Slurry bed hydrogenation iron-based catalyst as well as preparation method and application thereof

Abstract

The invention provides a slurry reactor hydrogenation iron-based catalyst as well as a preparation method and application thereof. The slurry bed hydrogenation iron-based catalyst comprises a carrier and a metal oxide, wherein the metal in the metal oxide comprises an active component metal and a co-metal in a molar ratio of (1-100): 1; the active component metal comprises iron and zinc, and the auxiliary metal comprises one or a combination of more than two of cobalt, molybdenum, nickel and tungsten; the slurry bed hydrogenation iron-based catalyst is prepared by loading an active component metal element on a carrier through a precipitation method and then loading a cometallic element through an impregnation method. The preparation method of the slurry bed hydrogenation iron-based catalyst is simple, and the slurry bed hydrogenation iron-based catalyst has good catalytic activity and impurity removal effect.

Description

Technical Field

[0001] The present invention belongs to the field of petrochemical industry, and particularly relates to a slurry bed hydrogenation iron-based catalyst, a preparation method thereof and an application thereof. Background Art

[0002] CN104383922 B provides a heavy oil hydrogenation iron-based catalyst and an application thereof. The heavy oil hydrogenation iron-based catalyst is a catalyst in which iron is used as the active component metal, and one or a combination of two of zinc, copper and silver is used as the promoter metal, and the two are loaded on a carrier; wherein, the molar ratio of the active component metal to the promoter metal is 1-20:1. The application includes the application of the heavy oil hydrogenation iron-based catalyst in the hydrogenation treatment of a mixed oil of one or several of crude oil, atmospheric residue, vacuum residue, coal tar, deasphalted oil, and heavy oil extracted from oil sand or shale. The iron-based catalyst has the advantages of cheap and easily available raw materials, simple production process, etc., and can greatly reduce the production cost of the hydrogenation catalyst while having high heavy oil hydrogenation activity. However, this preparation method is more inclined to the preparation of fixed bed process catalysts and the method is relatively complex.

[0003] CN104918698 B relates to an iron-based hydrogenation catalyst, which uses iron as the main active component metal and zinc and potassium as the first promoter active component metals; wherein, the molar ratio of the main active component to the first promoter active component metals is 0.5-200:1. The iron-based hydrogenation catalyst breaks through the limitation of the active component metal of traditional hydrogenation catalysts that has been used for decades, and thus has long-term industrial application value. However, this preparation method is more inclined to the preparation of fixed bed process catalysts, and the preparation method is relatively complex and the cost is higher.

[0004] CN114797883 A discloses a preparation method of an Fe-Si supported catalyst and its application in heavy oil suspension bed hydrocracking reaction, belonging to the fields of catalytic material preparation and energy technology. The catalyst is prepared by using a novel amorphous Fe-Si material as the carrier and a Group VIB or VIII transition metal as the metal active phase. The catalyst has a mesoporous channel structure and appropriate acidity, which is helpful for the diffusion and conversion of macromolecules in heavy oil. At the same time, under the condition of no supported active metal or low active metal loading, the heavy oil conversion rate in the suspension bed hydrocracking reaction of residue oil is as high as about 89 wt%, the yields of naphtha and middle distillates can reach 60%, and the gas and coke yields are low. This type of catalyst has good application prospects in the heavy oil suspension bed hydroconversion process. However, this preparation method is relatively complex and there is no report on the hydrogenation desulfurization activity.

[0005] CN105363450 B discloses an emulsifiable iron-based catalyst, its preparation method and application. The method comprises the following steps: (1) preparing a ferrous sulfate solution; (2) when the promoter contains SiO 2 and / or Al 2 O 3 , adding a silicon source and / or an aluminum source into the ferrous sulfate solution, and adding a precipitant for coprecipitation to obtain a precipitate slurry; (3) washing the precipitate slurry with water and filtering to obtain a filter cake; (4) obtaining the emulsifiable iron-based catalyst according to the following 1) or 2): 1) mixing the filter cake with a solvent oil or a mixture of a solvent oil and a dispersant to obtain a mixture, and crushing the mixture by mechanical stirring; the material after crushing is sheared to obtain the emulsifiable iron-based catalyst, and the shearing process is accompanied by a dehydration process; 2) when the promoter contains MgO and / or CaO, proceed according to the following a) or b). This emulsifiable catalyst system has a stable state, does not delaminate during storage, can be continuously stored for more than three months without deterioration, and is therefore very suitable for large-scale industrial use. However, this iron-based catalyst does not involve slurry bed hydrogenation reaction. Summary of the Invention

[0006] In order to solve the above problems, the object of the present invention is to provide a slurry bed hydrogenation iron-based catalyst, its preparation method and application. The preparation method of this slurry bed hydrogenation iron-based catalyst is simple, and it has good catalytic activity and impurity removal effect.

