CN103480422B - There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrotreating method - Google Patents

Abstract

The invention provides a kind of Catalysts and its preparation method and the application with hydrogenation catalyst effect, this catalyst contains carrier and load at least one group VIII metallic element on the carrier and at least one group vib metallic element, wherein, described carrier is article shaped containing hydrated alumina or aluminium oxide article shaped, material forming containing at least one component A, at least one B component and at least one component C is obtained, described component A is selected from hydrated alumina, and described B component is selected from Al ₂o ₃with aluminium oxide leftover bits and pieces, described component C is selected from cellulose ether.Present invention also offers a kind of method for hydrotreating hydrocarbon oil, the method comprises under hydroprocessing conditions, by hydrocarbon ils and catalyst exposure provided by the invention.Catalyst of the present invention shows higher catalytic activity in the hydrotreatment of hydrocarbon ils.

Description

Catalyst with hydrogenation catalysis, preparation method and application thereof, and hydrogenation treatment method

technical field

The invention relates to a catalyst with hydrogenation catalysis, its preparation method and application, and also relates to a hydrogenation treatment method.

Background technique

Hydrogenation technology is one of the main technologies to reduce the impurity content in oil and improve the quality of oil, and its core is hydrogenation catalyst. Conventional hydrogenation catalysts can be prepared by loading active ingredients with hydrogenation catalysis on porous supports, wherein the most commonly used porous supports are alumina moldings.

The heavy oil hydrogenation catalyst that RichardA.Kemp reports is that the solution that will contain active metal component is added in the pseudo-boehmite gel, then carries out extrusion molding, drying and roasting and prepares (RichardA.Kemp, CharlesT.Adam, Applied Catalysis A: General, 134(1996):299-317).

The hydrodesulfurization catalyst reported by D.Minoux is prepared by mixing nickel nitrate and ammonium molybdate with boehmite, then shaping, drying and roasting (D.Minoux, F.Diehl, P.Euzen, Jean- Pierre Jolivetb, Edmond Payen, Studies in Surface Science and Catalysis, 143 (2002): 767-775).

However, with the increasingly stringent environmental protection requirements worldwide, countries have increasingly stringent requirements on the quality of vehicle fuel; and, due to the reduction of oil resources, the quality of crude oil has become heavier and worse, and refineries have to process lower-quality crude oil. Therefore, it is urgent There is a need for hydrogenation catalysts with higher catalytic activity.

Contents of the invention

The object of the present invention is to provide a catalyst with hydrogenation catalysis, its preparation method and application, and a hydrotreatment method. The catalyst according to the invention has improved catalytic activity.

The first aspect of the present invention provides a catalyst with hydrogenation catalysis, the catalyst contains a carrier, and at least one metal element of Group VIII and at least one metal element of Group VIB supported on the carrier, wherein , the carrier is an alumina molding or a molding containing hydrated alumina, which is obtained by molding a raw material containing at least one component A, at least one component B and at least one component C, said Component A is selected from hydrated alumina, the component B is selected from Al ₂ O ₃ and alumina waste, and the component C is selected from cellulose ether.

The second aspect of the present invention provides a method for preparing a catalyst with hydrogenation catalysis, the method comprising supporting at least one metal element of Group VIII and at least one metal element of Group VIB on a carrier, wherein the The carrier is a shaped product of alumina or a shaped product containing hydrated alumina, which is obtained by shaping a raw material containing at least one component A, at least one component B and at least one component C, said component A It is selected from hydrated alumina, the component B is selected from Al ₂ O ₃ and alumina waste, and the component C is selected from cellulose ether.

A third aspect of the invention provides a catalyst prepared by the process of the invention.

The fourth aspect of the present invention provides the use of the catalyst of the present invention in hydroprocessing of hydrocarbon oil.

The fifth aspect of the present invention provides a hydroprocessing method, which comprises contacting hydrocarbon oil with a catalyst under hydroprocessing conditions, wherein the catalyst is the catalyst provided by the present invention.

The catalysts according to the invention show higher catalytic activity in the hydrotreatment of hydrocarbon oils.

detailed description

The first aspect of the present invention provides a catalyst having hydrogenation catalysis, the catalyst contains a carrier, and at least one metal element of Group VIII and at least one metal element of Group VIB supported on the carrier. The term "at least one" means one or more than two.

According to the catalyst of the present invention, the content of the Group VIII metal element and the Group VIB metal element can be properly selected according to the specific application of the catalyst. For example, when the catalyst according to the present invention is used for the hydrotreating of hydrocarbon oil, based on the total amount of the catalyst, the content of the carrier can be 40-80% by weight, preferably 50-75% by weight; In terms of oxides, the content of the Group VIII metal element may be 2-15% by weight, preferably 4-10% by weight; in terms of oxides, the content of the Group VIB metal element may be 15-45% by weight , preferably 20-40% by weight.

According to the catalyst of the present invention, the Group VIII metal element and the Group VIB metal element may be various elements commonly used in the art with hydrogenation catalytic effect. Preferably, the Group VIII metal element is cobalt and/or nickel, and the Group VIB metal element is molybdenum and/or tungsten.

According to the catalyst of the present invention, the form of the Group VIII metal element and the Group VIB metal element on the carrier is not particularly limited, and may be a conventional choice in the art. From the perspective of further improving the catalytic activity of the catalyst according to the present invention, the Group VIII metal element and the Group VIB metal element are basically (ie, mainly or substantially) supported on the carrier in the form of a salt. That is, the Group VIII metal element is preferably supported on the carrier in the form of a salt containing the Group VIII metal element, and the Group VIB metal element is preferably supported on the carrier in the form of a salt containing the Group VIB metal element. on the carrier. That is, the Group VIII metal element and the Group VIB metal element are preferably substantially (ie, mainly or substantially) supported on the carrier in a non-oxide form.

According to the catalyst of the present invention, the carrier is obtained by molding a raw material containing at least one component A, at least one component B and at least one component C, the component A being selected from hydrated alumina, The component B is selected from Al ₂ O ₃ and alumina leftovers, and the component C is selected from cellulose ethers.

According to the invention, the raw material contains at least one component A, at least one component B and at least one component C, but does not contain peptizers (for example: aluminum sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid , malonic acid, hydrochloric acid and trichloroacetic acid). According to the catalyst of the present invention, the composition of the raw material can be properly selected according to the application of the catalyst, as long as the carrier prepared from the raw material can meet the use requirements. Generally, based on the total amount of raw materials, the content of component C can be 0.5-12% by weight, preferably 1-10% by weight, more preferably 3-8% by weight; calculated as Al ₂ O ₃ The total content of the component A and the component B calculated as Al ₂ O ₃ may be 88-99% by weight, preferably 90-98% by weight, more preferably 92-96% by weight. In the present invention, when calculating the total amount of raw materials, component A (that is, hydrated alumina) is counted as Al ₂ O ₃ , and the alumina scraps in component B are counted as Al ₂ O ₃ , and the raw materials do not include Water introduced during the shaping of raw materials.

