A hydrodesulfurization catalyst and its preparation method

Abstract

This invention discloses a hydrodesulfurization catalyst and its preparation method. The hydrodesulfurization catalyst is a sulfided catalyst, comprising a support, active metals Mo and Ni, and Zn. Characterized by TEM-EDS, the Zn content distributed in the Ni-Mo-S active phase region accounts for 70%-90% of the total Zn content. The catalyst of this invention exhibits excellent hydrodesulfurization performance while maintaining a high hydrogenation saturation capacity, making it particularly suitable for processing high-sulfur feedstocks.

Description

Technical Field

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

[0002] During the hydrotreating process, the thiophene sulfides in the residue oil molecules have complex structures and often contain a large number of substituents, making it difficult to remove the CS bond by hydrogenation. In order to promote the breaking of the CS bond, the interaction between the hydrogenation active phase and the sulfide molecules can be strengthened, especially the interaction between the active center and the sulfur atom.

[0003] CN103627425A discloses a method for hydrodesulfurization of residual oil. This method uses a sodium salt solution of Group VIII acids, then impregnates nickel or cobalt salt talc into the sodium salt solution of Group VIII acids. After heat treatment, a catalyst is obtained. The resulting catalyst has highly dispersed metal loading and exhibits high catalytic activity. However, the introduction of a large amount of sodium into the catalyst severely damages its mechanical strength and surface properties. In industrial reactors, catalyst pulverization and breakage can lead to significant pressure drops, affecting long-term catalyst operation.

[0004] CN105441126A discloses a method for hydrodesulfurization of residual oil. This method mixes residual oil feedstock and streams from different product zones with hydrogen from different pipelines, and injects the separated gaseous effluent into a second high-pressure separator for further separation. This method exhibits good operational stability and uniform product distribution, but its desulfurization activity is not significantly improved.

[0005] CN111195525A discloses a residue oil hydrodesulfurization catalyst and its preparation method. This method utilizes activated carbon that has undergone high-temperature graphitization, acidification, and treatment with oxygen and inert gases as a support, and impregnates the activated carbon support with an active metal to obtain a highly active residue oil hydrodesulfurization catalyst. However, the hydrodesulfurization catalyst prepared by this method exhibits weak metal-support interaction and poor catalyst stability, making it unsuitable for long-term industrial operation. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a hydrodesulfurization catalyst and its preparation method. The catalyst of this invention exhibits excellent hydrodesulfurization performance while maintaining a high hydrogenation saturation capacity, making it particularly suitable for processing high-sulfur feedstocks.

[0007] The first aspect of the present invention provides a hydrodesulfurization catalyst, wherein the hydrodesulfurization catalyst is a sulfided catalyst, comprising a support and active metals Mo and Ni, and further comprising Zn, wherein, characterized by TEM-EDS, the Zn content distributed in the Ni-Mo-S active phase region accounts for 70%-90% of the total Zn content, preferably 75%-85%.

[0008] Furthermore, in the hydrodesulfurization catalyst, the sulfur content at the corner sites of the Ni-Mo-S active phase, characterized by TEM-EDS, is less than 5.0% of the total sulfur content in the Ni-Mo-S active phase, and further is 1.0%-4.0%.

[0009] Furthermore, the hydrodesulfurization catalyst, based on its mass, contains 10%-18% molybdenum (Mo), preferably 12-16%, and 1.5%-5.0% nickel (Ni), preferably 1.5%-4.0%.

[0010] Furthermore, the hydrodesulfurization catalyst, based on its mass, has a Zn content of 0.5%-3.0%, preferably 1.0%-2.5%.

[0011] Furthermore, the hydrodesulfurization catalyst, based on its mass, has a sulfur content (S) of 3.0%-10.0%, preferably 5.0-8.0%.

[0012] Furthermore, the hydrodesulfurization catalyst, based on the mass of the hydrodesulfurization catalyst, has a support content of 65%-85%, preferably 70%-80%.

