A hydrodechar catalyst and a method for preparing the same

Abstract

The application discloses a hydroresid catalyst and a preparation method thereof. The hydroresid catalyst is in a sulfidized state, and comprises a carrier, active metals Mo and Ni, and Se. The content of Se distributed in the Ni-Mo-S active phase region accounts for 65-95% of the total Se content by using a TEM-EDS method. The hydroresid catalyst has the function of providing high-energy active hydrogen, which can overcome the steric hindrance effect and effectively hydrogenate and saturate the condensed ring structure in the heavy oil macromolecule, thereby improving the effect of hydroresid of heavy oil.

Description

Technical Field

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

[0002] Heavy oil hydrotreating technology is a primary means of lightening and cleaning heavy oil. Compared to light distillate oils, heavy oil molecules have larger molecular weights, more aromatic rings, and a lower carbon-to-hydrogen ratio. During hydrotreating, the polycyclic aromatic ring structure of heavy oil molecules, due to the steric hindrance created by substituents and cycloalkane rings on the outer side of the macromolecules, hinders effective contact between the aromatic rings inside the reactant molecules and the active hydrogen. This not only makes hydrogenation of the large heavy oil molecules difficult but also leads to coking and carbon deposition of the fused ring structure on the active phase of the catalyst. Therefore, the steric hindrance effect can be overcome by increasing the kinetic energy of the activated hydrogen, thereby improving the catalyst's saturation capacity for heavy oil molecules.

[0003] CN103143373A discloses a method for preparing a hydrodesulfurization catalyst. This method involves impregnating molybdenum selenide onto an alumina or silica support using a precipitation method or a non-supported method. The prepared catalyst exhibits good hydrodesulfurization performance. However, the dispersion and crystal structure of molybdenum selenide alone are not suitable for use as a standalone active phase for hydrodesulfurization. Therefore, the catalyst obtained by this method is not suitable for the hydrodecarbonization of heavy oil.

[0004] CN106622264A discloses a hydrocracking catalyst containing an active metal component and a modified hydrogenation catalyst support. The modified hydrogenation catalyst support comprises a support and a metal promoter and an acidic promoter supported on the support. The metal promoter and acidic promoter are distributed in layers on the support, with a metal promoter in the shell and an acidic promoter in the core layer. The metal promoter is a Group IA metal component and / or a Group IIA metal component, and the acidic promoter is selected from at least one component of F, P, and B. The active metal component in this catalyst is still supported on the catalyst support using a conventional impregnation method, and the decarbonization performance of the catalyst still needs further improvement. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a hydrodecarbonization catalyst and its preparation method. The hydrodecarbonization catalyst of this invention has the function of providing high-energy activated hydrogen, which can overcome steric hindrance effects and effectively hydrogenate and saturate the fused ring structure within the heavy oil macromolecules, thereby improving the effect of hydrodecarbonization of heavy oil products.

[0006] The first aspect of the present invention provides a hydrodecarbonization catalyst, wherein the hydrodecarbonization catalyst is a sulfide-state catalyst, comprising a support and active metals Mo and Ni, and further comprising Se, wherein, characterized by TEM-EDS, the Se content distributed in the Ni-Mo-S active phase region accounts for 65%-95% of the total Se content, preferably 78%-95%.

[0007] Furthermore, the hydrogenation decarbonization catalyst, characterized by TEM-EDS, shows that the sulfur content at the corner sites of the Ni-Mo-S active phase is less than 6.0% of the total sulfur content in the Ni-Mo-S active phase, and further, is 0.5%-4.0%.

[0008] Furthermore, the hydrodecarbonization catalyst, based on its mass, contains 8.0%-20.0% molybdenum (Mo), preferably 12.5%-16.5%, and 1.5%-6.5% nickel (Ni), preferably 2.0%-5.0%.

[0009] Furthermore, the hydrodecarbonization catalyst, based on its mass, has a sulfur content of 4%-15% (S), preferably 6%-12%, and a se content of 0.5%-5.0% (Se), preferably 1.0%-4.0%.

[0010] Furthermore, the hydrodecarbonization catalyst, based on its mass, has a support content of 55%-80%, preferably 55%-70%.

[0011] 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 200-300m 2 / g, the pore volume of the carrier is 0.5-1.2cm. 3 / g, preferably 0.7-1.0cm 3 / g.