According to the present invention, the relative ratio between the component A and the component B is not particularly limited, and can be properly selected according to the specific application of the catalyst. Generally, the weight ratio of the component A to the component B is 9-1:1, preferably 9-2:1.

In the present invention, the component C is selected from cellulose ether, and the cellulose ether refers to an ether derivative formed after at least part of the hydrogen atoms on the hydroxyl groups in the cellulose molecule are replaced by one or more hydrocarbon groups, wherein , the multiple hydrocarbon groups may be the same or different. The hydrocarbyl group is selected from substituted hydrocarbyl groups and unsubstituted hydrocarbyl groups. The unsubstituted hydrocarbon group is preferably an alkyl group (for example: a C ₁ -C ₅ alkyl group). In the present invention, specific examples of C ₁ -C ₅ alkyl groups include C ₁ -C ₅ straight chain alkyl groups and C ₃ -C ₅ branched chain alkyl groups, which may be but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and tert-amyl. The substituted hydrocarbon group can be, for example, an alkyl group substituted by a hydroxyl group or a carboxyl group (for example: a C ₁ -C ₅ alkyl group substituted by a hydroxyl group, a C ₁ -C ₅ alkyl group substituted by a carboxyl group), specific examples of which can be Including but not limited to: hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, carboxymethyl, carboxyethyl and carboxypropyl.

In the present invention, the type of the cellulose ether and the number of substituents used to replace the hydrogen atoms on the hydroxyl groups in the cellulose molecule are not particularly limited, and may be various common cellulose ethers. Specifically, the cellulose ether (that is, the component C) may be selected from but not limited to: methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropyl Carboxymethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and carboxymethyl hydroxyethyl cellulose. Preferably, the cellulose ether (ie, the component C) is selected from methylcellulose, hydroxyethylmethylcellulose and hydroxypropylmethylcellulose.

According to the invention, said component A is selected from hydrated aluminum oxides. In the present invention, the type of the hydrated alumina is not particularly limited, and may be a conventional choice in the field. Preferably, the hydrated alumina (ie, the component A) is selected from boehmite, gibbsite, amorphous hydrated alumina and pseudoboehmite. More preferably, the hydrated alumina (ie, the component A) is pseudo-boehmite.

In the present invention, the component B is selected from Al ₂ O ₃ and alumina waste.

In the present invention, the type of Al ₂ O ₃ is not particularly limited, and it can be various Al ₂ O ₃ commonly used in this field, such as: γ-Al ₂ O ₃ , δ-Al ₂ O ₃ , θ-Al ₂ O ₃ and α - Al ₂ O ₃ . Preferably, the Al ₂ O ₃ is γ-Al ₂ O ₃ . More preferably, the γ-Al ₂ O ₃ has a pore volume of 0.8-1.2 mL/g and a specific surface area of 200-400 m ² /g. The pore volume and specific surface area are measured by nitrogen adsorption/desorption method.

In the present invention, the alumina waste refers to the preparation of various alumina moldings (including alumina moldings containing modifying elements and alumina moldings containing molecular sieves, and the modifying elements can be selected from, for example, silicon element, phosphorus element, titanium element, zirconium element, lithium element, magnesium element and boron element; the molecular sieve, for example, can be selected from Y molecular sieve and ZSM molecular sieve) waste generated during the process, for example: in the preparation of The waste generated during the process of acting on the catalyst support. In the present invention, the alumina scraps may specifically contain at least one selected from precursors capable of forming Al ₂ O ₃ and Al ₂ O ₃ under calcination conditions, adhesives, optional modifying elements, any The mixture of selected molecular sieves and optional extrusion aids is a waste generated during the preparation of alumina moldings. The precursor capable of forming alumina under calcination conditions can be a conventional choice in the field, for example: various forms of hydrated alumina (such as the aforementioned hydrated alumina). The leftovers of alumina can be roasted or uncalcined leftovers. The particle diameter of the alumina scraps is not particularly limited, as long as the raw material used to prepare the alumina hydrate-containing molding of the present invention can be shaped. Preferably, the average particle diameter of the alumina scraps is 50-120 microns. The average particle diameter of the alumina scraps can be within the above range by successively grinding and sieving the alumina scraps before use. In the present invention, the average particle diameter of the alumina leftovers is measured by a laser particle size analyzer.

According to the invention, the raw material may also contain at least one extrusion aid. The content of the extrusion aid can be conventionally selected in the art. Generally, based on the total amount of the raw materials, the total content of the extrusion aid may be 0.1-8% by weight, preferably 0.5-5% by weight. In the present invention, the type of the extrusion aid is not particularly limited, and it can be a conventional choice in the field. Preferably, the extrusion aid is starch (that is, the raw material also contains starch). The starch can be starch from various sources commonly used in this field, for example: powder obtained by crushing plant seeds, such as turnip powder.

According to the catalyst of the present invention, the raw materials can be shaped by various methods commonly used in the art. Preferably, the molded product is prepared from the raw material, dried and optionally calcined.

Various methods commonly used in the art can be used to prepare the molded body, and there is no particular limitation. For example: at least one component A, at least one component B and at least one component C can be mixed with water and the mixture can be shaped. The amount of water used to prepare the mixture is not particularly limited, as long as the amount of water used can ensure uniform mixing of various components.

According to the catalyst of the present invention, the molding method is not particularly limited, and various molding methods commonly used in the field can be used, such as extrusion, spheronization, spraying, tableting or combinations thereof. In a preferred embodiment of the present invention, the shape is formed by extrusion.

According to the catalyst of the present invention, the carrier can have various shapes according to specific usage requirements, for example: spherical, strip-shaped, ring-shaped, clover-shaped, honeycomb-shaped or butterfly-shaped.

According to the catalyst of the present invention, the temperature at which the shaped body is dried can be selected conventionally in the art. Generally, the drying temperature may be above 60°C and below 350°C, preferably 80-300°C, more preferably 120-250°C. The drying time can be properly selected according to the drying temperature, so as to ensure that the volatile content in the finally obtained molded product meets the requirements for use. Generally, the drying time may be 1-48 hours, preferably 2-24 hours, more preferably 2-12 hours. According to the present invention, the drying can be carried out under normal pressure or under reduced pressure.

According to the catalyst of the present invention, the shaped body prepared from the raw material can be directly used as the carrier of the catalyst of the present invention (that is, the carrier is a shaped body containing hydrated alumina) only through drying without roasting, or After being dried and calcined successively, it is used as the carrier of the catalyst of the present invention (that is, the carrier is an alumina molded product). In the present invention, the conditions for the calcination are not particularly limited, and may be conventional choices in the art. Specifically, the calcination temperature may be 450-950°C, preferably 500-900°C; the calcination time may be 2-8 hours, preferably 3-6 hours. From the point of view of further increasing the catalytic activity of the catalyst according to the invention, the carrier is preferably a shaped product comprising hydrated alumina.

