Modified alumina carrier, catalyst and preparation method and application thereof

Abstract

The invention discloses a modified alumina carrier, a catalyst and a preparation method and application thereof. The modified alumina carrier comprises alumina and a modification auxiliary agent, the modification auxiliary agent is M, and M is selected from at least one of IB, IIA, IIB, IIIA and VIA family elements; the hexa-coordinated Al on the carrier accounts for 75%-95% of the total aluminum. When the surface of the modified alumina carrier is mainly composed of hexa-coordinated aluminum, hydrogenation active metal components loaded subsequently can be uniformly dispersed, and the modified alumina carrier has high hydrogenation activity and stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of oil refining, and particularly relates to a modified alumina support, a catalyst, a preparation method thereof and an application thereof, and is particularly applicable to the process of residue oil hydrotreatment. Background Art

[0002] Residue oil hydrotreatment catalysts usually use γ-alumina as a support. The flatness of the support 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, very uneven metal distribution, rough surface, and stronger acidity in the areas with more cavities, and higher catalytic activity in the areas with higher dispersion of active metals, but poorer stability; on the contrary, in the areas with relatively flat surface and fewer cavities, the acidity is poor, the dispersion of active metals is low, and the catalyst has higher stability but poorer activity.

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

[0004] CN201310499295.7 discloses a preparation method of an alumina support for 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, impregnating the dried support with an unsaturated spray of a chemical pore-expanding agent; finally, drying and calcining the support impregnated with the chemical pore-expanding agent to obtain an alumina support for a residue oil hydrodemetallization catalyst. The alumina prepared by this method has 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 of an alumina support for a residue oil hydrotreatment 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 and molding with an alumina precursor, and then drying and calcining to obtain an alumina support. The specific surface area of the alumina support obtained by this method is relatively high, which is beneficial to removing large molecules in heavy and residue oils, thus being beneficial to maintaining the activity of the hydrotreatment catalyst and extending the operation cycle. However, as an alumina support, 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, wherein 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 subsequent loading of the active metal 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 modified alumina support, a catalyst, and their preparation methods and applications. The modified alumina support of the present invention has a uniform surface, enabling the subsequent loaded hydrogenation active metal components to be uniformly dispersed. When used in residue oil hydrogenation treatment, it has high hydrogenation activity and stability.

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

[0009] In a first aspect of the present invention, a modified alumina support is provided, which includes alumina and a modifying assistant. The modifying assistant is M, and M is selected from at least one of the elements in Groups IB, IIA, IIB, IIIA, and VIA; the six-coordinate Al on the support accounts for 75% - 95% of the total aluminum, preferably 80% - 93%.

[0010] Further, M is preferably selected from at least one of Cu, Ag, Au, Mg, Ca, Zn, Cd, Ga, and Se, and more preferably from at least one of Mg, Zn, and Ga.

[0011] Further, based on the mass of the modified alumina support, the mass content of M in terms of oxide is 1% - 12%, preferably 2% - 10%.

[0012] Further, based on the mass of the modified alumina support, the mass content of alumina is 83% - 99%, preferably 85% - 98%.

[0013] Further, the modified alumina support may also contain one or more of conventional additives such as silicon, phosphorus, boron, etc. Based on the mass of the modified alumina support, the mass content of the conventional additive in terms of the element is 5% or less.

[0014] Further, the modified alumina support is a support for a residue hydrotreating catalyst.

[0015] Further, the properties of the modified alumina support are as follows: the specific surface area is 150 - 420 m 2 / g, preferably 180 - 360 m 2 / g, the pore volume is 0.5 - 1.1 m 2 / g, preferably 0.6 - 0.9 m 2 / g.

[0016] The second aspect of the present invention provides a method for preparing the above-mentioned modified alumina support, including:

[0017] Mixing an alumina support with an organic solution of M chloride, performing 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 a residue hydrotreating catalyst. In the alumina support, in addition to alumina, it may 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 5% or less. Those skilled in the art can select the alumina support according to the requirements of the residue hydrotreating catalyst. For example, when preparing a residue hydrodenitrogenation catalyst, select an alumina support for a residue hydrodenitrogenation catalyst, and when preparing a hydrodesulfurization catalyst, select an alumina support for a residue hydrodesulfurization catalyst.

