Sulfided hydrogenation catalyst and method for preparing the same

Abstract

This invention discloses a sulfide-type hydrogenation catalyst and its preparation method. The sulfide-type hydrogenation catalyst includes a support, an active metal component, and a first auxiliary agent. The support is one or more inorganic refractory oxides. The active metal includes Group VIB and Group VIII metals, and the active metal component is distributed on the support in the form of sulfides. The catalyst preparation method includes the following steps: (1) preparing a solution containing an active metal; (2) mixing the solution containing the active metal with a second auxiliary agent, introducing a sulfide agent, and mixing the first auxiliary agent evenly to obtain an impregnation solution; (3) mixing the impregnation solution obtained in step (2) with the support material evenly, and then drying and calcining to obtain a sulfide-type hydrogenation catalyst. The catalyst preparation and pre-sulfidation process are organically combined to ensure that the active metal component is fully sulfided while ensuring that the active metal component is evenly distributed on the support, thereby improving the hydrogenation activity of the catalyst.

Description

Technical Field

[0001] This invention belongs to the field of petrochemical catalysis, and relates to a hydrogenation catalytic material and its preparation method, particularly to a sulfide-type hydrogenation catalyst and its preparation method. Background Technology

[0002] Currently, the active metals in commercially available hydrogenation catalysts are mainly in the form of metal oxides, while oxidized catalysts typically require sulfidation to achieve better performance. Pre-sulfidation of the catalyst during hydrogenation is a crucial step in its application. Currently, the preparation of sulfidation catalysts generally involves three steps: support preparation, catalyst preparation, and catalyst pre-sulfidation; this process is complex and has high overall manufacturing costs. Furthermore, each step in the catalyst preparation and sulfidation process affects the quality of the final catalyst product.

[0003] Sulfide-type catalysts prepared using traditional sulfidation methods exhibit strong interactions between the active component and the support, making complete sulfidation difficult and resulting in a lower number of type II active phase structures. Therefore, weakening the interactions between the active component and the support in sulfide-type catalysts can increase the degree of sulfidation, increase the number of type II active phase structures, and thus improve the hydrogenation activity of sulfide-type hydrogenation catalysts.

[0004] CN103801334A discloses a method for preparing a sulfide-type hydrogenation catalyst. The method involves mixing a supported precursor with elemental sulfur and an auxiliary agent, molding, drying, loading a hydrogenation active metal component, and then heat-treating to obtain the sulfide-type hydrogenation catalyst. This method is simple and low-cost. However, the elemental sulfur and the hydrogenation active metal component are added stepwise. The elemental sulfur reacts with the supported material first, which affects its interaction with the active metal component, thus hindering the sulfide reaction of the active metal component and impacting the utilization rate of the active metal and the catalyst activity.

[0005] Based on the above analysis, it can be seen that the development of novel sulfide catalyst preparation processes has broad application prospects. Summary of the Invention

[0006] To address the problems and shortcomings of existing technologies, the main objective of this invention is to provide a sulfidation-type hydrogenation catalyst and its preparation method. This method organically combines catalyst preparation and pre-sulfidation processes. Through the hydrogen bonding effect of a first promoter, the interaction between the active component of the hydrogenation catalyst and the support is weakened, and the interaction between the sulfur-containing compound and the active metal is improved, ensuring complete sulfidation of the active metal component while maintaining uniform distribution of the active metal component on the support, thereby enhancing the hydrogenation activity of the catalyst. The addition of the promoter effectively solves the problems of strong interaction between the active component and the support in sulfidation-type hydrogenation catalysts, difficulty in complete sulfidation of the catalyst, and a limited number of type II active phase structures.

[0007] The first aspect of the present invention provides a sulfide-type hydrogenation catalyst, the catalyst comprising a support, an active metal component, a sulfiding agent, and a first auxiliary agent; wherein the support is one or more inorganic refractory oxides; the active metal includes Group VIB metals and Group VIII metals, and the active metal component is distributed on the support in the form of sulfides.

[0008] Preferably, in the above-mentioned sulfide-type hydrogenation catalyst, as some specific embodiments, the first promoter is one or more selected from urea, thiourea, tert-butylthiourea, N-tert-butylurea, and squaramide, preferably squaramide. Based on the weight of the catalyst, the content of the first promoter is 2% to 10%, preferably 3% to 5%.

[0009] Preferably, in the above-mentioned sulfurized hydrogenation catalyst, as some specific embodiments, the first auxiliary agent utilizes the NH bond it contains to form S…HN bonds with the sulfur S in the active metal sulfide, and forms hydrogen bonds with the hydroxyl groups on the support surface.

