Residual oil hydrogenation carbon residue removal catalyst as well as preparation method and application thereof

Abstract

The invention discloses a residual oil hydrogenation carbon residue removal catalyst as well as a preparation method and application thereof. The residual oil hydrogenation carbon residue removal catalyst comprises a modified alumina carrier and a hydrogenation active metal component, the modified aluminum oxide carrier comprises aluminum oxide and a modification additive, the modification additive is magnesium, and hexa-coordinated Al on the carrier accounts for 75-95% of the total aluminum. The catalyst provided by the invention has good hydrogenation carbon residue removal performance, and is especially suitable for processing boiling bed hydrogenation tail oil with poor oil product properties.

Description

Technical Field

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

[0002] Residue hydrotreating catalysts usually use γ-aluminum oxide 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; on the contrary, 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 catalysts, researchers have proposed various modification methods for alumina carriers.

[0004] CN201310499295.7 discloses a preparation method for an alumina carrier of a residue hydrodemetallization catalyst. The method includes: first, physically expanding agent, pseudo-boehmite dry gel powder, extrusion aid, and peptizing agent are kneaded into a plastic body, extruded into strips, and dried; then the dried carrier is impregnated with an unsaturated spray of a chemical expanding agent; finally, the carrier impregnated with the chemical expanding agent is dried and calcined to obtain an alumina carrier of a residue hydrodemetallization catalyst. The alumina prepared by this method has an excellent pore structure, but its surface uniformity has 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 hydrotreating catalyst. The method uses activated carbon fibers with a well-developed pore structure as an expanding agent after impregnating and adsorbing inorganic aluminum salts, kneads and shapes them with an alumina precursor, and then dries and calcines them 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 oil and residue oil, thus being beneficial to maintaining the activity of the hydrotreating 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 preparation method for an alumina carrier. The method includes neutralizing acidic aluminum salt and basic aluminate, aging the neutralized material, and then filtering, washing, shaping, drying, and calcining to obtain an alumina carrier, where the aging is carried out under conditions of a temperature higher than the neutralization temperature and a pH value of neutralization. The surface of the alumina carrier prepared by this method also has poor uniformity, affecting the subsequent loading of active metals and the overall activity of the catalyst. SUMMARY OF THE INVENTION

[0007] In view of the deficiencies in the prior art, the present invention provides a residue hydrotreating catalyst for removing carbon residue, a preparation method thereof, and an application thereof. The catalyst of the present invention has good performance in hydrotreating carbon residue and is particularly suitable for processing the ebullated bed tail oil with poor oil properties.

[0008] In γ-aluminum oxide, there are mainly two forms of existence of Al. One is the stable six-coordinated framework aluminum, which shows a displacement of -10 - 30 ppm in the Al nuclear magnetic resonance. The other is the less stable four-coordinated non-framework aluminum, which shows a displacement of 40 - 80 ppm in the Al nuclear magnetic resonance. The inventors have found through research that when the surface of aluminum oxide is mainly composed of six-coordinated aluminum, it can make the surface of aluminum oxide flat and the properties uniform, while improving the activity and stability of the catalyst. The inventors creatively introduce magnesium element into the surface of aluminum oxide while removing non-framework aluminum, which can make the surface of aluminum oxide flat and the properties uniform, thereby realizing the present invention.

[0009] In a first aspect of the present invention, there is provided a residue hydrotreating catalyst for removing carbon residue, comprising a modified alumina support and a hydrogenation active metal component; the modified alumina support comprises alumina and a modifying assistant, the modifying assistant is magnesium, and the six-coordinated Al on the support accounts for 75% - 95% of the total aluminum, preferably 80% - 90%.

[0010] Further, based on the mass of the support, the mass content of magnesium calculated as MgO is 1% - 12%, preferably 2% - 10%.

[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 further 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 calculated as an element is less than 5%.

[0013] Further, the properties of the support are as follows: the specific surface area is 180 - 420 m 2 / g, preferably 220 - 360 m 2 / g, the pore volume is 0.5 - 1.1 m 2 / g, preferably 0.6 - 1.0 m 2 / g.