According to the catalyst of the present invention, the support has good strength and absorption properties.

Specifically, the radial crushing strength loss rate (ie, δ value) of the support after soaking is less than 10%, even less than 5%, for example, less than 3.5%.

In the present invention, the δ value is used to evaluate the strength retention rate of the carrier, which is defined by the following formula:

$\mathrm{<span\; class="notranslate">\; \&delta;</span>}<span\; class="notranslate">\; =</span>\frac{{\mathrm{<span\; class="notranslate">\; Q</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; Q</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}}{{\mathrm{<span\; class="notranslate">\; Q</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; \%</span><span\; class="notranslate">\; ,</span>$

Wherein, Q ₁ is the radial crushing strength of the carrier without water immersion, in N/mm,

Q ₂ is the radial crushing strength of the support after soaking in water for 30 minutes and drying at 120° C. for 4 hours, in N/mm.

The radial crush strength (ie, Q ₁ ) of the carrier can be above 12 N/mm, even above 15 N/mm, generally 15-30 N/mm (eg 15-25 N/mm).

In the present invention, the radial crushing strength is measured according to the method specified in RIPP25-90 recorded in "Petrochemical Analysis Methods" (Science Press, first edition in 1990, edited by Yang Cuiding, etc.).

According to the present invention, the water absorption of the carrier is 0.4-1.5, generally 0.6-1.

In the present invention, the water absorption refers to the ratio of the weight change before and after soaking the dry carrier with excess deionized water for 30 minutes to the weight of the dry carrier. The specific test method is: dry the carrier to be tested at 120°C for 4 hours, then sieve it with a 40-mesh standard sieve, weigh 20g of the sieved material as the sample to be tested (denoted as w ₁ ), and remove the sample to be tested with 50g Soak in deionized water for 30 minutes, after filtering, drain the solid phase for 5 minutes, then weigh the weight of the drained solid phase (denoted as w ₂ ), and calculate the water absorption rate with the following formula:

According to the catalyst of the present invention, the catalyst may also contain various components capable of improving the catalytic performance of the catalyst, such as phosphorus element. In the present invention, the content of the component capable of improving the catalytic performance of the catalyst is not particularly limited, and may be a conventional selection in the art. Generally, based on the total amount of the catalyst, the content of the component capable of improving the catalytic performance of the catalyst may be 0.1-10% by weight, preferably 0.5-5% by weight.

The second aspect of the present invention provides a method for preparing a catalyst with hydrogenation catalysis, the method comprising supporting at least one metal element of Group VIII and at least one metal element of Group VIB on a carrier, wherein the The carrier is a shaped product of alumina or a shaped product containing hydrated alumina, which is obtained by shaping a raw material containing at least one component A, at least one component B and at least one component C, said component A It is selected from hydrated alumina, the component B is selected from Al ₂ O ₃ and alumina waste, and the component C is selected from cellulose ether.

According to the method of the present invention, the loading amount of the metal element containing Group VIII and the metal element containing Group VIB on the carrier is such that in the catalyst finally prepared, the content of the metal element of Group VIII and the metal element of Group VIB is Can meet the specific use requirements shall prevail. When the catalyst prepared according to the method of the present invention is used for the hydrotreating of hydrocarbon oil, the loading amount of the metal element of the VIB group and the metal element of the VIII group on the carrier is such that the final prepared catalyst Based on the total amount, the content of the carrier is 40-80% by weight, preferably 50-75% by weight; in terms of oxides, the content of the Group VIII metal element is 2-15% by weight, preferably 4- 10% by weight; based on oxides, the content of the Group VIB metal element is 15-45% by weight, preferably 20-40% by weight.

According to the method of the present invention, the Group VIII metal elements and Group VIB metal elements can be supported on the carrier by various methods commonly used in the art, such as impregnation. The impregnation may be saturated or excessive impregnation.

According to the method of the present invention, the metal element of Group VIII and the metal element of Group VIB can be loaded on the carrier at the same time, or the metal element of Group VIII and the metal element of Group VIB can be loaded on the carrier in stages. on the carrier.

In one embodiment of the present invention, the manner of loading the Group VIII metal element and the Group VIB metal element on the support includes: using a salt containing at least one Group VIII metal element and The support is impregnated with an aqueous solution of at least one compound containing a Group VIB metal element, and the impregnated support is dried.

In another embodiment of the present invention, the manner of loading the Group VIII metal element and the Group VIB metal element on the support includes: using a salt containing at least one Group VIII metal element impregnating the carrier with an aqueous solution of an impregnated carrier, drying the impregnated carrier, impregnating the carrier loaded with the salt containing the group VIII metal element with an aqueous solution containing at least one compound containing the group VIB metal element, and impregnating The obtained carrier is dried.

In yet another embodiment of the present invention, the manner of loading the Group VIII metal element and the Group VIB metal element on the support includes: using a compound containing at least one Group VIB metal element impregnating the carrier with an aqueous solution of an impregnated carrier, drying the impregnated carrier, impregnating the carrier loaded with the compound containing the VIB group metal element with an aqueous solution containing at least one salt containing the VIII group metal element, and impregnating The obtained carrier is dried.

According to the method of the present invention, the present invention is not particularly limited to the concentration of the aqueous solution, as long as the content of the Group VIII metal element and the Group VIB metal element in the final prepared catalyst can meet the requirements for use (such as the aforementioned requirements ) can be.

According to the method of the present invention, the impregnated support can be dried under common conditions in the art. Generally, the drying conditions include: the temperature may be 100-200° C., preferably 120-150° C.; the time may be 1-15 hours, preferably 3-10 hours.

According to the present invention, the salt containing the Group VIII metal element can be various water-soluble salts containing the Group VIII metal element commonly used in the art, for example: the salt containing the Group VIII metal element can be selected from inorganic acids Water-soluble Group VIII metal salts, water-soluble Group VIII metal salts of organic acids, and water-insoluble salts containing Group VIII metal elements formed by contacting in water with acids (such as phosphoric acid) and/or bases (such as ammonia water) water soluble salt.

Specifically, the salt containing the Group VIII metal element may be selected from but not limited to: cobalt nitrate, cobalt acetate, cobalt subcarbonate formed by contacting with acid (such as phosphoric acid) and/or alkali (such as ammonia water) in water Water-soluble salt, cobalt chloride, water-soluble cobalt complex, nickel nitrate, nickel acetate, basic nickel carbonate formed in water with acid (such as phosphoric acid) and/or alkali (such as ammonia) in contact with water-soluble salt, chloride Nickel, and water-soluble nickel complexes. The water-soluble cobalt complex, for example, may be cobalt ethylenediaminetetraacetate; the water-soluble nickel complex, for example, may be nickel citrate. Preferably, the salt containing the Group VIII metal element is selected from the group consisting of cobalt nitrate, cobalt subcarbonate in water and acid (such as phosphoric acid) and/or alkali (such as ammonia) in contact with water-soluble salts, basic nickel carbonate in Water-soluble salts formed in water by contact with acids (such as phosphoric acid) and/or bases (such as ammonia), and nickel nitrate.