[0010] Preferably, in the above-mentioned sulfidation-type hydrogenation catalyst, as some specific embodiments, the Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co.

[0011] Preferably, in the above-mentioned sulfidation-type hydrogenation catalyst, as some specific embodiments, the active metal is further preferably Mo and Ni.

[0012] Preferably, in the above-mentioned sulfide-type hydrogenation catalyst, as some specific embodiments, the support is an inorganic refractory oxide, which can be selected from at least one of alumina, silicon oxide, zirconium oxide, titanium oxide, silicon-containing alumina, and silicon-containing zirconium oxide, preferably alumina.

[0013] Preferably, in the above-mentioned sulfidation-type hydrogenation catalyst, as some specific embodiments, the active metal component, based on the catalyst weight, has an elemental content of 22% to 28%, preferably 23% to 26%; the sulfur content is 6% to 10%, preferably 7% to 8.5%. The content of Group VIB metals is 18% to 24% and the content of Group VIII metals is 3% to 6%.

[0014] Preferably, in the above-mentioned sulfurized hydrogenation catalyst, as some specific embodiments, the average number of stacked layers of the active phase (MoS2) lamellae is 2.7 to 4.6 layers, preferably 3.8 to 4.6 layers, and the average length of the active phase (MoS2) lamellae is 4.9 to 7.8 nm, preferably 5.3 to 6.8 nm.

[0015] Preferably, in the above-mentioned sulfidation-type hydrogenation catalyst, as some specific embodiments, the mechanical strength of the catalyst is 230-250 N / cm.

[0016] Preferably, in some specific embodiments, the specific surface area of ​​the above-mentioned sulfide-type hydrogenation catalyst is 240–380 m². 2 / g, preferably 320-360m 2 / g.

[0017] Preferably, in the above-mentioned sulfurized hydrogenation catalyst, as some specific embodiments, the pore volume of the catalyst is 0.5 mL / g to 0.8 mL / g, more preferably 0.7 mL / g to 0.8 mL / g.

[0018] A second aspect of this invention provides a method for preparing a sulfide-type hydrogenation catalyst, comprising the following steps:

[0019] (1) Prepare a solution containing active metals;

[0020] (2) The solution containing active metal is mixed with the second auxiliary agent, and the sulfiding agent and the first auxiliary agent are mixed evenly to obtain the impregnation solution;

[0021] (3) The impregnation solution obtained in step (2) is mixed evenly with the carrier material, and then dried and calcined to obtain a sulfurized hydrogenation catalyst.

[0022] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the preparation of the solution containing the active metal in step (1) can be any of the methods existing in the art, and those skilled in the art can make optional and appropriate adjustments according to actual needs. Specifically, the active metal-containing compound can be mixed with water and optionally a phosphoric acid-containing compound, wherein the phosphoric acid-containing compound can be one or more of phosphoric acid, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, preferably phosphoric acid; furthermore, adding phosphoric acid and stirring under heating conditions can promote the dissolution of the active metal-containing compound in water, and the heating temperature is controlled at 60℃~95℃, preferably 80℃~90℃. The solution concentration can be adjusted by the amount of each compound used, thereby preparing a catalyst with the required active component content. The solution preparation method is known to those skilled in the art.

[0023] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the active metal in step (1) includes one or more of Group VIB metals and / or Group VIII metals; the compound containing Group VIB metals can be one or more of molybdenum oxide, ammonium molybdate, tungsten oxide, and ammonium tungstate, preferably one or more of molybdenum oxide and ammonium molybdate, and the compound containing Group VIII metals can be one of basic nickel carbonate, basic cobalt carbonate, nickel oxide, and cobalt oxide, preferably one or more of basic nickel carbonate and nickel oxide.

[0024] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the second auxiliary agent mentioned in step (2) can be one or more of alcohol solvents, ketone solvents, and nitrile solvents with 1-3 carbon atoms, preferably an alcohol solvent; more specifically, it can be one or more of ethanol, methanol, acetone, acetonitrile, ethylene glycol, n-propanol, and isopropanol, preferably one or more of ethanol, methanol, ethylene glycol, n-propanol, and isopropanol.

[0025] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the volume ratio of the solution containing the active metal to the second auxiliary agent is 1:1 to 4:1, and more preferably 1:1 to 2:1.

