Residual oil hydrodesulfurization catalyst as well as preparation method and application thereof

Abstract

The invention discloses a residual oil hydrogenation sulfur catalyst as well as a preparation method and application thereof. The residual oil hydrodesulfurization catalyst comprises a modified alumina carrier and a hydrogenation active metal component, the modified alumina carrier comprises alumina and a modification auxiliary agent zinc, and hexa-coordinated Al on the carrier accounts for 75-95% of the total aluminum. The hydrodesulfurization catalyst provided by the invention has good hydrodesulfurization performance, and is especially suitable for processing inferior residual oil raw materials with relatively high sulfur content.

Description

Technical Field

[0001] The present invention belongs to the technical field of heavy residue oil hydrogenation, and particularly relates to a residue oil hydrodesulfurization catalyst, a preparation method thereof, and an application thereof in the hydroprocessing of inferior residue oil. Background Art

[0002] Residue oil hydroprocessing catalysts usually use γ-alumina as a carrier. The flatness of the carrier surface is relatively low, the microscopic surface properties are too random, and the acid distribution is quite broad, resulting in great difficulty in finely regulating the active phase of the catalyst. The metal distribution is very uneven. In areas with rough surfaces and many cavities, the acidity is strong, and in areas with a high dispersion of active metals, the catalytic activity is high, but the stability is poor; conversely, in areas with relatively flat surfaces and few cavities, the acidity is poor, and in areas with a low dispersion of active metals, the catalyst stability is high, but the activity is poor.

[0003] In order to improve the performance of residue oil catalysts, researchers have proposed various modification methods for alumina carriers.

[0004] CN201310499295.7 discloses a preparation method for an alumina carrier of a residue oil hydrodemetallization catalyst. The method includes: first, kneading a physical pore-expanding agent, pseudoboehmite dry gel powder, an extrusion aid, and a peptizing agent into a plastic body, extruding into strips, and drying; then, subjecting the dried carrier to unsaturated spray impregnation with a chemical pore-expanding agent; finally, the carrier impregnated with the chemical pore-expanding agent is dried and calcined to obtain an alumina carrier of a residue oil hydrodemetallization catalyst. The alumina prepared by this method has an excellent pore structure, but its surface uniformity has still not been fully improved, thus affecting the dispersion effect of active metal components.

[0005] CN201110322448.1 discloses a preparation method for an alumina carrier of a residue oil hydrogenation catalyst. The method uses activated carbon fibers with a developed pore structure as a pore-expanding agent after impregnating and adsorbing inorganic aluminum salts, kneading with an alumina precursor, forming, and then drying and calcining to obtain an alumina carrier. The specific surface area of the alumina carrier obtained by this method is relatively high, which is beneficial to removing large molecules in heavy residue oil, thus being beneficial to maintaining the activity of the hydrogenation catalyst and extending the operation cycle. However, as an alumina carrier, its surface uniformity is poor, and it is easy to cause aggregation of active metals in a certain place during the process of loading active metals, affecting the efficient utilization of active metals.

[0006] CN200410050726.2 discloses a method for preparing an alumina support. The method includes neutralizing an acidic aluminum salt with an alkaline aluminate, aging the neutralized material, and then filtering, washing, forming, drying, and calcining to obtain the alumina support, where the aging is carried out under conditions of a temperature higher than the neutralization temperature and a pH value higher than the neutralization pH value. The alumina support prepared by this method also has poor uniformity on the surface, which affects the loading of subsequent active metals and the overall activity of the catalyst. Summary of the Invention

[0007] Aiming at the deficiencies in the prior art, the present invention provides a residue hydrodesulfurization catalyst, its preparation method and application. The residue hydrodesulfurization catalyst of the present invention has good hydrodesulfurization performance and is particularly suitable for processing inferior residue oil raw materials with a high sulfur content.

[0008] In γ-alumina, there are mainly two forms of existence of Al. One is stable six-coordinate framework aluminum, which shows a displacement of -10 - 30 ppm in Al NMR, and the other is less stable four-coordinate non-framework aluminum, which shows a displacement of 40 - 80 ppm in Al NMR. The inventors have found through research that the non-framework aluminum on the surface of γ-alumina is the key to causing the non-uniformity of the alumina surface properties. The inventors have further found that when the alumina surface is mainly composed of six-coordinate aluminum, the alumina surface can be made flat and the properties can be uniform, while improving the activity and stability of the catalyst. The inventors have creatively introduced zinc elements onto the alumina surface while removing the non-framework aluminum, which can make the alumina surface flat and the properties uniform, thus realizing the present invention.