[0007] To achieve the above object, the present invention provides a slurry bed hydrogenation iron-based catalyst, the composition of which comprises a carrier and a metal oxide. The metals in the metal oxide include an active component metal and a promoter metal with a molar ratio of 1-100:1; the active component metal includes iron and zinc, and the promoter metal includes one or a combination of two or more of cobalt, molybdenum, nickel, and tungsten; the slurry bed hydrogenation iron-based catalyst is prepared by loading the active component metal elements on the carrier by a precipitation method, and then loading the promoter metal elements by an impregnation method; preferably, the slurry bed hydrogenation iron-based catalyst is further dispersed in a solvent oil.

[0008] According to a specific embodiment of the present invention, preferably, the carrier comprises a combination of one or two of a silicon-based carrier and a carbon-based carrier.

[0009] According to a specific embodiment of the present invention, preferably, the silicon-based carrier comprises a combination of one or two or more of water glass, white carbon black, sodium silicate, silica sol, silica gel (type B or C), and tetraethyl orthosilicate.

[0010] According to a specific embodiment of the present invention, preferably, the carbon-based carrier comprises a combination of one or two of activated carbon and coconut shell activated carbon.

[0011] According to a specific embodiment of the present invention, preferably, in the active component metal, the molar ratio of iron to zinc is 0.1 - 20:1.

[0012] According to a specific embodiment of the present invention, preferably, based on the weight of the slurry bed hydrotreating iron-based catalyst being 100%, the total content of the oxides of the active component metal and the promoter metal is 20 - 90%.

[0013] According to a specific embodiment of the present invention, preferably, the solvent oil includes feedstock oil or hydrotreated tail oil, such as aromatic-rich oil, hydrocracked residue recycle oil, hydrocracked residue, coal tar, ethylene tar, catalytic cracking recycle oil, catalytic cracking slurry, pre-hydrotreated catalytic cracking recycle oil, and pre-hydrotreated catalytic cracking slurry, etc.

[0014] The present invention also provides a preparation method of the above slurry bed hydrotreating iron-based catalyst, which includes the following steps:

[0015] (1) Preparation of the precursor: Mix the salts of the active component metal, the carrier, and the precipitating agent in water, react at 40 - 95 °C for 1 - 24 h, adjust the pH value to 7.0 - 9.0, age at 40 - 95 °C for 2 - 48 h to obtain a precipitate. After filtering, washing, and drying the precipitate, calcine it at 200 - 800 °C for 1 - 10 h to obtain the precursor;

[0016] (2) Preparation of the slurry bed hydrotreating iron-based catalyst: Prepare an impregnation solution from the salts of the promoter metal, add the impregnation solution to the precursor, let it stand for 2 - 48 h and then dry it, and calcine it at 200 - 800 °C for 2 - 8 h to obtain the slurry bed hydrotreating iron-based catalyst.

[0017] According to a specific embodiment of the present invention, preferably, the above preparation method further includes step (3): Mix the slurry bed hydrotreating iron-based catalyst with solvent oil or solvent oil and a dispersant, and then crush it to obtain a dispersion of the slurry bed hydrotreating iron-based catalyst; the dispersant is more preferably one or a combination of two or more of sodium alkylbenzene sulfonate, sodium lignosulfonate, Tween 80, OP-10 (alkylphenol polyoxyethylene (10) ether), and polyethylene glycol.

[0018] According to a specific embodiment of the present invention, preferably, the solid content of the dispersion of the slurry bed hydrotreating iron-based catalyst is 1 - 10%, and the solid particle size is 0.1 - 1 μm.

[0019] According to a specific embodiment of the present invention, preferably, in step (1), the salts of the active component metal iron include one or a combination of two or more of iron nitrate, iron sulfate, ferrous sulfate, iron chloride, and iron phosphate.

[0020] According to a specific embodiment of the present invention, preferably, the salt of the active component metal zinc includes one or a combination of two or more of zinc nitrate, zinc sulfate, zinc chloride, and zinc phosphate.

[0021] According to a specific embodiment of the present invention, preferably, the precipitant includes one or a combination of two or more of sodium hydroxide, potassium hydroxide, ammonia water, and urea.

[0022] According to a specific embodiment of the present invention, preferably, in step (2), the salt of the promoter metal includes one or a combination of two or more of cobalt nitrate, ammonium molybdate, nickel nitrate, nickel sulfide, and ammonium metatungstate.