According to the present invention, the type of the compound containing the VIB group metal element is not particularly limited, and can be various water-soluble compounds containing the VIB group metal element commonly used in the art, for example, it can be selected from water-soluble VIB group VIB compounds of inorganic acids. Group metal salts, water-soluble Group VIB metal salts of organic acids, heteropolyacids containing Group VIB metal elements, heteropolyacid salts containing Group VIB metal elements, and oxides of Group VIB metals in water and acid (such as phosphoric acid) or a water-soluble compound formed by contact with an alkali.

Specifically, the compound containing Group VIB metal elements can be selected from water-soluble salts of molybdic acid, water-soluble salts of paramolybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl ammonium metatungstate, phosphorus Tungstic acid, phosphomolybdic acid, nickel phosphotungstate, cobalt phosphotungstate, nickel silicotungstate, cobalt silicotungstate, nickel phosphomolybdate, cobalt phosphomolybdate, nickel phosphomolybdate, cobalt phosphomolybdate, silicon Nickel molybdate, cobalt silicomolybdate, nickel silicomolybdenum tungstate, cobalt silicomolybdenum tungstate and molybdenum oxide are water-soluble compounds formed in contact with phosphoric acid in water. In the present invention, the water-soluble salt of molybdic acid includes a water-soluble metal salt of molybdic acid and ammonium molybdate; the water-soluble salt of paramolybdic acid includes a water-soluble metal salt of paramolybdic acid and ammonium molybdate. Preferably, the compound containing Group VIB metal elements is selected from water-soluble compounds formed by contacting ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, ammonium tungstate and molybdenum oxide in water with phosphoric acid.

According to the method of the present invention, the carrier loaded with the VIII group metal element and the VIB group metal element can be calcined (that is, in the prepared catalyst, the VIII group metal element and the VIB group metal are supported in the form of oxide on the carrier), or not to be calcined (that is, in the prepared catalyst, the metal elements of Group VIII and Group VIB are basically loaded on the carrier in the form of salt; that is, the prepared In the catalyst, the Group VIII metal elements and Group VIB metal elements are basically supported on the support in the form of non-oxides). From the viewpoint of further improving the catalytic activity of the catalyst prepared according to the method of the present invention, the metal elements of Group VIII and Group VIB are preferably loaded on the carrier substantially in the form of salts. That is, according to the method of the present invention, the support carrying the metal element of Group VIII and the metal element of Group VIB is preferably not calcined.

According to the method of the present invention, the carrier is obtained by molding a raw material containing at least one component A, at least one component B and at least one component C, the component A being selected from hydrated alumina, The component B is selected from Al ₂ O ₃ and alumina leftovers, and the component C is selected from cellulose ethers. The carrier may be a shaped product containing hydrated alumina, or a shaped product of alumina; from the perspective of further improving the catalytic activity of the prepared catalyst, the carrier is preferably a shaped product containing hydrated alumina. The preparation method of the carrier has been described above and will not be described in detail here.

According to the method of the present invention, the radial crushing strength of the carrier can be above 12N/mm, even above 15N/mm, generally 15-30N/mm, such as 15-25N/mm. The δ value of the carrier is 10% or less, even 5% or less, for example, 3.5% or less. The water absorption of the carrier is 0.4-1.5, generally 0.6-1.

According to the method of the present invention, it may also include introducing components capable of improving the catalytic performance of the final prepared catalyst, such as phosphorus element, onto the carrier. The component can be introduced onto the carrier before loading the Group VIII metal element and the VIB Group metal element; or while loading the Group VIII metal element and the VIB Group metal element, The components are loaded on the carrier. The introduction amount of the components capable of improving the performance of the catalyst can be selected conventionally in the art. Generally, based on the total amount of the catalyst, the content of the component capable of improving the catalytic performance of the catalyst may be 0.1-10% by weight, preferably 0.5-5% by weight.

The catalyst with hydrogenation catalysis prepared according to the method of the present invention shows higher catalytic activity in the hydroprocessing of hydrocarbon oil.

Thus, in a third aspect the present invention provides a catalyst having hydrogenation catalysis prepared by the process of the present invention.

The catalyst with hydrogenation catalytic effect provided by the invention is suitable for the hydrotreating process of various hydrocarbon oil raw materials.

Thus, the fourth aspect of the present invention provides an application of the catalyst having a hydrocatalytic effect according to the present invention in the hydroprocessing of hydrocarbon oil.

The fifth aspect of the present invention provides a hydroprocessing method, which comprises contacting the hydrocarbon oil with the catalyst of the present invention under the condition of hydrotreating the hydrocarbon oil.

According to the hydroprocessing method of the present invention, higher hydrogenation activity is obtained by using the catalyst provided by the present invention. There is no special limitation on the type of hydrocarbon oil and the hydroprocessing conditions, which can be conventional choices in this field.

Specifically, the hydrocarbon oil can be various heavy mineral oils, synthetic oils or their mixed distillates. , Fischer-Tropsch synthetic oil, coal liquefaction oil, light deasphalted oil and heavy deasphalted oil. The hydrotreating conditions include: the temperature can be 300-380°C; the pressure can be 4-8MPa in terms of gauge pressure; the liquid hourly volume space velocity of hydrocarbon oil can be 1-3 hours ^-1 ; the hydrogen-oil volume ratio can be For 200-1000.

According to the hydroprocessing method of the present invention, the catalyst can be presulfurized under conventional conditions in the art before use. The presulfurization conditions can be, for example, presulfurization with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370°C in the presence of hydrogen, and the presulfurization can be carried out outside the reactor or inside the reactor in-situ vulcanization.

The present invention will be described in detail below in conjunction with examples and comparative examples.

In the following examples and comparative examples, the radial crushing strength of the prepared carrier was measured by the method specified in RIPP25-90.