[0013] Further, the carrier is at least one selected from alumina, silicon oxide, and amorphous aluminum silicate. The specific surface area of ​​the carrier is 150-350 m². 2 / g, preferably 180-300m 2 / g, the pore volume of the carrier is 0.6-1.2cm. 3 / g, preferably 0.8-1.1cm 3 / g. The carrier may be doped with one or more modifying elements such as phosphorus, silicon, boron, fluorine, and sodium. The modifying element accounts for less than 6.0% of the carrier mass, preferably 0.5%-6.0%.

[0014] A second aspect of the present invention provides a method for preparing a hydrodesulfurization catalyst, the method comprising:

[0015] (1) The oxidized hydrogenation catalyst is fully sulfided to obtain the sulfided hydrogenation catalyst;

[0016] (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment;

[0017] (3) An organic solution containing Zn is passed into the catalyst obtained in step (2) to carry out the reaction and obtain a hydrodesulfurization catalyst.

[0018] Further, in step (1), the oxidized hydrogenation catalyst comprises: a support, active metal components molybdenum and nickel. Based on the mass of the oxidized hydrogenation catalyst, the content of the support is 60%-80%, the content of molybdenum as oxide is 10%-30%, and the content of nickel as oxide is 2%-15%.

[0019] 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 150-350 m². 2 / g, preferably 180-300m 2 / g, the pore volume of the carrier is 0.6-1.2cm. 3 / g, preferably 0.8-1.1cm 3 / g. The carrier may be doped with one or more modifying elements such as phosphorus, silicon, boron, fluorine, and sodium. The modifying element accounts for less than 6.0% of the carrier mass, preferably 0.5%-6.0%.

[0020] 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, such as a hydrodesulfurization catalyst for heavy oil.

[0021] Furthermore, in step (1), the complete sulfidation, meaning the active metal in the oxidized hydrogenation catalyst reaches a state of complete sulfidation, can be achieved using a known sulfidation method. For example, the conditions for complete sulfidation are as follows: temperature 240-400℃, preferably 280-380℃; sulfidation time 3-8h; during sulfidation, hydrogen pressure 2.0-12.0MPa, preferably 3.0-10.0MPa; and hydrogen flow rate 2.0-15.0mL·min. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3.0-10.0 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

[0022] Further, in step (1), the sulfidation liquid used in the sulfidation treatment includes 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 sulfidation liquid is 2%-6%, preferably 4%-6%. The flow rate of the sulfidation 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.

[0023] Furthermore, in step (2), the desulfurization treatment is a mild desulfurization treatment, carried out in at least one of the following ways:

[0024] (a) The sulfided hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment using hydrogen gas containing hydrogen sulfide;

[0025] (b) In the presence of hydrogen, the sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment with a sulfurized liquid.

[0026] Further, in step (2), the temperature of the desulfurization treatment is 180-370℃, preferably 250-300℃, the treatment time is 4-24 hours, preferably 8-16 hours, and the total pressure is 2.0-18.0MPa, preferably 4.0-15.0MPa.

[0027] Furthermore, the temperature of the desulfurization treatment in step (2) is 50-100°C lower than the temperature of the full sulfurization treatment in step (1).

[0028] 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.

[0029] Further, in method (b), the sulfiding liquid includes 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 amount of sulfiding liquid used 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.

[0030] Further, in step (3), the solvent in the organic solution containing Zn is one or more of toluene, cyclohexane, decahydronaphthalene, tetrahydronaphthalene, n-heptane, etc., and the Zn-containing compound is one or more of zinc naphthenate or zinc glycerol, preferably zinc glycerol. The Zn-containing compound in the organic solution contains 2%-10% by mass.

[0031] Further, in step (3), the reaction temperature is 100-300℃, preferably 130-250℃, the pressure is 1.0-8.0MPa, preferably 2.0-6.0MPa, and the hydrogen flow rate is 2-20mL·min. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 5-15 mL·min -1 ·g -1 An oxidized hydrogenation catalyst is used, with a reaction time of 1-8 hours, preferably 2-6 hours. The flow rate of the organic solution containing Zn is 2-10 mL / h. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3-8 mL·h -1 ·g -1 Oxidized hydrogenation catalyst.

[0032] A third aspect of the present invention provides the application of the above-mentioned hydrodesulfurization catalyst in the hydrodesulfurization of heavy oil.