[0019] Further, in the organic solution of M chloride, the organic solvent is one or several of glycerol, 1,4-butanediol, 1,2-butanediol.

[0020] Further, in the organic solution of M chloride, the mass content of M chloride is 2% - 15%, preferably 3% - 12%.

[0021] Further, the mass ratio of the alumina support to the organic solution of M chloride is 1:5 - 1:50, preferably 1:10 - 1:30.

[0022] Further, the conditions of the closed heating treatment are as follows: inert atmosphere, the pressure is 0.05 - 0.5 MPa, preferably 0.1 - 0.4 MPa, the treatment temperature is 160 - 230 °C, preferably 180 - 210 °C, and the treatment time is 4 - 24 hours, preferably 6 - 16 hours.

[0023] Further, after the closed heating treatment, the solid is separated and washed with deionized water, preferably 2 - 10 times, at a washing temperature of 30 - 80°C, preferably 40 - 70°C. 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 carrier is subjected to an activation treatment under the following conditions: 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 a modified alumina carrier.

[0024] The modified alumina carrier of the present invention is particularly suitable as a carrier for a residue hydrotreating catalyst.

[0025] During the research process, the inventors of the present invention found that when the modifying additive component is Ga, the modified alumina carrier is suitable as a carrier for a hydrodenitrogenation catalyst. The catalyst prepared therefrom has good hydrodenitrogenation selectivity, is particularly suitable for processing the ebullated bed tail oil with poor oil properties, and has good hydrodenitrogenation activity and stability.

[0026] During the research process, the inventors of the present invention found that when the modifying additive component is Zn, the modified alumina carrier is suitable as a carrier for a hydrodesulfurization and hydrodenitrogenation catalyst. The catalyst prepared therefrom has good hydrodesulfurization and hydrodenitrogenation selectivity, is particularly suitable for treating poor residue oil raw materials with high sulfur and nitrogen contents, and has good desulfurization and denitrogenation activity and stability.

[0027] During the research process, the inventors of the present invention found that when the modifying additive component is Mg, the modified alumina carrier is suitable as a carrier for a hydrodearbonization catalyst. The catalyst prepared therefrom has good hydrodearbonization selectivity, is particularly suitable for treating heavy feedstocks with high carbon residue content such as poor heavy oil or residue oil, and has good hydrodearbonization activity and stability.

[0028] The third aspect of the present invention provides a residue hydrodenitrogenation catalyst, comprising the above-mentioned modified alumina carrier and a hydrogenation active metal component, wherein the modifying additive is Ga.

[0029] 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. Based on the mass of the catalyst, the content of the metal of Group VIB in terms of its +6 valence oxide is 10% - 35%, preferably 15% - 28%, and the content of the metal of Group VIII in terms of its +2 valence oxide is 2% - 10%, preferably 3% - 8%.

[0030] The fourth aspect of the present invention provides a method for preparing the above-mentioned residue hydrodenitrogenation catalyst, which includes the step of loading active metal components on a modified alumina support.

[0031] Further, the method for loading active metal components on the modified alumina support preferably adopts the impregnation method. When using the impregnation method for loading, after impregnation, through drying and calcination, the catalyst is obtained. 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.

[0032] The fifth aspect of the present invention provides the application of the above-mentioned catalyst in residue hydroprocessing.

[0033] Further, in the above application, the catalyst is used as a hydrodenitrogenation catalyst.

[0034] 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.

[0035] Further, the residue raw material can also be the ebullated bed tail oil with poor processed oil properties. Further, the properties of the ebullated bed hydrotreating tail oil include: 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%.

[0036] 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 .

[0037] Compared with the prior art, the present invention has the following advantages:

[0038] 1. The modified alumina support of the present invention is an M-modified alumina support. Using nuclear magnetic resonance characterization, it is mainly six-coordinated aluminum, that is, six-coordinated Al accounts for 75% - 95% of the total aluminum (preferably 80% - 93%). When this support is used as the support of the residue hydroprocessing catalyst, it can improve the activity and stability of the catalyst simultaneously.