[0026] Preferably, in the above-mentioned method for preparing a sulfurized hydrogenation catalyst, the sulfurizing agent in step (2) can be one or more of sulfur powder or sulfur-containing compounds, wherein the sulfur-containing compound is one or more of carbon disulfide, dimethyl sulfoxide, and dimethyl disulfide. When sulfur powder is used as the sulfurizing agent, a sulfurizing aid is also required. The sulfurizing aid can be kerosene or a mixture of kerosene and diesel oil, preferably a mixture of kerosene and diesel oil, wherein the volume ratio of kerosene to diesel oil can be 1:1 to 10:1, preferably 2:1 to 4:1.

[0027] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the first auxiliary agent in step (2) can be one or more of urea, thiourea, tert-butylthiourea, N-tert-butylurea, and squaramide, preferably squaramide.

[0028] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the mixing in step (2) is carried out at 50°C to 75°C, preferably 60°C to 75°C.

[0029] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the support material in step (3) is an inorganic refractory oxide, which can be selected from at least one of alumina, silicon oxide, zirconium oxide, titanium oxide, silicon-containing alumina, and silicon-containing zirconium oxide, and is preferably alumina.

[0030] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the support material in step (3) is preferably a mixture of inorganic refractory oxide powder (such as γ-alumina powder) and a molding aid. The molding aid can be one or more of nitric acid, guar gum powder, silica sol, alumina sol, and water. Furthermore, the inorganic refractory oxide powder is first subjected to calcination treatment at a temperature of 450–600°C for 1.5–2.5 h.

[0031] Preferably, in the above-mentioned method for preparing the sulfurized hydrogenation catalyst, after the impregnation liquid and the carrier material are mixed evenly in step (3), a molding aid is added for kneading and molding treatment. The molding aid can be one or more of nitric acid, guar gum powder, silica sol, aluminum sol, and water. The molding method can be any of the existing molding methods in the art, such as extrusion.

[0032] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the drying temperature in step (3) is 80℃~150℃, more preferably 100℃~130℃. The drying time is 2~4h, more preferably 2.5~3.5h.

[0033] Preferably, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the calcination temperature in step (3) is 350℃~600℃, and the calcination time is 2~4h. Preferably, it includes two stages of calcination, wherein the first stage calcination temperature is 350℃~450℃, preferably 380℃~420℃; the calcination time is 1~2h, preferably 1.5~2h. The second stage calcination temperature is 450℃~600℃, preferably 500℃~550℃; the calcination time is 1~2h, preferably 1.5~2h.

[0034] Furthermore, in the above-mentioned method for preparing the sulfide-type hydrogenation catalyst, the calcination in step (3) is carried out under an inert atmosphere, specifically under a nitrogen or inert gas atmosphere.

[0035] A third aspect of the present invention provides a sulfide-type hydrogenation catalyst obtained by the above preparation method.

[0036] The fourth aspect of the present invention provides a process for hydrogenating hydrocarbon compounds, wherein the hydrocarbon compound and hydrogen are introduced into a reactor, and the reactor is filled with the above-mentioned sulfurized hydrogenation catalyst.

[0037] Furthermore, in the above-mentioned hydrogenation process for hydrocarbon compounds, the hydrocarbon compound can be at least one of gasoline, diesel, and wax oil.

[0038] Furthermore, in the above-mentioned hydrogenation process for hydrocarbon-containing compounds, the hydrogenation reaction conditions are generally as follows: reaction pressure of 3.0–10.0 MPa, reaction temperature of 300–420 °C, and liquid hourly space velocity of 1.0–2.0 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300–800.

[0039] The sulfide-type hydrogenation catalyst and its preparation method provided by this invention have the following advantages compared with existing methods:

[0040] (1) The novel integrated sulfurized hydrogenation catalyst preparation method provided by this invention can complete catalyst preparation and catalyst sulfidation in one step. The catalyst preparation process is simple, which greatly reduces the manufacturing cost of sulfurized catalysts, shortens start-up time, and avoids the use of toxic and harmful sulfurizing agents, providing technical support for safe and efficient production in enterprises. Especially when there are restrictions on the transportation of sulfurizing agents, it is of great practical significance in solving the problems of safe production and environmental protection in oil refining enterprises. At the same time, the obtained sulfurized hydrogenation catalyst has a large pore volume and specific surface area, a high degree of sulfidation, high dispersion of active metals, and high hydrogenation activity.