[0009] The first aspect of the present invention provides a residue hydrodesulfurization catalyst, which includes a modified alumina support and a hydrogenation active metal component; the modified alumina support includes alumina and a modifying assistant zinc, and the six-coordinate Al on the support accounts for 75% - 95% of the total aluminum, preferably 80% - 93%.

[0010] Further, based on the mass of the support, the mass content of zinc (calculated as ZnO) is 1% - 10%, preferably 2% - 8%.

[0011] Further, based on the mass of the support, the mass content of alumina is 83% - 99%, preferably 85% - 98%.

[0012] Further, the support may also contain one or more of conventional assistants such as silicon, phosphorus, and boron. Based on the mass of the support, the mass content of the conventional assistant in terms of elements is 5% or less.

[0013] Further, the properties of the support are as follows: the specific surface area is 150 - 390 m 2 / g, preferably 180 - 360 m 2 / g, the pore volume of the support is 0.6 - 1.1 m 3 / g, preferably 0.7 - 1.0 m 3 / g.

[0014] Furthermore, the hydrogenation active metal component is selected from at least one of the metals in Group VIB and Group VIII. Among them, the metal in Group VIB is preferably selected from at least one of tungsten and molybdenum, and the metal in Group VIII is preferably selected from at least one of nickel and cobalt. Based on the mass of the catalyst, the content of the metal in Group VIB calculated as the +6 valence oxide is 10% - 35%, preferably 15% - 28%, and the content of the metal in Group VIII calculated as the +2 valence oxide is 2% - 10%, preferably 3% - 8%.

[0015] The second aspect of the present invention provides a preparation method of the above catalyst, including: a step of loading an active metal component on a modified alumina support; wherein, the preparation method of the modified alumina support includes: mixing an alumina support with an organic solution of zinc chloride, performing a closed heating treatment, and an activation treatment to obtain a modified alumina support.

[0016] Furthermore, the alumina support is a γ-alumina support. The alumina support can be a conventional alumina support for residue hydrotreating catalysts, preferably an alumina support for residue hydrodesulfurization catalysts. In the alumina support, in addition to alumina, it can also contain promoters, such as one or more of silicon, phosphorus, boron, etc. In the alumina support, the mass content of the promoter calculated as an element accounts for less than 5%.

[0017] Furthermore, in the preparation method of the modified alumina support, in the organic solution of zinc chloride, the organic solvent is one or several of glycerol, 1,4-butanediol, and 1,2-butanediol.

[0018] Furthermore, in the preparation method of the modified alumina support, in the organic solution of zinc chloride, the mass content of zinc chloride is 2% - 15%, preferably 3% - 12%.

[0019] Furthermore, in the preparation method of the modified alumina support, the mass ratio of the alumina support to the organic solution of zinc chloride is 1:5 - 1:50, preferably 1:10 - 1:30.

[0020] Furthermore, in the preparation method of the modified alumina support, the conditions of the closed heating treatment are as follows: inert atmosphere, pressure of 0.05 - 0.5 MPa, preferably 0.1 - 0.4 MPa, treatment temperature of 160 - 230 °C, preferably 180 - 210 °C, treatment time of 4 - 24 hours, preferably 6 - 16 hours.

[0021] Further, in the preparation method of the modified alumina support, after the closed heating treatment, the solid is separated and washed with deionized water, preferably 2 - 10 times, the washing temperature is 30 - 80°C, preferably 40 - 70°C, and the amount of deionized water used each time is 5 - 50 times that of the solid to be washed, preferably 10 - 40 times. The washed support is subjected to an activation treatment, and the conditions of the activation treatment are as follows: the treatment temperature is 120 - 350°C, preferably 160 - 320°C, the treatment time is 2 - 10 hours, preferably 2 - 8 hours, and the treatment atmosphere is an oxygen-containing atmosphere, to obtain the modified alumina support.

