A heavy oil hydrogenation iron-based catalyst, a preparation method and application thereof

Abstract

The present application relates to a kind of preparation methods of heavy oil hydrogenation iron-based catalyst, it is characterized in that, including the following steps: (1) after the alkali treatment, washing, drying of silica carrier, ball milling treatment, wherein the BET specific surface area of silica carrier before and after treatment is greater than 50m 2 / g, the peak area ratio of two absorption peaks of surface infrared hydroxyl 3740cm ‑1 Nearby and 3685cm ‑1 Nearby is between 0.1-1.5;(2) after ball milling treatment, the mixture of iron-containing compound, the silica carrier obtained in step (1), auxiliary metal compound and complexing agent is mechanically mixed, wherein the molar ratio of metal iron in the iron-containing compound and the auxiliary metal in the auxiliary metal compound is 1:(0-20), and the molar ratio of the main metal component:complexing agent is 1:(0-10);(3) the mixture in step (2) is dried and calcined to obtain the heavy oil hydrogenation iron-based catalyst.

Description

Technical Field

[0001] This invention belongs to the field of catalyst preparation technology, specifically relating to an iron-based catalyst for heavy oil hydrogenation, its preparation method, and its application. Background Technology

[0002] In recent years, with the increasing production of heavy oil and increasingly stringent regulations on clean fuels, the development of petroleum processing has faced significant challenges. Heavy oil contains large amounts of sulfur, nitrogen, and metallic compound impurities; effectively removing these impurities is a crucial step in oil processing. Therefore, hydrogenation, as an important method for processing heavy oil, has received increasing attention and development. Through the attention and research of industry professionals, many new hydrogenation catalysts and their preparation methods have emerged.

[0003] CN1086534A discloses a heavy oil hydrotreating catalyst and its preparation method. The catalyst has a composition of W-Mo-Ni / SiO2-B2O3-Al2O3. CN1458236A discloses a heavy oil hydrotreating demetallization and desulfurization catalyst. The active components of this catalyst contain 1 wt%-20 wt% tungsten oxide and / or molybdenum oxide, 0.5 wt%-5.0 wt% nickel oxide and / or cobalt oxide, and the promoter contains 0.1 wt%-3.0 wt% alkali metal and / or alkaline earth metal oxides. The catalyst prepared by this method has both high demetallization and desulfurization activities, and high activity stability, especially good stability of desulfurization activity. CN1110304A discloses a heavy oil hydrotreating catalyst. This catalyst uses silicon and phosphorus-containing alumina as a support, supporting molybdenum, nickel, and phosphorus elements. This catalyst contains 10-30 wt% MoO3, 2-6 wt% NiO, and 2-6 wt% P, and exhibits good denitrification performance. CN109718815A discloses a support, catalyst, and preparation method for hydrodesulfurization. It primarily uses a mixed support consisting of a main alumina substrate with micron-sized pores and a small portion of rod-shaped alumina located on the surface and within the micron-sized pores of the main alumina substrate. Phosphorus and / or boron are used as auxiliary agents. The active metal component is one or both of Group VIB metals Mo and W, or one or both of Group VIII metals Co and Ni. The resulting catalyst exhibits high desulfurization, denitrification, and demetallization activity and good stability, but still suffers from drawbacks such as complex preparation methods and high cost. CN102039140A discloses a heavy oil hydrotreating catalyst and its preparation method, primarily using inexpensive natural clays such as kaolin, montmorillonite, diatomaceous earth, and natural clay as part of the support. This clay accounts for 0.5wt%-30wt% of the catalyst weight based on SiO2. The resulting catalyst possesses hydrotreating activity comparable to catalysts using pure alumina as the support, while also having the advantage of low cost. USP727980 discloses a hydrogenation demetallization catalyst and its preparation method. The catalyst uses a sintered oxide (Al₂O₃, SiO₂, TiO₂, or a mixture thereof) as a support. First, ferric nitrate is impregnated, followed by drying and calcination. Then, it is impregnated with ammonium molybdate solution, and further dried and calcined to obtain a finished catalyst with two crystalline phases. This catalyst has a high metal content and high hydrogenation activity; however, it suffers from drawbacks such as complex preparation process and high cost.

[0004] Therefore, although researchers have conducted extensive research over the years on supported catalysts and additive modification, as well as the groundbreaking preparation of unsupported catalysts in recent years, the basic combination of nickel and cobalt as additives and molybdenum and tungsten as the main active metal components has dominated the heavy oil hydrogenation catalyst market. However, a common drawback of all the above-mentioned existing preparation methods is their high cost. The fundamental reason for this is that nickel, cobalt, molybdenum, and tungsten, as active metals, are not abundant in the Earth's crust, and their prices are very high.