[0023] According to a specific embodiment of the present invention, preferably, when performing the calcination in step (2), the temperature is raised at a rate of 4-10 °C / min.

[0024] According to a specific embodiment of the present invention, preferably, the volume of the impregnating solution is the same as the saturated water absorption of the precursor.

[0025] According to a specific embodiment of the present invention, the above preparation method includes the following specific steps:

[0026] (1) Mix the aqueous solution of the salt of the active component metal, the carrier, and the aqueous solution of the precipitant evenly, then stir and react in a water bath at 40-95 °C for 1-24 h, adjust the pH value to 7.0-9.0, and then stand and age in a water bath at 40-95 °C for 2-48 h to obtain a precipitate; after filtering, washing with water, and drying the precipitate, calcine it in an air atmosphere at 200-800 °C for 1-10 h to obtain a precursor;

[0027] (2) Dissolve the salt of the promoter metal in deionized water to prepare an impregnating solution, add the impregnating solution to the precursor obtained in step (1), then stand in air for 2-48 h, and then dry at 80-150 °C; then calcine it in an air atmosphere at 200-800 °C for 2-8 h to obtain the slurry bed hydrotreating iron-based catalyst;

[0028] (3) After mixing the slurry bed hydrotreating iron-based catalyst with solvent oil or a mixture of solvent oil and a dispersant, break the mixture by mechanical stirring, wherein the solid content is 1-10%, and the solid particle size is 0.1-1 μm.

[0029] The present invention also provides a method for hydrotreating oil products, which is carried out using the above slurry bed hydrotreating iron-based catalyst.

[0030] According to a specific embodiment of the present invention, preferably, the oil products include one or a combination of two or more of crude oil, atmospheric residue, vacuum residue, coal tar, deasphalted oil, heavy oil (such as heavy oil extracted from oil sands or shale oil).

[0031] According to a specific embodiment of the present invention, preferably, the hydrotreating includes hydrofining, hydro-upgrading, hydrocracking or hydroisomerization, and more preferably hydrodesulfurization, hydrodenitrogenation, hydrodemetallization or hydrogenation saturation of aromatics.

[0032] According to a specific embodiment of the present invention, preferably, the temperature of the hydrotreating is 200 - 600 °C, the pressure is 2 - 20 Mpa, the liquid hourly space velocity is 0.3 - 20 h -1 , and the hydrogen-oil volume ratio is 100 - 2000.

[0033] According to a specific embodiment of the present invention, preferably, the slurry bed device used in the method for hydrotreating oil products includes a tail oil circulation system, and the recycled tail oil accounts for less than 10 wt% of the total feed, and the number of recycling times is preferably ≥ 3 times.

[0034] According to a specific embodiment of the present invention, preferably, the recycled tail oil includes hydrogenated tail oil and the slurry bed iron-based catalyst.

[0035] According to a specific embodiment of the present invention, preferably, the recycled tail oil contains 50 - 100 wt% of hydrogenated tail oil.

[0036] According to a specific embodiment of the present invention, preferably, the initial boiling point of the hydrogenated tail oil is ≥ 350 °C.

[0037] The present invention has the following beneficial effects:

[0038] 1. The active metals of the present invention are mainly iron and zinc elements, and a small amount of cobalt, molybdenum, nickel, and tungsten are added as promoter metals, which can not only greatly reduce the cost of the catalyst, but also effectively improve the activity of the catalyst;

[0039] 2. The slurry bed iron-based catalyst of the present invention is in an emulsified state, which greatly increases the dispersion of the active metals;

[0040] 3. The present invention adopts a tail oil circulation process, which greatly improves the utilization rate of the catalyst and reduces the usage amount of the catalyst;

[0041] 4. The hydrotreating of the present invention can include hydrofining, hydro-upgrading, hydrocracking and hydroisomerization, etc.; more specifically, the hydrotreating can include hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrogenation saturation of aromatics, etc., and has a high impurity removal effect. Detailed implementation manners

[0042] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solutions of the present invention are described in detail below, but it should not be construed as a limitation on the implementable scope of the present invention.

[0043] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.

[0044] Unless otherwise specified, the materials, reagents, etc. used in the following examples are all commercially available.

[0045] The properties of the feedstock oil used in the following examples and comparative examples are shown in Table 1.