[0022] Further, the method for loading the active metal component on the modified alumina support preferably adopts an impregnation method (such as a saturated impregnation method). When loading by the impregnation method, after impregnation, drying and calcination are carried out to obtain the catalyst. The drying and calcination can adopt conventional methods and conditions. Preferably, the drying temperature is 80 - 200°C, preferably 100 - 180°C, the drying time is 2.0 - 10.0 hours, preferably 4.0 - 8.0 hours; the calcination temperature is 300 - 600°C, preferably 350 - 500°C, and the calcination time is 2.0 - 8.0 hours, preferably 3.0 - 5.0 hours.

[0023] The third aspect of the present invention provides the application of the above catalyst in residue hydroprocessing.

[0024] Further, in the above application, the catalyst is used as a hydrodesulfurization catalyst.

[0025] Further, the residue raw material can be a conventional residue raw material, such as at least one of atmospheric residue, vacuum residue or deasphalted oil.

[0026] Further, the residue raw material can also be a poor-quality residue raw material with high sulfur and nitrogen contents. The properties of the poor-quality residue raw material are as follows: the density is 0.95 - 1.05 g / cm 3 , the mass content of sulfur is 10000 ppm - 50000 ppm, the mass content of nitrogen is 800 - 5000 ppm, and the mass content of residual carbon is 10% - 25%.

[0027] Further, the hydroprocessing conditions are as follows: the reaction temperature is 300 - 450°C, preferably 350 - 420°C, the reaction pressure is 12 - 25 MPa, preferably 15 - 22 MPa, and the liquid hourly space velocity is 0.05 - 0.6 h -1 preferably 0.1 - 0.4 h -1 .

[0028] Compared with the prior art, the present invention has the following advantages:

[0029] 1. The catalyst of the present invention uses a modified alumina support, namely a zinc-modified alumina support. By nuclear magnetic characterization, it mainly consists of six-coordinate aluminum, that is, six-coordinate Al accounts for 75%-95% of the total aluminum (preferably 80%-93%). When this support is used in a residue hydrodesulfurization catalyst, it can improve the activity and stability of the catalyst simultaneously.

[0030] 2. In the preparation process of the modified alumina support used in the catalyst of the present invention, the non-framework aluminum in the alumina support is dissolved in a chlorine-containing organic solution to generate AlCl 3 , Since aluminum chloride is a covalent compound with very low melting and boiling points and can sublime, it can volatilize from high-boiling liquids at relatively low temperatures, thereby promoting the continuous dissolution of four-coordinate aluminum in alumina into the solution to complete the dealumination process. At the same time, the zinc element in the solution will enter the alumina surface to balance the charge, playing a role in modifying the alumina surface throughout the process. The obtained modified alumina support mainly consists of six-coordinate aluminum on the surface, with good surface uniformity. During the impregnation and loading of active metals, it can be evenly dispersed on the support surface, with higher metal utilization rate. The prepared residue hydrodesulfurization catalyst has better hydrodesulfurization activity and stability.

[0031] 3. When the catalyst of the present invention is used to treat poor residue raw materials with high sulfur and nitrogen contents, it not only has good hydrodesulfurization activity but also shows good hydrodenitrogenation activity and hydrodearbonization activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is the 27 Al MAS NMR spectrum of the alumina support obtained in Example 1;

[0033] Figure 2 is the 27 Al MAS NMR spectrum of the alumina support obtained in Comparative Example 1;

[0034] Figure 3 is the transmission electron micrograph of the catalyst obtained in Example 1;

[0035] Figure 4 is the transmission electron micrograph of the catalyst obtained in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0036] The present invention will be further described below in conjunction with examples. However, it should be understood that the protection scope of the present invention is not limited by the examples. In the present invention, unless otherwise clearly stated, percentages and percentage contents are by mass.

[0037] In the present invention, the specific surface area and pore volume of the samples are measured by the physical adsorption method of liquid nitrogen on a Micromeritics ASAP 2020M.