[0005] Therefore, developing lower-cost, more efficient hydrogenation catalysts through the development of hydrogenation metal active phases and the improvement of corresponding preparation methods will be an important direction for the future development of heavy oil hydrodesulfurization. CN104383923A, CN104918698A, CN104383922A, and CN107185539A disclose a series of heavy oil hydrogenation catalysts with iron as the main active phase. By adding auxiliary elements or modifying the impregnation solution to iron-based catalysts, the hydrogenation activity of the single iron component can be multiplied, which can greatly reduce the cost of hydrogenation catalysts and lead the mainstream development direction of iron-based hydrogenation catalysts.

[0006] However, compared with the research on traditional catalyst systems using Ni, Co, etc. as promoters and Mo, W as main active components, the research on iron-based catalysts is still in its initial stage, and many issues, including suitable preparation methods, have not yet been studied in more detail.

[0007] Compared with Reference 1, CN 104383922 A, a heavy oil hydrogenation iron-based catalyst and its application are provided. This heavy oil hydrogenation iron-based catalyst uses iron as the active metal component and one or a combination of two of zinc, copper, and silver as auxiliary metals, with both supported on a carrier; wherein the molar ratio of the active metal component to the auxiliary metal is 1-20:1. The application includes the use of the heavy oil hydrogenation iron-based catalyst in the hydrogenation treatment of one or more of the following heavy oils: crude oil, atmospheric residue, vacuum residue, coal tar, deasphalted oil, or heavy oils extracted from oil sands and shale. The iron-based catalyst of this invention has the advantages of inexpensive and readily available raw materials and a simple manufacturing process. It can significantly reduce the production cost of hydrogenation catalysts while also exhibiting high heavy oil hydrogenation activity. The drawbacks of this technology, or the shortcomings compared to this invention, are that the preparation method in this reference is more inclined towards the preparation of fixed-bed process catalysts, and the preparation method provided in the reference is more complex than that of this patent.

[0008] Compared with reference 2, CN 104383923 A, a gasoline and diesel hydrogenation iron-based catalyst and its application are provided. This gasoline and diesel hydrogenation iron-based catalyst uses iron as the active metal component and zinc, copper, and silver (or a combination of two of these) as a promoter metal; wherein the molar ratio of the active metal component to the promoter metal is 1-20:1; and based on the total weight of the gasoline and diesel hydrogenation iron-based catalyst, the total amount of the active metal component and promoter metal in oxide form is 10-80%. The application of this gasoline and diesel hydrogenation iron-based catalyst includes its use in the hydrogenation treatment of straight-run gasoline, straight-run diesel, coking gasoline, coking diesel, catalytic cracking gasoline, and catalytic cracking diesel. The iron-based catalyst of this invention has the advantages of inexpensive and readily available raw materials and a simple manufacturing process. While significantly reducing the production cost of hydrogenation catalysts, it also exhibits high activity in the hydrogenation of gasoline and diesel. The drawback of this technology, or its relative deficiency compared to this invention, is that the catalyst preparation method in this reference is more complex than that of this patent, which provides a simpler and more advantageous preparation method.

[0009] Compared with reference 3, CN 107185539 A, a method for preparing and applying an iron-based catalyst for oil hydrogenation is provided. The active metal component of this catalyst is iron or a combination of iron and a promoter; the total content of the active metal component, based on the total weight of the catalyst and calculated as oxides, is 5-30%. It is prepared by a method including the following steps: mixing anhydrous ethanol, acetone, and 2,2-bipyridine to obtain a mixed solvent; dissolving a salt of the active metal component in the mixed solvent to obtain an impregnation solution; impregnating a support with the impregnation solution in equal volumes to obtain a catalyst semi-finished product; allowing the catalyst semi-finished product to stand in air, and then drying and calcining it to obtain the oil hydrogenation iron-based catalyst. This invention also provides a method for preparing the above catalyst and its application in oil hydrogenation. The drawback of this technology, or its deficiency compared to this invention, is that the catalyst preparation method in this reference is more complex than that of this patent. Summary of the Invention

[0010] In view of the shortcomings of the above-mentioned technologies, the purpose of this invention is to provide an iron-based catalyst for heavy oil hydrotreating, its preparation method, and its application. This iron-based catalyst for heavy oil hydrotreating uses iron as the active metal component, zinc, alkali metals, and a combination of two rare earth metals as auxiliary metals, and silica as a support. It has the advantages of lower preparation cost, simple preparation process, and high hydrogenation activity.