[0046] Table 1 Properties of the mixed residue oil

[0047] Item Data <![CDATA[Density (20 °C), g / cm 3 > 1.0003 Sulfur content, wt% 3.75 Nitrogen content, wt% 0.55 Residual carbon, wt% 14.89 Metal content Ni+V, μg / g 558.86 Four components, wt% Saturates 19 Aromatics 41 Resin 28 Asphaltenes 12

[0048] Comparative Example 1

[0049] This comparative example provides a comparative catalyst for a slurry bed hydroprocessing iron-based catalyst, which is prepared by the following steps:

[0050] (1) Dissolve 0.1 g of iron chloride, 0.02 g of zinc chloride, 6.63 g of metatungstic acid, 15.84 g of nickel nitrate and 0.92 g of coconut shell activated carbon in 250 mL of aqueous solution for mixing to obtain a mixed system;

[0051] (2) Slowly add the sodium hydroxide solution (prepared by dissolving 12 g of sodium hydroxide in 80 mL of deionized water) to the above mixed system while stirring; wherein, the molar ratio of sodium hydroxide to total metal is 3.82:1;

[0052] (3) Stir and react in a water bath at 80 °C for 4 hours, then cool to 60 °C and stand for aging for 24 hours, and filter to obtain a precipitate product;

[0053] (4) Wash the precipitate product with hot deionized water until the pH value is approximately equal to 7, then dry it in an oven at 120 °C for 12 h, and then heat it up at a rate of 5 °C / min and calcine it in an air atmosphere at 500 °C for 2 hours to obtain a slurry bed hydroprocessing iron-based catalyst B1.

[0054] (5) First pre-grind the above slurry bed hydroprocessing iron-based catalyst B1 for 5 - 10 min, then weigh 1 g of the ground slurry bed hydroprocessing iron-based catalyst B1, 1.0 g of Tween 80 and 90.0 g of the solvent oil of the whole fraction ethylene tar, and mix them evenly by mechanical stirring to obtain a slurry bed hydroprocessing iron-based catalyst dispersion B1 with a solid particle size of 1 μm.

[0055] Hydroprocessing is carried out using the above slurry bed hydroprocessing iron-based catalyst:

[0056] The hydroprocessing is carried out in a 0.5 L high-temperature and high-pressure slurry bed reactor, and the process operating conditions are a hydroprocessing temperature of 430 °C, a pressure of 16 MPa, and a liquid hourly space velocity of 0.5 h -1, the hydrogen-to-oil volume ratio is 900, the concentration of the slurry bed hydrogenation iron-based catalyst is 10wt%, the circulating tail oil accounts for 10% of the total material, and the circulating tail oil is 100% of the slurry bed hydrogenation tail oil (including catalyst), its initial boiling point is 350°C, and the number of cycles is 3. The reaction evaluation results are shown in Table 2.

[0057] Table 2 Evaluation results of slurry bed hydrogenation iron-based catalyst B1

[0058]

[0059] Comparative Example 2

[0060] This comparative example provides a comparative catalyst of a slurry bed hydrogenation iron-based catalyst, which is prepared by the following steps:

[0061] (1) Dissolve 2.5 g of ferric phosphate, 2.5 g of ferric sulfate, 0.15 g of zinc phosphate, 11.02 g of cobalt nitrate and 3.18 g of ammonium molybdate in 15.0 g of deionized water and stir thoroughly to obtain a uniform aqueous solution of metal salts. Then weigh 10.0 g of type B silica gel and drop the above aqueous solution of metal salts onto the type B silica gel, stir thoroughly and set aside;

[0062] (2) After the sample was naturally air-dried for 12 h, it was placed in an oven at 120° C. for drying, and then heated at a rate of 5° C. / min and calcined at 500° C. in an air atmosphere for 3 h to obtain a slurry bed hydrogenation iron-based catalyst B2;

[0063] (3) The slurry bed hydrogenation iron-based catalyst B2 is pre-grinded for 5-10 min, and then 1 g of the ground slurry bed hydrogenation iron-based catalyst B2 is weighed and mixed with 100.0 g of solvent oil of catalytic cracking oil slurry, and the mixture is crushed by mechanical stirring to obtain a slurry bed hydrogenation iron-based catalyst dispersion B2, the solid particle size of which is 0.8 μm.

[0064] The above-mentioned slurry bed hydrogenation iron-based catalyst is used for hydrogenation treatment:

[0065] The hydroprocessing was carried out in a 0.5L high-temperature and high-pressure hydrogenation slurry bed reactor. The process operating conditions were as follows: the hydroprocessing temperature was 430°C, the pressure was 16MPa, and the liquid hourly space velocity was 0.5h -1 , the hydrogen-to-oil volume ratio is 900, the concentration of the slurry bed hydrogenation iron-based catalyst is 10wt%, the circulating tail oil accounts for 10% of the total material, and the circulating tail oil is 100% of the slurry bed hydrogenation tail oil (including catalyst), its initial boiling point is 350°C, and the number of cycles is 3. The reaction evaluation results are shown in Table 3.