[0014] Further, the hydrogenation active metal component is selected from at least one of the metals of Group VIB and Group VIII. Among them, the metal of Group VIB is preferably selected from at least one of tungsten and molybdenum, and the metal of Group VIII is preferably selected from at least one of nickel and cobalt.

[0015] Further, based on the mass of the catalyst, the content of the Group VIB metal in terms of its +6 valent oxide is 10% - 32%, preferably 15% - 26%, and the content of the Group VIII metal in terms of its +2 valent oxide is 2% - 8%, preferably 3% - 7%.

[0016] Further, based on the mass of the catalyst, the content of the modified alumina support is 55% - 88%, preferably 64% - 82%.

[0017] In the second aspect of the present invention, there is provided a method for preparing the above catalyst, including the preparation of a modified alumina support and the loading of a hydrogenation active metal component, wherein the method for preparing the modified alumina support includes: mixing an alumina support with an organic solution of magnesium chloride, subjecting it to a closed heating treatment, and an activation treatment to obtain a modified alumina support.

[0018] Further, 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 additives, such as one or more of silicon, phosphorus, boron, etc. In the alumina support, the mass content of the additive in terms of the element accounts for less than 5%.

[0019] Further, in the method for preparing the modified alumina support, in the organic solution of magnesium chloride, the organic solvent is one or several of glycerol, 1,4 - butanediol, and 1,2 - butanediol.

[0020] Further, in the method for preparing the modified alumina support, in the organic solution of magnesium chloride, the mass content of magnesium chloride is 2% - 10%, preferably 3% - 8%.

[0021] Further, in the method for preparing the modified alumina support, the mass ratio of the alumina support to the organic solution of magnesium chloride is 1:5 - 1:50, preferably 1:10 - 1:30.

[0022] Further, in the method for preparing 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.

[0023] 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, preferably 10 - 40 times that of the solid to be washed. 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.

[0024] Further, the method for loading the active metal component on the modified alumina support preferably adopts the impregnation method, and more preferably the equal-volume 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.

[0025] The third aspect of the present invention provides the application of the above catalyst in residue hydrotreatment. Further, in the said application, the catalyst is used as a hydrodesulfurization catalyst.

[0026] 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.

[0027] Further, the residue raw material can also be the ebullated bed hydrotreating tail oil with poor processed oil properties. Further, the properties of the ebullated bed hydrotreating tail oil include: the density is 0.90 - 1.05 g / cm 3 , the sulfur mass content is 1000 - 15000 ppm, preferably 1500 - 12000 ppm, the nitrogen mass content is 500 - 5000 ppm, and the residue carbon mass content is 5% - 25%.

[0028] Further, the hydrotreatment 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 .

[0029] Compared with the prior art, the present invention has the following advantages:

[0030] 1. The catalyst of the present invention uses a modified alumina support. By nuclear magnetic resonance characterization, it mainly consists of six - coordinated aluminum, that is, six - coordinated Al accounts for 75% - 95% of the total aluminum (preferably 80% - 90%). When used in the residue hydrotreating process, it can improve the hydro - decarbonization activity and stability of the catalyst.

[0031] 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 form AlCl 3 , since aluminum chloride is a covalent compound with very low melting and boiling points and can sublime, it can volatilize from a high - boiling liquid at a relatively low temperature, thereby promoting the continuous dissolution of four - coordinated aluminum in alumina into the solution to complete the dealumination process. At the same time, magnesium elements in the solution will enter the alumina surface to balance the charge and play a role in modifying the alumina surface during the whole process. The obtained modified alumina support mainly consists of six - coordinated aluminum on the surface and has 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 hydro - decarbonization catalyst has better hydro - decarbonization activity and stability. 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, nuclear magnetic resonance spectroscopy (NMR method) is used to obtain 27Al MAS NMR spectra were obtained to determine 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) was performed using a Bruker AVANCE III 500 NMR spectrometer, with Topspin 2.0 software. During the measurement 27 of the Al MAS NMR spectra, aluminum chloride was used as the reference substance, and the resonance frequency was 133 MHz. The experimental conditions were: a pulse width of 4 - 6 microseconds and a relaxation delay of 60 - 120 seconds. The obtained 27 Al MAS NMR spectra showed that the chemical shift corresponding to six - coordinated framework aluminum was - 10 - 30 ppm, and the chemical shift corresponding to four - coordinated non - framework aluminum was 40 - 80 ppm. Total aluminum refers to the sum of six - coordinated aluminum and four - coordinated aluminum.