[0011] The preparation method of the heavy oil hydrogenation iron-based catalyst used in this invention includes the following steps:

[0012] (1) The silica support is subjected to alkali treatment, washing, drying, and then ball milling. The BET specific surface area of ​​the silica support before and after treatment is greater than 50 m². 2 / g, surface infrared hydroxyl group 3740cm -1 Nearby and 3685cm -1 The peak area ratio of the two nearby absorption peaks is between 0.1 and 1.5; (2) The iron-containing compound is ball-milled and then mechanically mixed with the silica support, auxiliary metal compound and complexing agent obtained in step (1), wherein the molar ratio of metallic iron in the iron-containing compound to auxiliary metal in the auxiliary metal compound is 1:(0-20), and the molar ratio of the main metal component to the complexing agent is 1:(0-10); (3) The mixture in step (2) is dried and calcined to obtain the heavy oil hydrogenation iron-based catalyst.

[0013] It is prepared by mechanically mixing iron or a combination of iron and additives as the active metal component with a certain amount of silica carrier; it has the advantages of lower preparation cost, simple preparation process and high hydrogenation activity.

[0014] In the preparation method of the present invention, the conditions for the alkali treatment in step (1) are: solid-liquid ratio of 1:10-100, alkali concentration of 0.01-2 mol / L, water bath temperature of 40-95℃, treatment for 0.5-4 h.

[0015] In the preparation method of the present invention, the alkali treatment is performed using an organic alkali or an inorganic alkali, wherein the organic alkali includes triethylamine, urea, pyridine, potassium methoxide, potassium ethoxide, and sodium ethoxide, and the inorganic alkali includes sodium hydroxide, potassium hydroxide, and ammonia.

[0016] In the preparation method of the present invention, in step (2), the iron-containing compound is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride, and ferric phosphate; the complexing agent is selected from any one of monoethanolamine, diethanolamine, triethanolamine, oxalic acid, tartaric acid, citric acid, adipic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), acetylacetone, thiourea, and sulfosalicylic acid; the auxiliary metal compound is added in the form of an auxiliary metal salt, wherein the auxiliary metal salt is selected from at least one of nitrate, sulfate, chloride, and phosphate; and the auxiliary metal is selected from at least one of zinc, alkali metal, and rare earth elements.

[0017] In the preparation method of the present invention, in step (2), the mechanical mixing method is selected from at least one of mechanical stirring, air mixing, grinding, and ball milling.

[0018] In the preparation method of the present invention, in step (1), the washing solution is selected from at least one of water and ethanol; the drying conditions are: temperature 60-130℃, time 4-36h.

[0019] In the preparation method of the present invention, the drying conditions in step (3) are: temperature 60-120℃, time 6-24h;

[0020] The calcination conditions of this invention are: temperature 350-600℃, time 2-6h.

[0021] This invention also provides a heavy oil hydrogenation iron-based catalyst prepared according to the above preparation method, characterized in that iron is used as the active metal component, at least one of zinc, alkali metal, and rare earth metal is used as a co-metal, and silicon oxide is used as a support, wherein the molar ratio of the active metal component to the co-metal is 1:0-20; based on the total weight of the iron-based catalyst, the total amount of active metal component and co-metal in oxide form is 10-90%, and the total amount of silicon oxide support is 10%-50%; the silicon oxide support is characterized by a surface infrared hydroxyl group of 3740 cm⁻¹. -1 Nearby and 3685cm -1 The ratio of the peak areas of the two nearby absorption peaks is between 0.1 and 1.5.

[0022] The iron-based catalyst for heavy oil hydrotreating of the present invention, obtained by the above preparation method, can be used directly without pre-sulfurization treatment. However, according to a specific embodiment of the present invention, the pre-sulfurization treatment can be carried out using conventional pre-sulfurization technology for hydrotreating catalysts in the art, and the pre-sulfurized oil or pre-sulfurizing agent used can also be conventionally used pre-sulfurized oil or pre-sulfurizing agent in the art.