[0066] Table 3 Slurry bed hydrogenation iron-based catalyst B2 reaction evaluation results

[0067]

[0068] Example 1

[0069] This example provides a slurry bed hydrogenation iron-based catalyst, which is prepared by the following steps:

[0070] (1) Dissolve 10.0 g of iron phosphate, 10.0 g of iron sulfate and 10.1 g of zinc phosphate in 100 g of deionized water to obtain an aqueous solution of iron phosphate, iron sulfate and zinc phosphate. Then weigh 3.2 g of silica and add it to the aqueous solution of iron phosphate, iron sulfate and zinc phosphate. Dissolve 4.0 g of sodium hydroxide in 100 g of deionized water to obtain a sodium hydroxide solution. While stirring, slowly add the sodium hydroxide solution to the aqueous solution of iron phosphate, iron sulfate and zinc phosphate containing silica, stir at 80 °C for 2 h, adjust the pH value to 8, then cool down to 50 °C and let it stand for aging for 12 h to obtain a precipitate;

[0071] Filter the precipitate while it is hot, wash it with deionized water 2 - 3 times the volume of the precipitate solution, then dry it in an oven at 120 °C, and then heat it up at a rate of 5 °C / min and calcine it in an air atmosphere at 500 °C for 3 hours to obtain a precursor;

[0072] (2) Dissolve 2.33 g of cobalt nitrate in 6.0 g of deionized water to prepare an impregnation solution. Slowly add the impregnation solution to 10.0 g of the precursor, mix evenly, let it stand in the air for 4 h, then dry it in an oven at 120 °C, and then heat it up at a rate of 4 °C / min and calcine it in an air atmosphere at 500 °C for 3 hours to obtain the slurry bed hydrogenation iron-based catalyst;

[0073] (3) First pre-grind the above slurry bed hydrogenation iron-based catalyst for 5 - 10 min, then weigh 1 g of the ground slurry bed hydrogenation iron-based catalyst and mix it with 90 g of the solvent oil of the whole fraction ethylene tar, and use mechanical stirring to break the mixture to obtain a slurry bed hydrogenation iron-based catalyst dispersion A1, and its solid particle size is 0.2 μm.

[0074] Use the above slurry bed hydrogenation iron-based catalyst for hydrogenation treatment:

[0075] The hydrogenation treatment is carried out in a 0.5 L high-temperature and high-pressure hydrogenation slurry bed reactor. The process operating conditions are that the temperature of the hydrogenation treatment is 430 °C, the pressure is 16 MPa, the liquid hourly space velocity is 0.5 h -1 ⁻¹, the hydrogen-oil volume ratio is 900, the concentration of the slurry bed hydrogenation iron-based catalyst is 8 wt%, the recycled tail oil accounts for 10% of the total feed, and the recycled tail oil is 100% of the slurry bed hydrogenation tail oil (containing catalyst), its initial boiling point is 350 °C, and the number of recycling times is 3. The reaction evaluation results are shown in Table 4.

[0076] Table 4 Reaction evaluation results of the slurry bed hydrogenation iron-based catalyst A1

[0077]

[0078]

[0079] Example 2

[0080] This example provides a slurry bed hydrogenation iron-based catalyst, which is prepared by the following steps:

[0081] (1) Dissolve 12.0 g of iron nitrate, 12.0 g of ferrous sulfate and 4.19 g of zinc sulfate in 100.0 g of deionized water to obtain an aqueous solution of iron nitrate, ferrous sulfate and zinc sulfate. Then weigh 7.0 g of silica gel of type B and add it to the aqueous solution of iron nitrate, ferrous sulfate and zinc sulfate. Dissolve 3.5 g of potassium hydroxide in 100.0 g of deionized water to obtain a potassium hydroxide solution. While stirring, slowly add the potassium hydroxide solution to the aqueous solution of iron nitrate, ferrous sulfate and zinc sulfate containing silica gel of type B, stir at 90 °C for 2 h, adjust the pH value to 7.5, then cool to 60 °C and let it stand for aging for 6 h to obtain a precipitate;

[0082] Filter the precipitate while it is hot, wash it with deionized water 2 - 3 times the volume of the precipitate solution, then dry it in an oven at 120 °C, and then heat it up at a rate of 6 °C / min and calcine it in an air atmosphere at 300 °C for 5 hours to obtain a precursor;