[0033] Furthermore, the sulfur content of the heavy oil is 2.0 wt% or more, especially 3.0 wt% or more.

[0034] Furthermore, the heavy oil has a carbon residue content of 10.0 wt% or higher, and the total content (Ni+V) of nickel and vanadium in the heavy oil is less than 100 μg / g. The heavy oil may be, for example, deasphalted oil.

[0035] Furthermore, the application conditions are as follows: reaction temperature of 320-410℃, preferably 360-400℃; hydrogen pressure of 10.0-25.0 MPa, preferably 15.0-22.0 MPa; and liquid hourly space velocity of 0.05-0.6 h⁻¹. -1 Preferably 0.1-0.4h -1 The hydrogen-to-oil volume ratio is 800:1-1600:1, preferably 900:1-1300:1.

[0036] Compared with the prior art, the present invention has the following advantages:

[0037] The catalyst of this invention exhibits high hydrodesulfurization capability while also possessing hydrodenitrification and hydroresidual carbon removal capabilities. The catalyst also demonstrates good long-term stability.

[0038] The method of this invention first subjectes the oxidized hydrogenation catalyst to initial sulfidation and specific desulfurization, so that the metal active phase to be modified is in a highly active state with slight desulfurization. The outer layer of the active phase edge is exposed active metal, while effectively preserving the tricoordinated sulfur atoms and stable Ni-Mo-S crystal structure inside the hydrogenation active phase. This allows Zn to contact the outer metal phase of the active phase more effectively, resulting in a Zn-Ni-Mo-S combined mixed active phase in the modified hydrogenation catalyst. At the same time, it weakens the strength of acid centers on the catalyst support surface that are not covered by metal, thereby reducing the strong interaction between the metal and unsaturated hydrocarbons and reducing the acidity of the catalyst. Detailed Implementation

[0039] 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.

[0040] In this invention, the hydrodesulfurization 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 Zn content distribution was statistically analyzed. The ratio of Zn content distributed in the Ni-Mo-S active phase region to the total Zn content (using Zn-Ni-Mo-S / Mg) was obtained based on the corresponding peak area of ​​Zn. 总 (This is an example of how the present invention uses the average value obtained by combining 20 TEM images with EDS analysis.)

[0041] 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.

[0042] The oxidized hydrogenation catalysts used in the following embodiments and comparative examples of this invention were all prepared by the following methods:

[0043] Weigh 1000.0g of alumina dry adhesive powder, add 10.0g of citric acid and 30.0g of guar gum powder, mix well, then add 1000.0g of an aqueous solution containing 0.5% nitric acid. After pressing for 10.0min, extrude the mixture using a 2.0mm diameter clover-shaped perforated plate. Dry at 120℃ for 6.0h, then calcine at 800℃ for 6.0h. The calcined carrier is designated S-0 (analysis showed the specific surface area of ​​the carrier to be 271m²). 2 / g, the pore volume of the carrier is 0.93cm³. 3 / g).

[0044] Weigh 50.0g ammonium heptamolybdate tetrahydrate, 30.0g nickel nitrate hexahydrate, and 150.0g deionized water. Stir thoroughly at 60℃ for 30 minutes, cool to room temperature, and then dilute to 200.0mL with deionized water. The resulting solution is denoted as Q-0.

[0045] 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 480℃ for 4.0 hours. The resulting oxidized hydrogenation catalyst is denoted as CT-0 (by weight of catalyst, the content of support is 72.1%, the content of molybdenum as oxide is 24.9%, and the content of nickel as oxide is 3.0%).

[0046] Example 1

[0047] Take 1000g of cyclohexane and 50.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as SQ-0.

[0048] Take 1000g of cyclohexane and 2.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as TQ-1.

[0049] Take 1000g of cyclohexane and 25.0g of zinc glycerol, and prepare an organic solution containing zinc, denoted as ZQ-1.

[0050] 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 sulfidated catalyst is denoted as SCT-0.

[0051] 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.

[0052] The reaction tube temperature was lowered to 140℃, the hydrogen pressure was adjusted to 3.0 MPa, and the gas flow rate was 120.0 mL / min. ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h for 3.0 hours. The resulting catalyst was designated ECT-1.