[0041] (2) In the preparation method of the sulfide-type hydrogenation catalyst provided by the present invention, by adding an auxiliary agent, the NH bond contained in the auxiliary agent has a strong proton-donating ability, which can form S…HN hydrogen bonds with sulfur in the active metal sulfide and hydrogen bonds with hydroxyl groups on the support surface, thus coating the active metal sulfide, weakening the interaction force between the active component of the hydrogenation catalyst and the support, effectively inhibiting the growth and aggregation of the active component, increasing the degree of sulfidation of the catalyst, thereby increasing the number of type II active phase structures of the sulfide-type catalyst, and improving the hydrogenation activity of the sulfide-type hydrogenation catalyst. At the same time, the auxiliary agent has a large steric hindrance, which can better disperse the active metal and inhibit its growth and aggregation.

[0042] (3) In the preparation method of the integrated sulfidation-type hydrogenation catalyst provided by the present invention, the problem of the incompatibility between the active metal and the sulfiding agent is solved by adding an organic solvent and an appropriate heating temperature. By selecting a suitable organic solvent, a suitable processing temperature, and a specific ratio of active metal solution to organic solvent, the active metal and the sulfiding agent can be fully mixed to form a homogeneous and stable solution, thus solving the problem of the incompatibility between the active metal and the sulfiding agent.

[0043] (4) In the preparation method of the integrated sulfurized hydrogenation catalyst provided by the present invention, since the drying and calcination unit of the novel integrated sulfurized catalyst is quite different from that of the conventional oxidized catalyst, the influence of the heat treatment process on the mechanical strength of the catalyst is a problem that must be solved. Through the investigation of different treatment conditions, it was found that the mechanical strength of the catalyst is improved after drying and then calcining. The reason may be that after drying to remove excess moisture and cooling to room temperature, the surface of the catalyst strip shrinks. During the process of reheating to the calcination temperature, the internal stress of the catalyst is reduced, which increases the mechanical strength of the finished product and can obtain better mechanical strength to meet the requirements of the catalyst. Attached Figure Description

[0044] Figure 1 The image shows the AHRTEM image of the catalyst prepared in Example 1 of this invention.

[0045] Figure 2The image shows the AHRTEM image of the catalyst prepared in Comparative Example 1 of this invention.

[0046] Figure 3 The results are from the SEM-EDS analysis of catalyst A. Detailed Implementation

[0047] The following examples and comparative examples further illustrate the novel integrated sulfurized hydrogenation catalyst and its preparation method involved in this invention in detail, in order to help readers better understand this invention, but do not constitute any limitation on the scope of this invention.

[0048] Unless otherwise specified, the experimental methods used in the following examples are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following examples were purchased from conventional biochemical reagent stores.

[0049] The analytical method of this invention: specific surface area and pore volume are measured by low-temperature liquid nitrogen physical adsorption method.

[0050] The active phase of this invention was analyzed using transmission electron microscopy (TEM) to obtain the microstructure of the active metal phase. Twenty randomly selected TEM images from each sample were analyzed using Digital Micrograph software to determine the average number of stacked layers and the average lamellar length of the molybdenum disulfide wafers, which were then used to calculate the distribution of the active phase on the support surface. The formulas for calculating the average lamellar length and the average number of stacked layers are as follows:

[0051] L=∑S i L i / ∑S i

[0052]

[0053] Where S i For a slice length of L i The number of layers, L in nm; X i For having N i The number of lamellar crystals in the layer. In this paper, the degree of sulfidation of the catalyst is the percentage of sulfur consumed in actual sulfidation relative to the sulfur theoretically required for complete sulfidation.

[0054] In this paper, lateral pressure strength was measured using a strength gauge according to the Q / SH 361 926-2020 method.

[0055] In this paper, SEM-EDS technology utilizes scanning electron microscopy and energy dispersive spectroscopy (EDS) to achieve precise analysis of samples. It allows direct observation of the sample surface via scanning electron microscopy and compositional analysis via EDS, thereby obtaining elemental distribution images and corresponding analytical data of the sample surface. The scanning electron microscope used was a Nova NanoSEM450, and the EDS instrument was an AZtec X-MaxN80.

[0056] Example 1

[0057] 70g of γ-alumina powder was calcined in a muffle furnace for 2 hours at 600℃. Then, 35g of SB powder and 5g of guar gum powder were added and mixed thoroughly to obtain a solid material. Next, 44.9g of molybdenum trioxide and 16.5g of basic nickel carbonate were mixed, and 95mL of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 19.5g of dimethyl sulfoxide was added to 35mL of anhydrous ethanol and stirred thoroughly. Then, 3g of squaramide was added, followed by the molybdenum-nickel-phosphorus solution. The mixture was stirred thoroughly at 70℃ until the solution became homogeneous and transparent. Then, 5.4g of nitric acid was added and mixed thoroughly. This mixture was then added to the previously mixed solid material and mixed thoroughly. The mixture was kneaded, extruded into strips, and dried at 120℃ under nitrogen for 3 hours. Subsequently, it was calcined at 400℃ for 2 hours and then at 500℃ for 1.5 hours under nitrogen to obtain catalyst A.