[0012] A second aspect of the present invention provides a method for preparing a hydrodecarbonization catalyst, the method comprising:

[0013] (1) Sulfide treatment is performed on the oxidized hydrogenation catalyst to obtain the sulfide hydrogenation catalyst;

[0014] (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment;

[0015] (3) The catalyst treated in step (2) is reacted with a mixture of hydrogen selenide and hydrogen to obtain a hydrogenation decarbonization catalyst.

[0016] Further, in step (1), the oxidized hydrogenation catalyst comprises: a support, active metal components molybdenum and nickel. Based on the mass of the catalyst, the content of the support is 65%-80%, the content of molybdenum as oxide is 12%-30%, and the content of nickel as oxide is 2%-8%.

[0017] 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 200-300m 2 / g, the pore volume of the carrier is 0.5-1.2cm. 3 / g, preferably 0.7-1.0cm 3 / g.

[0018] 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.

[0019] Furthermore, in step (1), the sulfidation treatment is a full sulfidation treatment, 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 sulfidation treatment 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 the sulfidation process. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 3.0-10.0 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

[0020] Further, in step (1), the sulfidation liquid used in the sulfidation treatment 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 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.

[0021] Furthermore, in step (2), the desulfurization treatment is a mild desulfurization treatment, carried out in at least one of the following ways:

[0022] (a) The sulfided hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment using hydrogen gas containing hydrogen sulfide;

[0023] (b) In the presence of hydrogen, the sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment with a sulfurized liquid.

[0024] 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.

[0025] Furthermore, the temperature of the desulfurization treatment in step (2) is 50-100°C lower than the temperature of the sulfurization treatment in step (1).

[0026] 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.

[0027] 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 treatment, 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.

[0028] Further, in step (3), the reaction conditions are as follows: the reaction temperature is 120-250℃, preferably 150-220℃; the reaction time is 1-8 hours, preferably 2-6 hours; the reaction pressure is 2.0-12.0 MPa, preferably 4.0-8.0 MPa; in the mixed gas, the volume fraction of hydrogen selenide is 1%-20%, preferably 3%-15%, and the volume fraction of hydrogen is 80%-99%, preferably 85%-97%. The flow rate of the mixed gas is 5-40 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst, preferably 10-30 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

[0029] A third aspect of the present invention also provides the application of the above-mentioned hydrodecarbonization catalyst in the hydrodecarbonization of heavy feedstock oil.

[0030] Furthermore, the heavy feedstock is a heavy feedstock with a residual carbon content of 10% or more, especially a heavy feedstock with a residual carbon content of 15% or more. The heavy feedstock can be derived from inferior heavy oil or residual oil.

[0031] Furthermore, the operating conditions for the application are as follows: reaction temperature of 300-400℃, reaction pressure of 8.0-25.0 MPa, hydrogen-to-oil volume ratio of 2000:1-500:1, and liquid hourly space velocity of 0.1-1.0 h⁻¹. -1 .

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] The catalyst provided by this invention has high hydrotreating and carbon removal capabilities and selectivity. In the process of processing heavy oil products, the catalyst exhibits good hydrotreating saturation activity and good stability in use.

[0034] The preparation method provided by this invention places the metal active phase to be modified in a highly active state with slight desulfurization. The outer layer of the active phase edge is an exposed active metal, while effectively retaining the tri-coordinated sulfur atoms and stable MoS2 crystal structure inside the hydrogenated active phase. This allows the modified Se auxiliary agent to contact the outer metal phase of the active phase more effectively, forming a Se-Ni-Mo-S combined mixed active phase with Ni, Mo, and S, thus achieving the purpose of modification. Detailed Implementation

[0035] 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.

[0036] In this invention, the hydrodecarbonization 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 mesh. 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 content distribution of Se was statistically analyzed. The ratio of the Se content distributed in the Ni-Mo-S active phase region to the total Se content (Se-Ni-Mo-S / Se) was obtained based on the corresponding peak area of ​​Se. 总 (This is an example of how the present invention uses the average value obtained by combining 20 TEM images with EDS analysis.)

[0037] 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.

[0038] The oxidized hydrogenation catalysts used in the following embodiments and comparative examples of this invention were all prepared by the following methods:

[0039] Weigh 1000.0g of alumina dry adhesive powder, add 20.0g of citric acid and 20.0g of guar gum powder, mix well, then add 1000.0g of an aqueous solution containing 1.0% nitric acid by mass. After rolling for 20.0min, extrude the mixture using a clover-shaped perforated plate with a diameter of 1.8mm. Dry at 120℃ for 6.0h, then calcine at 700℃ for 6.0h. The calcined carrier is designated S-0. (Analysis shows the following properties of the carrier: specific surface area of ​​270m²). 2 / g, pore volume 0.9cm 3Weigh 74.2 g of ammonium heptamolybdate tetrahydrate, 47.3 g of nickel nitrate hexahydrate, and 150.0 g of deionized water. Stir thoroughly at 60 °C for 20 min, cool to room temperature, and then dilute to 200.0 mL with deionized water. The resulting solution is denoted as Q-0.