[0023] The heavy oil hydrogenation iron-based catalyst of the present invention is characterized in that the heavy oil hydrogenation iron-based catalyst is a heavy oil hydrogenation iron-based catalyst that has undergone pre-sulfurization treatment, wherein the pre-sulfurization treatment temperature is 200-450℃, the pressure is 1-10MPa, the pre-sulfurization treatment time is 4-48h, and the liquid hourly space velocity is 0.5-10h. -1 The hydrogen-to-oil volume ratio is 100-800; preferably, the pre-sulfurization treatment temperature is 280-380℃, the pressure is 2-6MPa, the pre-sulfurization treatment time is 6-24h, and the liquid hourly space velocity is 1-4h. -1 The hydrogen-to-oil volume ratio is 200-500.

[0024] This invention also provides the application of a heavy oil hydrotreating iron-based catalyst in the hydrotreating of one or more of the following: crude oil, atmospheric residue, vacuum residue, coal tar, deasphalted oil, or heavy oil extracted from oil sands or shale.

[0025] In this invention, the heavy oil, or heavy quality oil, is a recognized petroleum product in the petroleum processing field. It generally refers to various primary and secondary processed residues and their deasphalted oils with boiling points above 350℃, as well as various primary and secondary processed vacuum distillate oils and catalytic cracking slurry oils with boiling points above 350℃. The hydrotreating process can include hydrorefining, hydromodification, hydrocracking, and hydroisomerization; more specifically, the hydrotreating process can include hydrodesulfurization, hydrodenitrogenation, hydrometallurgization, and hydrosaturation of aromatics.

[0026] In this invention, the apparatus, method, and process flow for hydrotreating can be conventional heavy oil hydrotreating apparatus, methods, and processes in the art. The hydrotreating can be carried out in a single reactor or in multiple parallel or series reactors; that is, the catalyst of this invention can be loaded into one or more reactors in a single process for hydrotreating. Without altering existing heavy oil hydrotreating processes, the catalyst of this invention exhibits superior hydrotreating performance. Specifically, in slurry bed hydrotreating applications, the hydrotreating temperature is 200-500°C, the pressure is 3-30 MPa, and the liquid hourly space velocity is 0.3-5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 200-2000; preferably, the hydrotreating temperature is 350-450℃, the pressure is 7-25MPa, and the liquid hourly space velocity is 0.5-2h. -1 The hydrogen-to-oil volume ratio is 300-1000;

[0027] In fixed-bed hydrotreating applications, the hydrotreating temperature is 200-500℃, the pressure is 2-20 MPa, and the liquid hourly space velocity is 0.3-15 h⁻¹. -1 The hydrogen-to-oil volume ratio is 200-2000; preferably, the hydrotreating temperature is 300-500℃, the pressure is 5-10 MPa, and the liquid hourly space velocity is 0.5-6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-1000.

[0028] The beneficial effects of this invention are:

[0029] Beneficial Effect 1: This invention uses iron as the active metal component, and zinc, alkali metals, and rare earth metals (one or more combinations) as auxiliary metals. It utilizes silicon dioxide, characterized by its surface infrared hydroxyl groups at 3740 cm⁻¹. -1 Nearby and 3685cm -1A support with a peak area ratio between 0.1 and 1.5 for two nearby absorption peaks provides suitable and adequate hydroxyl sites on the silica support surface, which is beneficial for the formation of well-dispersed metal oxides during the preparation process. This effectively increases the number of reactive sites and improves the reactivity of the hydrotreating catalyst. A highly active iron-based catalyst for heavy oil hydrotreating was prepared using one or a combination of mature and simple mechanical stirring, air mixing, grinding, and ball milling.

[0030] Beneficial Effect 2: The hydrogenation catalyst of this invention replaces the traditional hydrogenation catalyst used for heavy oil hydrogenation. Compared with traditional heavy oil hydrogenation catalysts that use molybdenum and tungsten of Group VIA as active metal components and cobalt and nickel of Group VIII as auxiliary metals, the iron-based catalyst of this invention has the advantages of inexpensive and readily available raw materials and simple manufacturing process. While greatly reducing the production cost of hydrogenation catalysts, it also has high hydrogenation activity for heavy oil. Attached Figure Description

[0031] Figure 1 The OH-IR spectrum of silicon oxide in Example 1 is shown below.

[0032] Figure 2 The OH-IR spectrum of silicon oxide in Example 3 is shown below.

[0033] Figure 3 The image shows the OH-IR spectrum of silicon oxide in Example 6. Detailed Implementation

[0034] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.

[0035] Unless otherwise specified, the experimental methods described in the following embodiments are conventional methods; unless otherwise specified, the reagents and compounds are commercially available.