[0058] Example 2

[0059] 70g of silica-containing alumina powder was calcined in a muffle furnace for 2.5 hours at 550℃. Then, 35g of SB powder and 5g of guar gum powder were added and mixed thoroughly to obtain a solid material. Subsequently, 44.9g of molybdenum trioxide and 7.5g of nickel oxide were mixed, and 88mL of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 12g of dimethyl disulfide was added to 40mL of isopropanol and stirred thoroughly. Then, 3.5g of N-tert-butylurea was added, followed by the molybdenum-nickel-phosphorus solution. The mixture was stirred thoroughly at 65℃ until the solution became homogeneous and transparent. This solution was added to the previously mixed solid material, and then 5.4g of nitric acid was added. The mixture was kneaded, extruded into strips, and dried at 110℃ for 2.5 hours under nitrogen. Then, it was calcined at 420℃ for 1.5 hours and 500℃ for 2 hours under nitrogen to obtain catalyst B.

[0060] Example 3

[0061] 70g of γ-alumina powder was calcined in a muffle furnace for 2 hours at 500℃. Then, 5g of guar gum powder was added and mixed thoroughly to obtain a solid material. Next, 60.0g of ammonium molybdate and 7.5g of nickel oxide were mixed, and 90ml of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 9.5g of carbon disulfide was added to 35ml of ethylene glycol and stirred thoroughly. Then, 4g of tert-butylthiourea was added, followed by the molybdenum-nickel-phosphorus solution. The mixture was stirred thoroughly at 75℃ until the solution became homogeneous and transparent. This solution was added to the previously mixed solid material, and finally, 68.0g of aluminum sol was added and mixed thoroughly. The mixture was kneaded, extruded, and dried at 130℃ under nitrogen for 3 hours, followed by calcination at 360℃ for 1.5 hours and 580℃ for 2 hours under nitrogen to obtain catalyst C.

[0062] Example 4

[0063] 70g of γ-alumina powder was calcined in a muffle furnace for 2.5 hours at 450℃. Then, 35g of SB powder and 5g of guar gum powder were added and mixed thoroughly to obtain a solid material. Subsequently, 44.9g of molybdenum trioxide and 16.5g of basic nickel carbonate were mixed, and 95mL of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 12g of dimethyl disulfide was added to 40mL of isopropanol and stirred thoroughly. Then, 3g of squaramide was added, followed by the molybdenum-nickel-phosphorus solution. The mixture was stirred thoroughly at 70℃ until the solution became homogeneous and transparent. 5.4g of nitric acid was then added and mixed thoroughly. This mixture was then added to the previously mixed solid material and mixed thoroughly. The mixture was kneaded, extruded into strips, and dried at 140℃ under nitrogen for 2 hours, followed by calcination at 500℃ under nitrogen for 3 hours to obtain catalyst D.

[0064] Example 5

[0065] 70g of γ-alumina powder was calcined in a muffle furnace for 2 hours at 600℃. Then, 35g of SB powder and 5g of guar gum powder were added and mixed thoroughly to obtain a solid material. Next, 44.9g of molybdenum trioxide and 16.5g of basic nickel carbonate were mixed, and 95mL of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 12g of dimethyl disulfide was added to 35mL of ethylene glycol and stirred thoroughly. Then, 3g of squaramide was added, followed by the molybdenum-nickel-phosphorus solution. The mixture was stirred thoroughly at 70℃ until the solution became homogeneous and transparent. Then, 5.4g of nitric acid was added and mixed thoroughly. This mixture was then added to the previously mixed solid material and mixed thoroughly. The mixture was kneaded, extruded, and dried at 90℃ under nitrogen for 4 hours. Finally, it was calcined at 450℃ for 1 hour and 580℃ for 1.5 hours under nitrogen to obtain catalyst E.