[0038] In the present invention, an Al MAS NMR spectrum is obtained by nuclear magnetic resonance spectroscopy (NMR method), so as to obtain the ratio of six-coordinated framework aluminum and four-coordinated non-framework aluminum in the support, calculated based on Al atoms. Nuclear magnetic resonance spectroscopy (NMR method) uses a Bruker AVANCE III 500 nuclear magnetic resonance spectrometer, and the software used is Topspin 2.0. When measuring 27 the Al MAS NMR spectrum, the standard substance used is aluminum trichloride, the resonance frequency is 133 MHz, and the experimental conditions are: a pulse width of 4 - 6 microseconds and a relaxation delay of 60 - 120 seconds. In the obtained 27 Al MAS NMR spectrum, the chemical shift corresponding to six-coordinated framework aluminum is -10 - 30 ppm, and the chemical shift corresponding to four-coordinated non-framework aluminum is 40 - 80 ppm. Among them, the total aluminum refers to the sum of six-coordinated aluminum and four-coordinated aluminum. 27

[0039] In the present invention, the morphology of the metal active phase platelets of the sulfide catalyst can be statistically characterized by TEM. The transmission electron microscope used is a JEOL JEM 2100 transmission electron microscope, and the accelerating voltage used is 120 kV. The sulfided catalyst is stored in ethanol. During the test, the sample is placed in a mortar, a small amount of alcohol is added and ground for 10 minutes, left standing for a while, the upper clear liquid is taken and put into a sample bottle, diluted with alcohol and then placed in an ultrasonic oscillator for 20 min, 2 - 3 drops are added dropwise to the ultra-thin carbon film with a dropper, and the ethanol is volatilized with a baking lamp. After drying is completed, the sample is tested under the microscope. To analyze the platelet dispersion state of the active metal on the catalyst, the field of view is adjusted to the 10 nm range, and each sample needs to obtain no less than 30 pictures with good shooting quality from different positions.

[0040] In the present invention, the unmodified alumina support S-0 used in the following examples and comparative examples is prepared by the following method:

[0041] Weigh 1000.0 g of alumina dry gel powder, add 20.0 g of acetic acid, 20.0 g of citric acid, 20.0 g of sesbania powder, and 20.0 g of cellulose, mix them evenly, then add 1100.0 g of an aqueous solution containing 2.0% by mass of nitric acid, roll for 15.0 min, and extrude with a clover-shaped orifice plate with a diameter of 2.2 mm. After drying at 140 °C for 4.0 h, it is calcined at 700 °C for 4.0 h. The calcined support is denoted as S-0. The properties of the support are as follows: the specific surface area is 278 m 2 / g, and the pore volume is 0.95 cm 3 / g.

[0042] Example 1

[0043] Dissolve 250.0 g of zinc chloride in 3000 g of glycerol, and the resulting solution is denoted as G-1.​

[0044] Add 200.0 g of S-0 and G-1 into the reactor, seal it with nitrogen, control the pressure of the reactor at 0.2 MPa, heat the reactor to 210 °C, and stir well. After reacting for 10.0 hours, the separated solid is denoted as Z-1.

[0045] Wash Z-1 with deionized water at 40 °C, with a dosage of 6000 ml of deionized water each time. After washing 6 times, perform activation treatment at 240 °C in an air atmosphere for 4.0 hours to obtain the carrier denoted as S-1.

[0046] Take 25.0 g of ammonium heptamolybdate tetrahydrate and 18.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 120 ml solution denoted as Q-1.

[0047] Take 100.0 g of the S-1 carrier, impregnate it with Q-1, let it stand for 12 hours, dry it at 120 °C for 4.0 hours, and then calcine it at 400 °C for 6.0 hours to obtain the catalyst denoted as Cat-1.

[0048] Example 2

[0049] Dissolve 200.0 g of zinc chloride in 3000 g of 1,4-butanediol to obtain a solution denoted as G-2.

[0050] Add 200.0 g of S-0 and G-2 into the reactor, seal it with nitrogen, control the pressure of the reactor at 0.3 MPa, heat the reactor to 190 °C, and stir well. After reacting for 10.0 hours, the separated solid is denoted as Z-2.

[0051] Wash Z-2 with deionized water at 50 °C, with a dosage of 6000 ml of deionized water each time. After washing 6 times, perform activation treatment at 240 °C in an air atmosphere for 4.0 hours to obtain the carrier denoted as S-2.

[0052] Take 22.0 g of ammonium heptamolybdate tetrahydrate and 16.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 120 ml solution denoted as Q-2.

[0053] Take 100.0 g of the S-2 carrier, impregnate it with Q-2, let it stand for 12 hours, dry it at 120 °C for 4.0 hours, and then calcine it at 420 °C for 6.0 hours to obtain the catalyst denoted as Cat-2.

