CN110773188A

CN110773188A - Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof

Info

Publication number: CN110773188A
Application number: CN201810857085.3A
Authority: CN
Inventors: 孙淑玲; 杨清河; 马云海; 胡大为; 王振; 曾双亲; 桑小义; 邵志才
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 2018-07-31
Filing date: 2018-07-31
Publication date: 2020-02-11

Abstract

The invention relates to a heavy oil hydrogenation deasphalting catalyst and a preparation method and application thereof, wherein the catalyst contains a carrier and hydrogenation active metal components, wherein the carrier contains alumina, IVB group metal elements and hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, the content of the hydrogenation metal elements is 0.3-20 wt% and the content of the IVB group metal elements is 0.5-8 wt% based on oxides and the carrier. The preparation method of the heavy oil hydrogenation deasphalting catalyst comprises the steps of preparing an alumina carrier containing alumina, IVB group metal elements and hydrogenation metal elements and introducing hydrogenation active components. The hydrogenation deasphalted catalyst provided by the invention is used for heavy oil processing, and shows better hydrogenation demetalization activity, deasphalted and carbon residue removal activity.

Description

Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof

Technical Field

The invention relates to a heavy oil hydrogenation catalyst, in particular to a heavy oil hydrogenation deasphalting catalyst and preparation and application thereof.

Background

The deep processing of heavy oil including residual oil is favorable to raising the utilization rate of crude oil, remitting the tension trend of energy supply, reducing environmental pollution and reaching the clean utilization of energy. Compared with distillate oil, heavy oil contains a large amount of macromolecular reactants such as asphaltene and colloid, and heteroatom compounds such as sulfur, nitrogen, oxygen and the like, heavy metals such as nickel, vanadium and the like and polycyclic aromatic hydrocarbon in the heavy oil are mostly concentrated in the asphaltene, and the impurities and the heavy metals can pollute corresponding catalysts in the subsequent processing process, so that the hydroconversion of the asphaltene is a critical step in the residual oil hydrogenation process. In the process of converting and removing asphaltene, a catalyst with high activity, good stability and excellent performance needs to be selected according to the characteristics of the asphaltene.

For deasphalted hydrogenation catalysts, the pore size distribution of the catalyst has very important significance on the performance of the catalyst. The molecular size of asphaltene is about tens to hundreds of nanometers, and if the distance between the active centers of the catalyst is smaller than that of asphaltene molecules, the asphaltene molecules are difficult to contact with the active centers of the catalyst through diffusion, but are mainly adsorbed on the outer surface or the pore openings of the catalyst, and only coke can be formed due to thermal condensation as the reaction progresses, so that the catalyst is deactivated. The macroporous catalyst is favorable for removing the asphaltene, but the pore diameter and the specific surface of the catalyst are mutually in negative correlation, namely the catalyst with large average pore diameter has small specific surface area. Therefore, to compromise this property, a reasonable pore distribution is required for the catalyst.

The existing heavy oil hydrogenation catalyst has the disadvantage that the S, N removal rate, the heavy metal removal rate and the asphaltene removal rate cannot be well matched, for example, the catalyst with high metal removal activity is usually low in both the S, N removal rate and the asphaltene removal rate. The reasons for such problems are complicated. Firstly, the raw material, each component in the residual oil is characterized by large molecular weight, complex structure, low saturation degree (high aromaticity) and high S, N content. Most of the impurities, except sulfur, are present in asphaltenes, so to remove S, N, the asphaltene molecules must be subjected to moderate conversion (including saturation, ring opening, hydrogenolysis, etc.). And secondly in the catalyst. Catalysts having pore sizes suitable for carrying out such reactions are in the prior art protective catalysts and demetallization catalysts, for example:

CN1267537C discloses a hydrodemetallization catalyst with lower carbon deposition amount and higher activity and a preparation method thereof. CN1796500A discloses a residual oil hydrodemetallization catalyst, which is composed of a carrier with double pores and molybdenum and/or tungsten and cobalt and/or nickel metal components loaded on the carrier. The preparation method of the carrier used for the catalyst comprises the steps of mixing an alumina precursor and a nitrogen-containing compound except acid, forming and roasting. CN1233795C discloses a heavy oil fixed bed hydrotreating catalyst and a preparation method thereof. However, the asphaltene removal rate of these catalysts is generally low.

Disclosure of Invention

The invention aims to provide a novel catalyst with better hydrogenation and deasphalting performance, a preparation method and application thereof. Specifically, the present invention relates to the following:

the invention provides a heavy oil hydrogenation deasphalting catalyst, which comprises a carrier and hydrogenation active metal components, wherein the carrier contains alumina, at least one IVB group metal element and hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, the content of the IVB group metal elements in the carrier is 0.5-8 wt% and the content of the hydrogenation metal elements is 0.3-20 wt% based on oxides and the carrier.

According to the heavy oil hydrodeasphaltene catalyst provided by the invention, preferably, the hydrogenation metal elements comprise at least one VIB group metal element, at least one VIII group metal element and optionally a VB group metal element, and the content of the VIB group metal element, the VIII group metal element and the VB group metal element is 0.2-10 wt%, 0.1-5 wt% and 0-12 wt% based on the oxide and the carrier.

According to any one heavy oil hydrodeasphaltene catalyst provided by the invention, preferably, in the carrier, the VIB group metal element is molybdenum and/or tungsten, the VIII group metal element is cobalt and/or nickel, the VB group metal element is vanadium and/or niobium, and the IVB group metal element is one or more selected from titanium, zirconium and hafnium; the content of the IVB metal element in the carrier is preferably 1-6 wt%, more preferably 1.5-4 wt%, and the content of the VIB metal element in the carrier is 0.5-9 wt%, preferably 1-8 wt%, calculated by oxide and based on the carrier; the content of the group VIII metal element is 0.1 to 4% by weight, preferably 0.1 to 3% by weight, and the content of the group VB metal element is 0 to 10% by weight, preferably 0 to 8% by weight.

According to any one of the heavy oil hydrodeasphaltene catalysts provided by the invention, preferably, the support is characterized by a mercury intrusion method, the support is in bimodal pore distribution at a diameter of 5-20nm and a diameter of 100-500nm, the pore volume of the pores with the diameter of 5-20nm accounts for 55-80% of the total pore volume, and the pore volume of the pores with the diameter of 100-500nm accounts for 10-35% of the total pore volume; further preferably, the pore volume of pores with a diameter of 5-20nm accounts for 60-75% of the total pore volume, and the pore volume of pores with a diameter of 100-500nm accounts for 15-30% of the total pore volume.