[0036] Analysis method:

[0037] All supports used in the examples were analyzed using hydroxyl infrared spectroscopy (OH-IR) to determine changes in hydroxyl groups. Instrument model: Thermo Fisher Nicolet IS10 infrared spectrometer. Test method: First, the sample to be tested (approximately 12 mg) was thoroughly ground and dried at 393 K for 2 hours. The sample was then fabricated into a self-supporting wafer with a diameter of 6.0 mm under a pressure of 5 MPa and dried before testing. First, an infrared vacuum cell without the sample and equipped with a CaCl2 window was heated at 673 K and 10... -6Pre-treated under vacuum for 2 hours, cooled to 298K, and then background data was collected. The pressed, dried wafers were then weighed and placed in an infrared vacuum cell with a CaCl2 window, and tested at 673K ​​and 10... -6 Sample data were collected after pretreatment under vacuum for 2 hours and cooling to 298 K. The hydroxyl infrared spectrum of the sample was obtained after background subtraction.

[0038] Example 1

[0039] This embodiment provides an iron-based catalyst for heavy oil hydrotreating, the preparation method of which includes the following steps:

[0040] (1) First, the silica support was treated with 0.5 mol / L sodium hydroxide at a solid-liquid ratio of 1:10 in a water bath at 90°C for 2 hours. After washing with water, it was dried at 120°C for 8 hours to obtain isolated surface hydroxyl groups 3740 cm⁻¹. -1 3685cm adjacent hydroxyl site -1 The peak area ratio is 0.91, and the specific surface area is 189 m². 2 / g of silica support.

[0041] (2) 10.0g of silica support (isolated surface hydroxyl groups 3740cm) was placed separately. -1 3685cm adjacent hydroxyl site -1 The peak area ratio was 0.91) and 25.2 g of ferric nitrate were ball-milled for 5 min each. Then the milled ferric nitrate was mixed with the silica carrier and ball-milled for 5 min.

[0042] (3) The ground catalyst precursor was then placed in an oven at 120°C and dried for 12 hours. Finally, it was calcined in a muffle furnace at 500°C for 4 hours to obtain catalyst A1.

[0043] Example 2

[0044] This embodiment provides an iron-based catalyst for heavy oil hydrotreating, the preparation method of which includes the following steps:

[0045] (1) First, the silica support was treated with 0.1 mol / L ammonia water at a solid-liquid ratio of 1:20 in a water bath at 80°C for 4 hours. After washing with water, it was dried at 100°C for 12 hours to obtain isolated surface hydroxyl groups 3740 cm⁻¹. -1 3685cm adjacent hydroxyl site -1 The peak area ratio is 0.55, and the specific surface area is 201 m². 2 / g of silica support.

[0046] (2) 10.0g of silica support (isolated surface hydroxyl groups 3740cm) was placed separately. -13685cm adjacent hydroxyl site -1 The peak area ratio was 0.55) and 25.2g of ferric nitrate were ball-milled for 5 minutes each. Then the milled ferric nitrate was mixed with the silica carrier and ball-milled for 5 minutes.

[0047] (3) The ground catalyst precursor was then placed in an oven at 120°C and dried for 12 hours. Finally, it was calcined in a muffle furnace at 450°C for 4 hours to obtain catalyst A2.

[0048] Example 3

[0049] This embodiment provides an iron-based catalyst for heavy oil hydrotreating, the preparation method of which includes the following steps:

[0050] (1) First, the silica support was treated with 2 mol / L potassium ethoxide at a solid-liquid ratio of 1:80 in a water bath at 60°C for 3 hours. After washing with ethanol, it was dried at 80°C for 10 hours to obtain isolated surface hydroxyl groups 3740 cm⁻¹. -1 3685cm adjacent hydroxyl site -1 The peak area ratio is 0.35, and the specific surface area is 245 m². 2 / g of silica support.

[0051] (2) 10.0g of silica support (isolated surface hydroxyl groups 3740cm) was placed separately. -1 3685cm adjacent hydroxyl site -1 The peak area ratio was 0.35. 25.2 g of ferric nitrate and 10.2 g of zinc nitrate were ball-milled for 5 min each. Then the milled ferric nitrate was mixed with the silica carrier and ball-milled for 5 min.

[0052] (3) The ground catalyst precursor was then placed in an oven at 120°C and dried for 12 hours. Finally, it was calcined in a muffle furnace at 500°C for 5 hours to obtain catalyst A3.