[0053] Example 2

[0054] 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.

[0055] Take 1000g of cyclohexane and 3.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as TQ-2.

[0056] Take 1000g of toluene and 30.0g of zinc glycerol, and prepare an organic solution containing zinc, denoted as ZQ-2.

[0057] 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.

[0058] The reaction tube temperature was lowered to 160℃, the pressure adjusted to 4.0 MPa, the gas flow rate was 150.0 mL / min, and ZQ-2 was introduced into the reaction tube at a flow rate of 100.0 mL / h for 4.0 hours. The resulting catalyst was designated ECT-2.

[0059] Example 3

[0060] 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.

[0061] Take 1000g of cyclohexane and 4.0g of dimethyl disulfide, and the resulting sulfidation solution is designated as TQ-3.

[0062] Take 1000g of toluene and 40.0g of zinc glycerol, and prepare an organic solution containing zinc, denoted as ZQ-3.

[0063] 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.

[0064] The reaction tube temperature was lowered to 190℃, the pressure adjusted to 5.0 MPa, the gas flow rate was 180.0 mL / min, and ZQ-3 was introduced into the reaction tube at a flow rate of 120.0 mL / h for 5.0 hours. The resulting catalyst was designated ECT-3.

[0065] Example 4

[0066] 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.

[0067] 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 350:1. The total flow rate of the mixed gas was 350 mL / min, and the treatment time was 12 hours. The resulting catalyst was designated TCT-4.

[0068] The reaction tube temperature was lowered to 140℃, the hydrogen pressure was adjusted to 3.0 MPa, and the gas flow rate was 120.0 mL / min. ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was 3.0 hours. The resulting catalyst was designated ECT-4.

[0069] Example 5

[0070] 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.

[0071] The reaction tube temperature was lowered to 300℃, 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 450:1. The total flow rate of the mixed gas was 450 mL / min, and the treatment time was 12 hours. The resulting catalyst was designated TCT-5.

[0072] The reaction tube temperature was lowered to 140℃, the hydrogen pressure was adjusted to 3.0 MPa, and the gas flow rate was 120.0 mL / min. ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h, and the treatment time was 3.0 hours. The resulting catalyst was designated ECT-5.

[0073] Comparative Example 1

[0074] 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 6.0 hours. The catalyst after sulfidation was designated as DCT-1.

[0075] Comparative Example 2

[0076] The preparation process of catalyst DCT-1 is the same as that of comparative example 1.

[0077] 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.

[0078] Comparative Example 3

[0079] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0080] The reaction tube containing SCT-0 was cooled to 140℃, the pressure was adjusted to 3.0 MPa, and the gas flow rate was 120.0 mL / min. ZQ-1 was then introduced into the reaction tube at a flow rate of 80.0 mL / h for 3.0 hours. The resulting catalyst was designated DCT-3.

[0081] Comparative Example 4

[0082] The preparation process of catalyst DCT-1 is the same as that of comparative example 1.

[0083] The reaction tube containing DCT-1 was cooled to 260°C, the hydrogen pressure was adjusted to 5.0 MPa, the hydrogen flow rate was 200.0 mL / min, and the treatment time was 9 hours. The resulting catalyst was designated DTCT-4.

[0084] The reaction tube temperature was lowered to 140℃, the pressure adjusted to 3.0 MPa, the gas flow rate was 120.0 mL / min, and ZQ-1 was introduced into the reaction tube at a flow rate of 80.0 mL / h for 3.0 hours. The resulting catalyst was designated DCT-4.

[0085] Comparative Example 5

[0086] The preparation process of carrier S-0 is the same as in Example 1.

[0087] Weigh out 50.0g ammonium heptamolybdate tetrahydrate, 30.0g nickel nitrate hexahydrate, 80.0g anhydrous zinc nitrate, and 150.0g deionized water. Stir thoroughly at 60℃ for 30 minutes, cool to room temperature, and then dilute to 200.0mL with deionized water. The resulting solution is denoted as DQ-5.

[0088] 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.

[0089] 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.

[0090] Table 1 shows the physicochemical composition of the catalysts obtained in each example.

