CN106140308B - A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils - Google Patents

Abstract

A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils, the catalyst contain carrier and at least one selected from group VIII and at least one metal component selected from group VIB, which is characterized in that the carrier is contains R₁R₂R₃R₄N⁺X^‑Aluminium oxide molding, on the basis of the carrier, the R₁R₂R₃R₄N⁺X^‑Mass fraction be 0.1%-10%, the catalyst also contains except R₁R₂R₃R₄N⁺X^‑The second outer organic matter, on the basis of catalyst, the mass fraction of second organic matter is 0.1-30%.Compared with prior art, the performance that the present invention provides catalyst is improved.

Description

A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils

Technical field

The present invention relates to a kind of hydrogenation catalyst and its applications.

Background technique

It is raw that the environmental consciousness being increasingly enhanced and the environmental regulation being increasingly stringenter force oil refining circle more to focus on clean fuel Technological development is produced, how the production super-low sulfur oil product of economical rationality, which has become, needs weight in oil refining circle's current and expected future regular period One of the project that point solves.And developing the novel hydrogenation catalyst with more high activity and selectivity then is to produce clear gusoline most Economic one of method.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of hydrogenation catalyst that performance is improved and its applications.

The present invention relates to the following contents:

1. a kind of hydrogenation catalyst is selected from group VIB containing carrier and at least one group VIII and at least one of being selected from Metal component, which is characterized in that the carrier be contain R₁R₂R₃R₄N⁺X^-Aluminium oxide molding, using the carrier as base Standard, the R₁R₂R₃R₄N⁺X^-Mass fraction be 0.1%-10%, the R₁R₂R₃R₄N⁺X^-Selected from primary amine salt, secondary amine salt, tertiary amine One or more of salt or quaternary ammonium salt, wherein the R₁、R₂、R₃、R₄Selected from hydrogen, hydrocarbon substituent and its derivative；The catalysis Agent also contains except R₁R₂R₃R₄N⁺X^-The second outer organic matter, on the basis of catalyst, the mass fraction of second organic matter is 0.1-30%.

2. the catalyst according to 1, which is characterized in that on the basis of the carrier, the R₁R₂R₃R₄N⁺X^-Quality Score is 0.3%-5%, and on the basis of catalyst, the mass fraction of second organic matter is 1-22%.

3. the catalyst according to 1, which is characterized in that the hydrocarbon substituent is selected from the linear chain or branched chain alkane of C1-C20 Base, or the naphthenic base selected from C3-C20, or the aryl selected from C6-C20；The derivative of the hydrocarbon substituent is selected from band There is the alkyl of hydroxyl and/or heterocyclic substituent.

4. the catalyst according to 3, which is characterized in that the hydrocarbon substituent is selected from the linear chain or branched chain alkane of C1-C18 Base；Either it is selected from the naphthenic base of C6-C18；Either it is selected from the aryl of C6-C18.

5. according to the described in any item catalyst in 1,2 or 3, which is characterized in that the X is selected from chlorine, bromine or iodine.

6. the catalyst according to 5, which is characterized in that the X is selected from chlorine or bromine.

7. according to the described in any item catalyst in 1,2 or 3, which is characterized in that the R₁R₂R₃R₄N⁺X^-Selected from cetyl Trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, myristyl Trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, Didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecyls two Ammonio methacrylate, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double octadecyldimethyl brominations Ammonium, dioctadecyl dimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride one kind or It is a variety of.

8. according to the described in any item catalyst in 1,2 or 3, which is characterized in that the R₁R₂R₃R₄N⁺X^-Selected from ethanolamine salt, Dococylpyridinium hydrochloride.

9. the catalyst according to 1, which is characterized in that second organic matter is in organic carboxyl acid and its ammonium salt It is one or more of.

10. the catalyst according to 9, which is characterized in that the organic carboxyl acid is selected from trans- 1,2- cyclohexanediamine tetrem Acid, ethylenediamine tetra-acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and apple One of acid is a variety of.

11. the catalyst according to 1, which is characterized in that the group VIII metal is selected from nickel and/or cobalt, and described the Group vib metal is selected from molybdenum and/or tungsten, and on the basis of the catalyst, the mass fraction of the group VIII metal component is 1- 10%, the mass fraction of vib metals component is 5-40%.

12. the catalyst according to 11, which is characterized in that on the basis of the catalyst, the group VIII metal The mass fraction of component is 1.5-6%, and the mass fraction of vib metals component is 10-35%.

