Residue hydrodecarbon residue catalyst, preparation method and application thereof

Abstract

The application discloses a residual carbon hydro-deoxygenation catalyst for residual oil, a preparation method and application thereof. The catalyst comprises a carrier, a hydrogenation active metal component and an additive, wherein the hydrogenation active metal component comprises tungsten sulfide, molybdenum sulfide and nickel sulfide; the additive is magnesium; the catalyst is characterized by a TEM-EDS method, and the atomic ratio of W to Mo in the active phase center is 3-70 times of the atomic ratio of W to Mo in the active phase edge. The catalyst can obviously improve the hydro-deoxygenation activity and stability in the process of residual carbon hydro-deoxygenation of residual oil.

Description

Technical Field

[0001] This invention belongs to the field of hydrogenation technology, and specifically relates to a hydrogenation decarbonization catalyst and its preparation method, as well as its application in the hydrogenation treatment of residual oil. Background Technology

[0002] Currently, the active phases of commonly used hydrogenation catalysts in the field of residue hydrotreating technology are mainly of two types: Ni-Mo-S and Ni-WS. The former is dominated by a MoS2 crystal structure, while the latter is dominated by a WS2 crystal structure. Each of these active phases has its advantages. The advantage of the MoS2-dominated active phase is its high surface sulfidation degree and relatively high hydrogenation activity. The disadvantage is that MoS2 itself has poor stability and is prone to aggregation. The WS2-dominated active phase has good stability and dispersibility, but its surface sulfidation degree is slightly lower, resulting in the hydrogenation activity of the Ni-WS active phase being generally slightly lower than that of the Ni-Mo-W active phase. Modification and optimization of the active phase is also one of the key research focuses in this field.

[0003] CN107899586A discloses a rare-earth-containing residue oil hydrotreating catalyst. The catalyst is made from the following raw materials: diatomaceous earth, rare earth compounds, iron oxide, methylcellulose, activated carbon, magnesium oxide, silicon dioxide, zirconium oxide, and molybdenum dioxide. This rare-earth-containing residue oil hydrotreating catalyst can be used to treat asphalt and low-quality residue oil with high metal content, as well as extra-heavy oil. However, this catalyst does not contain nickel and cannot form a conventional active phase, resulting in significantly insufficient hydrotreating performance.

[0004] CN1448486A discloses a novel catalyst for the hydrotreating of residual oil. This hydrotreating catalyst contains a molybdenum and / or tungsten-containing oil colloid, wherein the average particle size of MoS2 and WS2 is below 500 nanometers. This catalyst is suitable for use in slurry-bed hydrocracking processes. In use, the catalyst is first uniformly dispersed in heavy residual oil, and then, in the presence of hydrogen, the low-quality heavy residual oil containing the catalyst undergoes a hydrotreating reaction. This highly dispersible catalyst exhibits excellent dispersion with the oil, but its catalytic performance still needs further improvement due to its relatively low overall activity.

[0005] CN104096584A discloses a residue oil hydrotreating catalyst and its preparation method. The catalyst uses an alumina and activated carbon mixture as a support, and the active components are Ni₂P, MoO₃ and / or WO₃, CoO and / or NiO. This catalyst has the ability to remove impurities such as sulfur dioxide and residual carbon; however, the low-valence phosphorus contained in the catalyst is easily converted into PH₃ gas and lost during use, leading to a decrease in catalyst stability. Summary of the Invention

[0006] To address the inherent challenge of balancing activity and stability in existing residue hydrotreating catalysts, this invention provides a residue hydrotreating decarbonization catalyst, its preparation method, and its application. The catalyst of this invention, when used in the residue hydrotreating decarbonization process, significantly improves both the activity and stability of the decarbonization process.

[0007] The first aspect of this invention provides a catalyst for hydrotreating and removing residual carbon from residual oil, comprising a support, a hydrotreating active metal component, and an additive, wherein the hydrotreating active metal component comprises tungsten sulfide, molybdenum sulfide, and nickel sulfide; the additive is magnesium; the catalyst is characterized by TEM-EDS, and the atomic ratio of W to Mo at the active phase center is 3-70 times that at the active phase edge, preferably 8-50 times.

[0008] Furthermore, the catalyst is characterized by TEM-EDS, and the ratio of W to Mo atoms at the active phase center is 3-70 times that at the active phase edge, preferably 8-50 times, for example, but not limited to 3 times, 5 times, 8 times, 10 times, 15 times, 20 times, 25 times, 30 times, 32 times, 35 times, 38 times, 40 times, 42 times, 45 times, 50 times, 55 times, 60 times, 65 times, 70 times, etc., and any value within the range formed by any two of these values.

[0009] Furthermore, the catalyst was characterized using TEM-EDS. Tungsten sulfide was mainly distributed at the center of the active phase, while molybdenum sulfide was mainly distributed at the edge of the active phase. The center of the active phase is defined as a location at least 3.0 nm from the endpoint of the active phase edge, while the active phase edge is defined as a location 0-2 nm from the endpoint of the active phase edge.

[0010] Furthermore, the support can be a conventional support for residue hydrotreating catalysts, preferably a support for residue hydrotreating decarbonization catalysts. The support is selected from at least one of alumina, silica, amorphous silica-alumina, titanium-aluminum composite oxides, and titanium-silicon composite oxides, preferably alumina, and more preferably γ-alumina. The support may also contain one or more conventional additives, such as phosphorus and boron. The conventional additives in the support account for less than 5% by mass, based on elemental composition.