[0053] Example 4

[0054] This embodiment provides an iron-based catalyst for heavy oil hydrotreating, the preparation method of which includes the following steps:

[0055] (1) First, the silica support was treated with 0.1 mol / L triethylamine at a solid-liquid ratio of 1:10 in a water bath at 80°C for 2 hours. After washing with water and ethanol, it was dried at 100°C for 6 hours to obtain isolated surface hydroxyl groups 3740 cm⁻¹. -1 3685cm adjacent hydroxyl site -1 The peak area ratio is 0.38, and the specific surface area is 218 m². 2 / g of silica support.

[0056] (2) 10.0g of silicon dioxide carrier treated with triethylamine (isolated surface hydroxyl groups 3740cm) was placed separately. -1 3685cm adjacent hydroxyl site -1 The peak area ratio was 0.38) and 25.2g of ferric nitrate were ball-milled for 5 minutes each. Then the milled ferric nitrate was mixed with the silica carrier and ball-milled for 5 minutes.

[0057] (4) The ground catalyst precursor was then placed in an oven at 120°C and dried for 12 hours. Finally, it was calcined in a muffle furnace at 500°C for 4 hours to obtain catalyst A4.

[0058] Example 5

[0059] This embodiment provides an iron-based catalyst for heavy oil hydrotreating, the preparation method of which includes the following steps:

[0060] (1) First, the silica support was treated with 0.8 mol / L ammonia water at a solid-liquid ratio of 1:15 in a water bath at 60°C for 1 hour. After washing with water, it was dried at 130°C for 4 hours to obtain isolated surface hydroxyl groups 3740 cm⁻¹. -1 3685cm adjacent hydroxyl site -1 The peak area ratio is 0.42, and the specific surface area is 260 m². 2 / g of silica support.

[0061] (2) 10.0g of silica carrier treated with ammonia (isolated surface hydroxyl groups 3740cm) were respectively placed in the ammonia water. -1 3685cm adjacent hydroxyl site -1 The peak area ratio was 0.42. 25.2 g of ferric nitrate and 10.2 g of zinc nitrate were ball-milled for 5 min each. Then the milled ferric nitrate and zinc nitrate were mixed with the silica carrier in sequence and ball-milled for 5 min each.

[0062] (4) The ground catalyst precursor was then placed in an oven at 120°C and dried for 12 hours. Finally, it was calcined in a muffle furnace at 400°C for 4 hours to obtain catalyst A5.

[0063] Example 6

[0064] This embodiment provides an iron-based catalyst for heavy oil hydrotreating, the preparation method of which includes the following steps:

[0065] (1) First, the silica support was treated with 0.5 mol / L triethylamine at a solid-liquid ratio of 1:20 in a water bath at 50°C for 3 hours. After washing with water, it was dried at 80°C for 24 hours to obtain isolated surface hydroxyl groups 3740 cm⁻¹. -1 3685cm adjacent hydroxyl site-1 The peak area ratio is 0.60, and the specific surface area is 239 m². 2 / g of silica support.

[0066] (2) 10.0g of silica support (isolated surface hydroxyl groups 3740cm) was placed separately. -1 3685cm adjacent hydroxyl site -1 The peak area ratio was 0.60. 25.2 g of ferric nitrate and 5.0 g of citric acid were ball-milled for 5 min each. Then the milled citric acid and ferric nitrate were mixed with the silica carrier in sequence and ball-milled for 5 min each.

[0067] (4) The ground catalyst precursor was then placed in an oven at 120°C and dried for 12 hours. Finally, it was calcined in a muffle furnace at 550°C for 4 hours to obtain catalyst A6.

[0068] Example 7

[0069] This embodiment provides an iron-based catalyst for heavy oil hydrotreating, the preparation method of which includes the following steps:

[0070] (1) First, the silica support was treated with 2 mol / L urea at a solid-liquid ratio of 1:50 in a water bath at 90°C for 0.5 h. After washing with water, it was dried at 120°C for 12 h to obtain isolated surface hydroxyl groups 3740 cm⁻¹. -1 3685cm adjacent hydroxyl site -1 The peak area ratio is 0.7, and the specific surface area is 264 m². 2 / g of silica support.

[0071] (2) 10.0g of silica support (isolated surface hydroxyl groups 3740cm) was placed separately. -1 3685cm adjacent hydroxyl site -1 The peak area ratio was 0.7. 25.25g of ferric nitrate, 4.0g of tartaric acid and 8.0g of zinc nitrate were ball-milled for 5min. Then the milled ferric nitrate, zinc nitrate and tartaric acid were mixed with the silica carrier in sequence and ball-milled for 5min each.

[0072] (4) The ground catalyst precursor was then placed in an oven at 120°C and dried for 12 hours. Finally, it was calcined in a muffle furnace at 550°C for 4 hours to obtain catalyst A7.