[0040] 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 450℃ for 5.0 hours. The resulting oxidized hydrogenation catalyst is denoted as CT-0 (by weight of catalyst, the content of support is 73.3%, the content of molybdenum as oxide is 22.2%, and the content of nickel as oxide is 4.5%).

[0041] Example 1

[0042] Take 1000g of cyclohexane and 50.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as SQ-0.

[0043] Take 1000g of cyclohexane and 2.0g of dimethyl disulfide, and the resulting sulfidation solution is denoted as TQ-1.

[0044] 20.0g of CT-0 was loaded into a reaction tube and subjected to sulfidation treatment using SQ-0. During the sulfidation process, the hydrogen pressure was 6.0 MPa, the hydrogen flow rate was 300.0 mL / min, the flow rate of the sulfidation liquid SQ-0 was 40.0 mL / h, the sulfidation temperature was 350℃, and the sulfidation time was 6 hours. The resulting sulfidated hydrogenation catalyst was denoted as SCT-0.

[0045] 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.

[0046] The reaction tube temperature was lowered to 160℃, the pressure adjusted to 5.0 MPa, and a mixture of hydrogen and hydrogen selenide was introduced into the reaction tube. The hydrogen component of the mixture was 95%, and the volume fraction of hydrogen selenide was 5%. The flow rate of the mixture was 300.0 mL / min, and the treatment time was 3.0 hours. The resulting catalyst was designated ECT-1.

[0047] Example 2

[0048] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0049] Take 1000g of cyclohexane and 3.0g of carbon disulfide to prepare a sulfidation liquid, which is denoted as TQ-2.

[0050] The temperature of the reaction tube containing the sulfurized hydrogenation catalyst SCT-0 was reduced 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 resulting catalyst was designated TCT-2.

[0051] The reaction tube temperature was lowered to 180℃, the pressure adjusted to 8.0 MPa, and a mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with hydrogen comprising 93% and hydrogen selenide comprising 7% by volume. The flow rate of the mixed gas was 400.0 mL / min, and the treatment time was 4.0 hours. The resulting catalyst was designated ECT-2.

[0052] Example 3

[0053] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0054] Take 1000g of cyclohexane and 4.0g of dimethyl sulfoxide, and the resulting sulfidation solution is designated as TQ-3.

[0055] The temperature of the reaction tube containing the sulfurized hydrogenation catalyst SCT-0 was reduced 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 resulting catalyst was designated TCT-3.

[0056] The reaction tube temperature was lowered to 200℃, the pressure adjusted to 7.0 MPa, and a mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with hydrogen comprising 90% and hydrogen selenide comprising 10% by volume. The flow rate of the mixed gas was 500.0 mL / min, and the treatment time was 5.0 hours. The resulting catalyst was designated ECT-3.

[0057] Example 4

[0058] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0059] The temperature of the reaction tube containing the sulfurized hydrogenation catalyst SCT-0 was reduced to 270℃, the reaction pressure was adjusted to 6.0 MPa, and a mixture of hydrogen and hydrogen sulfide was simultaneously introduced at a partial pressure ratio of 400:1 and a flow rate of 400.0 mL / min for 12 hours. The resulting catalyst was designated TCT-4.

[0060] The reaction tube temperature was lowered to 180℃, the pressure adjusted to 8.0 MPa, and a mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with hydrogen comprising 93% and hydrogen selenide comprising 7% by volume. The flow rate of the mixed gas was 500.0 mL / min, and the treatment time was 4.0 hours. The resulting catalyst was designated ECT-4.

[0061] Example 5

[0062] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0063] The temperature of the reaction tube containing the sulfurized hydrogenation catalyst SCT-0 was reduced to 250℃, the reaction pressure was adjusted to 6.0 MPa, and a mixture of hydrogen and hydrogen sulfide was simultaneously introduced. The partial pressure ratio of hydrogen to hydrogen sulfide was 400:1, the flow rate of the mixed gas was 400.0 mL / min, and the treatment time was 12 hours. The resulting catalyst was designated TCT-5.

