%-4.0%, and the content of sulfur (calculated as S) is 8%-16%.

8. The hydrodenitrification catalyst according to claim 7, characterized in that: Based on the mass of the hydrodenitrification catalyst, the content of Ga (calculated as Ga) is 0.8%-3.0%, and the content of sulfur (calculated as S) is 9%-15%.

9. A method for preparing a hydrodenitrification catalyst according to any one of claims 1-8, comprising: (1) The oxidized hydrogenation catalyst is subjected to primary sulfidation to obtain the sulfidated hydrogenation catalyst, wherein the primary sulfidation is full sulfidation; (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment, wherein the desulfurization treatment is a mild desulfurization treatment; (3) Pass an organic solution containing Ga and a stabilizer into the catalyst treated in step (2) to carry out the reaction and obtain a hydrodenitrification catalyst.

10. The method according to claim 9, characterized in that: In step (1), the oxidized hydrogenation catalyst includes: a support, active metal components molybdenum and nickel; based on the weight of the oxidized hydrogenation catalyst, the content of the support is 50%-80%, the content of molybdenum as oxide is 15%-40%, and the content of nickel as oxide is 3%-10%.

11. The method according to claim 9, characterized in that: In step (1), the initial vulcanization conditions are as follows: temperature is 240-400℃, vulcanization time is 3-8h, and during the vulcanization process, the hydrogen pressure is 2.0-12.0MPa and the hydrogen flow rate is 2.0-15.0 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst.

12. The method according to claim 9, characterized in that: In step (2), the desulfurization treatment is carried out in one of the following ways: (a) The sulfided hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment using hydrogen gas containing hydrogen sulfide; (b) In the presence of hydrogen, the sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment with a sulfurized liquid.

13. The method according to claim 12, characterized in that: In step (2), the temperature of the desulfurization treatment is 180-370℃, the treatment time is 4-24 hours, and the total pressure is 2.0-18.0MPa.

14. The method according to claim 13, characterized in that: In step (2), the temperature of the desulfurization treatment is 200-300℃, the treatment time is 6-16 hours, and the total pressure is 4.0-15.0MPa.

15. The method according to claim 13, characterized in that: In step (2), the temperature of the desulfurization treatment is 50-100°C lower than the temperature of the sulfurization treatment in step (1).

16. The method according to claim 12, characterized in that: In method (a), the volume ratio of hydrogen sulfide to hydrogen is 200:1-800:1, and the total gas flow rate is 5-30 mL / min. -1 ·g -1 Oxidized hydrogenation catalyst.

17. The method according to claim 16, characterized in that: In method (a), the volume ratio of hydrogen sulfide to hydrogen is 300:1-600:1, and the total gas flow rate is 10-20 mL / min. -1 ·g -1 Oxidized hydrogenation catalyst.

18. The method according to claim 12, characterized in that: In method (b), the sulfiding liquid comprises a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one selected from dimethyl disulfide, carbon disulfide, diethyl sulfide, ethanethiol, n-butanethiol, di-tert-nonyl polysulfide, and dimethyl sulfoxide; the organic solvent is at least one selected from cyclohexane, n-heptane, aviation kerosene, and diesel oil; the mass fraction of the sulfur-containing compound in the sulfiding liquid is 0.1%-0.6%; and the flow rate of the sulfiding liquid during the desulfurization treatment is 0.2-2.0 mL·h. -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate 5-30 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

19. The method according to claim 18, characterized in that: In method (b), during the desulfurization treatment, the flow rate of the sulfurizing liquid is 0.4-1.5 mL·h. -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate 0-20 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

20. The method according to claim 9, characterized in that: In the organic solution containing Ga and a stabilizer, the solvent is one or more of toluene, cyclohexane, decahydronaphthalene, tetrahydronaphthalene, and n-heptane, and the Ga-containing compound is one or more of gallium acetylacetonate and triethylgallium; the stabilizer is one or more of triethanolamine, diethanolamine, monoethanolamine, and aniline; wherein, in the organic solution containing Ga and a stabilizer, the mass content of the Ga-containing compound is 0.5%-5%, and the mass content of the stabilizer is 2%-8%.

21. The method according to claim 9, characterized in that: In step (3), the reaction temperature is 80-200℃, the pressure is 0.2-4.0 MPa, and the reaction time is 2-12 hours; the hydrogen flow rate is 2-20 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst; flow rate of organic solution containing Ga and stabilizer is 2-10 mL·h -1 ·g -1 Oxidized hydrogenation catalyst.

22. The method according to claim 21, characterized in that: In step (3), the reaction temperature is 100-160℃ and the pressure is 0.5-2.0 MPa.

23. The application of a hydrodenitrification catalyst according to any one of claims 1-8 or a hydrodenitrification catalyst prepared according to any one of claims 9-22 in the hydrodenitrification of heavy oil.

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