According to the heavy oil hydrodeasphaltene catalyst provided by the invention, preferably, the pore volume of the carrier is 0.95-1.6 ml/g, and the specific surface area is 50-400 m ²Per gram; further preferably, the carrier has a pore volume of0.95-1.55 ml/g, specific surface area of 80-350 m ²Per gram.

According to any one of the heavy oil hydrodeasphaltene catalysts provided by the invention, preferably, the alumina is selected from bimodal porous aluminas having single or mixed crystalline phases of gamma-, η -, theta-, and delta-.

According to the heavy oil hydrodeasphaltene catalyst provided by the invention, preferably, the hydrogenation active metal component is selected from at least one VIB group metal component, at least one VIII group metal component and optionally a VB group metal component, wherein the content of the VIB group metal component is 1-10 wt%, the content of the VIII group metal component is 0.5-6 wt% and the content of the VB group metal component is 0-12 wt% calculated by oxide and based on the catalyst; further preferably, the metal component of the VIB group is selected from molybdenum and/or tungsten, the metal component of the VIII group is selected from cobalt and/or nickel, and the content of the metal component of the VIB group is 2-8 wt%, the content of the metal component of the VIII group is 0.8-4 wt% and the content of the metal component of the VB group is 0-10 wt% calculated on oxide and based on the catalyst.

The invention also provides a preparation method of the heavy oil hydrogenation deasphalted catalyst, preferably, the heavy oil hydrogenation deasphalted catalyst is any one of the heavy oil hydrogenation deasphalted catalysts; the preparation method comprises preparing a carrier and loading a hydrogenation active metal component on the carrier, wherein the preparation of the carrier comprises mixing hydrated alumina P1 containing pseudo-boehmite and a modifier P2 of P1, and introducing a compound containing a group IVB metal into the mixture, followed by molding, drying and calcining; the weight mixing ratio of the P1 to the P2 is 20-95: 5-80, wherein the P2 contains hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, and the dosage of the P1, P2 and the compound containing IVB group metal elements ensures that the content of IVB group metal elements in the final carrier is 0.5-8 wt% and the content of hydrogenation metal elements is 0.4-22 wt%; the drying conditions include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is more than 300 to less than or equal to 900 ℃, and the time is 1 to 8 hours.

According to any one of the preparation methods provided by the present invention, preferably, the hydrogenation metallic element comprises at least one metallic element of group vib, at least one metallic element of group viii and optionally metallic element of group VB, and P2 is used in an amount such that the metallic element of group vib is contained in an amount of 0.2 to 10 wt%, further preferably 1 to 10 wt%, the metallic element of group viii is contained in an amount of 0.1 to 6 wt%, further preferably 0.5 to 6 wt%, and the metallic element of group VB is contained in an amount of 0 to 12 wt%, further preferably 0 to 10 wt%, in terms of oxide, in the final carrier. Wherein, the drying conditions are preferably as follows: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is more than 300 to less than or equal to 900 ℃, and the time is 1 to 8 hours.

According to any one of the preparation methods provided by the invention, preferably, the metallic element in the VIB group is molybdenum and/or tungsten, the metallic element in the VIII group is cobalt and/or nickel, and the metallic element in the VB group is vanadium and/or niobium; p2 is used in such an amount that the final carrier contains, as oxides, from 2 to 8% by weight of group VIB metal elements, from 0.8 to 4% by weight of group VIII metal elements and from 0 to 10% by weight of group VB metal elements.

According to any one of the production methods provided by the present invention, preferably, P2 has a k value of 0 to 0.9 or less, where DI is ₂/DI ₁，DI ₁Acid peptization index, DI, of pseudo-boehmite containing hydrated alumina P1 ₂Acid peptization index of a modification P2 of a hydrated alumina P1 containing pseudoboehmite; preferably, the P2 has a kappa value of 0 to 0.6 or less.

According to any one of the preparation methods provided by the present invention, preferably, the hydrated alumina P1 containing pseudo-boehmite has a pore volume of 0.9-1.4 ml/g and a specific surface of 100-350 m ²Per gram, most probable pore diameter is 8-30 nm; preferably, the hydrated alumina P1 containing the pseudo-boehmite has the pore volume of 0.95-1.3 ml/g and the specific surface of 120-300 m ²A few pores with a diameter of 10-25 nm.

According to any preparation method provided by the invention, preferably, the P2 is a particle with 80-300 meshes; preferably, the P2 is a 100-200 mesh particulate.

According to any one of the preparation methods provided by the invention, preferably, the P2 is a modified substance of P1, and the method for modifying P1 into P2 comprises the following steps: (a) forming, drying and roasting the pseudo-boehmite-containing hydrated alumina P1; (b) impregnating the carrier obtained in the step (a) with impregnation liquid containing hydrogenation metal elements, drying, roasting, grinding and screening all or part of the carrier to obtain a modified substance P2, wherein the introduction amount of the hydrogenation metal elements is that the content of the hydrogenation metal elements is not more than 0.4-25 wt% based on the modified substance P2; the drying conditions of step (a) include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is 300-900 ℃ and the time is 1-10 hours; the drying conditions of step (b) include: the temperature is 100 ℃ and 250 ℃, the time is 1-10 hours, and the roasting conditions comprise: the temperature is 360-500 ℃ and the time is 1-10 hours.

According to any one of the production methods provided by the present invention, preferably, the hydrogenation metal element is introduced in the step (B) in such an amount that the content of the group VIB metal element, the content of the group VIII metal element and the content of the group VB metal element are 0.2 to 10% by weight, respectively, based on the modifier P2.

According to any one preparation method provided by the invention, preferably, the P2 is particles with 80-300 meshes in the P1 modified substance, and the P2 is further preferably particles with 100-200 meshes in the P1 modified substance.