[0066] Comparative Example 1

[0067] 70g of γ-alumina powder was calcined in a muffle furnace for 2 hours at 600℃. Then, 35g of SB powder and 5g of guar gum powder were added and mixed thoroughly to obtain a solid material. Next, 44.9g of molybdenum trioxide and 16.5g of basic nickel carbonate were mixed, and 95ml of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 19.5g of dimethyl sulfoxide was added to the molybdenum-nickel-phosphorus solution and stirred thoroughly. Then, 3g of squaramide was added and stirred thoroughly at 70℃. 5.4g of nitric acid was then added and mixed thoroughly. This mixture was then added to the previously mixed solid material and mixed thoroughly. The mixture was kneaded, extruded into strips, and dried at 120℃ under nitrogen for 3 hours. Subsequently, it was calcined at 400℃ for 2 hours and then at 500℃ for 1.5 hours under nitrogen to obtain catalyst F.

[0068] Comparative Example 2

[0069] 70g of γ-alumina powder was calcined in a muffle furnace for 2 hours at 600℃. Then, 35g of SB powder and 5g of guar gum powder were added and mixed thoroughly to obtain a solid material. Subsequently, 44.9g of molybdenum trioxide and 16.5g of basic nickel carbonate were mixed, and 95ml of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 19.5g of dimethyl sulfoxide was added to 35mL of anhydrous ethanol and stirred thoroughly. Then, the molybdenum-nickel-phosphorus solution was added and stirred thoroughly at 70℃ until the solution became homogeneous and transparent. 5.4g of nitric acid was then added and mixed thoroughly. This mixture was then added to the previously mixed solid material and mixed thoroughly. The mixture was kneaded, extruded into strips, and dried at 120℃ under nitrogen for 3 hours. Subsequently, it was calcined at 400℃ for 2 hours and then at 500℃ for 1.5 hours under nitrogen to obtain catalyst G.

[0070] Comparative Example 3

[0071] 70g of γ-alumina powder was calcined in a muffle furnace for 2 hours at 600℃. Then, 35g of SB powder and 5g of guar gum powder were added and mixed thoroughly to obtain a solid material. Subsequently, 44.9g of molybdenum trioxide and 16.5g of basic nickel carbonate were mixed, and 95ml of purified water was added. The mixture was heated and stirred at 90℃, and 3.1g of phosphoric acid was gradually added until the solution became clear and transparent. The mixture was then filtered to obtain a molybdenum-nickel-phosphorus solution. 19.5g of dimethyl sulfoxide was added to the molybdenum-nickel-phosphorus solution and stirred thoroughly at 70℃. Then, 5.4g of nitric acid was added and mixed thoroughly. This mixture was then added to the previously mixed solid material and mixed thoroughly. The mixture was kneaded, extruded into strips, and dried at 120℃ for 3 hours under nitrogen atmosphere. Subsequently, it was calcined at 400℃ for 2 hours and then at 500℃ for 1.5 hours under nitrogen atmosphere to obtain catalyst H.

[0072] Table 1. Properties of catalyst samples

[0073]

[0074]

[0075] Table 1 shows the average number of stacked layers and the average length of the active phase crystals in the catalysts obtained statistically. The results show that Examples 1-5 all have a high number of stacked layers and a short average length, indicating that the active components are uniformly distributed on the support and have many metal active sites. Comparative Examples 1 and 2 have a lower number of stacked layers and a higher average length compared to the five examples, indicating that the dispersibility of the active components is lower than in the five examples. Comparative Example 3 has a lower number of stacked layers compared to Comparative Examples 1 and 2, but a higher average length, indicating that the dispersibility of the active components is lower than in Comparative Examples 1 and 2. Increasing the number of stacked layers can generate a highly active type II active phase, improving the hydrogenation activity of the catalyst. However, on the other hand, MoS2 crystals are prone to agglomeration, leading to a decrease in the dispersion of the active metal components. Therefore, a suitable number of stacked layers and a slightly shorter average length are beneficial for improving the hydrogenation activity of the catalyst. Generally, a metal stack of about 3 to 5 layers is considered optimal.

[0076] Evaluation Test:

[0077] The catalyst samples prepared in both the examples and comparative examples were evaluated for activity using a microreactor. The properties of the feedstock oil used for the evaluation are shown in Table 2. The microreactor evaluation conditions were 350°C, 3.4 MPa, a hydrogen-to-oil volume ratio of 500, and a volume hourly space velocity of 1.5 h⁻¹. -1 The catalyst activity evaluation results are shown in Table 3.