[0011] Furthermore, the carrier has the following properties: a specific surface area of ​​180-400 m². 2 / g, preferably 220-360m 2 / g, pore volume 0.6-1.2m 3 / g, preferably 0.7-1.1m 3 / g.

[0012] Furthermore, based on the mass of the catalyst, the mass content of the support is 55%-85%, preferably 60%-80%.

[0013] Furthermore, based on the mass of the catalyst, the mass content of tungsten, calculated as an element, is 5%-14%, preferably 6%-12%; the mass content of molybdenum, calculated as an element, is 3%-14%, preferably 4%-12%; the mass content of nickel, calculated as an element, is 1%-5%, preferably 2%-4%; and the mass content of magnesium, calculated as an element, is 0.3%-3.0%, preferably 0.5%-2.5%.

[0014] A second aspect of this invention provides a method for preparing a catalyst for hydrotreating and decarbonizing residual oil, comprising:

[0015] (1) Impregnate the support with a tungsten-containing impregnation solution, dry and calcine to obtain a catalyst intermediate containing tungsten oxide;

[0016] (2) Sulfide the catalyst intermediate from step (1) to obtain sulfidated catalyst intermediate I;

[0017] (3) The sulfidated catalyst intermediate I obtained in step (2) is mixed with an organic solution containing sulfur and organic molybdenum and reacted in the presence of hydrogen to obtain the sulfidated catalyst intermediate II.

[0018] (4) The sulfidated catalyst intermediate II obtained in step (3) is mixed with an organic solution containing sulfur, organonitrile and organomagnesium, and reacted in the presence of hydrogen to obtain the catalyst.

[0019] Further, in step (1), the support can be a conventional support for residue hydrotreating catalysts, preferably a support for residue hydrotreating decarbonization catalysts. The support is selected from at least one of alumina, silica, amorphous silica-alumina, titanium-aluminum composite oxides, and titanium-silicon composite oxides, preferably alumina, and more preferably γ-alumina. The support may also contain one or more conventional additives, such as phosphorus and boron. The conventional additives in the support account for less than 5% by mass, based on elemental composition. Preferably, the support has the following properties: a specific surface area of ​​180-400 m². 2 / g, preferably 220-360m 2 / g, pore volume 0.6-1.2m 3 / g, preferably 0.7-1.1m 3 / g。 .

[0020] Further, in step (1), the tungsten source in the tungsten-containing impregnation solution can be a commonly used tungsten-containing compound, such as a soluble tungsten source, selected from at least one of ammonium tungstate, ammonium metatungstate, and ammonium paratungstate. The concentration of tungsten in the tungsten-containing impregnation solution is 0.1-2.0 mol / L, preferably 0.2-1.5 mol / L.

[0021] Furthermore, the impregnation in step (1) can be carried out using conventional impregnation methods, preferably equal-volume impregnation methods.

[0022] Further, in step (1), the drying conditions after impregnation are as follows: the drying temperature is 100-180℃, preferably 120-160℃, and the drying time is 2-10 hours, preferably 4.0-8.0 hours; the calcination conditions are as follows: the calcination temperature is 350-550℃, preferably 400-500℃, and the calcination time is 2.0-10.0 hours, preferably 4.0-8.0 hours.

[0023] In step (1), based on the mass of the catalyst intermediate, the mass content of tungsten, calculated by element, is 6%-18%, preferably 7%-16%.

[0024] Furthermore, in step (2), the sulfidation is carried out using conventional sulfidation methods in the art. The present invention does not have any particular limitations, but preferably the sulfidation is to fully sulfidate the active metal tungsten.

[0025] Further, in step (2), the sulfidation is preferably wet sulfidation. The sulfidation liquid used consists of a sulfiding agent and a solvent. The sulfiding agent is one or more of carbon disulfide, dimethyl disulfide, diallyl trisulfide (DATS), and diallyl disulfide (DADS). The solvent is one or more of cyclohexane, n-heptane, toluene, tetrahydronaphthalene, decahydronaphthalene, industrial white oil, refined diesel oil, and refined jet fuel. The mass content of the sulfiding agent in the sulfidation liquid is preferably 1%-10%. Preferably, the wet sulfidation is carried out in the presence of hydrogen, where the catalyst intermediate obtained in step (1) is contacted with the sulfidation liquid to carry out the sulfidation reaction, wherein the flow rate of the sulfidation liquid is 0.5-5.0 ml / h·g. 催化剂 The vulcanization temperature is 280-380℃, preferably 300-360℃; the vulcanization time is 4.0-12.0 hours, preferably 6.0-10.0 hours; the hydrogen pressure is 1.0-10.0 MPa, preferably 2.0-8.0 MPa; and the hydrogen flow rate is 10-30 Nml / min·g. 催化剂。

[0026] Further, in step (3), the organic solution containing sulfur and organic molybdenum includes organic molybdenum, a vulcanizing agent, and an organic solvent. The organic molybdenum is one or more of dialkyl dithiophosphate molybdenum, dialkyl dithiocarbamate molybdenum, dithiocarbamate molybdenum, naphthenic acid molybdenum, alkyl salicylate molybdenum, and carbonyl molybdenum. The alkyl group has 3-20 carbon atoms, preferably 4-15. The vulcanizing agent is one or more of dimethyl disulfide, carbon disulfide, diallyl trisulfide (DATS), and diallyl disulfide (DADS), and the organic solvent is at least one of n-hexadecane, hydrotreated diesel, refined jet fuel, and industrial white oil. In the organic solution containing sulfur and organic molybdenum, the mass content of organic molybdenum is 0.1%-10.0%, preferably 0.5%-8.0%, and the mass content of the vulcanizing agent is 0.5%-5.0%, preferably 1.0%-3.0%.