According to any one of the production methods provided by the present invention, preferably, the method of supporting the hydrogenation active metal component on the carrier is an impregnation method, which comprises preparing a solution containing a hydrogenation active metal compound and impregnating the carrier with the solution, followed by drying, calcination or no calcination; the hydrogenation active metal component is selected from at least one VIB group metal component, at least one VIII group metal component and an optional VB group metal component, and the concentration and the using amount of the impregnation solution are calculated by oxides and based on the catalyst, so that the content of the VIB group metal component in the final catalyst is 1-10 wt%, the content of the VIII group metal component is 0.5-6 wt%, and the content of the VB group metal component is 0-12 wt%; the drying conditions after the loading of the hydrogenation active metal component include: the temperature is 100 ℃ and 250 ℃, the time is 1-10 hours, and the roasting conditions comprise: the temperature is 360-500 ℃, and the time is 1-10 hours;

further preferably, the group VIB metal component is selected from molybdenum and/or tungsten, the group VIII metal component is selected from cobalt and/or nickel, the group VB metal component is selected from vanadium and/or niobium, and the concentration and the amount of the impregnation solution are such that the content of the group VIB metal component, the content of the group VIII metal component and the content of the group VB metal component in the final catalyst are respectively 2-8 wt%, 0.8-4 wt% and 0-10 wt%, respectively, calculated by oxide and based on the catalyst; the drying conditions after the loading of the hydrogenation active metal component include: the temperature is 100-140 ℃, the time is 1-6 hours, and the roasting conditions comprise: the temperature is 360-450 ℃ and the time is 2-6 hours.

Furthermore, the invention also provides an application of any one of the heavy oil hydrogenation deasphalting catalysts in heavy oil hydrogenation treatment.

The carrier of the heavy oil hydrogenation deasphalting catalyst provided by the invention can be made into various easy-to-operate molded products according to different requirements, such as spheres, honeycombs, bird nests, tablets or strips (clovers, butterflies, cylinders and the like). The method for mixing the pseudo-boehmite-containing hydrated alumina P1 and the modified product P2 of P1 is a conventional method, for example, powder P1 and powder P2 are put into a stirring mixer according to the feeding proportion and mixed.

The method of introducing the group IVB metal-containing compound into the mixture of P1 and P2 is a conventional method, and for example, the required amount of the group IVB metal-containing compound may be directly mixed in during the aforementioned mixing of P1 and P2.

In a specific embodiment of the method for preparing the carrier, the group IVB metal-containing compound is introduced into the mixture of the pseudo-boehmite-containing hydrated alumina P1 and the P1-modified product P2 by formulating the group IVB metal-containing compound into an aqueous solution, mixing the aqueous solution with the P1 and the P2 or mixing the aqueous solution after mixing the P1 and the P2, followed by molding, drying and calcining. The group IVB metal-containing compound may be one or more of any group IVB metal-containing water-soluble compounds. For example, one or more water-soluble inorganic salts containing a group IVB metal.

The shaping can be carried out in a conventional manner, for example, by one or a combination of rolling, tabletting and extrusion. In the molding, for example, extrusion molding, in order to ensure that the molding proceeds smoothly, water, an extrusion aid and/or an adhesive, with or without a pore-expanding agent, may be added to the mixture, followed by extrusion molding, followed by drying and firing. The kind and amount of the extrusion aid and peptizing agent are well known to those skilled in the art, for example, common extrusion aid may be one or more selected from sesbania powder, methyl cellulose, starch, polyvinyl alcohol, and polyvinyl alcohol, the peptizing agent may be inorganic acid and/or organic acid, and the pore-expanding agent may be one or more selected from starch, synthetic cellulose, polymeric alcohol, and surfactant. The synthetic cellulose is preferably one or more of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether, the polymeric alcohol is preferably one or more of polyethylene glycol, polypropylene alcohol and polyvinyl alcohol, and the surfactant is preferably one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, and an allyl alcohol copolymer and a maleic acid copolymer with the molecular weight of 200-10000.

Wherein, the acid peptization index DI in the carrier preparation refers to that after the hydrated alumina containing the pseudo-boehmite is added with nitric acid according to a certain acid-aluminum ratio, the peptized hydrated alumina containing the pseudo-boehmite is mixed with Al in a certain reaction time ₂O ₃Calculated in percent, DI ═ 1-W ₂/W ₁)×100％，W ₁And W ₂Respectively before reaction of pseudo-boehmite with acid and after reaction with acid, and Al ₂O ₃The weight of the meter.

The DI measurement involves ⑴ measuring the calcination base content of the hydrated alumina containing pseudoboehmite (the calcination base content means that a given quantity of pseudoboehmite is calcined at 600 ℃ for 4 hoursThe ratio of the weight after firing to the weight before firing) is a, ⑵ the hydrated alumina W containing pseudo-boehmite is weighed by an analytical balance ₀G, W ₀In an amount sufficient for Al ₂O ₃W of meter ₁Is 6g (W) ₁/a＝W ₀) Weighing deionized water W g, W is 40.0-W ₀Adding weighed hydrated alumina containing pseudoboehmite and deionized water into a beaker for mixing under stirring, ⑶ transferring 20mL of dilute nitric acid solution with the concentration of 0.74N by using a 20mL pipette, adding the acid solution into the beaker in the step (2), reacting for 8 minutes under stirring, ⑷ centrifugally separating the slurry reacted in the step (3) in a centrifuge, putting the precipitate into a weighed crucible, drying the precipitate for 4 hours at 125 ℃, roasting the precipitate for 3 hours at 850 ℃ in a muffle furnace, weighing and burning the precipitate to obtain the W sample amount ₂G; (5) according to the formula DI ═ 1-W ₂/W ₁) X 100% calculated.

The present invention has no special requirement on the pseudo-boehmite-containing hydrated alumina P1, and can be any pseudo-boehmite prepared by the prior art, and can also be a mixture of pseudo-boehmite and other hydrated alumina, wherein the other hydrated alumina is one or more selected from the group consisting of monohydrate alumina, trihydrate alumina and amorphous hydrated alumina, on the premise that the final carrier can meet the requirements of the present invention. For example, the pore volume is 0.9-1.4 ml/g, the specific surface is 100-350 m ²Per gram, most probable pore diameter is 8-30 nm; preferably, the pore volume is 0.95-1.3 ml/g, the specific surface is 120-300 m ²Hydrated alumina containing pseudoboehmite with a pore diameter of up to a few 10-25nm is particularly suitable for use in the present invention.

In the present invention, the pore volume, specific surface area and most accessible pore diameter of the pseudo-boehmite-containing hydrated alumina are obtained by BET nitrogen adsorption characterization after the pseudo-boehmite-containing hydrated alumina is calcined at 600 ℃ for 4 hours. In a further preferred embodiment, the pseudoboehmite-containing hydrated alumina has a pseudoboehmite content of not less than 50%, and more preferably not less than 60%, as characterized by X-ray diffraction.