13. the catalyst according to 1, which is characterized in that containing selected from silica, oxidation in the aluminium oxide molding One or more of titanium, magnesia, zirconium oxide, thorium oxide, beryllium oxide adjuvant component, it is described to help on the basis of the carrier The mass fraction of agent component is 10% or less.

14. the molding according to 13, which is characterized in that on the basis of the carrier, the quality of the adjuvant component Score is 0.3%-5%.

15. according to catalyst described in 1 or 13, which is characterized in that contain clay in the aluminium oxide molding and/or divide Son sieve, on the basis of the carrier, the mass fraction of the clay and/or molecular sieve is 35% or less.

16. the catalyst according to 15, which is characterized in that on the basis of the carrier, the clay and/or molecular sieve Mass fraction be 1%-20%.

17. a kind of hydrogenation method for hydrocarbon oils, is included under hydrogenation conditions, special by hydrocarbon ils and catalyst haptoreaction Sign is that the catalyst is catalyst described in 1-16 any one above-mentioned.

In the present invention, the aluminium oxide be can be selected from one or more of γ, η, θ, δ and χ, preferably gamma oxidation Aluminium.The aluminium oxide has the specific surface and pore volume of conventional alumina, and the specific surface of preferential oxidation aluminium is 150-350 meters²/ Gram, further preferably 180-320 meters²/ gram, the preferably Kong Rongwei 0.4-1.1 ml/g of aluminium oxide, further preferably 0.5-0.9 mls/g.They can be commercially available commodity and can also be prepared by any one method in the prior art.For example, can be with Be by being formed, being roasted selected from one or more of hibbsite, monohydrate alumina and amorphous hydroted alumina after It is made.

The molding of the aluminium oxide is carried out using customary way, such as the methods of tabletting, spin, extrusion.It is using When customary way forms, to ensure molding go on smoothly to material to be formed above-mentioned (for example, hibbsite, one The mixture of one or more of hydrated alumina and amorphous hydroted alumina) in introduce auxiliary agent and be allowed, such as when squeezing When, suitable peptizing agent, extrusion aid and water can be introduced into material to be formed above-mentioned, extrusion molding later.The glue Solvent, the type of extrusion aid and dosage may each be this field routine, such as common peptizing agent can be selected from nitric acid, vinegar One or more of acid, citric acid, formic acid, trichloroacetic acid, hydrochloric acid, malonic acid, the extrusion aid can be selected from sesbania powder, first One or more of base cellulose, starch, polyvinyl alcohol, polyethanol.

In one preferred embodiment, the aluminium oxide molding is boehmite and/or the vacation of a kind of modification Boehmite formed, roast after obtained gama-alumina.

The method of the modified boehmite and/or false boehmite includes: (1) by least one alumina hydration Object roasting, the roasting condition include: that temperature is 300 DEG C -950 DEG C, and the time is -24 hours 0.5 hour；(2) step (1) is obtained The product of roasting arrived is mixed at least one boehmite and/or false boehmite and water, obtains a kind of mixture； (3) mixture that step (2) obtains is subjected to hydro-thermal process in closed reactor, hydrothermal conditions include: that temperature is 60 DEG C -250 DEG C, the time is -48 hours 0.5 hour；(4) product for obtaining step (3) is dry, obtains modified boehmite And/or false boehmite.

Wherein, it is 300-750 DEG C that the roasting condition of the preferred step (1), which includes: temperature, and the time is 1-24 hours. The roasting condition of the further preferred step (1) includes: that temperature is 350-650 DEG C, and the time is 2-10 hours.

It is preferred that the product of roasting and at least one boehmite or a false water that the step (2) obtains step (1) are soft In the mixture that aluminium stone and water are mixed to get, solid content in mass is 1%-80%, wherein the product of roasting with The mass ratio of the boehmite of butt meter or false boehmite is 0.1-20.The further preferred step (2) is by step (1) in the mixture that the product of roasting and at least one boehmite or false boehmite and water obtained is mixed to get, Solid content in mass be 5%-70%, wherein the product of roasting in terms of butt boehmite or vacation one water it is soft The mass ratio of aluminium stone is 0.2-12.

When the water content in the mixture is enough to make the mixture slurries (for example, solid content in mass It is 35% or less) when, the step of filtering is preferably included before the drying of the step (4).