[0064] The reaction tube temperature was lowered to 210℃, the pressure adjusted to 7.0 MPa, and a mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with hydrogen comprising 88% and hydrogen selenide comprising 12% by volume. The flow rate of the mixed gas was 300.0 mL / min, and the treatment time was 5.0 hours. The resulting catalyst was designated ECT-5.

[0065] Comparative Example 1

[0066] 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.

[0067] Comparative Example 2

[0068] The preparation process of catalyst DCT-1 is the same as that of comparative example 1.

[0069] 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.

[0070] Comparative Example 3

[0071] The preparation process of the sulfurized hydrogenation catalyst SCT-0 is the same as in Example 1.

[0072] The reaction tube containing SCT-0 was cooled to 180°C, and the hydrogen pressure was adjusted to 8.0 MPa. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with hydrogen comprising 93% of the volume and hydrogen selenide comprising 7% of the volume. The gas flow rate was 400.0 mL / min, and the treatment time was 4.0 hours. The resulting catalyst was designated DCT-3.

[0073] Comparative Example 4

[0074] The preparation process of catalyst DCT-1 is the same as that of comparative example 1.

[0075] 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.

[0076] The reaction tube temperature was lowered to 160℃, the pressure adjusted to 5.0 MPa, and a mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with hydrogen comprising 95% and hydrogen selenide comprising 5% by volume. The flow rate of the mixed gas was 300.0 mL / min, and the treatment time was 3.0 hours. The resulting catalyst was designated DCT-4.

[0077] Comparative Example 5

[0078] 20.0 g of CT-0 was placed in a reaction tube. A mixture of hydrogen and hydrogen selenide was introduced into the reaction tube, with hydrogen comprising 90% by volume and hydrogen selenide comprising 10% by volume. The reaction temperature was 200 °C, the reaction pressure was 7.0 MPa, the flow rate of the mixed gas was 500.0 mL / min, and the treatment time was 5.0 hours. The resulting catalyst was designated DCT-5.

[0079] Table 1 shows the physicochemical composition of the catalysts obtained in each example.

[0080] Catalyst number Mo, wt% Ni, wt% Se, wt% S, wt% ECT-1 13.9 3.30 2.29 8.61 ECT-2 14.1 3.28 2.41 8.56 ECT-3 13.8 3.27 2.66 8.51 ECT-4 14.3 3.25 2.57 8.46 ECT-5 14.1 3.18 2.70 8.37 DCT-1 14.1 3.29 - 9.70 DCT-2 14.0 3.21 - 8.68 DCT-3 14.1 3.18 1.26 9.39 DCT-4 14.0 3.17 4.68 4.65 DCT-5 13.9 3.28 17.67 -

[0081] The hydrodecarbonization catalyst was characterized by TEM-EDS to obtain the percentage of Se 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.

[0082] Table 2

[0083] Catalyst number ECT-1 ECT-2 ECT-3 ECT-4 ECT-5 DCT-1 DCT-2 DCT-3 DCT-4 <![CDATA[Se-Ni-Mo-S / Se 总 ,%]]> 93 95 94 96 98 - - 51 35 <![CDATA[S 边角位 / S 总 ,%]]> 2.6 2.4 2.7 2.9 2.7 9.6 3.1 5.7 6.9

[0084] Examples 6-10

[0085] The catalysts obtained in Examples 1-5 were evaluated for activity, and the properties of the residue feedstock are shown in Table 3. A fixed-bed process was used, with a hydrotreating protectant (FZC-100B), a hydrodemetallization catalyst (FZC-204A), and a hydrodesulfurization catalyst (FZC-33B) loaded before the above catalysts. The loading volume ratio of the protectant, hydrodemetallization catalyst, hydrodesulfurization catalyst, and the catalysts obtained in the examples was 1.5:2.0:2.0:4.5. The operating conditions were: reaction temperature 380℃, reaction pressure 16.0 MPa, hydrogen-to-oil volume ratio 1200:1, and liquid hourly space velocity (LHSV) 0.2 h⁻¹. -1 After 2000 hours of reaction evaluation, the residual carbon value, saturated fraction, and nitrogen content of the hydrogenated oil fraction at temperatures not lower than 200℃ were analyzed, and the results are shown in Table 4.