[0083] (2) Dissolve 3.88 g of nickel nitrate in 10.8 g of deionized water to prepare an impregnation solution. Slowly drip the impregnation solution onto 10.0 g of the precursor, mix evenly, let it stand in the air for 6 h, then dry it in an oven at 120 °C, and then heat it up at a rate of 4 °C / min and calcine it in an air atmosphere at 600 °C for 5 hours to obtain the slurry bed hydrogenation iron-based catalyst;

[0084] (3) First pre-grind the above slurry bed hydrogenation iron-based catalyst for 5 - 10 min, then weigh 1 g of the ground slurry bed hydrogenation iron-based catalyst and mix it with 20 g of the solvent oil of hydrocatalytic cracking slurry oil, and then add 0.1 g of the dispersant of sodium alkylbenzene sulfonate. Crush the mixture by mechanical stirring to obtain a slurry bed hydrogenation iron-based catalyst dispersion A2, and its solid particle size is 0.4 μm.

[0085] Perform hydrogenation treatment using the above slurry bed hydrogenation iron-based catalyst:

[0086] The hydrogenation treatment is carried out in a 0.5 L high-temperature and high-pressure hydrogenation slurry bed reactor. The process operating conditions are that the temperature of the hydrogenation treatment is 430 °C, the pressure is 16 MPa, and the liquid hourly space velocity is 0.5 h -1, the hydrogen-oil volume ratio is 900, the concentration of the iron-based catalyst for slurry bed hydrogenation is 5 wt%, the recycled tail oil accounts for 5% of the total feed, and the recycled tail oil is 100% slurry bed hydrogenation tail oil (containing catalyst), its initial boiling point is 400 °C, and the number of cycles is 3. The reaction evaluation results are shown in Table 5.

[0087] Table 5 Reaction Evaluation Results of Iron-based Catalyst A2 for Slurry Bed Hydrogenation

[0088]

[0089] Example 3

[0090] This example provides an iron-based catalyst for slurry bed hydrogenation, which is prepared by the following steps:

[0091] (1) Dissolve 20.0 g of ferric sulfate, 20.0 g of ferrous sulfate and 2.56 g of zinc nitrate in 200.0 g of deionized water to obtain an aqueous solution of ferric sulfate, ferrous sulfate and zinc nitrate. Then weigh 1.7 g of silica sol and add it to the aqueous solution of ferric sulfate, ferrous sulfate and zinc nitrate. Dissolve 12.0 g of sodium hydroxide in 100.0 g of deionized water to obtain a sodium hydroxide solution; while stirring, slowly add the sodium hydroxide solution to the aqueous solution of ferric sulfate, ferrous sulfate and zinc nitrate containing silica sol, stir at 80 °C for 4 h, adjust the pH value to 8, then cool to 40 °C and let it stand for aging for 10 h to obtain a precipitate;

[0092] Filter the precipitate while it is hot, wash it with deionized water 2 - 3 times the volume of the precipitate solution, then dry it in an oven at 120 °C, and then heat it up at a rate of 5 °C / min and calcine it in an air atmosphere at 400 °C for 4 hours to obtain a precursor;

[0093] (2) Dissolve 2.63 g of ammonium metatungstate in 9.0 g of deionized water to prepare an impregnation solution. Slowly drip the impregnation solution onto 10.0 g of the precursor, mix evenly, let it stand in air for 8 h, then dry it in an oven at 120 °C, and then heat it up at a rate of 6 °C / min and calcine it in an air atmosphere at 600 °C for 8 hours to obtain the iron-based catalyst for slurry bed hydrogenation;

[0094] (3) First pre-grind the above iron-based catalyst for slurry bed hydrogenation for 5 - 10 min, then weigh 1 g of the ground iron-based catalyst for slurry bed hydrogenation and mix it with 60 g of the solvent oil of hydrogenation residue oil, and break the mixture by mechanical stirring to obtain a dispersion liquid A3 of the iron-based catalyst for slurry bed hydrogenation, and its solid particle size is 0.5 μm.

[0095] Use the above iron-based catalyst for slurry bed hydrogenation for hydrogenation treatment:

[0096] Hydroprocessing was carried out in a 0.5 L high-temperature and high-pressure hydrogenation slurry bed reactor. The process operating conditions were as follows: the temperature for hydroprocessing was 450 °C, the pressure was 12 MPa, the liquid hourly space velocity was 0.5 h -1 , the hydrogen-oil volume ratio was 1200, the concentration of the iron-based catalyst for slurry bed hydrogenation was 6 wt%, the recycled tail oil accounted for 10% of the total feed, and the recycled tail oil was 90 wt% of the slurry bed hydrogenation tail oil with an initial boiling point of 400 °C, and 10% of the iron-based catalyst dispersion liquid A3 for slurry bed hydrogenation. The number of recycling times was 3. The reaction evaluation results are shown in Table 6.