[0091] Catalyst number Mo, wt% Ni, wt% Zn, wt% S, wt% ECT-1 10.8 2.6 1.15 6.9 ECT-2 10.9 2.6 1.24 6.8 ECT-3 10.5 2.5 1.32 7.1 ECT-4 10.6 2.6 1.21 6.7 ECT-5 10.8 2.5 1.37 6.9 DCT-1 10.5 2.7 - 7.6 DCT-2 10.6 2.7 - 6.9 DCT-3 10.3 2.5 1.30 3.8 DCT-4 10.5 2.6 1.35 8.0 DCT-5 10.7 2.6 1.32 7.8

[0092] The Zn-modified hydrodesulfurization catalyst was characterized by TEM-EDS to obtain the percentage of Zn 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 relative to the total sulfur content in the Ni-Mo-S active phase. See Table 2 for details.

[0093] Table 2

[0094]

[0095]

[0096] Examples 6-10

[0097] The activity of the catalysts obtained in Examples 1-5 was evaluated, and the properties of the deasphalted oil are shown in Table 2. 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 hydrodesulfurization catalyst obtained in the examples was 1:4. The operating conditions were: reaction temperature 385℃, reaction pressure 18.0 MPa, hydrogen-to-oil volume ratio 800:1, and liquid hourly space velocity 0.15 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 3.

[0098] Comparative Examples 6-10

[0099] The activity of the catalysts obtained in Comparative Examples 1-5 was evaluated, and the properties of the deasphalted oil are shown in Table 2. 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 hydrodesulfurization catalyst obtained in the examples was 1:4. The operating conditions were: reaction temperature 385℃, reaction pressure 18.0 MPa, hydrogen-to-oil volume ratio 800:1, and liquid hourly space velocity 0.15 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 3.

[0100] Table 3 Properties of Deasphalted Oil

[0101] <![CDATA[Density, kg / m 3 > 962 Vanadium + Nickel content, μg / g 51.0 Sulfur content, μg / g 36185 Nitrogen content, μg / g 2514 Saturated fraction, wt% 43.9 Aromatic components, wt% 39.1 Gel, wt% 16.6 Asphalt, wt% 0.4 Carbon residue value, wt% 11.2

[0102] Table 4 Evaluation Results

[0103]

[0104]

[0105] As can be seen from the evaluation results in Table 4, the hydrodesulfurization catalyst of the present invention not only has a good hydrodesulfurization capacity, but also a good hydrodenitrification capacity and hydrodecarbonization capacity.

Claims

1. A hydrodesulfurization catalyst, characterized in that: The hydrodesulfurization catalyst is a sulfide-state catalyst, comprising a support and active metals Mo and Ni, and also including Zn. Characterized by TEM-EDS, the Zn content distributed in the Ni-Mo-S active phase region accounts for 70%-90% of the total Zn content. The preparation method of the hydrodesulfurization catalyst includes: (1) The oxidized hydrogenation catalyst is fully sulfided to obtain the sulfided hydrogenation catalyst; (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment, wherein the desulfurization treatment is a mild desulfurization treatment; (3) An organic solution containing Zn is passed into the catalyst obtained in step (2) to carry out the reaction and obtain a hydrodesulfurization catalyst.

2. The hydrodesulfurization catalyst according to claim 1, characterized in that: Characterized by TEM-EDS, the Zn content distributed in the Ni-Mo-S active phase region accounts for 75%-85% of the total Zn content.

3. The hydrodesulfurization 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 5.0% of the total sulfur content in the Ni-Mo-S active phase. The sulfur content at the corner sites of the active phase refers to the sulfur content at the edge endpoint of the active phase, which is less than 1 nm away from the edge endpoint.

4. The hydrodesulfurization 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 1.0%-4.0% of the total sulfur content in the Ni-Mo-S active phase.

5. The hydrodesulfurization catalyst according to claim 1, characterized in that: Based on the mass of the hydrodesulfurization catalyst, the molybdenum content (Mo) is 10%-18% and the nickel content (Ni) is 1.5%-5.0%.

6. The hydrodesulfurization catalyst according to claim 5, characterized in that: Based on the mass of the hydrodesulfurization catalyst, the molybdenum content (Mo) is 12%-16% and the nickel content (Ni) is 1.5%-4.0%.