[0054] Example 3

[0055] Dissolve 150.0 g of zinc chloride in 3000 g of 1,2-butanediol to obtain a solution denoted as G-3.

[0056] Add 150.0 g of S-0 and G-3 into the reaction kettle, seal it with nitrogen, control the pressure of the reaction kettle at 0.3 MPa, heat the reaction kettle to 200 °C, and stir well. After reacting for 8.0 hours, the obtained solid is denoted as Z-3.

[0057] Wash Z-3 with deionized water at 50 °C, with the amount of deionized water used each time being 6000 ml. After washing 6 times, perform activation treatment at 300 °C in an air atmosphere for 3.0 hours. The obtained carrier is denoted as S-3.

[0058] Take 20.0 g of ammonium heptamolybdate tetrahydrate and 14.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 120 ml solution, denoted as Q-3.

[0059] Take 100.0 g of S-3 carrier, impregnate it with Q-3, let it stand for 12 hours, dry it at 120 °C for 4.0 hours, and then calcine it at 420 °C for 6.0 hours to obtain the catalyst denoted as Cat-3.

[0060] Comparative Example 1

[0061] Take 100.0 g of S-0 carrier, impregnate it with 120 ml of Q-2, let it stand for 12 hours, dry it at 120 °C for 4.0 hours, and then calcine it at 400 °C for 6.0 hours to obtain the catalyst denoted as DCT-1.

[0062] Comparative Example 2

[0063] Take 12.0 g of zinc nitrate, dissolve it in deionized water, and prepare an 110 ml solution, denoted as DG-2.

[0064] Take 100.0 g of carrier S-0, impregnate S-0 with DG-2, let it stand for 12 hours, dry it at 120 °C for 4.0 hours, and then calcine it at 400 °C for 6.0 hours to obtain the carrier denoted as DS-2.

[0065] Impregnate DS-2 with 110 ml of Q-2, let it stand for 12 hours, dry it at 120 °C for 4.0 hours, and then calcine it at 400 °C for 6.0 hours to obtain the catalyst denoted as DCT-2.

[0066] Comparative Example 3

[0067] Dissolve 150.0 g of zinc chloride in 3000 g of deionized water, and the obtained solution is denoted as DG-3.

[0068] Add 200.0 g of S-0 and DG-3 into the reaction kettle, seal it with nitrogen, control the pressure of the reaction kettle at 0.3 MPa, heat the reaction kettle to 90 °C, and stir well. After reacting for 8.0 hours, the obtained solid is denoted as DZ-3.

[0069] The DZ-3 was rinsed with deionized water at 50 °C. The amount of deionized water used each time was 6000 ml. After rinsing 6 times, it was dried at 240 °C for 4.0 hours. The obtained support was denoted as DS-3.

[0070] 100.0 g of the DS-3 support was taken and impregnated with 110 ml of Q-2. After standing for 12 hours, it was dried at 120 °C for 4.0 hours, and then calcined at 400 °C for 6.0 hours to obtain the catalyst denoted as DCT-3.

[0071] Catalyst sulfidation

[0072] 20.0 g of each of the catalysts Cat-1, Cat-2, Cat-3, DCT-1, DCT-2, and DCT-3 were taken for sulfidation. The sulfidation temperature was 320 °C, the sulfidation time was 12.0 hours, the pressure of hydrogen during sulfidation was 6.0 MPa, the space velocity of hydrogen was 20 ml / min·g catalyst, and the liquid hourly space velocity of the sulfiding solution was 1.0 h -1 , and the sulfiding agent was a cyclohexane solution of 5.0 wt% DMDS. The sulfided catalysts were denoted as SCT-1, SCT-2, SCT-3, DSCT-1, DSCT-2, and DSCT-3, respectively.