[0027] Further, in step (3), the mass ratio of the sulfidated catalyst intermediate I obtained in step (2) to the organic solution containing sulfur and organic molybdenum is 1:3-1:30, preferably 1:5-1:20.

[0028] Further, in step (3), the reaction process is divided into two stages: in the first stage, the pressure is controlled at 0.5-10.0 MPa, preferably 1.0-8.0 MPa, the temperature is 200-320℃, preferably 210-290℃, and the reaction time is 1.0-6.0 hours, preferably 2.0-4.0 hours; in the second stage, the pressure is controlled at 0.5-10.0 MPa, preferably 1.0-8.0 MPa, the temperature is 260-380℃, preferably 280-370℃, and the reaction time is 2.0-8.0 hours, preferably 3.0-7.0 hours.

[0029] Further, in step (4), the organic solution containing sulfur, organonickel, and organomaglenium includes a sulfiding agent, organonickel, organomaglenium, and an organic solvent. The organonickel is one or more of nickel benzoate, nickel acetylacetonate, nickel salicylate, alkylphenyl salicylate, nickel citrate, nickel carbonyl, and nickel stearate. The alkyl group has 3-20 carbon atoms, preferably 4-15. The organomaglenium is one or more of magnesium acetylacetonate, magnesium p-aminobenzoate, magnesium stearate, magnesium palmitate, magnesium tetradecanoate, magnesium adipic acid, magnesium pyruvate, and magnesium p-aminosalicylate. The sulfiding agent is one or more of dimethyl disulfide, carbon disulfide, diallyl trisulfide (DATS), and diallyl disulfide (DADS). In the organic solution containing sulfur, organonickel, and organomagnesia, the organonickel content by mass is 0.1%-4.5%, preferably 0.2%-3.5%; and / or, the organomagnesia content by mass is 0.1%-2.0%, preferably 0.2%-1.0%; and / or, the vulcanizing agent content by mass is 0.5%-5.0%, preferably 1.0%-3.0%.

[0030] Furthermore, in step (4), the mass ratio of the organic solution containing sulfur, organonitrile and organomagnesium to the sulfidated catalyst intermediate II obtained in step (3) is 40:1-4:1, preferably 30:1-6:1.

[0031] Further, in step (4), the reaction process is divided into two stages: in the first stage, the pressure is controlled at 0.5-10.0 MPa, preferably 1.0-6.0 MPa, the temperature is 200-320℃, preferably 220-280℃, and the reaction time is 1.0-6.0 hours, preferably 2.0-4.0 hours; in the second stage, the pressure is controlled at 0.5-10.0 MPa, preferably 1.0-6.0 MPa, the temperature is 260-380℃, preferably 280-360℃, and the reaction time is 2.0-8.0 hours, preferably 3.0-6.0 hours.

[0032] Further, the catalyst obtained in step (4), based on the mass of the catalyst, has the following composition: tungsten content (based on elemental mass) of 5%-15%, preferably 6%-12%; molybdenum content (based on elemental mass) of 3%-15%, preferably 4%-12%; nickel content (based on elemental mass) of 1%-5%, preferably 2%-4%; and magnesium content (based on elemental mass) of 0.4%-3.5%, preferably 0.6%-3.0%.

[0033] Furthermore, the catalyst is characterized by TEM-EDS, and the ratio of W to Mo atoms at the active phase center is 3-70 times that at the active phase edge, preferably 8-50 times, for example, but not limited to 3 times, 5 times, 8 times, 10 times, 15 times, 20 times, 25 times, 30 times, 32 times, 35 times, 38 times, 40 times, 42 times, 45 times, 50 times, 55 times, 60 times, 65 times, 70 times, etc., and any value within the range formed by any two of these values.

[0034] Furthermore, the catalyst was characterized using TEM-EDS. Tungsten sulfide was mainly distributed at the center of the active phase, while molybdenum sulfide was mainly distributed at the edge of the active phase. The center of the active phase is defined as a location at least 3.0 nm from the endpoint of the active phase edge, while the active phase edge is defined as a location 0-2 nm from the endpoint of the active phase edge.

[0035] A third aspect of the present invention provides a catalyst prepared by the above method.

[0036] The fourth aspect of this invention provides the application of the above-mentioned catalyst in the hydrotreating of residual oil.

[0037] Furthermore, in the aforementioned application, the catalyst is used as a hydrodecarbonization catalyst.

[0038] Furthermore, the residual oil feedstock can be at least one of atmospheric residue, vacuum residue, or deasphalted oil.

[0039] Furthermore, the hydrogenation treatment conditions are as follows: reaction temperature 300-450℃, preferably 350-420℃; reaction pressure 12-25MPa, preferably 15-22MPa; hydrogen-to-oil volume ratio 500-2000; and liquid hourly space velocity 0.05-0.6h⁻¹. -1 Preferably 0.1-0.4h -1 .