[0073] Example 8

[0074] This embodiment provides the application of the catalysts of Examples 2, 4, 5 and 6 in the fixed-bed hydrotreating of atmospheric residue oil.

[0075] The catalysts in Examples 2, 4, 5, and 6 were all pre-sulfurized before application to improve their hydrogenation performance. Pre-sulfurization was performed using a 10 mL high-temperature, high-pressure hydrogenation microreactor, employing a wet in-situ pre-sulfurization method. This means that the catalyst was not removed after pre-sulfurization and continued the hydrogenation reaction directly in the reactor. The pre-sulfurized oil was a n-decane solution containing 5 wt% CS2. The pre-sulfurization temperature was 300°C, the pressure was 4 MPa, and the liquid hourly space velocity (LISH) was 1.5 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300.

[0076] In this embodiment, the hydrotreating was performed using a 10 mL high-temperature, high-pressure hydrotreating microreactor. The feedstock was Dalian Xitai atmospheric residue oil, with a sulfur content of 3100 ppm and a total metal (Ni+V) content of 68.7 ppm. The feedstock was pumped in using a plunger pump. After reaction, the oil sample was cooled in a high-pressure separator and then collected and analyzed in a low-pressure separator. The hydrotreating temperature was 390°C, the pressure was 17 MPa, and the liquid hourly space velocity (LISH) was 1.0 h⁻¹. -1 The hydrogen-to-oil volume ratio was 800. Table 1 lists the evaluation results of catalysts A2, A4, A5, and A6 after hydrotreating.

[0077] Table 1

[0078] Desulfurization rate % 42 69 72 75 Demetallization rate % 30 42 45 50

[0079] Example 9

[0080] This embodiment provides the application of the catalysts of Examples 1, 3, 5 and 7 in the slurry bed hydrotreating of atmospheric residue oil.

[0081] The catalysts in Examples 1, 3, 5, and 7 were not pre-sulfurized; the hydrotreating was carried out in a 0.5L high-temperature, high-pressure hydrotreating slurry bed reactor. The evaluation feedstock was Golmud residue oil with a sulfur content of 3900 ppm and a nitrogen content of 2000 ppm. The hydrotreating temperature was 400℃, the pressure was 9 MPa, the liquid hourly space velocity was 0.5 h⁻¹, and the hydrogen-to-oil volume ratio was 300. Table 2 lists the evaluation results of the A1, A3, A5, and A7 catalysts after hydrotreating.

[0082] Table 2

[0083] Desulfurization rate % 35 55 60 69 Denitrification rate % 21 42 48 46

[0084] In the above embodiments, the methods for determining and calculating the desulfurization rate, denitrification rate, and demetallization rate of the catalyst are all well-known in the art.

[0085] The results in Tables 1 and 2 demonstrate that the hydrogenated iron-based catalyst of the present invention has high hydrodesulfurization and denitrification activity.

[0086] In summary, the active metal components, additives, and support used in the iron-based catalyst of this invention are significantly cheaper than those used in traditional hydrogenation catalysts, such as nickel salts, cobalt salts, tungsten salts, and molybdenum salts. The method employed in this invention is also relatively simple. Furthermore, this iron-based hydrogenation catalyst breaks through the limitations imposed on the active metal components by traditional hydrogenation catalysts for decades, providing a catalyst preparation method with long-term industrial application value in the face of current challenges related to crude oil properties and declining oil prices.

[0087] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an iron-based catalyst for heavy oil hydrogenation, characterized in that, Includes the following steps: (1) The silica support is subjected to alkali treatment, washing, drying, and then ball milling, wherein the BET specific surface area of ​​the treated silica support is greater than 50 m². 2 / g, surface infrared hydroxyl group 3740cm -1 With 3685cm -1 The peak area ratio of the two absorption peaks is between 0.35 and 0.91; (2) The iron-containing compound is ball-milled and then mechanically mixed with the silica carrier, auxiliary metal compound and complexing agent obtained in step (1), wherein the molar ratio of metallic iron in the iron-containing compound to auxiliary metal in the auxiliary metal compound is 1:(0-20), and the molar ratio of metallic iron to complexing agent in the iron-containing compound is 1:(0-10). (3) The mixture in step (2) is dried and calcined to obtain the heavy oil hydrogenation iron-based catalyst; The auxiliary metal is selected from zinc; The heavy oil hydrogenation iron-based catalyst can be used directly or after pre-sulfurization treatment; In step (1), the conditions for alkali treatment are: solid-liquid ratio of 1:(10-100), alkali concentration of 0.01-2 mol / L, and treatment at a water bath temperature of 40-95℃ for 0.5-4 h; The alkaline treatment uses an organic or inorganic alkali, wherein the organic alkali is selected from triethylamine, urea, pyridine, potassium methoxide, potassium ethoxide, or sodium ethoxide, and the inorganic alkali is selected from sodium hydroxide, potassium hydroxide, or ammonia.