The inventor of the invention also finds that the peptization index of the modified alumina P1 containing pseudo-boehmite is changed, and the carrier obtained by mixing, molding, drying and roasting the modified alumina P1 which is not heat-treated has obvious bimodal pore distribution. In particular, after the 80-300 mesh particles, preferably 100-200 mesh particles, are mixed with the non-heat-treated fraction, shaped, dried and calcined, the pore distribution of each single peak in the double peak of the resulting support is particularly concentrated. Here, the particles of 80-300 mesh, preferably 100-200 mesh particles, means particles of which the modified material is sieved (including a crushing or grinding step as necessary) and whose sieved material (undersize material) satisfies 80-300 mesh, preferably 100-200 mesh particles in a percentage (by weight) of the total amount of not less than 60%, further preferably not less than 70%.

In specific implementation, the P2 can be conveniently obtained by the following method:

⑴ the drying process is carried out to obtain P2, which comprises forming hydrated alumina P1 containing pseudo-boehmite by conventional method and impregnating active metal to prepare conventional hydrotreating catalyst, and the tail material by-produced from the drying process of the impregnated strip, for example, the tail material by-produced from the drying and shaping process of the impregnated strip (conventionally called dry waste), grinding the tail material, and sieving to obtain P2.

⑵ is obtained by calcining, and comprises forming and impregnating the hydrated alumina P1 containing pseudo-boehmite with active metal by a conventional method to prepare a conventional hydrotreating catalyst, and grinding and sieving the tailings to obtain P2, wherein the tailings are by-produced by calcining (conventionally referred to as finished waste), for example, the tailings are by-produced in the process of impregnating, strip calcining and shaping.

⑶ is obtained based on the mixing of two or more of the modifications P2 obtained by the methods described above when P2 is obtained by the mixing method, there is no limitation on the mixing ratio of the modifications P2 obtained by the methods described above respectively.

In the carrier, the VIB group metal element is preferably molybdenum and/or tungsten, the VIII group metal element is preferably nickel and/or cobalt, and the VB group metal element is selected from vanadium and/or niobium. The content of the group VIII metal element is preferably 0.5 to 6% by weight, more preferably 0.8 to 4% by weight, the content of the group VIB metal element is preferably 1 to 10% by weight, more preferably 2 to 8% by weight, and the content of the group VB metal element is 0 to 12% by weight, more preferably 0 to 10% by weight, based on the oxide and based on the carrier.

The hydrogenation active metal component in the catalyst provided by the invention is derived from two parts, wherein one part is a hydrogenation metal element which is introduced in the process of preparing the carrier and exists in the carrier, and the other part is the hydrogenation active metal component which is introduced after the preparation of the carrier is finished. Wherein, the hydrogenation active metal component introduced after the preparation of the carrier is completed can be at least one VIB group metal component, at least one VIII group metal component and an optional VB group metal component, and further, the VIB group metal component is preferably molybdenum and/or tungsten, the VIII group metal component is preferably nickel and/or cobalt, and the VB group metal component is preferably vanadium and/or niobium.

Preferably, the catalyst of the present invention contains 1-10 wt% of group VIB metal component, 0.5-6 wt% of group VIII metal component and 0-12 wt% of group VB metal component, calculated on oxide basis and based on the catalyst.

The present invention is not particularly limited to the supporting method on the premise that it is sufficient to support the hydrogenation-active metal component on the alumina support, and a preferable method is an impregnation method comprising preparing an impregnation solution of a compound containing the metal, and thereafter impregnating the alumina support with the solution. The impregnation method is a conventional method, and for example, the impregnation method can be excess liquid impregnation and pore saturation impregnation.

Wherein, the metal-containing compound is selected from one or more of water-soluble compounds (including compounds soluble in water in the presence of a cosolvent). Taking the molybdenum in the VIB group as an example, the molybdenum can be selected from one or more of molybdenum oxide, molybdate and paramolybdate, and the molybdenum oxide, ammonium molybdate and paramolybdate are preferable; tungsten of the VIB group is taken as an example, and can be selected from one or more of tungstate, metatungstate and ethyl metatungstate, and ammonium metatungstate and ethyl ammonium metatungstate are preferred; nickel of group VIII metal is exemplified and can be selected from cobalt nitrate, basic cobalt carbonate; one or more of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and soluble complex of nickel, preferably nickel nitrate and basic nickel carbonate; taking the group VB vanadium as an example, the vanadium can be selected from one or more of vanadium pentoxide, ammonium vanadate, ammonium metavanadate, vanadium sulfate and vanadium heteropoly acid, and the ammonium metavanadate and ammonium vanadate are preferred.

The alumina carrier provided by the invention can also contain any substance which does not affect the performance of the carrier provided by the invention or can improve the performance of the catalyst prepared by the carrier provided by the invention.

When the catalyst also contains other components, the other components can be introduced by any method, such as directly mixing with the pseudo-boehmite, forming and roasting; the compound containing the corresponding component and the compound containing the hydrogenation active metal component are prepared into a mixed solution and then are contacted with the carrier; or preparing a compound containing other components into a solution separately, contacting the solution with the carrier, and roasting the solution. When the other components and the hydrogenation-active metal component are introduced separately into the support, it is preferred that the support is first contacted with a solution containing the promoter compound and calcined, and then contacted with a solution containing the hydrogenation-active metal component, for example by impregnation, at a calcination temperature of 400 ℃ to 600 ℃, preferably 420 ℃ to 500 ℃, for a calcination time of 2 to 6 hours, preferably 3 to 6 hours.

According to the heavy oil hydrotreating method provided by the present invention, the reaction conditions for the heavy oil hydrotreating are not particularly limited, and in a preferred embodiment, the hydrodeasphaltene reaction conditions are: the reaction temperature is 300-550 ℃, the further optimization is 330-480 ℃, the hydrogen partial pressure is 4-20 MPa, the further optimization is 6-18 MPa, and the volume space velocity is 0.1-3.0 hours ^-1More preferably 0.15 to 2 hours ^-1The hydrogen-oil volume ratio is 200-.

The hydrogenation apparatus may be any reactor sufficient to contact and react the feedstock oil with the catalyst under hydrotreating reaction conditions, for example, in the fixed bed reactor, moving bed reactor or ebullating bed reactor.