[0040] Compared with the prior art, the present invention has the following advantages:

[0041] 1. Mo and W belong to the same group VIB elements. Studies have found that Mo and W have almost the same atomic radius and completely identical coordination. Under fully sulfided conditions, molybdenum and tungsten, as six-coordinate elements, can substitute for each other in any proportion within the Ni-Mo(W)-S active phase while maintaining the structural stability of the active phase. This invention proposes a coated active phase with a WS2 crystal structure as the core support, MoS2 as the outer layer, and a surface modified with low-coordinate element A (such as nickel or magnesium). This active phase possesses both the stability and dispersibility of WS2 and the high surface activity of MoS2. Further surface modification with low-coordinate heteroatoms can further improve the hydrodecarbonization function of the catalyst. Therefore, the catalyst of this invention not only combines the advantages of both MoS2 and WS2 active phases but also significantly improves the activity and stability of the hydrodecarbonization catalyst.

[0042] 2. In the catalyst preparation process of this invention, the supported tungsten species are first sulfided to form highly dispersed WS2 lamellar crystals, which have a certain adsorption and hydrogenation capacity for organomolybdenum. This allows molybdenum species to be deposited in metallic form at the edges of the WS2 lamellar crystals. Further sulfidation of the molybdenum species results in a coated active phase where molybdenum sulfide species encapsulate tungsten sulfide species. The active phase is then modified with low-coordination metals such as nickel and magnesium. The catalyst prepared in this way not only combines the advantages of both MoS2 and WS2 active phases but also significantly improves the activity and stability of the hydrocracking catalyst. Detailed Implementation

[0043] The present invention will be further described below with reference to embodiments, but it should be understood that the scope of protection of the present invention is not limited to the embodiments. In the present invention, unless otherwise expressly stated, percentages and contents are all expressed by mass.

[0044] In this invention, the active phase characterization was obtained using TEM-EDS (Transmission Electron Microscopy-Energy Dispersion X-ray Spectroscopy). The instrument used was a JEOL JEM2200FS emission transmission electron microscope (Japan), equipped with a scanning transmission accessory and an EDAX X-ray energy dispersion accessory (USA). The electron microscope accelerating voltage was 200 kV, and in STEM mode, the condenser aperture was set to 2, and the spectrophotometer size was 0.5 nm. The measurement process was as follows: the catalyst particles were ground and prepared using the suspension method. 0.1 g of the catalyst sample was placed in a 2 mL container and ultrasonically dispersed with anhydrous ethanol. The supernatant was collected, and two to three drops were taken with a dropper and dropped onto a 3 mm diameter sample grid. After drying, the sample to be tested was obtained. Then, the sample to be tested was observed and analyzed using TEM. The content distribution of W and Mo in the active phase region observed by TEM was then statistically analyzed using EDS. In this invention, the active phase edge is defined as the location 0-2 nm away from the endpoint of the active phase edge, and the location more than 3 nm away from the edge is defined as the active phase center. The atomic ratio of W to Wo distributed in the center and edge of the active phase is obtained based on peak area. This invention uses the average value of data obtained from 40 TEM images combined with EDS analysis.

[0045] In this invention, the specific surface area and pore volume are measured using a Micromeritics TriStar II 2020 porosimeter at -196°C via N2 adsorption and desorption to determine the pore structure characteristics of the catalytic material.

[0046] The unmodified alumina support S-0 used in the following embodiments and comparative examples of this invention was prepared by the following method:

[0047] Weigh 2000.0g of alumina dry adhesive powder, add 40.0g of acetic acid, 30.0g of citric acid, 20.0g of guar gum powder, and 30.0g of cellulose, mix well, then add 2000.0g of an aqueous solution containing 2.0% nitric acid. After rolling for 15.0min, extrude the mixture using a clover-shaped perforated plate with a diameter of 1.8mm. Dry at 140℃ for 4.0h, then calcine at 550℃ for 4.0h. The calcined carrier is designated S-0. The pore properties of the S-0 carrier are as follows: specific surface area is 321m². 2 / g, pore volume is 0.89cm 3 / g.

[0048] Example 1

[0049] Weigh 20.0g of ammonium tungstate and dissolve it in 110ml of deionized water to prepare solution WQ-1.

[0050] Weigh 100.0g of carrier S-0, impregnate S-0 with WQ-1, let stand for 12 hours, dry at 120℃ for 4.0h and calcine at 450℃ for 4.0h. The intermediate obtained is denoted as OW-1.

[0051] Prepare a sulfidation solution by mixing 100.0g of DMDS with 3000g of cyclohexane, denoted as SQ-1.

[0052] OW-1 was loaded into a tubular reactor for sulfidation. The flow rate of SQ-1 was 200 ml / h, the reaction temperature was 320℃, the hydrogen pressure in the reaction tube was controlled at 4.0 MPa, and the reaction time was 6.0 hours. After cooling, the intermediate was taken out, and the sulfidated catalyst intermediate I was obtained, which was denoted as SW-1.

[0053] Weigh 25.0g of molybdenum carbonyl and 25.0g of carbon disulfide, dissolve them in 1000.0g of industrial white oil, and the resulting solution is denoted as MQ-1.