[0086] Comparative Examples 6-10

[0087] The activity of the catalysts obtained in Comparative Examples 1-5 was evaluated, and the properties of the residue feedstock are shown in Table 3. A fixed-bed process was used, with a hydrotreating protectant (FZC-100B), a hydrodemetallization catalyst (FZC-204A), and a hydrodesulfurization catalyst (FZC-33B) loaded before the above catalysts. The volume ratio of the protectant, hydrodemetallization catalyst, hydrodesulfurization catalyst, and the catalyst obtained in the comparative examples was 1.5:2.0:2.0:4.5. The operating conditions were: reaction temperature 380℃, reaction pressure 16.0 MPa, hydrogen-to-oil volume ratio 1200:1, and liquid hourly space velocity (LISH) 0.2 h⁻¹. -1 After 2000 hours of reaction evaluation, the residual carbon value, saturated fraction, and nitrogen content of the hydrogenated oil fraction at temperatures not lower than 200℃ were analyzed, and the results are shown in Table 4.

[0088] Table 3 Properties of Feed Oil

[0089] <![CDATA[Density, kg / m 3 > 1002 Vanadium + Nickel content, μg / g 99.8 Sulfur content, μg / g 39745 Nitrogen content, μg / g 4153 Saturated fraction, wt% 37.7 Aromatic components, wt% 29.0 Gel, wt% 30.5 Asphalt, wt% 2.8 Carbon residue value, wt% 19.8

[0090] Table 4. Hydrogenation evaluation results of each catalyst after 2000 h.

[0091] Catalyst number Nitrogen content, μg / g Carbon residue value, wt% Saturated fraction, wt% Example 6 ECT-1 952 3.1 57.4 Example 7 ECT-2 921 3.4 56.6 Example 8 ECT-3 904 2.7 58.1 Example 9 ECT-4 895 3.0 59.3 Example 10 ECT-5 901 2.8 58.4 Comparative Example 6 DCT-1 1569 5.7 48.7 Comparative Example 7 DCT-2 1711 5.9 47.1 Comparative Example 8 DCT-3 1274 3.9 52.0 Comparative Example 9 DCT-4 1952 6.3 45.4 Comparative Example 10 DCT-5 2546 10.4 42.8

[0092] As can be seen from the evaluation results in Table 4, the catalyst of the present invention has good hydrodecarbonization, hydrosaturation and good hydrodenitrification capabilities.

Claims

1. A hydrodecarbonization catalyst, characterized in that: The hydrogenation decarbonization catalyst is a sulfide-state catalyst, comprising a support and active metals Mo and Ni, and also including Se. Characterized by TEM-EDS, the Se content distributed in the Ni-Mo-S active phase region accounts for 65%-95% of the total Se content. The hydrogenation decarbonization catalyst is prepared by the following method, including the following steps: (1) The oxidized hydrogenation catalyst is subjected to sulfidation treatment to obtain the sulfidated hydrogenation catalyst, wherein the sulfidation treatment is a full sulfidation treatment; (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment, wherein the desulfurization treatment is a mild desulfurization treatment; (3) The catalyst treated in step (2) is reacted with a mixture of hydrogen selenide and hydrogen to obtain a hydrogenation decarbonization catalyst. In step (2), the temperature of the desulfurization treatment is 50-100°C lower than the temperature of the sulfurization treatment in step (1); 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; The desulfurization treatment is carried out at a temperature of 180-370℃, for a duration of 4-24 hours, and with a total pressure of 2.0-18.0 MPa. 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; In method (b), the amount of sulfiding liquid used in the desulfurization treatment process is 0.4-1.5 mL / h. -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate 10-20 mL·min -1 ·g -1 Oxidized hydrogenation catalyst.

2. The hydrodecarbonization catalyst according to claim 1, characterized in that: Characterized by TEM-EDS, the Se content distributed in the Ni-Mo-S active phase region accounts for 78%-95% of the total Se content.

3. The hydrodecarbonization catalyst according to claim 1, characterized in that: The hydrogenation decarbonization catalyst is a sulfide-state hydrogenation decarbonization catalyst, characterized by TEM-EDS. The sulfur content at the corner sites of the Ni-Mo-S active phase is less than 6.0% 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 of the active phase less than 1 nm away from the edge endpoint.

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

5. The hydrodecarbonization catalyst according to claim 1, characterized in that: Based on the mass of the hydrodecarbonization catalyst, the molybdenum content (Mo) is 8.0%-20.0%, and the nickel content (Ni) is 1.5%-6.5%.

6. The hydrodecarbonization catalyst according to claim 5, characterized in that: Based on the mass of the hydrodecarbonization catalyst, the molybdenum content (Mo) is 12.5%-16.5% and the nickel content (Ni) is 2.0%-5.0%.