The hydrogenation catalyst may be presulfided prior to use with sulfur, hydrogen sulfide or a sulfur-containing feedstock, typically in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃, either ex situ or in situ, to convert its supported hydrogenation-active metal component to a metal sulfide component, according to methods conventional in the art.

Compared with the catalyst provided by the prior art, the catalyst provided by the invention adopts a specific carrier containing at least one IVB group metal element, alumina and at least one hydrogenation metal element, in particular a bimodal pore alumina carrier with bimodal pore diameters concentrated in the range of 5nm-20nm and 100nm-500 nm. The catalyst shows better hydrogenation deasphalting performance when being used for processing heavy oil. The catalyst provided by the invention can be used independently or combined with other catalysts, and is particularly suitable for hydrotreating heavy oil, particularly inferior residual oil, so as to provide qualified raw oil for subsequent processes (such as a catalytic cracking process).

Detailed Description

The following examples further illustrate the invention but should not be construed as limiting it. The reagents used in the examples, except where specifically indicated, were all chemically pure reagents. The pseudoboehmite employed in the following examples includes:

p1-1: dry rubber powder (pore volume 1.3 ml/g, specific surface 350 m) from Changling catalyst division ²A few pores with a diameter of 18.8 nm. 69% on a dry basis, with a pseudoboehmite content of 65%, a gibbsite content of 4% by weight, the balance being amorphous alumina, DI value 14.8).

P1-2: dry glue powder (pore volume 1.2 ml/g, specific surface 260 m) produced by cigarette Tai Henghui chemical Co., Ltd ²Pergram, most probable pore diameter 14 nm. 71% on a dry basis, with a pseudo-boehmite content of 67%, a gibbsite content of 5% by weight, and the balance amorphous alumina, a DI value of 17.2).

Examples 1 to 6 illustrate the P1 modified product P2 and the process for preparing the carrier of the present invention.

Example 1: 5000 g of P1-1 is weighed, and then 7200 ml of aqueous solution containing 50 ml of nitric acid (product of Tianjin chemical reagent, Mitsui) is added, and a butterfly-shaped strip with the external diameter phi of 1.4mm is extruded on a double-screw extruder. Drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, roasting the dry strips at 600 ℃ for 4 hours to obtain carriers, impregnating the carriers with a solution containing nickel nitrate and molybdenum oxide by adopting a saturated impregnation method to obtain wet strips containing active metals Ni and Mo, drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, shaping and sieving the dry strips, grinding dry strip materials (generally called industrial dry strip waste materials) with the length of less than 2mm, sieving the dry strips, and screening the dry strips by 100-200 meshes to obtain a modified P2A of P1-1. The k value of P2A is shown in Table 1. NiO content 2 wt.% on P2A calculated as oxide, MoO ₃The content is 10% by weight.

Example 2: 1000 g of the dried strip containing the active metals Ni and Mo obtained in example 1 were weighed and calcined at 400 ℃ for 4 hours to obtain P1-1 modified product P2B. The k value of P2B is shown in Table 1.

Example 3: 200 g each of P2A obtained in example 1 and P2B obtained in example 2 were uniformly mixed to obtain P2C which is a modified product of P1-1. The k value of P2C is shown in Table 1.

Example 4: 1000 g of P1-2 is weighed, then 10 ml of aqueous solution 1440 ml containing nitric acid (product of Tianjin chemical reagent, three factories) is added, and a butterfly-shaped strip with the external diameter phi of 1.4mm is extruded on a double-screw extruder. Drying the wet strips at 120 ℃ for 4 hours, roasting the wet strips at 800 ℃ for 4 hours to obtain a carrier, impregnating the carrier with a solution containing cobalt nitrate and molybdenum oxide by adopting a saturated impregnation method to obtain wet strips containing active metals Co and Mo, drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, shaping and sieving the dry strips, grinding and sieving dry strip materials (generally called industrial dry strip waste materials) with the length of less than 2mm, and sieving the dry strips by taking 100-200 meshes to obtain a modified P2D of P1-2. The k value of P2D is shown in Table 1. CoO content 3 wt.% on P2D calculated as oxide, MoO ₃The content was 15% by weight.

Example 5: 1000 g of the dried strip containing the active metals Co and Mo obtained in example 4 were weighed and calcined at 500 ℃ for 4 hours to obtain P1-2 modified product P2E. The k value of P2E is shown in Table 1.

Example 6: 5000 g of P1-1 is weighed, and then 7200 ml of aqueous solution containing 50 ml of nitric acid (product of Tianjin chemical reagent, Mitsui) is added, and a butterfly-shaped strip with the external diameter phi of 1.4mm is extruded on a double-screw extruder. Drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, roasting the dry strips at 600 ℃ for 4 hours to obtain carriers, impregnating the carriers with a solution containing nickel nitrate and ammonium vanadate by adopting a saturated impregnation method to obtain wet strips containing active metals Ni and V, drying the wet strips at 120 ℃ for 4 hours to obtain dry strips, shaping and sieving the dry strips, grinding dry strip materials (generally called industrial dry strip waste materials) with the length of less than 2mm, sieving the dry strips, and screening the dry strip materials with the size of 100-200 meshes to obtain a modified P2F of P1-1. The kappa values of P2F are shown in Table 1. NiO content 2 wt.% in P2F calculated as oxide, V ₂O ₅The content is 10% by weight.

TABLE 1

Examples	Raw materials	κ
			1	P2A	0.7
2	P2B	0.5
			3	P2C	0.6
4	P2D	0.4
			5	P2E	0.3
6	P2F	0.7

Examples 7-14 illustrate the preparation of alumina supports for use in the preparation of the catalysts of the present invention. Comparative examples 1-3 illustrate the preparation of conventional catalyst supports.

Example 7: 800 g of P1-1 was weighed, and mixed with 200 g of the raw material P2A obtained in example 1, 10 ml of an aqueous solution containing nitric acid (a product of Tianjin chemical reagent Co., Ltd.) and 16.6g of titanium tetrachloride (1440 ml) was added, and a butterfly-shaped rod having an outer diameter of 3.4mm was extruded on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support Z1. The properties of vector Z1 are listed in Table 2.