[0073] Table 1 Elemental analysis of the catalysts obtained in each example

[0074] Catalyst Number <![CDATA[MoO 3 / wt%]]> NiO / wt% ZnO / wt% <![CDATA[Al 2 O 3 / wt%]]> Cat-1 16.1 3.7 5.1 75.1 Cat-2 14.5 3.4 4.5 77.6 Cat-3 13.4 3.0 3.9 79.7 DCT-1 14.4 3.5 0 82.1 DCT-2 14.7 3.3 4.2 77.8 DCT-3 14.5 3.2 3.7 78.6

[0075] Table 2 Aluminum NMR analysis of the supports obtained in each example

[0076]

[0077]

[0078] Table 3 Properties of the supports obtained in each example

[0079] Support Number <![CDATA[Specific surface area, m 2 / g]]> Pore Volume, mL / g S-1 252 0.88 S-2 253 0.86 S-3 255 0.87 S-0 278 0.95 DS-2 251 0.88 DS-3 249 0.86

[0080] Table 4 TEM characterization analysis of the catalysts obtained in each example

[0081]

[0082] Examples 4 - 6

[0083] Poor-quality residue oil was selected as the raw material, and a fixed-bed hydrogenation process was used to conduct hydrogenation evaluation experiments on the sulfided catalysts SCT-1, SCT-2, and SCT-3 obtained in Examples 1 - 3 above. The properties of the residue oil hydrogenation product oil are shown in Table 5.

[0084] Table 5 Properties of the feedstock oil

[0085] Item Value Item Value <![CDATA[Density / g·cm -3 > 0.992 Nitrogen Content, μg / g 3599 Vanadium + Nickel Content, μg / g 37.30 H / C Atomic Ratio 1.62 Sulfur Content, μg / g 36690 Conradson Carbon Residue, % 18.6

[0086] Prior to the above catalyst, a hydrogenation protective agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), the protective agent, the hydrodemetallization catalyst, and the catalyst obtained in the example were loaded in a volume ratio of 1:2:4. The operating conditions were as follows: reaction temperature 395°C, reaction pressure 19.0 MPa, hydrogen-oil volume ratio 1600:1, and liquid hourly space velocity 0.15 h -1 . After 1500 h of reaction evaluation, the carbon residue value, sulfur content, and nitrogen content in the fraction of the hydrogenated product oil not lower than 300°C were analyzed, and the results are shown in Table 6.

[0087] Comparative Examples 4-6

[0088] Poor-quality residue oil (see Table 4) was selected as the raw material, and the fixed-bed process was used to evaluate the activities of the catalysts DSCT-1, DSCT-2, and DSCT-3 obtained in Comparative Examples 1-3, respectively. Prior to the above catalyst, a hydrogenation protective agent (FZC-100B), a hydrodemetallization catalyst (FZC-204A), the protective agent, the hydrodemetallization catalyst, and the catalyst obtained in the comparative example were loaded in a volume ratio of 1:2:4. The operating conditions were as follows: reaction temperature 395°C, reaction pressure 19.0 MPa, hydrogen-oil volume ratio 1600:1, and liquid hourly space velocity 0.15 h -1 . After 1500 h of reaction evaluation, the carbon residue value, sulfur content, and nitrogen content in the fraction of the hydrogenated product oil not lower than 300°C were analyzed, and the results are shown in Table 6.

[0089] Table 6 Properties of Fixed-Bed Hydrogenated Product Oil

[0090] Number Catalyst Nitrogen Content, μg / g Conradson Carbon Residue, % Sulfur Content, μg / g Example 4 Cat-1 663 3.3 671 Example 5 Cat-2 708 3.5 704 Example 6 Cat-3 721 3.7 556 Comparative Example 4 DCT-1 1362 5.6 1838 Comparative Example 5 DCT-2 1205 5.8 1968 Comparative Example 6 DCT-3 981 6.1 1702

[0091] It can be seen from the evaluation results in Table 6 that the catalyst of the present invention has good hydrodesulfurization, hydrodearbonization, and hydrodenitrogenation activities when deeply processing poor-quality residue oil raw materials.

Claims

1. A residue hydrodesulfurization catalyst, comprising a modified alumina support and a hydrogenation active metal component; the modified alumina support comprises alumina and a modifying assistant zinc, and the six-coordinated Al on the support accounts for 75%-95% of the total aluminum, preferably 80%-93%.

2. The catalyst according to claim 1, wherein, based on the mass of the support, the mass content of zinc calculated as ZnO is 1%-10%, preferably 2%-8%; and / or, based on the mass of the support, the mass content of alumina is 83%-99%, preferably 85%-98%.