In the following examples and comparative examples, the following method was used to measure the δ value of the prepared carrier: the method specified in RIPP25-90 was used to measure the radial crushing strength of the carrier without water soaking (denoted as Q ₁ ); the prepared The carrier was placed in 50g of deionized water, soaked for 30 minutes, then filtered, and the obtained solid was dried at a temperature of 120°C for 4 hours, and the radial crushing strength of the dried solid was measured according to the method specified in RIPP25-90 (denoted as Q ₂ ), the δ value was calculated using the following formula,

$\mathrm{<span\; class="notranslate">\; \&delta;</span>}<span\; class="notranslate">\; =</span>\frac{{\mathrm{<span\; class="notranslate">\; Q</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}<span\; class="notranslate">\; -</span>{\mathrm{<span\; class="notranslate">\; Q</span>}}_{\mathrm{<span\; class="notranslate">\; 2</span>}}}{{\mathrm{<span\; class="notranslate">\; Q</span>}}_{\mathrm{<span\; class="notranslate">\; 1</span>}}}<span\; class="notranslate">\; \&times;</span>\mathrm{<span\; class="notranslate">\; 100</span>}<span\; class="notranslate">\; \%</span><span\; class="notranslate">\; .</span>$

In the following examples and comparative examples, the following method was used to measure the water absorption of the prepared carrier: the carrier to be tested was dried at 120°C for 4 hours, then sieved with a 40-mesh standard sieve, and 20 g of the sieved material was weighed as the sample to be tested (denoted as w ₁ ), soak the sample to be tested in 50g deionized water for 30 minutes, after filtering, drain the solid phase for 5 minutes, then weigh the weight of the drained solid phase (denoted as w ₂ ), use the following Formula to calculate water absorption:

In the following examples and comparative examples, the dry content is determined by roasting the test sample at 600° C. for 4 hours.

In the following examples and comparative examples, the pore volume and specific surface area were measured by nitrogen adsorption/desorption method.

In the following examples and comparative examples, the average particle diameter is measured by using a laser particle size analyzer commercially available from Micromeritics Company as Saturn DigiSizer 5200.

Examples 1-9 are used to illustrate the catalyst of the present invention and its preparation method.

Example 1

(1) 80.0g of pseudo-boehmite powder (purchased from Sinopec Catalyst Changling Branch, with a dry basis content of 69.5% by weight), 20g of γ-Al ₂ O ₃ (with a pore volume of 0.95mL/g and a specific surface area of 290m ² /g), 4.0 g of methylcellulose (purchased from Zhejiang Haishen Chemical Co., Ltd.), 3.0 g of scallop powder and 95 mL of deionized water were mixed evenly. The resulting mixture is fed into an extruder and extruded to obtain a wet strip. The extruded wet strip was placed in an oven and dried at 150° C. for 12 hours, thereby obtaining the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Dissolve 5.88g basic nickel carbonate (NiO content is 51% by weight), 15.0g molybdenum oxide and 2.79g phosphoric acid in water to prepare a 60mL solution; impregnate 20.0g of the carrier prepared in step (1) into the obtained solution (diameter of 1.1mm, particle length of 2-5mm, dry basis content of 77.0% by weight), and the impregnation time was 4 hours. After filtration, the obtained solid product was dried at 120° C. for 4 hours to obtain catalyst B1 according to the present invention. The catalyst was analyzed by XRF and the results are shown in Table 2.

Comparative example 1

(1) Mix 80.0g of pseudoboehmite powder (same as in Example 1), 20.0g of γ-Al ₂ O ₃ (same as in Example 1), 2.5mL of concentrated nitric acid, 4.0g of scallop powder and 95mL of deionized water. The resulting mixture is fed into an extruder and extruded to obtain a wet strip. The extruded wet strip was placed in an oven, dried at 150° C. for 12 hours, and then calcined at 600° C. for 4 hours to obtain a carrier. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) 2.24g basic nickel carbonate (NiO content: 51% by weight), 5.69g molybdenum oxide and 1.06g phosphoric acid were dissolved in water to prepare 12.0mL nickel-molybdenum-phosphorus solution. The resulting solution was impregnated with 14.3 g of the carrier (1.1 mm in diameter and 2-5 mm in particle length) prepared in step (1) for 1 hour. The obtained solid product was dried at 120° C. for 4 hours, and then calcined at 600° C. for 3 hours to obtain catalyst A1. The catalysts were analyzed by XRF, and the results are listed in Table 2.

Comparative example 2

(1) The carrier was prepared by the same method as in Comparative Example 1, except that the calcination was not carried out at 600°C to obtain the carrier, and its radial crushing strength, water absorption and δ value are listed in Table 1.

(2) The catalyst was prepared by the same method as in Comparative Example 1. The difference was that the carrier was the carrier prepared in Step (1) of Comparative Example 2. During the impregnation process, the carrier appeared to dissolve and collapse, and as a result, a formed catalyst could not be obtained. .

Comparative example 3

(1) The carrier was prepared by the same method as in Comparative Example 1, and its radial crushing strength, water absorption and δ values are listed in Table 1.

(2) The catalyst was prepared by the same method as in Comparative Example 1, except that the calcination was not performed at 600° C., thereby obtaining catalyst A2. The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 2

(1) 50.0g of pseudoboehmite (purchased from Sinopec Catalyst Changling Branch, with a dry basis content of 69.5% by weight), 20.0g of gibbsite (purchased from Guangxi Pingguo Aluminum Company, with a dry basis content of 64.5% by weight), 30.0g of alumina scraps (the scraps are roasted at 600°C for 4 hours, and the average particle diameter is 100 microns. The alumina scraps are made of pseudo thin water The mixture of bauxite, nitric acid and sage powder, produced in the process of preparing alumina moldings as the carrier of catalysts with hydrogenation catalysis by extrusion), 2.0g methyl cellulose (purchased from Zhejiang Haishen Chemical Co., Ltd.), 3.0 g of hydroxyethyl methylcellulose (purchased from Shanghai Huiguang Fine Chemical Co., Ltd.) and 95 mL of deionized water were stirred evenly. The resulting mixture is fed into an extruder and extruded to obtain a wet strip. The obtained wet strip was placed in an oven and dried at 220° C. for 6 hours, thereby obtaining the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Dissolve 6.00g of basic cobalt carbonate (CoO content is 70% by weight), 21.00g of molybdenum oxide and 3.91g of phosphoric acid in water to prepare 60mL of nickel-molybdenum-phosphorus solution. The obtained solution was impregnated with 20.0 g of the carrier (1.1 mm in diameter, 2-5 mm in particle length, and 79.2% by weight on a dry basis) prepared in step (1) for 4 hours. After filtration, the obtained solid was dried at 120° C. for 4 hours to obtain catalyst B2 of the present invention. The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 3