[0054] SW-1 and MQ-1 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 6.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 270℃ for 3.0 hours. Then the temperature was increased to 340℃ and the reaction was carried out for another 6.0 hours. The resulting sulfidated catalyst intermediate II was designated as SMW-1.

[0055] Weigh 18.0g of nickel acetylacetonate, 18.0g of magnesium acetylacetonate, and 30.0g of carbon disulfide, and dissolve them in 1000.0g of refined diesel oil. The resulting solution is denoted as NQ-1.

[0056] SMW-1 and NQ-1 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 6.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 270℃ for 3.0 hours. Then the temperature was increased to 340℃ and the reaction was continued for another 6.0 hours to obtain the catalyst, which was designated CAT-1.

[0057] Example 2

[0058] Weigh 20.0g of ammonium metatungstate and dissolve it in 110ml of deionized water to prepare a solution called WQ-2.

[0059] Weigh 100.0g of carrier S-0, impregnate S-0 with WQ-2, let stand for 12 hours, dry at 120℃ for 4.0h and calcine at 450℃ for 4.0h. The intermediate obtained is denoted as OW-2.

[0060] Take 100.0g of carbon disulfide and 3000g of cyclohexane to prepare a sulfidation liquid, denoted as SQ-2.

[0061] OW-2 was loaded into a tubular reactor for sulfidation. The flow rate of the sulfidation liquid SQ-2 was 200 ml / h, the reaction temperature was 320℃, the hydrogen pressure in the reaction tube was controlled at 4.0 MPa, and the reaction time was 6.0 hours. After cooling, the intermediate was taken out, and the sulfidated catalyst intermediate I was obtained, which was denoted as SW-2.

[0062] Weigh 75.0g of molybdenum dodecyl salicylate and 20.0g of DMDS, dissolve them in 1000.0g of industrial white oil, and the resulting solution is denoted as MQ-2.

[0063] SW-2 and MQ-2 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 5.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 250℃ for 4.0 hours. Then the temperature was increased to 320℃ and the reaction was carried out for another 6.0 hours to obtain the sulfidated catalyst intermediate II, denoted as SMW-2.

[0064] Weigh 20.0g of nickel benzoate, 40.0g of magnesium stearate, and 30.0g of carbon disulfide, and dissolve them in 1000.0g of refined diesel oil. The resulting solution is denoted as NQ-2.

[0065] SMW-2 and NQ-2 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 5.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 250℃ for 4.0 hours. Then the temperature was increased to 320℃ and the reaction was continued for 6.0 hours to obtain the catalyst, which was designated as CAT-2.

[0066] Example 3

[0067] Weigh 20.0g of ammonium paratungstate and dissolve it in 110ml of deionized water to prepare solution WQ-3.

[0068] Weigh 100.0g of carrier S-0, impregnate S-0 with WQ-3, let stand for 12 hours, dry at 120℃ for 4.0h and calcine at 450℃ for 4.0h. The intermediate obtained is denoted as OW-3.

[0069] Take 150.0g of diallyl disulfide and 3000g of cyclohexane to prepare a sulfidation solution, denoted as SQ-3.

[0070] OW-3 was loaded into a tubular reactor for sulfidation. The flow rate of the sulfidation liquid SQ-3 was 200 ml / h, the reaction temperature was 320℃, the hydrogen pressure in the reaction tube was controlled at 4.0 MPa, and the reaction time was 6.0 hours. After cooling, the intermediate was taken out, and the sulfidated catalyst intermediate I was obtained, which was denoted as SW-3.

[0071] Weigh 40.0g of molybdenum dithiocarbamate and 25.0g of diallyl disulfide, dissolve them in 1000.0g of industrial white oil, and the resulting solution is denoted as MQ-3.

[0072] SW-3 and MQ-3 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 6.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 270℃ for 3.0 hours. Then the temperature was increased to 340℃ and the reaction was carried out for another 6.0 hours to obtain the sulfidated catalyst intermediate II, denoted as SMW-3.

[0073] Weigh 40.0g of nickel citrate monohydrate, 40.0g of magnesium palmitate, and 20.0g of diallyl disulfide, dissolve them in 1000.0g of refined diesel oil, and the resulting solution is denoted as NQ-3.

[0074] SMW-3 and NQ-3 were loaded together into a high-pressure reactor, sealed, and stirred. The reaction pressure was controlled at 6.0 MPa using hydrogen gas. The reactor was heated to 270°C for 3.0 hours, and then the temperature was increased to 340°C for another 6.0 hours. The resulting catalyst was designated CAT-3.

[0075] Comparative Example 1

[0076] Weigh out 20.0g of ammonium tungstate, 17.0g of ammonium heptamolybdate tetrahydrate, 20.0g of nickel nitrate hexahydrate, and 18.0g of magnesium nitrate hydrate, dissolve them in 110ml of deionized water, and prepare a solution labeled DQ-1.

[0077] Weigh 100g of S-0 support, impregnate it with DQ-1, let it stand for 12 hours, dry it at 120℃ for 4.0 hours, and then calcine it at 480℃ for 4.0 hours. The resulting catalyst is DOCT-1.

[0078] The catalyst DOCT-1 was placed in a reaction tube, and a cyclohexane solution containing 4.0 wt% DMDS was used as the sulfiding liquid to sulfide the catalyst. During sulfidation, the hydrogen pressure was 6.0 MPa and the liquid hourly space velocity (LHSV) was 1.0 h⁻¹. -1 The catalyst obtained after sulfidation at 350°C for 8.0 hours with a hydrogen-to-oil volume ratio of 300:1 is designated as DCT-1.