3. The catalyst according to claim 1, wherein, The properties of the carrier are as follows: the specific surface area is 150 - 390 m 2 / g, preferably 180 - 360 m 2 / g, the pore volume of the carrier is 0.6 - 1.1 m 3 / g, preferably 0.7 - 1.0 m 3 / g.

4. The catalyst according to claim 1, wherein, the hydrogenation active metal component is selected from at least one of the metals in Group VIB and Group VIII; wherein, the metal in Group VIB is preferably selected from at least one of tungsten and molybdenum, and the metal in Group VIII is preferably selected from at least one of nickel and cobalt; preferably, based on the mass of the catalyst, the content of the metal in Group VIB calculated as the +6 valence oxide is 10%-35%, preferably 15%-28%, and the content of the metal in Group VIII calculated as the +2 valence oxide is 2%-10%, preferably 3%-8%.

5. The catalyst according to claim 1, wherein, the support further contains one or more of the conventional assistants silicon, phosphorus, and boron, and based on the mass of the support, the mass content of the conventional assistant calculated as the element is less than 5%.

6. A method for preparing the catalyst according to any one of claims 1-5, comprising: a step of loading the active metal component on the modified alumina support; wherein, the preparation method of the modified alumina support comprises: mixing an alumina support with an organic solution of zinc chloride, performing a closed heating treatment, and performing an activation treatment to obtain the modified alumina support.

7. The preparation method according to claim 6, wherein, the alumina support is an alumina-based support for a residue hydrotreating catalyst, preferably an alumina-based support for a residue hydrodesulfurization catalyst.

8. The preparation method according to claim 6, wherein, in the organic solution of zinc chloride, the organic solvent is one or more of glycerol, 1,4-butanediol, and 1,2-butanediol; and / or, in the organic solution of zinc chloride, the mass content of zinc chloride is 2%-15%, preferably 3%-12%.

9. The preparation method according to claim 6, wherein, the mass ratio of the alumina support to the organic solution of zinc chloride is 1:5-1:50, preferably 1:10-1:

30.

10. The preparation method according to claim 6, wherein, in the preparation method of the modified alumina support, the conditions of the closed heating treatment are as follows: inert atmosphere, pressure of 0.05-0.5 MPa, preferably 0.1-0.4 MPa, treatment temperature of 160-230 °C, preferably 180-210 °C, and treatment time of 4-24 hours, preferably 6-16 hours.

11. The preparation method according to claim 6, wherein, In the preparation method of the modified alumina support, the activation treatment conditions are as follows: the treatment temperature is 120 - 350 °C, preferably 160 - 320 °C, the treatment time is 2 - 10 hours, preferably 2 - 8 hours, and the treatment atmosphere is an oxygen-containing atmosphere.

12. According to the preparation method described in claim 6, wherein, the method for loading the active metal component on the modified alumina support adopts an impregnation method (preferably a saturated impregnation method). Preferably, the drying and calcination conditions after impregnation are as follows: the drying temperature is 80 - 200 °C, preferably 100 - 180 °C, the drying time is 2.0 - 10.0 hours, preferably 4.0 - 8.0 hours; the calcination temperature is 300 - 600 °C, preferably 350 - 500 °C, and the calcination time is 2.0 - 8.0 hours, preferably 3.0 - 5.0 hours.

13. Application of the catalyst according to any one of claims 1 - 5 or the catalyst prepared by the method according to any one of claims 6 - 12 in residue oil hydrotreating.

14. According to the application described in claim 13, wherein, The residue feedstock is a low-quality residue feedstock with high sulfur and nitrogen contents. The properties of the low-quality residue feedstock are as follows: the density is 0.95 - 1.05 g / cm 3 , the mass content of sulfur is 10000 ppm - 50000 ppm, the mass content of nitrogen is 800 - 5000 ppm, and the mass content of residual carbon is 10% - 25%.

15. According to the application described in claim 13 or 14, wherein, In the said application, the catalyst is used as a hydrodesulfurization catalyst; the hydroprocessing conditions are as follows: the reaction temperature is 300 - 450 °C, preferably 350 - 420 °C, the reaction pressure is 12 - 25 MPa, preferably 15 - 22 MPa, and the liquid hourly space velocity is 0.05 - 0.6 h -1 , preferably 0.1 - 0.4 h -1 .

Images