2. The preparation method according to claim 1, characterized in that, In step (2), the iron-containing compound is selected from at least one of ferric nitrate, ferric sulfate, ferric chloride, and ferric phosphate; The complexing agent is selected from any one of monoethanolamine, diethanolamine, triethanolamine, oxalic acid, tartaric acid, citric acid, adipic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), acetylacetone, thiourea, and sulfosalicylic acid. The metal-adding compound is added in the form of a metal salt, which is selected from at least one of nitrates, sulfates, chlorides, and phosphates.

3. The preparation method according to claim 1, characterized in that, In step (2), the mechanical mixing method is selected from at least one of mechanical stirring, air mixing, grinding, and ball milling.

4. The preparation method according to any one of claims 1-3, characterized in that, In step (1), the washing solution is selected from at least one of water and ethanol; The drying conditions are: temperature 60-130℃, time 4-36h.

5. The preparation method according to claim 1, characterized in that, In step (3), the drying conditions are: temperature 60-120℃, time 6-24h; The roasting conditions are: temperature 350-600℃, time 2-6h.

6. A heavy oil hydrogenation iron-based catalyst prepared by the method according to any one of claims 1-5, characterized in that, The catalyst uses iron as the active metal component, zinc as the auxiliary metal component, and silicon oxide as the support, wherein the molar ratio of the active metal component to the auxiliary metal component is 1:0-20; based on the total weight of the iron-based catalyst, the total amount of active metal component and auxiliary metal component in oxide form is 10-90%, and the total amount of silicon oxide support is 10%-50%; the silicon oxide support is characterized by a surface infrared hydroxyl group of 3740 cm⁻¹. -1 With 3685cm -1 The ratio of the peak areas of the two absorption peaks is between 0.35 and 0.

91.

7. The heavy oil hydrotreating iron-based catalyst according to claim 6, characterized in that, The heavy oil hydrogenation iron-based catalyst is a pre-sulfurized heavy oil hydrogenation iron-based catalyst. The pre-sulfurization treatment temperature is 200-450℃, the pressure is 1-10MPa, the pre-sulfurization treatment time is 4-48h, and the liquid hourly space velocity is 0.5-10h. -1 The hydrogen-to-oil volume ratio is 100-800.

8. The heavy oil hydrotreating iron-based catalyst according to claim 7, characterized in that, The pre-vulcanization treatment is carried out at a temperature of 280-380℃, a pressure of 2-6 MPa, a time of 6-24 h, and a liquid hourly space velocity of 1-4 h⁻¹. -1 The hydrogen-to-oil volume ratio is 200-500.

9. The use of a catalyst according to any one of claims 6-8 in the hydrotreating of one or more of crude oil, atmospheric residue, vacuum residue, coal tar, deasphalted oil, or heavy oil extracted from oil sands or shale.

10. The application according to claim 9, characterized in that, The hydrogenation process is carried out in one reactor, or in multiple reactors in parallel or in series; In the slurry bed hydrotreating application, the hydrotreating temperature is 200-500℃, the pressure is 3-30MPa, and the liquid hourly space velocity is 0.3-5h. -1 The hydrogen-to-oil volume ratio is 200-2000; In fixed-bed hydrotreating applications, the hydrotreating temperature is 200-500℃, the pressure is 2-20 MPa, and the liquid hourly space velocity is 0.3-15 h⁻¹. -1 The hydrogen-to-oil volume ratio is 200-2000.

11. The application according to claim 10, characterized in that, In slurry bed hydrotreating applications, the hydrotreating temperature is 350-450℃, the pressure is 7-25MPa, and the liquid hourly space velocity is 0.5-2h. -1 The hydrogen-to-oil volume ratio is 300-1000.

12. The application according to claim 10, characterized in that, In fixed-bed hydrotreating applications, the hydrotreating temperature is 300-500℃, the pressure is 5-10 MPa, and the liquid hourly space velocity is 0.5-6 h⁻¹. -1 The hydrogen-to-oil volume ratio is 300-1000.

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