(1) 70.0g of pseudo-boehmite (purchased from Sinopec Catalyst Changling Branch, with a dry basis content of 69.5% by weight), 30.0g of γ-Al ₂ O ₃ (with a pore volume of 0.95mL/g and a specific surface area of 290m ² /g), 1.0g methyl cellulose (purchased from Zhejiang Haishen Chemical Co., Ltd.), 2.0g hydroxypropyl methylcellulose (purchased from Zhejiang Haishen Chemical Co., Ltd.), 3.0g squash powder and 95mL Deionized water and stir well. The resulting mixture is fed into an extruder and extruded to obtain a wet strip. The obtained wet strip was placed in an oven and dried at 80° C. for 12 hours, thereby obtaining the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Dissolve 7.10g nickel nitrate (Ni(NO ₃ ) ₂ 6H ₂ O) and 28.19g ammonium metatungstate ((NH ₄ ) ₆ W ₇ O ₂₄ 4H ₂ O) in water to prepare 21.4mL nickel tungsten solution. The obtained solution was impregnated with 20.0 g of the carrier (1.1 mm in diameter, 2-5 mm in particle length, and 78.2% by weight on a dry basis) prepared in step (1) for 1 hour. The obtained support was dried at 120° C. for 4 hours, thereby obtaining catalyst B3 according to the invention. The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 4

(1) In a 2L reaction tank, add 2000mL of aluminum sulfate solution with a concentration of 48g/L and sodium metaaluminate solution (with an Al ₂ O ₃ content of 200g/L and a caustic coefficient of 1.58) in parallel to carry out precipitation reaction , the reaction temperature is 50°C, the pH value is 6.0, and the reaction residence time is 15 minutes; the obtained slurry is filtered with a vacuum filter, and after the filtration is completed, 20L deionized water is added to the filter cake (the temperature is 40± 5°C) to rinse the filter cake for about 60 minutes. Add the washed filter cake to 1.5L deionized water and stir to form a slurry, then pump the slurry into the spray dryer for drying, control the outlet temperature of the spray dryer within the range of 100-110°C, and the material drying time for 2 minutes to obtain hydrated alumina, wherein the content of Al ₂ O ₃ was 63% by weight, which was determined to be amorphous by XRD analysis.

(2) 50.0g of pseudo-boehmite SB powder (purchased from Sasol, with a dry basis content of 75.0% by weight), 25.0g of amorphous hydrated alumina prepared in step (1), and 25.0g of alumina waste (the The leftovers are not roasted, the average particle diameter is 80 microns, the _Al2O3 content is 68.8% by weight, and the Y _- type molecular sieve content is 10% by weight. The alumina leftovers are made of pseudoboehmite and Y-type molecular sieve with nitric acid and The mixture of kale powder, produced in the process of preparing the aluminum oxide molded product as the carrier of the catalyst with hydrogenation catalysis by extrusion), 3.0g hydroxyethyl methylcellulose (purchased from Shanghai Huiguang Fine Chemical Co., Ltd.), 3.0g of sage powder and 90mL of deionized water were stirred evenly. The resulting mixture is fed into an extruder and extruded to obtain a wet strip. The obtained wet strip was placed in an oven and dried at 150° C. for 12 hours, so as to obtain the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(3) Dissolve 5.00g of basic nickel carbonate (NiO content is 51% by weight), 13.25g of molybdenum oxide and 1.32g of phosphoric acid in water to prepare 60mL of nickel-molybdenum-phosphorus solution. The obtained solution was impregnated with 20 g of the carrier (1.1 mm in diameter, 2-5 mm in particle length, and 75.9% by weight on a dry basis) prepared in step (1) for 4 hours. After filtration, the obtained solid product was dried at 120° C. for 4 hours, thereby obtaining catalyst B4 according to the present invention. The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 5

(1) 85.0g of pseudo-boehmite SB powder (purchased from Sasol Company, with a dry basis content of 75.0% by weight), 15.0g of alumina scraps (the scraps have not been roasted, and the average particle diameter is 120 microns, Al The content of ₂ O ₃ is 79.7% by weight, and the content of titanium element is 10% by weight in terms of oxides. The alumina leftovers are prepared by extruding a mixture of pseudo-boehmite, nitric acid and turmeric powder Produced in the process of alumina molding used as a catalyst carrier with hydrogenation catalysis), 3.0g hydroxyethyl methylcellulose (purchased from Shanghai Huiguang Fine Chemical Co., Ltd.), 2.0g hydroxypropyl methylcellulose Base cellulose (purchased from Shanghai Huiguang Fine Chemical Co., Ltd.), 3.0 g of scallop powder and 90 mL of deionized water were mixed evenly. The resulting mixture is fed into an extruder and extruded to obtain a wet strip. The obtained wet strip was placed in an oven and dried at 250° C. for 4 hours to obtain the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Dissolve 3.50g basic nickel carbonate (NiO content: 51% by weight), 9.10g molybdenum oxide and 0.90g phosphoric acid in water to prepare 60mL nickel-molybdenum-phosphorus solution. The obtained solution was impregnated with 20 g of the carrier prepared in step (1) (1.1 mm in diameter, 2-5 mm in particle length, and 81.5% by weight on a dry basis), and the impregnation time was 4 hours. After filtration, the obtained solid was dried at 150° C. for 3 hours to obtain catalyst B5 of the present invention. The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 6

(1) 90.0g of pseudo-boehmite (purchased from Shandong Yantai Henghui Chemical Co., Ltd., with a dry basis content of 71.0% by weight), 10.0g of γ-Al ₂ O ₃ (with a pore volume of 0.95mL/g and a specific surface area of 290m ² /g), 5.0g of hydroxypropyl methylcellulose (purchased from Shanghai Huiguang Fine Chemical Co., Ltd.), 3.0g of celadon powder and 90mL of deionized water were mixed evenly. The resulting mixture is fed into an extruder and extruded to obtain a wet strip. The obtained wet strip was placed in an oven and dried at 120° C. for 4 hours to obtain the carrier in the catalyst of the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Dissolve 10.40g of basic nickel carbonate (NiO content is 51% by weight), 25.28g of molybdenum oxide and 2.34g of phosphoric acid in water to prepare 60mL of nickel-molybdenum-phosphorus solution. The obtained solution was impregnated with 20 g of the carrier (1.1 mm in diameter, 2-5 mm in particle length, and 74.2% by weight on a dry basis) obtained in step (1) for 4 hours. After filtration, the obtained solid product was dried at 120° C. for 4 hours, thereby obtaining catalyst B6 according to the present invention. The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 7

(1) A hydrated alumina molded product was prepared by the same method as in Example 6, except that the content of hydroxypropyl methylcellulose was 6.6 g, so as to obtain the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Catalyst B7 was prepared in the same manner as in Example 6, except that the carrier was the carrier prepared in step (1) of Example 7 (1.1 mm in diameter, 2-5 mm in particle length, and a dry basis content of 73.0 wt. %). The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 8

(1) The molded article was prepared by the same method as in Example 3, except that the obtained wet strip was placed in an oven and dried at 120° C. for 12 hours, so as to obtain the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Catalyst B8 was prepared in the same manner as in Example 3, except that the carrier was the carrier prepared in step (1) of Example 8 (1.1 mm in diameter, 2-5 mm in particle length, and a dry basis content of 79.7 wt. %). The catalysts were analyzed by XRF, and the results are listed in Table 2.