[0097] Table 6 Reaction Evaluation Results of Iron-based Catalyst A3 for Slurry Bed Hydrogenation

[0098]

[0099] Example 4

[0100] This example provides an iron-based catalyst for slurry bed hydrogenation, which is prepared by the following steps:

[0101] (1) Dissolve 15.0 g of ferric chloride, 15.0 g of ferric sulfate and 1.77 g of zinc chloride in 150.0 g of deionized water to obtain an aqueous solution of ferric chloride, ferric sulfate and zinc chloride. Then weigh 3.5 g of activated carbon and add it to the aqueous solution of ferric chloride, ferric sulfate and zinc chloride. Dissolve 42.0 g of ammonia water in 100.0 g of deionized water to obtain an ammonia water solution. While stirring, slowly add the ammonia water solution to the aqueous solution of ferric chloride, ferric sulfate and zinc chloride containing activated carbon, stir at 80 °C for 4 h, adjust the pH value to 7, then cool down to 60 °C and stand for aging for 2 h to obtain a precipitate;

[0102] Filter the precipitate while it is hot, wash it with 2 - 3 times the volume of deionized water of the precipitate solution, then dry it in an oven at 120 °C, and then heat it up at a rate of 5 °C / min and calcine it in an air atmosphere at 400 °C for 2 hours to obtain a precursor;

[0103] (2) Dissolve 5.45 g of ammonium molybdate in 12.0 g of deionized water to prepare an impregnation solution. Slowly drip the impregnation solution onto 10.0 g of the precursor, mix evenly, stand in the air for 6 h, then dry it in an oven at 120 °C, and then heat it up at a rate of 4 °C / min and calcine it in an air atmosphere at 600 °C for 5 hours to obtain the iron-based catalyst for slurry bed hydrogenation;

[0104] (3) First pre-grind the above iron-based catalyst for slurry bed hydrogenation for 5 - 10 min. Then weigh 1 g of the ground iron-based catalyst for slurry bed hydrogenation and mix it with 10 g of the solvent oil of the hydrogenation residue oil recycle oil. Then add 0.15 g of the dispersant Tween 80, and use mechanical stirring to break the mixture to obtain an iron-based catalyst dispersion liquid A4 for slurry bed hydrogenation, and its solid particle size is 0.25 μm.

[0105] Hydrotreating is carried out using the above-mentioned slurry bed hydrotreating iron-based catalyst:

[0106] The hydrotreating is carried out in a 0.5 L high-temperature and high-pressure hydrogenation slurry bed reactor. The process operating conditions are as follows: the temperature of hydrotreating is 450 °C, the pressure is 10 MPa, the reaction space velocity is 0.5 h -1 , the hydrogen-oil volume ratio is 900, the concentration of the slurry bed hydrotreating iron-based catalyst is 6 wt%, the recycled tail oil accounts for 8% of the total feed, and the recycled tail oil is 80% of the slurry bed hydrotreating tail oil with an initial boiling point of 350 °C and 20% of the slurry bed hydrotreating iron-based catalyst dispersion A4, and the number of circulation times is 3. The reaction evaluation results are shown in Table 7.

[0107] Table 7 Reaction evaluation results of the slurry bed hydrotreating iron-based catalyst A4

[0108]

[0109] It can be seen from the data in Tables 4-7 that the slurry bed hydrotreating iron-based catalyst prepared by the method of the present invention can be recycled multiple times and all maintain excellent desulfurization, demetallization, denitrification, deasphalting ability and coke inhibition ability. Compared with the comparative example, the slurry bed hydrotreating iron-based catalyst prepared by the present invention can effectively reduce the catalyst dosage and show better reaction activity. Therefore, the iron-based catalyst of the present invention will have good application prospects in the slurry bed hydrotreating reaction process.

[0110] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A slurry bed hydrogenation iron-based catalyst, the composition of which includes a carrier and metal oxides, and the metals in the metal oxides include active component metals and promoter metals with a molar ratio of 1-100:1; the active component metals include iron and zinc, and the promoter metals include one or more combinations of cobalt, molybdenum, nickel, and tungsten; The slurry bed hydrogenation iron-based catalyst is prepared by loading the active component metal elements on the carrier through a precipitation method, and then loading the promoter metal elements through an impregnation method; preferably, the slurry bed hydrogenation iron-based catalyst is further dispersed in solvent oil.