[0078] Table 2 Main Properties of Crude Oil

[0079]

[0080]

[0081] Table 3 Catalyst Evaluation Results

[0082] catalyst <![CDATA[Sulfur, μg.g -1 > <![CDATA[Nitrogen, μg / g -1 > A 23.5 ＜1.0 B 24.7 ＜1.0 C 27.1 ＜1.0 D 27.6 ＜1.0 E 25.1 ＜1.0 F 71.2 5.8 G 67.4 5.3 H 123.7 9.6

[0083] The catalyst evaluation results show that the novel integrated sulfurization-type hydrogenation catalyst has high hydrodesulfurization and denitrification activity.

[0084] Table 4. Degree of sulfidation of the catalyst

[0085]

[0086]

[0087] As shown in Table 4, catalyst AE has a high degree of sulfidation, and the active components are fully utilized, while catalyst FH has a relatively low degree of sulfidation, and the active components cannot be fully utilized.

[0088] Figure 3 The results of SEM-EDS analysis of sulfidation catalyst A are as follows: Figure 3 It is evident that the distribution of active metals and sulfur elements at various points along cross section A of the catalyst is relatively uniform, indicating that this method is beneficial for improving the dispersion of metals and sulfur. It can significantly improve the distribution of active metal components on the support surface, resulting in a larger amount of active phase per unit catalyst surface, thus enhancing the hydrogenation activity of the catalyst.

Claims

1. A sulfided hydroprocessing catalyst, the catalyst comprising a support, an active metal component, a first promoter; wherein the support is one or more of inorganic refractory oxides; the active metal comprises a Group VIB metal and a Group VIII metal, the active metal component is distributed on the support in the form of sulfides; the first promoter is squaric amide; The first promoter is connected to the sulfur S in the active metal sulfides by S…H-N bond formed by the N-H bond contained in the first promoter, and connected to the surface hydroxyl of the support by hydrogen bond.

2. The sulfided hydrocatalyst of claim 1, wherein, The Group VIB metal is Mo and / or W, and the Group VIII metal is Ni and / or Co.

3. The sulfided hydroprocessing catalyst of claim 1, wherein, The active metal is Mo and Ni.

4. The sulfided hydroprocessing catalyst of claim 1, wherein, The inorganic refractory oxide is selected from at least one of alumina, silica, zirconia, titania, silica-containing alumina, and silica-containing zirconia.

5. The sulfided hydroprocessing catalyst of claim 4, wherein, The inorganic refractory oxide is alumina.

6. The sulfided hydroprocessing catalyst of claim 1, wherein, The average number of stacking layers of the active phase crystallite is 2.7-4.6, and the average length of the active phase crystallite is 4.9-7.8 nm.

7. The sulfided hydroprocessing catalyst of claim 6, wherein, The average number of stacking layers of the active phase crystallite is 3.8-4.6, and the average length of the active phase crystallite is 5.3-6.8 nm.

8. The sulfided hydroprocessing catalyst of claim 1, wherein, The catalyst has a specific surface area of 240-380 m 2 / g; a pore volume of 0.5 mL / g-0.8 mL / g; and a mechanical strength of 230-250 N / cm.

9. The sulfided hydroprocessing catalyst of claim 8, wherein, The catalyst has a specific surface area of 320 to 360 m 2 / g; and a pore volume of 0.7 mL / g to 0.8 mL / g.

10. The sulfided hydroprocessing catalyst of claim 1, wherein, The active metal component contains 22-28% of the active metal in terms of element content, 6-10% of sulfur, 18-24% of the Group VIB metal in terms of element content, and 3-6% of the Group VIII metal in terms of element content, based on the weight of the catalyst.

11. The sulfided hydroprocessing catalyst of claim 10, wherein, The active metal component contains 23-26% of the active metal in terms of element content, and 7-8.5% of sulfur, based on the weight of the catalyst.

12. The sulfided hydroprocessing catalyst of claim 1, wherein, The first promoter contains 2-10% of the first promoter, based on the weight of the catalyst.

13. The sulfided hydroprocessing catalyst of claim 12, wherein, The first promoter contains 3-5% of the first promoter, based on the weight of the catalyst.

14. A method for preparing a sulfided hydroprocessing catalyst, comprising the following steps: (1) preparing a solution containing an active metal; the active metal comprises one or more of a Group VIB metal and / or a Group VIII metal; (2) mixing the solution containing the active metal with a second promoter, introducing a sulfidation agent and a first promoter, and uniformly mixing to obtain an impregnation solution; the first promoter is one or more of urea, thiourea, tert-butyl thiourea, N-tert-butyl urea, and squaric amide; the second promoter is one or more of an alcohol solvent, a ketone solvent, and a nitrile solvent having 1-3 carbon atoms; (3) uniformly mixing the impregnation solution obtained in step (2) with a support material, and then drying and calcining to obtain the sulfided hydroprocessing catalyst.