Example 9

(1) The molded article was prepared by the same method as in Example 5, except that the obtained wet strip was placed in an oven and dried at 300° C. for 4 hours, so as to obtain the carrier in the catalyst according to the present invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 1.

(2) Catalyst B9 was prepared in the same manner as in Example 5, except that the carrier was the carrier prepared in step (1) of Example 9 (the diameter was 1.1 mm, the particle length was 2-5 mm, and the dry basis content was 82.3 wt. %). The catalysts were analyzed by XRF, and the results are listed in Table 2.

Table 1

Numbering Crushing strength (N/mm) water absorption δ value (%) Example 1 21.6 0.87 2.8 Comparative example 1 21.9 0.96 2.2 Comparative example 2 19.5 0.93 52.0 Comparative example 3 21.9 0.96 2.2 Example 2 17.7 0.83 2.1 Example 3 15.4 0.94 3.2 Example 4 20.9 0.80 1.5 Example 5 18.9 0.73 2.0 Example 6 18.3 0.82 3.4 Example 7 20.5 0.80 2.9 Example 8 15.9 0.96 3.1 Example 9 19.3 0.69 2.2

The results in Table 1 show that the carrier in the catalyst according to the present invention has a good strength retention rate, and still has a high crushing strength even after soaking in water.

Table 2

Examples 10-18 are used to illustrate the catalyst of the present invention and its application and hydroprocessing method.

Examples 10-18

Using 4,6-dimethyldibenzothiophene (4,6-DMDBT) as a model compound, the activities of the catalysts prepared in Examples 1-9 were evaluated on a high-pressure hydrogenation microreactor, and the specific conditions were as follows.

Reaction raw material: n-decane solution of 4,6-DMDBT, wherein the concentration is 0.45% by weight;

Catalyst sulfidation conditions: temperature is 360°C, pressure is 4.2MPa, flow rate of _H2 is 400mL/min, sulfide oil adopts cyclohexane solution with CS2 mass fraction of ₅ % by weight, and feed rate of sulfide oil is 0.4mL/min , Vulcanization was carried out for 3 hours.

Hydrodesulfurization reaction conditions: the reaction temperature is 280°C, the pressure is 4.2MPa, the _H2 flow rate is 400mL/min, the feed rate of the reaction raw materials is 0.2mL/min, after the reaction is stable for 3 hours, samples are taken for analysis by gas chromatography.

Calculate the desulfurization rate according to the following formula, thereby evaluating the hydrodesulfurization activity of the catalyst, and the results are listed in Table 3,

Desulfurization rate (%) = conversion rate of 4,6-DMDBT × (S _DMBCH + S _DMCHB + S _DMBP ) × 100%

Among them, S _DMBCH , S _DMCHB and S _DMBP are the selectivities of dimethylbicyclohexane, dimethylcyclohexylbenzene and dimethylbiphenyl in the products obtained by hydrodesulfurization of 4,6-DMDBT, respectively.

Comparative example 4-5

The hydrodesulfurization activities of the catalysts prepared in Comparative Examples 1 and 3 were evaluated by the same method as in Examples 9-18, and the results are listed in Table 3.

table 3

Numbering Catalyst number Desulfurization rate (%) Example 10 B1 77.7 Comparative example 4 A1 55.1 Comparative example 5 A2 50.6 Example 11 B2 73.8 Example 12 B3 74.9 Example 13 B4 76.8 Example 14 B5 75.6 Example 15 B6 82.5 Example 16 B7 81.3 Example 17 B8 76.2 Example 18 B9 75.1

Examples 19-22 illustrate the catalysts of the present invention and their preparation.

Example 19

The catalyst is prepared in the same manner as in Example 1, except that the carrier prepared in step (1) of Example 1 is calcined under the conditions listed in Table 4 to obtain the carrier used in the catalyst according to the present invention, This in turn gives catalyst B10 according to the invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 4. The catalysts were analyzed by XRF, and the results are listed in Table 5.

Example 20

The catalyst is prepared in the same manner as in Example 2, except that the carrier prepared according to the step (1) of Example 2 is calcined under the conditions listed in Table 4 to obtain the carrier used in the catalyst according to the present invention, This in turn gives catalyst B11 according to the invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 4. The catalysts were analyzed by XRF, and the results are listed in Table 5.

Example 21

The catalyst is prepared in the same manner as in Example 4, except that the carrier prepared in step (1) of Example 4 is calcined under the conditions listed in Table 4 to obtain the carrier used in the catalyst according to the present invention, This in turn gives catalyst B12 according to the invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 4. The catalysts were analyzed by XRF, and the results are listed in Table 5.

Example 22

The catalyst is prepared in the same manner as in Example 5, except that the carrier prepared according to step (1) of Example 5 is calcined under the conditions listed in Table 4 to obtain the carrier used in the catalyst according to the present invention, This in turn gives catalyst B13 according to the invention. The radial crushing strength, water absorption and δ value of the obtained carrier were measured, and the results are listed in Table 4. The catalysts were analyzed by XRF, and the results are listed in Table 5.

Table 4

table 5

Examples 23-26 serve to illustrate the catalyst according to the invention and its use and hydrotreatment process.

Examples 23-26

The hydrodesulfurization activities of the catalysts prepared in Examples 19-22 were respectively evaluated by the same method as in Examples 10-18, and the results are listed in Table 6.

Table 6

Numbering Catalyst number Desulfurization rate (%) Example 23 B10 69.7 Example 24 B11 66.2 Example 25 B12 68.6 Example 26 B13 67.6

The results in Table 3 and Table 6 show that the catalyst according to the present invention shows higher catalytic activity in the hydroprocessing of hydrocarbon oil.

Claims (39)

1. A catalyst with hydrogenation catalysis effect comprises a carrier, and at least one VIII group metal element and at least one VIB group metal element loaded on the carrier, and is characterized in that the carrier is an alumina forming product or a forming product containing hydrated alumina, and is obtained by forming a raw material, wherein the raw material comprises at least one component A, at least one component B, at least one component C and at least one extrusion aid with or without, the component A is selected from the hydrated alumina, and the component B is selected from the Al₂O₃And oxidation ofAluminum scraps, wherein the component C is selected from cellulose ether;

based on the total amount of the raw materials, the content of the component C is 0.5 to 12 weight percent, and Al is used₂O₃The component A and Al₂O₃The total content of the component B is 88-99 wt%, and the weight ratio of the component A to the component B is 9-1: 1.

2. the catalyst according to claim 1, wherein the carrier is present in an amount of 40 to 80 wt%, the group VIII metal element is present in an amount of 2 to 15 wt%, and the group VIB metal element is present in an amount of 15 to 45 wt%, calculated as oxides, based on the total amount of the catalyst.

3. The catalyst according to claim 1 or 2, wherein the group VIII metal element is cobalt and/or nickel and the group VIB metal element is molybdenum and/or tungsten.