[0039] 2. During the preparation of the modified alumina support 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 a high-boiling liquid at a relatively low temperature, thereby promoting the continuous dissolution of tetracoordinated aluminum in alumina into the solution to complete the dealumination process. At the same time, the M element in the solution will enter the surface of alumina to balance the charge, playing a role in modifying the surface of alumina during the whole process. The obtained modified alumina support mainly has hexacoordinated aluminum on the surface and has good surface uniformity. During the impregnation and loading of the active metal, it can be evenly dispersed on the surface of the support, with higher metal utilization rate. The prepared residue hydrotreating catalyst has better hydrogenation activity and stability.

[0040] 3. The hydrodenitrogenation catalyst of the present invention is particularly suitable for the residue hydrodenitrogenation treatment process and can improve the denitrification activity and stability of the catalyst simultaneously. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is the 27 Al MAS NMR spectrum of the alumina support obtained in Example 1;

[0042] Figure 2 is the 27 Al MAS NMR spectrum of the alumina support obtained in Comparative Example 1;

[0043] Figure 3 is the transmission electron micrograph of the catalyst obtained in Example 1;

[0044] Figure 4 is the transmission electron micrograph of the catalyst obtained in Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0045] The present invention will be further described below in conjunction with embodiments. However, it should be understood that the protection scope of the present invention is not limited by the embodiments. In the present invention, unless otherwise clearly stated, percentages and percentage contents are by mass.

[0046] In the present invention, the specific surface area and pore volume of the sample are measured by the physical adsorption method of liquid nitrogen on a Micromeritics ASAP 2020M.

[0047] 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 nuclear magnetic resonance spectrometer, with Topspin 2.0 software. During the measurement 27 of the Al MAS NMR spectra, aluminum chloride was used as the standard substance, with a resonance frequency of 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. Among them, the total aluminum refers to the sum of six - coordinated aluminum and four - coordinated aluminum.

[0048] 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 supernatant was taken and put into a sample bottle. After dilution with alcohol, it was placed in an ultrasonic oscillator for 20 min, 2 - 3 drops were added dropwise to the ultra - thin carbon film with a dropper, and the ethanol was evaporated 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 range of 10 nm, and each sample required at least 30 pictures with good shooting quality from different positions.

[0049] In the present invention, the unmodified alumina support S - 0 used in the following examples and comparative examples was prepared by the following method:

[0050] 1000.0 g of alumina dry gel powder was weighed, and 10.0 g of acetic acid, 10.0 g of citric acid, 20.0 g of sesbania powder, and 10.0 g of cellulose were added. After mixing evenly, 1200.0 g of an aqueous solution containing 2.0% by mass of nitric acid was added. After rolling for 20.0 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 294 m 2 / g, and pore volume was 0.90 cm 3 / g.

[0051] Example 1

[0052] 120.0 g of gallium chloride was dissolved in 3000 g of glycerol, and the resulting solution was denoted as G - 1.

[0053] Add 200.0 g of S-0 and G-1 into the reactor, seal it with nitrogen, control the reactor pressure at 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.

[0054] Wash Z-1 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-1.

[0055] Take 35.0 g of ammonium heptamolybdate tetrahydrate and 20.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 110 ml solution denoted as Q-1.

[0056] 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 400 °C for 6.0 hours to obtain the catalyst denoted as Cat-1.

[0057] Example 2

[0058] Dissolve 150.0 g of gallium chloride in 3000 g of 1,2-butanediol to obtain the solution denoted as G-2.

[0059] Add 200.0 g of S-0 and G-2 into the reactor, seal it with nitrogen, control the reactor pressure at 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.

[0060] 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.

[0061] Take 30.0 g of ammonium heptamolybdate tetrahydrate and 16.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 110 ml solution denoted as Q-2.

[0062] 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 400 °C for 6.0 hours to obtain the catalyst denoted as Cat-2.