15. The process for preparing a vulcanized-type hydrogenation catalyst according to claim 14, wherein, In step (1), the solution containing the active metal is prepared by mixing a compound containing the active metal with water and optionally a compound containing P; the compound containing P is one or more of phosphoric acid, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.

16. A process for the preparation of a sulfided hydroprocessing catalyst according to claim 15 wherein, The compound containing P is phosphoric acid.

17. A process for the preparation of a sulfided hydroprocessing catalyst according to claim 15 wherein, The compound containing the Group VIB metal is one or more of molybdenum oxide, ammonium molybdate, tungsten oxide, and ammonium tungstate, and the compound containing the Group VIII metal is one of basic nickel carbonate, basic cobalt carbonate, nickel oxide, and cobalt oxide.

18. A process for the preparation of a sulfided hydroprocessing catalyst according to claim 17 wherein, The compound containing the Group VIB metal is molybdenum oxide and / or ammonium molybdate, and the compound containing the Group VIII metal is basic nickel carbonate and / or nickel oxide.

19. The process for preparing a sulfided hydroprocessing catalyst according to claim 14 wherein, The second assistant in step (2) is one or more of ethanol, methanol, acetone, acetonitrile, ethylene glycol, n-propanol, isopropanol.

20. The process for preparing a sulfided hydroprocessing catalyst according to claim 19 wherein, The second assistant is one or more of ethanol, methanol, ethylene glycol, n-propanol, isopropanol.

21. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, The volume ratio of the active metal-containing solution to the second assistant is 1:1 to 4:

1.

22. The process for preparing a sulfided hydroprocessing catalyst according to claim 21 wherein, The volume ratio of the active metal-containing solution to the second assistant is 1:1 to 2:

1.

23. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, The vulcanizing agent in step (2) is one or more of sulfur powder or sulfur-containing compounds, and the sulfur-containing compounds are one or more of carbon disulfide, dimethyl sulfoxide, dimethyl disulfide.

24. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, The mixing in step (2) is at 50-75°C.

25. The process for preparing a sulfided hydroprocessing catalyst according to claim 24 wherein, The mixing is at 60-75°C.

26. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, The carrier material in step (3) is an inorganic refractory oxide, and the inorganic refractory oxide is at least one of alumina, silica, zirconia, titania, silicon-containing alumina, and silicon-containing zirconia.

27. A process for the preparation of a sulfided hydroprocessing catalyst according to claim 26 wherein, The carrier material is alumina.

28. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, The carrier material in step (3) is a mixture of inorganic refractory oxide powder and a forming assistant, and the forming assistant is one or more of nitric acid, sesbania powder, silica sol, alumina sol, and water; the inorganic refractory oxide powder is first subjected to a calcination treatment, the calcination temperature is 450-600°C, and the calcination time is 1.5-2.5h.

29. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, After the impregnation solution and the carrier material are mixed uniformly, a forming assistant is added to perform a kneading and forming treatment, and the forming assistant is one or more of nitric acid, sesbania powder, silica sol, alumina sol, and water.

30. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, The drying temperature in step (3) is 80-150°C, and the drying time is 2-4h.

31. The process for preparing a sulfided hydroprocessing catalyst according to claim 30 wherein, The drying temperature is 100-130°C, and the drying time is 2.5-3.5h.

32. The process for preparing a vulcanized shaped hydrogenation catalyst according to claim 14, wherein, The calcination temperature in step (3) is 350-600°C.

33. A process for the preparation of a sulfided hydroprocessing catalyst according to claim 32, said calcination comprising a two-stage calcination, wherein, The first-stage calcination temperature is 350-450°C, and the second-stage calcination temperature is 450-600°C.

34. A process for the preparation of a vulcanized shaped hydrogenation catalyst according to claim 33, said two-stage calcination, wherein, The first-stage calcination temperature is 380-420°C, and the second-stage calcination temperature is 500-550°C.

35. A sulfided hydrogenation catalyst prepared by the preparation method of any one of claims 14-34.

36. A hydrocarbon compound hydrogenation treatment process, in which hydrocarbon compounds and hydrogen are introduced into a reactor, and the reactor is filled with the sulfided hydrogenation catalyst of any one of claims 1-13 and / or the sulfided hydrogenation catalyst prepared by the preparation method of any one of claims 14-34.

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