[0079] Comparative Example 2

[0080] Weigh 35.0g of ammonium tungstate and dissolve it in 110ml of deionized water to prepare a solution called DWQ-2.

[0081] Weigh 100.0g of carrier S-0, impregnate S-0 with DWQ-2, let stand for 12 hours, dry at 120℃ for 4.0h and calcine at 450℃ for 4.0h. The intermediate obtained is denoted as DOW-2.

[0082] Weigh 18.0g of nickel acetylacetonate, 18.0g of magnesium acetylacetonate, and 30.0g of carbon disulfide, dissolve them in 1000.0g of refined diesel oil, and the resulting solution is denoted as DNQ-2.

[0083] DOW-2 and DNQ-2 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 6.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 270℃ for 3.0 hours. Then the temperature was increased to 340℃ and the reaction was carried out for another 6.0 hours to obtain the catalyst, which was designated as DCT-2.

[0084] Comparative Example 3

[0085] Weigh 70.0g of molybdenum dithiocarbamate and 50.0g of diallyl disulfide, dissolve them in 1000.0g of industrial white oil, and the resulting solution is denoted as DMQ-3.

[0086] 100.0 g of S-0 support and DMQ-3 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 6.0 MPa using hydrogen gas. The reactor was heated to 270 °C for 3.0 hours, and then the temperature was increased to 340 °C for another 6.0 hours. The resulting sulfidized catalyst intermediate was designated DM-3.

[0087] Weigh 40.0g of nickel citrate monohydrate, 40.0g of magnesium palmitate, and 20.0g of diallyl disulfide, dissolve them in 1000.0g of refined diesel oil, and the resulting solution is denoted as DNQ-3.

[0088] DM-3 and DNQ-3 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 6.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 270℃ for 3.0 hours. Then the temperature was increased to 340℃ and the reaction was carried out for another 6.0 hours to obtain the catalyst, which was designated as DCT-3.

[0089] Comparative Example 4

[0090] The preparation of the sulfidated catalyst intermediate SMW-1 is the same as in Example 1.

[0091] Weigh 18.0g of nickel acetylacetone and 30.0g of carbon disulfide, dissolve them in 1000.0g of refined diesel oil, and the resulting solution is denoted as DNQ-4.

[0092] SMW-1 and DNQ-4 were loaded into a high-pressure reactor, sealed, stirred, and the reaction pressure was controlled at 6.0 MPa with hydrogen. The reactor was heated and the reaction temperature was controlled at 270℃ for 3.0 hours. Then the temperature was increased to 340℃ and the reaction was carried out for another 6.0 hours to obtain the catalyst, which was designated as DCT-4.

[0093] Table 1 shows the elemental analysis of the catalysts obtained in each example.

[0094] CAT-1 9.9 6.6 3.0 1.2 CAT-2 10.6 6.9 2.8 1.2 CAT-3 10.0 7.2 2.9 1.3 DCT-1 10.0 6.6 2.9 1.2 DCT-2 17.8 0 3.1 1.2 DCT-3 0 17.1 2.8 1.3 DCT-4 10.2 6.8 3.0 0

[0095] TEM-EDS analysis was performed on the catalyst, and the ratio of the average W / Mo atomic ratio at the center of the active phase to that at the edge is shown in Table 2.

[0096] Table 2. Metal distribution on the active phase of the catalysts obtained in each example.

[0097] CAT-1 39.1 CAT-2 48.4 CAT-3 37.3 DCT-1 1.6 DCT-2 - DCT-3 - DCT-4 34.8

[0098] Examples 4-6

[0099] Vacuum residue was selected as feedstock, and a fixed-bed hydrotreating process was used to evaluate the hydrogenation of the catalysts obtained in Examples 1-3. The properties of the vacuum residue are shown in Table 3.

[0100] Table 3 Properties of vacuum residue

[0101] <![CDATA[Density / g·cm -3 > 0.982 Nitrogen content, μg / g 2745 Vanadium + Nickel content, μg / g 40.48 H / C atomic ratio 1.54 Sulfur content, μg / g 33692 Kang's carbon residue, % 17.7

[0102] A hydroprotective agent (FZC-100B) and a hydrodemetallization catalyst (FZC-204A) were loaded before the aforementioned catalyst. The volume ratio of the protective agent, the hydrodemetallization catalyst, and the catalyst obtained in the examples was 1:2:4. The operating conditions were: reaction temperature 395°C, reaction pressure 19.0 MPa, hydrogen-to-oil volume ratio 1500:1, and liquid hourly space velocity (LHSV) 0.2 h⁻¹. -1 After 1000 hours of reaction evaluation, the nitrogen content, carbon residue, and sulfur content of the hydrogenated oil fraction at temperatures not lower than 300°C were analyzed, and the results are shown in Table 4.