[0063] Example 3

[0064] Dissolve 250.0 g of gallium chloride in 3000 g of 1,4-butanediol to obtain the solution denoted as G-3.

[0065] Add 200.0 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 6.0 hours, the obtained solid is denoted as Z-3.

[0066] 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.

[0067] Take 25.0 g of ammonium heptamolybdate tetrahydrate and 15.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 110 ml solution, denoted as Q-3.

[0068] Take 100.0 g of the 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 400 °C for 6.0 hours to obtain the catalyst denoted as Cat-3.

[0069] Example 4

[0070] Dissolve 110.0 g of zinc chloride in 3000 g of glycerol to obtain a solution denoted as G-4.

[0071] Add 200.0 g of S-0 and G-4 into the reaction kettle, seal it with nitrogen, control the pressure of the reaction kettle at 0.2 MPa, heat the reaction kettle to 200 °C, and stir well. After reacting for 10.0 hours, the separated solid is denoted as Z-4.

[0072] Wash Z-4 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 240 °C in an air atmosphere for 4.0 hours. The obtained carrier is denoted as S-4.

[0073] Take 35.0 g of ammonium heptamolybdate tetrahydrate and 20.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 110 ml solution, denoted as Q-4.

[0074] Take 100.0 g of the S-4 carrier, impregnate it with Q-4, 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-4.

[0075] Example 5

[0076] Dissolve 80.0 g of magnesium chloride in 3000 g of glycerol to obtain a solution denoted as G-5.

[0077] Add 200.0 g of S-0 and G-5 into the reaction kettle, seal it with nitrogen, control the pressure of the reaction kettle at 0.2 MPa, heat the reaction kettle to 200 °C, and stir well. After reacting for 10.0 hours, the separated solid is denoted as Z-5.

[0078] Wash Z-5 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 240 °C in an air atmosphere for 4.0 hours to obtain the carrier denoted as S-5.

[0079] Take 35.0 g of ammonium heptamolybdate tetrahydrate and 20.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 110 ml solution denoted as Q-5.

[0080] Take 100.0 g of S-5 carrier, impregnate it with Q-5, 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-5.

[0081] Example 6

[0082] Dissolve 110.0 g of copper chloride in 3000 g of glycerol to obtain the solution denoted as G-6.

[0083] Add 200.0 g of S-0 and G-6 into the reaction kettle, seal it with nitrogen, control the pressure of the reaction kettle at 0.2 MPa, heat the reaction kettle to 200 °C, and stir well. After reacting for 10.0 hours, the separated solid is denoted as Z-6.

[0084] Wash Z-6 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 240 °C in an air atmosphere for 4.0 hours to obtain the carrier denoted as S-6.

[0085] Take 35.0 g of ammonium heptamolybdate tetrahydrate and 20.0 g of nickel nitrate hexahydrate, dissolve them in deionized water, and prepare a 110 ml solution denoted as Q-6.

[0086] Take 100.0 g of S-6 carrier, impregnate it with Q-6, 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-6.

[0087] Comparative Example 1

[0088] Take 100.0 g of S-0 carrier, impregnate it 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-1.

[0089] Comparative Example 2

[0090] Take 12.0 g of gallium nitrate and dissolve it in deionized water to prepare a 110 ml solution, denoted as DG-2.

[0091] Take 100.0 g of support S-0, impregnate S-0 with DG-2, after standing 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 a support denoted as DS-2.

[0092] Impregnate DS-2 with 110 ml of Q-2, after standing 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 a catalyst denoted as DCT-2.

[0093] Comparative Example 3

[0094] Dissolve 150.0 g of gallium chloride in 3000 g of deionized water, and the resulting solution is denoted as DG-3.

[0095] Add 200.0 g of S-0 and DG-3 together to a reaction kettle, seal it with nitrogen, control the pressure of the reaction kettle to 0.3 MPa, heat the reaction kettle to 90 °C, and stir well. After reacting for 6.0 hours, the resulting solid is denoted as DZ-3.