Example 8: weighing 700 g of P1-1, uniformly mixing with 300 g of the raw material P2B prepared in the example 2, adding 10 ml of Tianjin chemical reagent-containing product from the third plant of Nippon laboratories, and 16.6g of titanium tetrachloride-containing aqueous solution 1440 ml, and extruding into butterfly-shaped strips with the outer diameter phi of 3.4mm on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support Z2. The properties of vector Z2 are listed in Table 2.

Example 9: 900 g of P1-1 is weighed and evenly mixed with 100 g of the raw material P2C prepared in the embodiment 3, 10 ml of Tianjin chemical reagent-containing product from the third factory) and 1440 ml of aqueous solution containing 16.6g of titanium tetrachloride are added, and a butterfly-shaped strip with the external diameter phi of 3.4mm is extruded on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 750 ℃ for 3 hours to give a support Z3. The properties of vector Z3 are listed in Table 2.

Comparative example 1: 1000 g of P1-1 is weighed, added with a product of Tianjin chemical reagent III) containing nitric acid 10 ml and a water solution 1440 ml containing 16.6g of titanium tetrachloride, and extruded into a butterfly-shaped strip with the external diameter phi of 3.4mm on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support DZ 1. The properties of vector DZ1 are listed in Table 2.

Example 10: 800 g of P1-2 was weighed, and mixed with 200 g of the raw material P2D obtained in example 4, 10 ml of an aqueous solution containing nitric acid (a product of Tianjin chemical reagent Co., Ltd.) and 29.9g of titanium tetrachloride (1440 ml) was added, and a butterfly-shaped rod having an outer diameter of 3.4mm was extruded on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 700 ℃ for 3 hours to give a support Z4. The properties of vector Z4 are listed in Table 2.

Example 11: 900 g of P1-1 was weighed, and after uniformly mixing with 100 g of the raw material P2E obtained in example 5, 10 ml of Tianjin chemical reagent-containing product from the third plant of Mitsui chemical reagent) and 1440 ml of an aqueous solution containing 29.9g of titanium tetrachloride were added, and a butterfly-shaped rod with an outer diameter of phi 3.4mm was extruded on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were baked at 800 ℃ for 3 hours to give a support Z5. The properties of vector Z5 are listed in Table 2.

Example 12: 850 g of P1-2 was weighed, and after uniformly mixing with 150 g of the raw material P2C obtained in example 3, 10 ml of Tianjin chemical reagent III) nitrate-containing product and 1440 ml of titanium tetrachloride-containing 29.9g of aqueous solution were added, and a butterfly-shaped bar having an outer diameter of 3.4mm was extruded on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 650 ℃ for 3 hours to give a support Z6. The properties of vector Z6 are listed in Table 2.

Comparative example 2: 1000 g of P1-2 is weighed, added with a product of Tianjin chemical reagent III) nitrate of 10 ml and titanium tetrachloride of 29.9g of aqueous solution of 1440 ml, and extruded into a butterfly-shaped bar with the external diameter phi of 3.4mm on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 650 ℃ for 3 hours to give a support DZ 2. The properties of vector DZ2 are listed in Table 2.

Example 13: 900 g of P1-2 was weighed, and after uniformly mixing with 100 g of the raw material P2D obtained in example 4, 10 ml of Tianjin chemical reagent III) nitrate-containing product and 1440 ml of an aqueous solution containing 41.6g of titanium tetrachloride were added, and a butterfly-shaped bar with an outer diameter of phi 3.4mm was extruded on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 700 ℃ for 3 hours to give a support Z7. The properties of vector Z7 are listed in Table 2.

Example 14: 800 g of P1-1 was weighed, and mixed with 200 g of the raw material P2F obtained in example 6, 10 ml of an aqueous solution containing nitric acid (a product of Tianjin chemical reagent Co., Ltd.) and 41.6g of titanium tetrachloride (1440 ml) were added, and a butterfly bar having an outer diameter of 1.4mm was extruded on a twin-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 600 ℃ for 3 hours to give a support Z8. The properties of vector Z8 are listed in Table 2.

Comparative example 3:

according to the method provided by the patent CN101890381A example 7, butterfly-shaped strips with the outer diameter of 3.4mm are extruded on a double-screw extruder. The wet strands were dried at 120 ℃ for 4 hours to give moldings, and the moldings were calcined at 700 ℃ for 3 hours to give a support DZ 3. The properties of vector DZ3 are listed in Table 2.

TABLE 2

Examples 15 to 22 are provided to illustrate the catalyst and the preparation method thereof according to the present invention.

Wherein, the content of the hydrogenation active metal component in the catalyst is measured by an X-ray fluorescence spectrometer (all instruments are 3271 type X-ray fluorescence spectrometers of Japan science and electronics industries Co., Ltd., and the specific method is shown in petrochemical industry analysis method RIPP 133-90).

Example 15: 200 g of vector Z1 was taken and 220 ml of MoO-containing solution was added ₃52.5 g/L of NiO 11 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃ to obtain the hydrogenation deasphalted catalyst C1, and the composition of C1 is shown in Table 3.

Example 16: 200 g of vector Z2 was taken and 220 ml of MoO-containing solution was added ₃25 g/L of NiO 6 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃, and the hydrogenation deasphalting catalyst C2 is obtained, wherein the composition of C2 is shown in Table 3.

Example 17: 200 g of vector Z3 was taken and 220 ml of MoO-containing solution was added ₃13 g/l of a mixed solution of ammonium heptamolybdate and cobalt nitrate with 3 g/l of CoO was immersed for 1 hour, dried at 120 ℃ for 4 hours and calcined at 400 ℃ for 3 hours to obtain the hydrodeasphaltenic catalyst CZ3, the composition of C3 is shown in Table 3.

Comparative example 4: 200 g of vector DZ1 was taken and 220 ml of MoO-containing solution was added ₃80 g/L of CoO 16 g/L of ammonium heptamolybdate and cobalt nitrate mixed solution is soaked for 1 hour, dried for 4 hours at 120 ℃ and roasted for 2 hours at 400 ℃ to obtain the hydrodeasphaltic catalyst DC1, and the composition of DC1 is shown in Table 3.

Comparative example 5: 200 g of DZ2 was taken and 220 ml of MoO-containing solution was added ₃80 g/L of NiO 16 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 2 hours at the temperature of 400 ℃ to obtain the hydrogenation deasphalting catalyst DC2, and the composition of DC2 is shown in Table 3.