[0103] Comparative Examples 5-8

[0104] Vacuum residue (see Table 3) was selected as feedstock, and a fixed-bed process was used to evaluate the activity of the catalysts obtained in Comparative Examples 1-4. A hydrotreating protectant (FZC-100B) and a hydrodemetallization catalyst (FZC-204A) were loaded before the above catalysts. The loading volume ratio of the protectant, hydrodemetallization catalyst, and the catalysts obtained in the comparative examples was 1:2:4. The operating conditions were: reaction temperature 395℃, reaction pressure 19.0 MPa, hydrogen-to-oil volume ratio 1500:1, and liquid hourly space velocity (LISH) 0.2 h⁻¹.-1 After 1000 hours of reaction evaluation, the nitrogen content, carbon residue, and sulfur content of the hydrogenated oil fraction at temperatures not lower than 300°C were analyzed, and the results are shown in Table 4.

[0105] Table 4 Properties of Oils Generated by Fixed-Bed Hydrogenation

[0106] Example 4 Cat-1 329 2.7 1268 Example 5 Cat-2 337 2.5 1517 Example 6 Cat-3 361 2.4 1396 Comparative Example 5 DCT-1 952 6.3 3681 Comparative Example 6 DCT-2 896 6.4 3669 Comparative Example 7 DCT-3 907 6.7 3635 Comparative Example 8 DCT-4 462 4.8 2118

[0107] As can be seen from the evaluation results in Table 4, the catalyst of the present invention has good hydrodecarbonization activity, as well as good hydrodenitrogenation and hydrodesulfurization activity when used in the hydrotreating process of residual oil.

Claims

1. A catalyst for hydrotreating and removing residual carbon from residual oil, comprising a support, a hydrotreating active metal component, and an additive, wherein the hydrotreating active metal component comprises tungsten sulfide, molybdenum sulfide, and nickel sulfide; the additive is magnesium; the catalyst is characterized by TEM-EDS, and the W to Mo atomic ratio at the center of the active phase is 3-70 times that at the edge of the active phase; in the catalyst, tungsten sulfide is mainly distributed at the center of the active phase, and molybdenum sulfide is mainly distributed at the edge of the active phase, wherein... The active phase center is located at a distance of more than 3.0 nm from the edge endpoint of the active phase, while the active phase edge refers to a distance of 0-2 nm from the edge endpoint of the active phase. The active phase in the catalyst is a coated active phase with a WS2 crystal structure as the core support, MoS2 as the outer layer, and low-coordination elements nickel and magnesium modified on the surface.

2. The catalyst according to claim 1, characterized in that, The catalyst was characterized by TEM-EDS, and the ratio of W to Mo atoms at the active phase center was 8-50 times that at the active phase edge.

3. The catalyst according to claim 1, characterized in that, The carrier is selected from at least one of alumina, silicon oxide, amorphous silicon-aluminum, titanium-aluminum composite oxide, and titanium-silicon composite oxide.

4. The catalyst according to claim 3, characterized in that, The carrier is aluminum oxide.

5. The catalyst according to claim 4, characterized in that, The carrier also contains conventional additives, which are one or more of phosphorus and boron. The mass content of the conventional additives in the carrier, calculated by element, is less than 5%.

6. The catalyst according to claim 1 or 3, characterized in that, The carrier has the following properties: specific surface area of ​​180-400 m². 2 / g, pore volume 0.6-1.2 m 3 / g.

7. The catalyst according to claim 6, characterized in that, The carrier has the following properties: specific surface area of ​​220-360 m². 2 / g, pore volume 0.7-1.1 m 3 / g.

8. The catalyst according to claim 1 or 3, characterized in that, Based on the quality of the catalyst, the mass content of the support is 55%-85%.

9. The catalyst according to claim 8, characterized in that, Based on the quality of the catalyst, the mass content of the support is 60%-80%.

10. The catalyst according to claim 1, characterized in that, Based on catalyst mass, the tungsten content is 5%-14% by mass, the molybdenum content is 3%-14% by mass, the nickel content is 1%-5% by mass, and the magnesium content is 0.3%-3.0% by mass.

11. The catalyst according to claim 10, characterized in that, Based on the mass of the catalyst, the mass content of tungsten (by element) is 6%-12%, the mass content of molybdenum (by element) is 4%-12%, the mass content of nickel (by element) is 2%-4%, and the mass content of magnesium (by element) is 0.5%-2.5%.

12. A method for preparing the catalyst according to any one of claims 1-11, comprising: (1) Impregnate the support with a tungsten-containing impregnation solution, dry and calcine to obtain a catalyst intermediate containing tungsten oxide; (2) Sulfide the catalyst intermediate from step (1) to obtain sulfidated catalyst intermediate I; (3) The sulfidated catalyst intermediate I obtained in step (2) is mixed with an organic solution containing sulfur and organic molybdenum and reacted in the presence of hydrogen to obtain the sulfidated catalyst intermediate II. (4) The sulfidated catalyst intermediate II obtained in step (3) is mixed with an organic solution containing sulfur, organonitrile and organomagnesium, and reacted in the presence of hydrogen to obtain the catalyst.

13. The preparation method according to claim 12, characterized in that, In step (1), based on the mass of the catalyst intermediate, the mass content of tungsten, calculated as an element, is 6%-18%.

14. The preparation method according to claim 13, characterized in that, In step (1), based on the mass of the catalyst intermediate, the mass content of tungsten, calculated as an element, is 7%-16%.

15. The preparation method according to claim 12, characterized in that, In step (3), the organic solution containing sulfur and organic molybdenum includes organic molybdenum, a sulfiding agent, and an organic solvent.