[0096] Wash DZ-3 with deionized water at 50 °C, with the amount of deionized water used each time being 6000 ml. After washing 6 times, dry it at 240 °C for 4.0 hours to obtain a support denoted as DS-3.

[0097] Take 100.0 g of the DS-3 support, impregnate it with 110 ml of Q-2, after standing 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 a catalyst denoted as DCT-3.

[0098] Catalyst sulfidation

[0099] Sulfidate catalysts Cat-1, Cat-2, Cat-3, Cat-4, Cat-5, Cat-6, DCT-1, DCT-2, DCT-3 respectively. The sulfidation temperature is 320 °C, the sulfidation time is 12.0 hours, the pressure of hydrogen during sulfidation is 5.0 MPa, the space velocity of hydrogen is 20 ml / min·g 催化剂 , and the liquid hourly space velocity of the sulfidation solution is 1.0 h -1 , and the sulfiding agent is a cyclohexane solution of 5.0% by mass of DMDS. The sulfided catalysts are denoted as SCT-1, SCT-2, SCT-3, SCT-4, SCT-5, SCT-6, DSCT-1, DSCT-2, DSCT-3 respectively.

[0100] Table 1 conducts elemental analysis on the catalysts obtained in each example

[0101]

[0102]

[0103] Table 2 Aluminum NMR analysis of the carriers obtained in each example

[0104]

[0105] Table 3 Properties of the carriers obtained in each example

[0106] Carrier Number <![CDATA[Specific surface area, m 2 / g]]> Pore Volume, mL / g S-1 265 0.82 S-2 263 0.80 S-3 266 0.81 S-4 268 0.80 S-5 262 0.81 S-6 271 0.79 S-0 294 0.90 DS-2 260 0.80 DS-3 262 0.79

[0107] Table 4 TEM characterization analysis of the catalysts obtained in each example

[0108]

[0109] Examples 7 - 12

[0110] The hydrotreated residuum from ebullated bed was selected as the raw material, and the fixed - bed hydrotreating process was adopted. The hydrotreating evaluation experiments were carried out on the catalysts SCT - 1, SCT - 2, SCT - 3, SCT - 4, SCT - 5, and SCT - 6 which were obtained from the above Examples 1 - 6 and sulfided. The properties of the hydrotreated residuum from ebullated bed are shown in Table 5.

[0111] Table 5 Properties of the hydrotreated residuum from ebullated bed

[0112] Item Value Item Value <![CDATA[Density / g·cm -3 > 0.963 Nitrogen Content, μg / g 3411 Vanadium + Nickel Content, μg / g 53.20 H / C Atomic Ratio 1.74 Sulfur Content, μg / g 8385 Conradson Carbon Residue, % 13.1

[0113] The hydrotreating protective agent (FZC - 100B), the hydrodemetallization catalyst (FZC - 204A) were loaded before the above catalysts. The loading volume ratio of the protective agent, the hydrodemetallization catalyst, and the catalysts obtained in the examples was 1:2:4. The operating conditions were: reaction temperature 385 °C, reaction pressure 18.0 MPa, hydrogen - to - oil volume ratio 1500:1, and liquid hourly space velocity 0.2 h -1 . After 1500 h of reaction evaluation, the carbon residue value, sulfur content, and nitrogen content in the fraction of the hydrotreated oil not lower than 300 °C were analyzed, and the results are shown in Table 6.

[0114] Comparative Examples 4 - 6

[0115] The fluidized-bed residue hydroprocessing product oil (see Table 4) was selected as the raw material, and the fixed-bed process was adopted to evaluate the activities of the catalysts DSCT-1, DSCT-2, and DSCT-3 obtained in Comparative Examples 1-3, respectively. A hydrotreating protective agent (FZC-100B) and a hydrodemetallization catalyst (FZC-204A) were loaded in front of the above catalysts. The loading volume ratio of the protective agent, the hydrodemetallization catalyst, and the catalyst obtained in the comparative example was 1:2:4. The operating conditions were: reaction temperature 385 °C, reaction pressure 18.0 MPa, hydrogen-oil volume ratio 1500:1, and liquid hourly space velocity 0.2 h -1 . After 1500 h of reaction evaluation, the carbon residue value, sulfur content, and nitrogen content in the fraction of the hydroprocessing product oil not lower than 300 °C were analyzed, and the results are shown in Table 6.