2. The slurry bed hydrogenation iron-based catalyst according to claim 1, wherein, the carrier includes one or more combinations of a silicon-based carrier and a carbon-based carrier; preferably, the silicon-based carrier includes one or more combinations of sodium silicate, silica, sodium silicate, silica sol, silica gel, and tetraethyl orthosilicate; preferably, the carbon-based carrier includes one or more combinations of activated carbon and coconut shell activated carbon.

3. The slurry bed hydrogenation iron-based catalyst according to claim 1, wherein, in the active component metals, the molar ratio of iron to zinc is 0.1-20:

1.

4. The slurry bed hydrogenation iron-based catalyst according to claim 1, wherein, calculated based on the weight of the slurry bed hydrogenation iron-based catalyst being 100%, the total content of the oxides of the active component metals and the promoter metals is 20-90%.

5. The slurry bed hydrogenation iron-based catalyst according to claim 1, wherein, the solvent oil includes one or more combinations of crude oil, aromatic-rich oil, hydrocracked residue recycle oil, hydrocracked residue, coal tar, ethylene tar, catalytic cracking recycle oil, catalytic cracking slurry, pre-hydrotreated catalytic cracking recycle oil, and pre-hydrotreated catalytic cracking slurry.

6. The preparation method of the slurry bed hydrogenation iron-based catalyst according to any one of claims 1-5, which includes the following steps: (1) Preparation of the precursor: Mix the salts of the active component metals, the carrier, and the precipitant in water, react at 40-95°C for 1-24 h, adjust the pH value to 7.0-9.0, age at 40-95°C for 2-48 h to obtain a precipitate, filter, wash, and dry the precipitate, and then calcine at 200-800°C for 1-10 h to obtain the precursor; (2) Preparation of the slurry bed hydrogenation iron-based catalyst: Prepare an impregnation solution from the salts of the promoter metals, add the impregnation solution to the precursor, let it stand for 2-48 h and then dry, and calcine at 200-800°C for 2-8 h to obtain the slurry bed hydrogenation iron-based catalyst; preferably, the above preparation method further includes step (3): Mix the slurry bed hydrogenation iron-based catalyst with solvent oil or solvent oil and a dispersant, and then crush to obtain a dispersion of the slurry bed hydrogenation iron-based catalyst; the dispersant is preferably one or more combinations of sodium alkylbenzene sulfonate, sodium lignosulfonate, Tween 80, OP-10, and polyethylene glycol; preferably, the solid content of the dispersion of the slurry bed hydrogenation iron-based catalyst is 1-10%, and the solid particle size is 0.1-1 μm.

7. The preparation method according to claim 6, wherein, In step (1), the salts of the active component metallic iron include one or a combination of two or more of ferric nitrate, ferric sulfate, ferrous sulfate, ferric chloride, and ferric phosphate; Preferably, the salts of the active component metallic zinc include one or a combination of two or more of zinc nitrate, zinc sulfate, zinc chloride, and zinc phosphate; Preferably, the precipitants include one or a combination of two or more of sodium hydroxide, potassium hydroxide, ammonia water, and urea.

8. The preparation method according to claim 6, wherein, In step (2), the salts of the promoter metals include one or a combination of two or more of cobalt nitrate, ammonium molybdate, nickel nitrate, nickel sulfide, and ammonium metatungstate; Preferably, when calcination is carried out in step (2), the temperature is raised at a rate of 4-10 °C / min; Preferably, the volume of the impregnation solution is the same as the saturated water absorption of the precursor.

9. A method for hydrotreating oil products, which is carried out using the slurry bed hydrotreating iron-based catalyst according to any one of claims 1-5; Preferably, the oil products include one or a combination of two or more of crude oil, atmospheric residue, vacuum residue, coal tar, deasphalted oil, and heavy oil; Preferably, the hydrotreating includes hydrorefining, hydro-upgrading, hydrocracking, or hydroisomerization, more preferably hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, or hydrogenation saturation of aromatics; Preferably, the temperature of the hydrotreating is 200 - 600 °C, the pressure is 2 - 20 Mpa, the liquid hourly space velocity is 0.3 - 20 h -1 , and the hydrogen-oil volume ratio is 100 - 2000.

10. The method for hydrotreating oil products according to claim 9, wherein, The slurry bed device used in the method for hydrotreating oil products includes a recycle system for tail oil, and the recycled tail oil accounts for less than 10 wt% of the total feed, and the number of recycling times is preferably ≥3 times; Preferably, the recycled tail oil includes hydrotreated tail oil and the slurry bed hydrotreating iron-based catalyst; Preferably, the recycled tail oil contains 50-100 wt% of hydrotreated tail oil; Preferably, the initial boiling point of the hydrotreated tail oil is ≥350 °C.

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