Comparative example 6: 200 g of vector DZ3 was taken and 500 ml of MoO-containing solution was added ₃59 g/L of NiO 14 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃ to obtain the hydrogenation deasphalting catalyst DC3, and the composition of DC3 is shown in Table 3.

Example 18: 200 g of vector Z4 was taken and 220 ml of MoO-containing solution was added ₃20 g/L of NiO 6 g/L of ammonium heptamolybdate and nickel nitrate mixed solution is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃ to obtain the hydrogenation deasphalting catalyst C4, and the composition of C4 is shown in Table 3.

Example 19: 200 g of Z5 was taken and 220 ml of MoO was added ₃38 g/L of mixed solution of ammonium heptamolybdate and nickel nitrate is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃, and the composition of the hydrogenation deasphalted catalyst C5 and C5 are shown in Table 3.

Example 20: taking 200 g of Z6, use220 ml of WO-containing solution ₃The mixed solution of 25 g/L and 6 g/L of CoO and ammonium tungstate and cobalt nitrate is soaked for 1 hour, dried for 4 hours at 120 ℃ and roasted for 3 hours at 400 ℃ to obtain the hydrogenation deasphalted catalyst C6, and the composition of C6 is shown in Table 3.

Example 21

200 g of Z7 was taken and 220 ml of MoO was added ₃44 g/l, V ₂O ₅12 g/l of a mixed solution of ammonium heptamolybdate and ammonium vanadate is soaked for 1 hour, dried at 120 ℃ for 4 hours and roasted at 400 ℃ for 3 hours to obtain a hydrodeasphaltic catalyst C7, and the composition of C7 is shown in Table 3.

Example 22

200 g of Z8 was taken and 220 ml of MoO was added ₃44 g/L of NiO 6 g/L of mixed solution of ammonium heptamolybdate and nickel nitrate is soaked for 1 hour, dried for 4 hours at the temperature of 120 ℃ and roasted for 3 hours at the temperature of 400 ℃ to obtain the hydrogenation deasphalting catalyst C8, and the composition of C8 is shown in Table 3.

TABLE 3

Examples 23 to 30

Examples 23-30 illustrate the deasphalting, demetallization, decarbonization and desulfurization rates of the hydrogenation catalysts provided by the present invention.

The catalyst was evaluated on a 100 ml small fixed bed reactor using the kowitt slag as the raw material.

The catalyst C1-C8 was crushed into particles of 2-3 mm in diameter, the catalyst loading was 100 ml. The reaction conditions are as follows: the reaction temperature is 380 ℃, the hydrogen partial pressure is 14 MPa, and the liquid hourly space velocity is 0.7 h ^-1The hydrogen-oil volume ratio was 1000, and a sample was taken after 200 hours of reaction.

The specific calculation method of the demetallization rate and the desulfurization rate is as follows:

the properties of the stock oils are shown in Table 4, and the evaluation results are shown in Table 5.

Comparative examples 7 to 9

The demetallization and desulfurization rates of catalysts DC1, DC2 and DC3 were evaluated in the same manner as in the examples, and the results are shown in Table 5.

TABLE 4

Raw oil name	Cowitte slag
		Density (20 ℃), kg/m ³	0.998
Average molecular weight	804
		Carbon residue,% (m)	15.9
Four Components,% (m)
		Saturation fraction	20
Aromatic component	49.3
		Glue	23
Asphaltenes	7.7
		S，m％	5.0
N，m％	0.21
		Ni，ppm	26.5
V，ppm	80

TABLE 5

The results given in table 5 are results after the evaluation reaction was carried out for 200 hours, and a comparison shows that the hydrodemetallization activity, deasphalted product activity and residual carbon removal activity of the hydrodeasphaltene catalyst provided by the invention are significantly higher than those of the reference catalyst.

Claims

1. A heavy oil hydrogenation deasphalting catalyst comprises a carrier and hydrogenation active metal components, wherein the carrier contains alumina, IVB group metal elements and hydrogenation metal elements, the content of the IVB group metal elements in the carrier is 0.5-8 wt%, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, and the content of the hydrogenation metal elements is 0.3-20 wt% based on oxides and the carrier.

2. The catalyst according to claim 1, wherein the hydrogenation metallic elements comprise at least one metallic element of group VIB, at least one metallic element of group VIII and optionally metallic elements of group VB, and the content of the metallic elements of group VIB, the content of the metallic elements of group VIII and the content of the metallic elements of group VB are respectively 0.2-10 wt%, 0.1-5 wt% and 0-12 wt%, calculated on oxide basis and based on the carrier.

3. The catalyst according to claim 2, wherein the carrier contains molybdenum and/or tungsten as a group VIB metal element, cobalt and/or nickel as a group VIII metal element, vanadium and/or niobium as a group VB metal element, and the group IVB metal element is one or more selected from titanium, zirconium and hafnium; based on the oxide and the carrier, the content of the IVB metal element in the carrier is 1-6 wt%, preferably 1.5-4 wt%, and the content of the VIB metal element in the carrier is 0.5-9 wt%, preferably 1-8 wt%; the content of the group VIII metal element is 0.1 to 4% by weight, preferably 0.1 to 3% by weight, and the content of the group VB metal element is 0 to 10% by weight, preferably 0 to 8% by weight.

4. The catalyst as claimed in claim 1 or 2, wherein the support has a bimodal pore distribution, characterized by mercury intrusion, at a diameter of 5-20nm and a diameter of 100-500nm, the pore volume of the pores with a diameter of 5-20nm representing 55-80% of the total pore volume, and the pore volume of the pores with a diameter of 100-500nm representing 10-35% of the total pore volume; preferably, the pore volume of pores with a diameter of 8-20nm accounts for 60-75% of the total pore volume, and the pore volume of pores with a diameter of 200-500nm accounts for 15-30% of the total pore volume.

5. The catalyst according to claim 1 or 2, wherein the carrier has a pore volume of 0.95 to 1.6 ml/g and a specific surface area of 50 to 400 m ²Per gram; preferably, the carrier has a pore volume of 0.95 to 1.55 ml/g and a specific surface area of 80 to 350 m ²Per gram.

6. The catalyst according to any one of claims 1 to 5, wherein the alumina is selected from bimodal porous aluminas having single or mixed crystalline phases of γ -, η -, θ -and δ -.