16. The preparation method according to claim 15, characterized in that, The organic molybdenum is one or more of dialkyl dithiophosphate molybdenum, dialkyl dithiocarbamate molybdenum, dithiocarbamate molybdenum, naphthenic acid molybdenum, alkyl salicylate molybdenum, and carbonyl molybdenum, wherein the alkyl carbon number is 3-20; and / or, the vulcanizing agent is one or more of dimethyl disulfide, carbon disulfide, diallyl trisulfide, and diallyl disulfide; and / or, the organic solvent is at least one of n-hexadecane, hydrotreated diesel, refined jet fuel, and industrial white oil.

17. The preparation method according to claim 16, characterized in that, The alkyl group has 4-15 carbon atoms.

18. The preparation method according to claim 16, characterized in that, In the organic solution containing sulfur and organic molybdenum, the mass content of organic molybdenum is 0.1%-10.0%; and / or, the mass content of the vulcanizing agent is 0.5%-5.0%.

19. The preparation method according to claim 18, characterized in that, In the organic solution containing sulfur and organic molybdenum, the mass content of organic molybdenum is 0.5%-8.0%; and / or, the mass content of the vulcanizing agent is 1.0%-3.0%.

20. The preparation method according to claim 12, characterized in that, In step (3), the mass ratio of the sulfidated catalyst intermediate I obtained in step (2) to the organic solution containing sulfur and organic molybdenum is 1:3-1:

30.

21. The preparation method according to claim 12, characterized in that, In step (3), the mass ratio of the sulfidated catalyst intermediate I obtained in step (2) to the organic solution containing sulfur and organic molybdenum is 1:5-1:

20.

22. The preparation method according to claim 12, characterized in that, In step (3), the reaction process is divided into two stages: in the first stage, the pressure is controlled at 0.5-10.0 MPa, the temperature at 200-320℃, and the reaction time is 1.0-6.0 hours; in the second stage, the pressure is controlled at 0.5-10.0 MPa, the temperature at 260-380℃, and the reaction time is 2.0-8.0 hours.

23. The preparation method according to claim 22, characterized in that, In step (3), the reaction process is divided into two stages: in the first stage, the pressure is controlled at 1.0-8.0 MPa, the temperature is controlled at 210-290℃, and the reaction time is controlled at 2.0-4.0 hours; in the second stage, the pressure is controlled at 1.0-8.0 MPa, the temperature is controlled at 280-370℃, and the reaction time is controlled at 3.0-7.0 hours.

24. The preparation method according to claim 12, characterized in that, In step (4), the organic solution containing sulfur, organonickel and organomagnesium includes a sulfiding agent, organonickel, organomagnesium and an organic solvent.

25. The preparation method according to claim 24, characterized in that, The organonickel is one or more of nickel benzoate, nickel acetylacetonate, nickel salicylate, alkylphenyl salicylate, nickel citrate, nickel carbonyl, and nickel stearate, wherein the alkyl group has 3-20 carbon atoms; and / or, the organomagnesium is one or more of magnesium acetylacetonate, magnesium p-aminobenzoate, magnesium stearate, magnesium palmitate, magnesium tetradecanoate, magnesium adipic acid, magnesium pyruvate, and magnesium p-aminosalicylate; and / or, the vulcanizing agent is one or more of dimethyl disulfide, carbon disulfide, diallyl trisulfide, and diallyl disulfide.

26. The preparation method according to claim 25, characterized in that, The alkyl group has 4-15 carbon atoms.

27. The preparation method according to claim 25, characterized in that, In the organic solution containing sulfur, organocniole and organomagnesia, the mass content of organocniole is 0.1%-4.5%; and / or, the mass content of organomagnesia is 0.1%-2.0%; and / or, the mass content of vulcanizing agent is 0.5%-5.0%.

28. The preparation method according to claim 27, characterized in that, In the organic solution containing sulfur, organocniole and organomagnesia, the organocniole content is 0.2%-3.5% by mass; and / or, the organomagnesia content is 0.2%-1.0% by mass; and / or, the vulcanizing agent content is 1.0%-3.0% by mass.

29. The preparation method according to claim 12, characterized in that, In step (4), the mass ratio of the organic solution containing sulfur, organonitrile and organomagnesium to the sulfidated catalyst intermediate II obtained in step (3) is 40:1-4:

1.

30. The preparation method according to claim 29, characterized in that, In step (4), the mass ratio of the organic solution containing sulfur, organonitrile and organomagnesium to the sulfidated catalyst intermediate II obtained in step (3) is 30:1-6:

1.

31. The preparation method according to claim 12, characterized in that, In step (4), the reaction process is divided into two stages: in the first stage, the pressure is controlled at 0.5-10.0 MPa, the temperature at 200-320℃, and the reaction time is 1.0-6.0 hours; in the second stage, the pressure is controlled at 0.5-10.0 MPa, the temperature at 260-380℃, and the reaction time is 2.0-8.0 hours.

32. The preparation method according to claim 31, characterized in that, In step (4), the reaction process is divided into two stages: in the first stage, the pressure is controlled at 1.0-6.0 MPa, the temperature is controlled at 220-280℃, and the reaction time is controlled at 2.0-4.0 hours; in the second stage, the pressure is controlled at 1.0-6.0 MPa, the temperature is controlled at 280-360℃, and the reaction time is controlled at 3.0-6.0 hours.

33. The use of the catalyst according to any one of claims 1-11 in the hydrotreating of residual oil.