[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 was a JEOL JEM 2100 transmission electron microscope with an acceleration voltage of 120 kV. The sulfided catalyst was stored in ethanol. During the test, the sample was placed in a mortar, ground with a small amount of alcohol for 10 minutes, allowed to stand for a while, and the upper clear liquid was taken and put into a sample bottle. After dilution with alcohol, it was treated in an ultrasonic oscillator for 20 min, 2 - 3 drops were added to the ultra - thin carbon film with a dropper, and the ethanol was volatilized with a baking lamp. After drying was completed, the sample was tested under the microscope. To analyze the platelet dispersion state of the active metal on the catalyst, the field of view was adjusted to a 10 - nm range, and at least 30 pictures with good shooting quality from different positions were required for each sample.

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

[0041] 1000.0 g of alumina dry gel powder was weighed, 20.0 g of acetic acid, 20.0 g of citric acid, 30.0 g of sesbania powder, and 20.0 g of cellulose were added and mixed evenly. Then, 1100.0 g of an aqueous solution containing 1.5% by mass of nitric acid was added. After rolling for 15.0 min, it was extruded through a three - leaf orifice plate with a diameter of 1.8 mm. After drying at 140 °C for 4.0 h, it was calcined at 600 °C for 4.0 h. The calcined support was denoted as S - 0. The properties of the support were as follows: specific surface area was 312 m 2 / g, and pore volume was 0.88 cm 3 / g.

[0042] Example 1

[0043] 250.0 g of magnesium chloride was dissolved in 3000 g of glycerol, and the resulting solution was denoted as G - 1.

[0044] Add 200.0 g of S-0 and G-1 to the reactor, seal it with nitrogen, control the reactor pressure to 0.2 MPa, heat the reactor to 200 °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 60 °C, with a deionized water dosage of 6000 ml each time. After washing 6 times, perform activation treatment at 240 °C in an air atmosphere for 4.0 hours to obtain the support denoted as S-1.

[0046] Take 30.0 g of ammonium heptamolybdate tetrahydrate and 20.0 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 support, 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 420 °C for 6.0 hours to obtain the catalyst denoted as Cat-1.

[0048] Example 2

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

[0050] Add 200.0 g of S-0 and G-2 to the reactor, seal it with nitrogen, control the reactor pressure to 0.3 MPa, heat the reactor to 190 °C, and stir well. After reacting for 6.0 hours, the separated solid is denoted as Z-2.

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

[0052] 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-2.

[0053] Take 100.0 g of the S-2 support, 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 magnesium chloride in 3000 g of 1,2-butanediol to obtain the solution denoted as G-3.

[0056] Add 200.0 g of S-0 and G-3 to 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 6.0 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 support is denoted as S-3.

[0058] Take 22.0 g of ammonium heptamolybdate tetrahydrate and 15.0 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 the S-3 support, 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 the S-0 support, 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 420 °C for 6.0 hours to obtain the catalyst denoted as DCT-1.

[0062] Comparative Example 2

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

[0064] Take 100.0 g of the support 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 support 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 420 °C for 6.0 hours to obtain the catalyst denoted as DCT-2.

[0066] Comparative Example 3

[0067] Dissolve 150.0 g of magnesium 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 to 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 6.0 hours, the obtained solid is denoted as DZ-3.