7. The hydrodesulfurization catalyst according to claim 5, characterized in that: Based on the mass of the hydrodesulfurization catalyst, the Zn content (calculated as Zn) is 0.5%-3.0%, the sulfur content (calculated as S) is 3.0%-10.0%, and the support content is 65%-85%.

8. The hydrodesulfurization catalyst according to claim 7, characterized in that: Based on the mass of the hydrodesulfurization catalyst, the Zn content (calculated as Zn) is 1.0%-2.5%, the sulfur content (calculated as S) is 5.0%-8.0%, and the support content is 70%-80%.

9. The hydrodesulfurization catalyst according to claim 1, characterized in that: The carrier is at least one of alumina, silicon oxide, and amorphous aluminum silicate; the specific surface area of ​​the carrier is 150-350 m². 2 / g, the pore volume of the carrier is 0.6-1.2cm. 3 / g.

10. The hydrodesulfurization catalyst according to claim 9, characterized in that: The specific surface area of ​​the carrier is 180-300 m². 2 / g, the pore volume of the carrier is 0.8-1.1cm. 3 / g.

11. A method for preparing a hydrodesulfurization catalyst according to claim 1, comprising: (1) The oxidized hydrogenation catalyst is fully sulfided to obtain the sulfided hydrogenation catalyst; (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment, wherein the desulfurization treatment is a mild desulfurization treatment; (3) An organic solution containing Zn is passed into the catalyst obtained in step (2) to carry out the reaction and obtain a hydrodesulfurization catalyst.

12. The method according to claim 11, characterized in that: In step (1), the oxidized hydrogenation catalyst includes: a support, active metal components molybdenum and nickel; based on the mass of the oxidized hydrogenation catalyst, the content of the support is 60%-80%, the content of molybdenum as oxide is 10%-30%, and the content of nickel as oxide is 2%-15%.

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

14. The method according to claim 13, characterized in that: In step (1), the conditions for full sulfidation are as follows: the temperature is 280-380℃, and the pressure of hydrogen gas during sulfidation is 3.0-10.0 MPa.

15. The method according to claim 11, characterized in that: In step (2), the desulfurization 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.

16. The method according to claim 15, 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 2.0-18.0 MPa.

17. The method according to claim 16, characterized in that: In step (2), the temperature of the desulfurization treatment is 250-300℃; the treatment time is 8-16 hours; and the total pressure is 4.0-15.0 MPa.

18. The method according to claim 16, characterized in that: The temperature of the desulfurization treatment in step (2) is 50-100°C lower than the temperature of the full sulfurization treatment in step (1).

19. The method according to claim 15, 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.

20. The method according to claim 19, 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.

21. The method according to claim 15, 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 desulfurization 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.

22. The method according to claim 21, characterized in that: In method (b), the hydrogen flow rate during desulfurization is 10-20 mL / min. -1 ·g -1 Oxidized hydrogenation catalyst.

23. The method according to claim 11, characterized in that: In step (3), the solvent in the organic solution containing Zn is one or more of toluene, cyclohexane, decahydronaphthalene, tetrahydronaphthalene, and n-heptane, and the Zn-containing compound is one or more of zinc naphthenate or zinc glycerol. The Zn-containing compound in the organic solution contains 2%-10% by mass.

24. The method according to claim 11, characterized in that: In step (3), the reaction temperature is 100-300℃, the pressure is 1.0-8.0 MPa, and the hydrogen flow rate is 2-20 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst, reaction time of 1-8 hours, flow rate of organic solution containing Zn of 2-10 mL·h -1 ·g -1 Oxidized hydrogenation catalyst.

25. The method according to claim 24, characterized in that: In step (3), the reaction temperature is 130-250℃, the pressure is 2.0-6.0 MPa, and the hydrogen flow rate is 5-15 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst, reaction time 2-6 hours; flow rate of organic solution containing Zn 3-8 mL·h -1 ·g -1 Oxidized hydrogenation catalyst.

26. The use of a hydrodesulfurization catalyst according to any one of claims 1-10 or a hydrodesulfurization catalyst prepared according to any one of claims 11-25 in the hydrodesulfurization of heavy oil.

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