7. The hydrodecarbonization catalyst according to claim 1, characterized in that: Based on the mass of the hydrodecarbonization catalyst, the sulfur content (S) is 4%-15%, the se content (Se) is 0.5%-5.0%, and the support content is 55%-80%.

8. The hydrodecarbonization catalyst according to claim 7, characterized in that: Based on the mass of the hydrodecarbonization catalyst, the sulfur content (S) is 6%-12%, the se content (Se) is 1.0%-4.0%, and the support content is 55%-70%.

9. A method for preparing the hydrodecarbonization catalyst according to any one of claims 1-8, comprising the following steps: (1) The oxidized hydrogenation catalyst is subjected to sulfidation treatment to obtain the sulfidated hydrogenation catalyst, wherein the sulfidation treatment is a full sulfidation treatment; (2) The sulfurized hydrogenation catalyst obtained in step (1) is subjected to desulfurization treatment, wherein the desulfurization treatment is a mild desulfurization treatment; (3) The catalyst treated in step (2) is reacted with a mixture of hydrogen selenide and hydrogen to obtain a hydrogenation decarbonization catalyst. In step (2), the temperature of the desulfurization treatment is 50-100°C lower than the temperature of the sulfurization treatment in step (1); 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; The desulfurization treatment is carried out at a temperature of 180-370℃, for a duration of 4-24 hours, and with a total pressure of 2.0-18.0 MPa. 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; In method (b), the amount of sulfiding liquid used in the desulfurization treatment process is 0.4-1.5 mL / h. -1 ·g -1 Oxidized hydrogenation catalyst, hydrogen flow rate 10-20 mL·min -1 ·g -1 Oxidized hydrogenation 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 mass of the catalyst, the content of the support is 65%-80%, the content of molybdenum as oxide is 12%-30%, and the content of nickel as oxide is 2%-8%.

11. The method according to claim 9, characterized in that: In step (1), the conditions for the sulfidation treatment are as follows: temperature is 240-400℃, sulfidation time is 3-8h, and during the sulfidation 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 11, characterized in that: In step (1), the conditions for the sulfidation treatment are as follows: the temperature is 280-380℃, the hydrogen pressure during sulfidation is 3.0-10.0 MPa, and the hydrogen flow rate is 3.0-10.0 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst.

13. The method according to claim 9, characterized in that: The desulfurization treatment is carried out at a temperature of 200-300℃, for a duration of 6-16 hours, and with a total pressure of 4.0-15.0 MPa.

14. The method according to claim 9, 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.

15. The method according to claim 9, characterized in that: In method (b), the sulfiding liquid includes a sulfur-containing compound and an organic solvent, wherein the sulfur-containing compound is at least one of dimethyl disulfide, carbon disulfide, diethyl sulfide, ethanethiol, n-butanethiol, di-tert-nonyl polysulfide, and dimethyl sulfoxide; and the organic solvent is at least one of cyclohexane, n-heptane, aviation kerosene, and diesel oil.

16. The method according to claim 15, characterized in that: In method (b), the mass fraction of sulfur-containing compounds in the sulfidation solution is 0.1%-0.6%; during the desulfurization treatment, the amount of sulfidation solution used 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.

17. The method according to claim 9, characterized in that: In step (3), the reaction conditions are as follows: the reaction temperature is 120-250℃, the reaction time is 1-8 hours, and the reaction pressure is 2.0-12.0 MPa.

18. The method according to claim 17, characterized in that: In step (3), the reaction conditions are as follows: the reaction temperature is 150-220℃, the reaction time is 2-6 hours, and the reaction pressure is 4.0-8.0 MPa.

19. The method according to claim 9, characterized in that: In step (3), the volume fraction of hydrogen selenide in the mixed gas is 1%-20%, the volume fraction of hydrogen is 80%-99%, and the flow rate of the mixed gas is 5-40 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst.

20. The method according to claim 19, characterized in that: In step (3), the volume fraction of hydrogen selenide in the mixed gas is 3%-15%, and the volume fraction of hydrogen is 85%-97%; the flow rate of the mixed gas is 10-30 mL·min. -1 ·g -1 Oxidized hydrogenation catalyst.

21. The application of a hydrodecarbonization catalyst according to any one of claims 1-8 or a hydrodecarbonization catalyst prepared according to any one of claims 9-20 in the hydrodecarbonization of heavy oil.