4. The catalyst according to claim 1, wherein the content of the component C is 1 to 10% by weight based on the total amount of the raw material, as Al₂O₃The component A and Al₂O₃The total content of component B is 90-98 wt.%.

5. The catalyst according to claim 4, wherein the content of the component C is 3 to 8% by weight based on the total amount of the raw material, as Al₂O₃The component A and Al₂O₃The total content of component B is 92 to 96 wt.%.

6. The catalyst of any one of claims 1, 4 and 5, wherein the weight ratio of component A to component B is 9-2: 1.

7. the catalyst according to any one of claims 1, 4 and 5, wherein component C is selected from the group consisting of methylcellulose, hydroxyethylmethylcellulose and hydroxypropylmethylcellulose.

8. The catalyst of any one of claims 1, 4 and 5, wherein component A is selected from boehmite, gibbsite, amorphous hydrated alumina and pseudoboehmite.

9. The catalyst of claim 1, wherein the Al is₂O₃Is gamma-Al₂O₃。

10. The catalyst of claim 1 wherein the alumina trim has an average particle diameter of 50 to 120 microns.

11. The catalyst according to claim 1 or 2, wherein the water absorption of the carrier is 0.4-1.5, the value is 10% or less, Q₁Is more than 12N/mm, and the grain size is less than 12N/mm,

wherein, $\mathrm{\&delta;}=\frac{Q_1-Q_2}{Q_1}\&times;100\%,$

Q₁the radial crush strength, in N/mm, of the carrier that has not been soaked in water,

Q₂the radial crush strength in N/mm of the carrier after soaking in water for 30 minutes and drying at 120 ℃ for 4 hours.

12. The method of claim 11Wherein the carrier has a water absorption of 0.6 to 1 and a value of 5% or less, and Q₁Is 15-30N/mm.

13. The catalyst according to claim 1, wherein the extrusion aid is present in an amount of 0.1 to 8 wt.%, based on the total amount of the feedstock.

14. The catalyst according to claim 13, wherein the extrusion aid is present in an amount of 0.5-5 wt.%, based on the total amount of the feedstock.

15. The catalyst of any one of claims 1, 13 and 14, wherein the extrusion aid is starch.

16. The catalyst of any one of claims 1, 13, and 14, wherein the extrusion aid is sesbania powder.

17. A method for preparing a catalyst with hydrogenation catalysis effect, which comprises loading at least one VIII group metal element and at least one VIB group metal element on a carrier, and is characterized in that the carrier is alumina forming matter or forming matter containing hydrated alumina and is obtained by forming a raw material, wherein the raw material consists of at least one component A, at least one component B, at least one component C and at least one extrusion assistant containing or not, the component A is selected from the hydrated alumina, the component B is selected from the Al₂O₃And alumina trim, said component C being selected from cellulose ethers;

based on the total amount of the raw materials, the content of the component C is 0.5 to 12 weight percent, and Al is used₂O₃The component A and Al₂O₃The total content of the component B is 88-99 wt%, and the weight ratio of the component A to the component B is 9-1: 1.

18. the process according to claim 17, wherein the support is loaded with at least one group VIII metal element and at least one group VIB metal element by impregnation.

19. The process according to claim 17 or 18, wherein the group VIB and group VIII metal elements are supported on a carrier in such an amount that the carrier is present in an amount of 40 to 80 wt.%, the group VIII metal element is present in an amount of 2 to 15 wt.% and the group VIB metal element is present in an amount of 15 to 45 wt.%, calculated as oxide, based on the total amount of the finally prepared catalyst.

20. The process according to claim 17 or 18, wherein the group VIII metal element is cobalt and/or nickel and the group VIB metal is molybdenum and/or tungsten.

21. The method of claim 17, wherein the support is a molded alumina form and the method of preparing the support from the feedstock comprises: forming the raw materials, and drying and roasting the obtained formed bodies in sequence; or

The carrier is a molding containing hydrated alumina, and the method for preparing the carrier from the raw materials comprises the following steps: the raw material is molded, and the molded body obtained is dried.

22. The method of claim 21, wherein the firing conditions comprise: the temperature is 450 ℃ and 950 ℃, and the time is 2-8 hours;

the drying temperature is 60 ℃ or higher and lower than 350 ℃.

23. The method of claim 22, wherein the temperature of the drying is 80-300 ℃.

24. According to claim 17 or 2The method of 1, wherein the content of the component C is 1 to 10% by weight based on the total amount of the raw materials, as Al₂O₃The component A and Al₂O₃The total content of component B is 90-98 wt.%.

25. The method of claim 24, wherein the content of component C is 3-8 wt% based on the total amount of the raw material, as Al₂O₃The component A and Al₂O₃The total content of component B is 92 to 96 wt.%.

26. The method of claim 17 or 21, wherein component C is selected from methylcellulose, hydroxyethylmethylcellulose, and hydroxypropylmethylcellulose.

27. The process of claim 17 or 21 wherein component a is selected from boehmite, gibbsite, amorphous hydrated alumina and pseudoboehmite.

28. The method of claim 17 or 21, wherein the Al is₂O₃Is gamma-Al₂O₃。

29. A process as claimed in claim 17 or claim 21, in which the alumina trim has an average particle diameter of 50 to 120 microns.

30. The method of any one of claims 17, 18 and 21, wherein the carrier has a water absorption of 0.4-1.5 with a value of 10% or less, Q₁Is more than 12N/mm, and the grain size is less than 12N/mm,

wherein, $\mathrm{\&delta;}=\frac{Q_1-Q_2}{Q_1}\&times;100\%,$

Q₁the radial crush strength, in N/mm, of the carrier that has not been soaked in water,

Q₂the radial crush strength in N/mm of the carrier after soaking in water for 30 minutes and drying at 120 ℃ for 4 hours.

31. The method of claim 30, wherein the carrier has a radial crush strength of 15-30N/mm, a water absorption of 0.6-1, and a value of 5% or less.

32. The method according to claim 17, wherein the extrusion aid is present in an amount of 0.1-8 wt.%, based on the total amount of the feedstock.

33. The method of claim 32, wherein the extrusion aid is present in an amount of 0.5-5 wt% based on the total amount of the feedstock.

34. The method of any one of claims 17, 32, and 33, wherein the extrusion aid is starch.

35. The method of any one of claims 17, 32, and 33, wherein the extrusion aid is sesbania powder.

36. The method of claim 17, wherein the weight ratio of component a to component B is 9-2: 1.

37. a catalyst prepared by the process of any one of claims 17 to 36.

38. Use of a catalyst according to any one of claims 1 to 16 and 37 in the hydroprocessing of hydrocarbon oils.

39. A hydroprocessing process comprising contacting a hydrocarbon oil under hydroprocessing conditions with a catalyst, characterized in that the catalyst is as defined in any one of claims 1-16 and 37.