7. The catalyst of claim 1 wherein the hydrogenation active metal component is selected from the group consisting of at least one group vib metal component, at least one group viii metal component, and optionally a group VB metal component, the group vib metal component being present in an amount of from 1 to 10 wt.%, the group viii metal component being present in an amount of from 0.5 to 6 wt.%, and the group VB metal component being present in an amount of from 0 to 12 wt.%, calculated as oxides and based on the catalyst; preferably, the group VIB metal component is selected from molybdenum and/or tungsten, the group VIII metal component is selected from cobalt and/or nickel, the group VB metal component is selected from vanadium and/or niobium, and the content of the group VIB metal component is 2-8 wt%, the content of the group VIII metal component is 0.8-4 wt% and the content of the group VB metal component is 0-10 wt% calculated on oxide basis and based on the catalyst.

8. A process for producing a hydrodeasphaltene catalyst, which comprises preparing a carrier and supporting on the carrier a hydrogenation-active metal component, wherein the preparation of the carrier comprises mixing a hydrated alumina P1 containing pseudo-boehmite and a modification P2 of P1, and introducing a group IVB metal-containing compound into the mixture, followed by shaping, drying and calcining; the weight mixing ratio of the P1 to the P2 is 20-95: 5-80, wherein the P2 contains hydrogenation metal elements, the hydrogenation metal elements are selected from one or more of VIB group, VIII group and VB group, and the dosage of the P1, P2 and compounds containing IVB group metals ensures that the content of IVB group metal elements in the final carrier is 0.5-8 wt% and the content of hydrogenation metal elements is 0.4-22 wt%; the drying conditions include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is more than 300 to less than or equal to 900 ℃, and the time is 1 to 8 hours.

9. The process of claim 8, wherein the hydrogenation metal comprises at least one group VIB metal element, at least one group VIII metal element, and optionally a group VB metal element, and P2 is used in an amount such that the final support contains, on an oxide basis, from 1 to 10 wt.% of the group VIB metal element, from 0.5 to 6 wt.% of the group VIII metal element, and from 0 to 12 wt.% of the group VB metal element.

10. The method according to claim 8 or 9, wherein the metal element in the VIB group is molybdenum and/or tungsten, the metal element in the VIII group is cobalt and/or nickel, the metal element in the VB group is vanadium and/or niobium, and the metal element in the IVB group is one or more selected from titanium, zirconium and hafnium; the P2 is used in an amount such that the final carrier contains, in terms of oxide, 2-8 wt% of group VIB metal elements, 0.8-4 wt% of group VIII metal elements and 0-10 wt% of group VB metal elements; the content of the group IVB metal component is 1.5 to 4% by weight.

11. The method of claim 8 or 9, wherein P2 has a k value of 0 to 0.9 or less, and wherein the k is DI ₂/DI ₁，DI ₁Acid peptization index, DI, of pseudo-boehmite containing hydrated alumina P1 ₂Acid peptization index of a modification P2 of a hydrated alumina P1 containing pseudoboehmite; preferably, the P2 has a kappa value of 0 to 0.6 or less.

12. The method as claimed in claim 8 or 9, wherein the hydrated alumina P1 containing pseudo-boehmite has a pore volume of 0.9-1.4 ml/g and a specific surface area of 100-350 m ²Per gram, most probable pore diameter is 8-30 nm; preferably, the hydrated alumina P1 containing the pseudo-boehmite has the pore volume of 0.95-1.3 ml/g and the specific surface of 120-300 m ²A few pores with a diameter of 10-25 nm.

13. The method of claim 7 or 8, wherein the P2 is 80-300 mesh particulate matter; preferably, the P2 is a 100-200 mesh particulate.

14. The method of claim 8 or 9, wherein P2 is a modification of P1, and the method of modifying P1 to P2 comprises the steps of: (a) forming, drying and roasting the pseudo-boehmite-containing hydrated alumina P1; (b) impregnating the carrier obtained in the step (a) with impregnation liquid containing hydrogenation metal elements, drying, roasting, grinding and screening all or part of the carrier to obtain a modified substance P2, wherein the introduction amount of the hydrogenation metal elements is that the content of the hydrogenation metal elements is not more than 0.4-25 wt% based on the modified substance P2; the drying conditions of step (a) include: the temperature is 40-350 ℃, the time is 1-24 hours, and the roasting conditions comprise: the temperature is 300-900 ℃ and the time is 1-10 hours; the drying conditions of step (b) include: the temperature is 100 ℃ and 250 ℃, the time is 1-10 hours, and the roasting conditions comprise: the temperature is 360-500 ℃ and the time is 1-10 hours.

15. The method as claimed in claim 14, wherein the P2 is 80-300 mesh particles in P1 modification, and the P2 is preferably 100-200 mesh particles in P1 modification.

16. The process as claimed in claim 8 or 9, wherein the method of loading the carrier with the hydrogenation-active metal component is an impregnation method, comprising preparing a solution of a hydrogenation-active metal-containing compound and impregnating the carrier with the solution, followed by drying, calcining or not, the hydrogenation-active metal component being selected from at least one group vib metal component, at least one group viii metal component and optionally a group VB metal component, the concentration of the hydrogenation-active metal-containing compound in the solution and the amount of the solution being such that the content of the group vib metal component in the final catalyst is 1-10 wt%, the content of the group viii metal component is 0.5-6 wt% and the content of the group VB metal component is 0-12 wt%, calculated as oxides and based on the catalyst; the drying conditions after the loading of the hydrogenation active metal component include: the temperature is 100 ℃ and 250 ℃, the time is 1-10 hours, and the roasting conditions comprise: the temperature is 360-500 ℃, and the time is 1-10 hours; the drying conditions after the loading of the hydrogenation active metal component include: the temperature is 100-140 ℃, the time is 1-6 hours, and the roasting conditions comprise: the temperature is 360-450 ℃, and the time is 2-6 hours;

preferably, the group VIB metal component is selected from molybdenum and/or tungsten, the group VIII metal component is selected from cobalt and/or nickel, the group VB metal component is selected from vanadium and/or niobium, and the concentration of the compound containing the hydrogenation active metal component in the solution and the amount of the solution are such that the content of the group VIB metal component, the content of the group VIII metal component and the content of the group VB metal component in the final catalyst are respectively 2-8 wt%, 0.8-4 wt% and 0-10 wt%, respectively, calculated as oxides and based on the catalyst.

17. Use of the hydrodeasphaltene catalyst of any of claims 1-7 in the hydroprocessing of heavy oils.