[0116] Table 6 Properties of Fixed-Bed Hydroprocessing Product Oil

[0117] Number Catalyst Nitrogen Content, μg / g Conradson Carbon Residue, % Sulfur Content, μg / g Example 7 Cat-1 310 2.2 521 Example 8 Cat-2 357 2.4 563 Example 9 Cat-3 375 2.5 589 Example 10 Cat-4 490 2.7 410 Example 11 Cat-5 521 2.1 554 Example 12 Cat-6 514 3.0 688 Comparative Example 4 DCT-1 664 4.6 1121 Comparative Example 5 DCT-2 652 4.7 1061 Comparative Example 6 DCT-3 562 3.6 857

[0118] It can be seen from the evaluation results in Table 6 that the catalyst of the present invention has good hydrodenitrogenation, hydrodesulfurization, and hydrodearbonization activities when deeply processing the fluidized-bed residue hydroprocessing product oil with low sulfur. In particular, the hydrotreating catalyst using Ga as the promoter has outstanding hydrodenitrogenation performance.

Claims

1. A modified alumina support, comprising alumina and a modifying agent M, where M is selected from at least one of the elements in Groups IB, IIA, IIB, IIIA, and VIA; the six-coordinate Al on the support accounts for 75%-95% of the total aluminum, preferably 80%-93%.

2. The modified alumina support according to claim 1, wherein, M is selected from at least one of Cu, Ag, Au, Mg, Ca, Zn, Cd, Ga, and Se, preferably at least one of Mg, Zn, and Ga.

3. The modified alumina support according to claim 1, wherein, Based on the mass of the modified alumina support, the mass content of M in terms of oxide is 1%-12%, preferably 2%-10%; and / or, based on the mass of the modified alumina support, the mass content of alumina is 83%-99%, preferably 85%-98%.

4. The modified alumina support according to claim 1, wherein, The modified alumina support is a support for residue hydrotreating catalysts. Preferably, the properties of the modified alumina support are as follows: the specific surface area is 150 - 420 m 2 / g, preferably 180 - 360 m 2 / g, the pore volume is 0.5 - 1.1 mL / g, preferably 0.6 - 0.9 mL / g.

5. The modified alumina support according to claim 1, wherein, The modified alumina support further contains one or more of the conventional agents silicon, phosphorus, and boron, and based on the mass of the modified alumina support, the mass content of the conventional agent in terms of element is 5% or less.

6. A method for preparing the modified alumina support according to any one of claims 1-4, comprising: Mixing an alumina support with an organic solution of M chloride, performing a closed heating treatment, and 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.

8. The preparation method according to claim 6, wherein, In the organic solution of M chloride, the organic solvent is one or more of glycerol, 1,4-butanediol, and 1,2-butanediol; and / or, in the organic solution of M chloride, the mass content of M 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 M chloride is 1:5 - 1:50, preferably 1:10 - 1:

30.

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

12. The application of the modified alumina support according to any one of claims 1-5 or the modified alumina support prepared by the method according to any one of claims 6-11 in a residue hydrotreating catalyst.

13. A residue hydrodenitrogenation catalyst, comprising the modified alumina support as described in any one of claims 1-5 or the modified alumina support prepared by any one of the methods described in claims 6-11, and a hydrogenation active metal component, wherein the modifying agent in the modified alumina support is preferably Ga.

14. The catalyst according to claim 13, wherein, the hydrogenation active metal component is selected from at least one of the metals of Group VIB and Group VIII; wherein, 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; preferably, based on the mass of the catalyst, the content of the metal of Group VIB in terms of the +6 valence oxide is 10%-35%, preferably 15%-28%, and the content of the metal of Group VIII in terms of the +2 valence oxide is 2%-10%, preferably 3%-8%.

15. Use of the catalyst according to claim 13 or 14 in residue hydroprocessing.

16. The use according to claim 13, wherein, 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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