[0069] The DZ-3 was rinsed with deionized water at 50 °C, with 6000 ml of deionized water used each time. After rinsing 6 times, it was dried at 240 °C for 4.0 hours, and 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 420 °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 hydrogen pressure during sulfidation was 5.0 MPa, the hydrogen space velocity was 20 ml / min·g 催化剂 , and the liquid hourly space velocity of the sulfidation solution was 1.0 h -1 . 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% MgO / wt% <![CDATA[Al 2 O 3 / wt%]]> Cat-1 18.6 3.9 3.7 73.8 Cat-2 16.1 3.7 3.3 76.9 Cat-3 14.5 3.2 2.7 79.6 DCT-1 16.0 3.5 0 80.5 DCT-2 16.2 3.6 2.6 77.6 DCT-3 16.1 3.6 3.1 77.2

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

[0076]

[0077] Table 3 Properties of the supports obtained in each example

[0078] Support Number Specific Surface Area, m2 / g Pore Volume, mL / g S-1 266 0.79 S-2 271 0.80 S-3 270 0.79 S-0 312 0.88 DS-2 273 0.77 DS-3 275 0.78

[0079] Table 4 TEM characterization analysis of the catalysts obtained in each example

[0080]

[0081] Examples 4 - 6

[0082] The hydrocracked residue oil from the ebullated bed was selected as the raw material, and the fixed-bed hydrotreating process was used to conduct hydrotreating evaluation experiments on the sulfided catalysts SCT-1, SCT-2, and SCT-3 obtained in Examples 1 - 3 above. The properties of the hydrocracked residue oil from the ebullated bed are shown in Table 5.

[0083] Table 5 Properties of the hydrocracked residue oil from the ebullated bed

[0084] Item Value Item Value <![CDATA[Density / g·cm -3 > 0.980 Nitrogen Content, μg / g 3292 Vanadium + Nickel Content, μg / g 39.6 H / C Atomic Ratio 1.51 Sulfur Content, μg / g 23051 Conradson Carbon Residue, % 17.9

[0085] 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: reaction temperature 380 °C, reaction pressure 20.0 MPa, hydrogen-oil volume ratio 1800:1, and liquid hourly space velocity 0.25 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.

[0086] Comparative Examples 4-6

[0087] The fluidized bed residue hydroprocessing product 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: reaction temperature 380 °C, reaction pressure 20.0 MPa, hydrogen-oil volume ratio 1800:1, and liquid hourly space velocity 0.25 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.

[0088] Table 6 Properties of Fixed Bed Hydrogenated Product Oil

[0089]

[0090]

[0091] It can be seen from the evaluation results in Table 6 that the catalyst of the present invention has good hydrodesulfurization activity and good hydrodenitrogenation and hydrodesulfurization activities when deeply processing the fluidized bed residue hydroprocessing product oil with low sulfur.

Claims

1. A residue hydrodesulfurization catalyst for residue oil, comprising a modified alumina support and a hydrogenation active metal component; the modified alumina support comprises alumina and a modifying assistant, the modifying assistant is magnesium, and the six-coordinated Al on the support accounts for 75%-95% of the total aluminum, preferably 80%-90%.

2. The catalyst according to claim 1, wherein, based on the mass of the support, the mass content of magnesium calculated as MgO is 1%-12%, preferably 2%-10%; 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 180 - 420 m 2 / g, preferably 220 - 360 m 2 / g, the pore volume is 0.5 - 1.1 mL / g, preferably 0.6 - 1.0 mL / g.

4. 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 an element is 5% or less.

5. 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; 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; preferably, based on the mass of the catalyst, the content of the metal in Group VIB calculated as a +6 valence oxide is 10%-32%, preferably 15%-26%, and the content of the metal in Group VIII calculated as a +2 valence oxide is 2%-8%, preferably 3%-7%.

6. The preparation method of the catalyst according to any one of claims 1-5, comprising: preparation of a modified alumina support and loading of a hydrogenation active metal component, wherein the preparation method of the modified alumina support comprises: mixing an alumina support with an organic solution of magnesium chloride, performing a closed heating treatment, and performing an activation treatment to obtain a 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 magnesium chloride, the organic solvent is one or several of glycerol, 1,4-butanediol, and 1,2-butanediol; and / or, in the organic solution of magnesium chloride, the mass content of magnesium chloride is 2%-10%, preferably 3%-8%.

9. The preparation method according to claim 6, wherein, the mass ratio of the alumina support to the organic solution of magnesium 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, 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, it is characterized in that the method for loading the active metal component on the modified alumina support adopts the 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, it is characterized in that In the said application, the catalyst is used as a hydrodenitrogenation 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 .

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