The hydrothermal conditions of the preferred step (3) include: that temperature is 60 DEG C to less than 140 DEG C, time 0.5- 48 hours.The hydrothermal conditions of the further preferred step (3) include: that temperature is 80-120 DEG C, and the time is that 4-24 is small When.Either, it is more than or equal to 140 DEG C to less than to be equal to that the hydrothermal conditions of the preferred step (3), which include: temperature, 250 DEG C, the time is 0.5-48 hours；The hydrothermal conditions of the further preferred step (3) include: that temperature is 150- 220 DEG C, the time is 4-24 hours.

It is preferred that the drying temperature of the step (4) is 60 DEG C -180 DEG C, drying time is -24 hours 0.5 hour.Further It is preferred that the drying temperature of the step (4) is 80 DEG C -150 DEG C, drying time is -12 hours 1 hour.

In the present invention, the hydrated alumina is in hibbsite, false boehmite, boehmite It is one or more of.

Wherein, the hibbsite includes gibbsite (α-Al₂O₃·3H₂O), surge aluminium stone (β₁-Al₂O₃·3H₂O) With promise diaspore (β₂-Al₂O₃·3H₂O)。

The vacation boehmite is also known as boehmite, is one kind at 14.5 ° ± 0.5 ° (2 with X-ray diffraction characterization θ) there is the wide and hydrated alumina of (020) crystallographic plane diffraction peak of disperse.

The boehmite is also known as boehmite, with X-ray diffraction characterization, goes out to be a kind of at 14.5 ° ± 0.5 ° (2 θ) Existing strongest, narrow and sharp (020) crystallographic plane diffraction peak hydrated alumina (boehmite at 45.8 °, 51.6 ° and 55.2 ° occur corresponding to diffraction maximum not available for the false boehmite of (131), (220) and (151) crystal face respectively).

Inventors of the present invention have surprisingly found that by boehmite and/or false boehmite and one or more of warps 300 DEG C -950 DEG C of roastings (heat treatment) 0.5-24 hours, preferably through 300 DEG C -750 DEG C of roastings (heat treatment) 1-24 hours, into one The hydrated alumina and water that step preferably roasts (heat treatment) 2-10 hours through 350 DEG C -650 DEG C mix, and obtain a kind of mixing Object, and by the mixture in closed container in 60 DEG C -250 DEG C of hydro-thermal process 0.5-48 hours, be preferable over 80-220 DEG C of hydro-thermal Processing 4-24 hours, thus the relative crystallinity of modified obtained boehmite and/or false boehmite improves, and thus The aluminium oxide being fired maintains higher specific surface area and Kong Rong.

In the present invention, when controlling hydro-thermal process temperature is 140 DEG C or more, gained modified product is boehmite；Control When hydro-thermal process temperature processed is less than 140 DEG C, crystal phase and the starting material of products therefrom are consistent.

In a specific embodiment, preferably make the crystal phase of the modified product and the consistent step of starting material Suddenly it is 60 DEG C to less than 140 DEG C that the hydrothermal conditions of (3), which include: temperature, and the time is 0.5-48 hours；Further preferred institute It is 80-120 DEG C that the hydrothermal conditions for stating step (3), which include: temperature, and the time is 1-24 hours.

In another embodiment, preferably make the step (3) of the modified product boehmite Hydrothermal conditions include: temperature be more than or equal to 140 DEG C to less than be equal to 250 DEG C, the time be 0.5-48 hours；Further The hydrothermal conditions of the preferred step (3) include: that temperature is 150-220 DEG C, and the time is 4-24 hours.

In the present invention, the boehmite, false boehmite and gibbsite can be commercially available commodity, can also be with It is that this is not particularly limited using arbitrary prior art preparation.

Be enough by the hydrated alumina 300 DEG C -950 DEG C of roastings (heat treatment) 1-24 hours, preferably through 300 DEG C -750 DEG C roasting (heat treatment) 1-24 hours, the item further preferably through 350 DEG C of -650 DEG C of roastings (heat treatment) 2-10 hours Under part, method of roasting described in step (1) is not particularly limited in the present invention.For example, it may be by the hydrated alumina It is roasted, is also possible in the baking oven or roaster of vacuum-pumping under air atmosphere in usual baking oven or roaster Under vacuum conditions or it is passed through under inert gas conditions and carries out.When the roasting is passed through inert gas, the inert gas can To be arbitrary the not oxygen-containing gas for being enough to gasify under the roasting condition, for example, can be selected from nitrogen, argon gas, helium, One or more of carbon dioxide and water vapour.

Butt in the present invention refers to: a certain amount of hydrated alumina in air atmosphere in Muffle furnace with 4 DEG C/ Minute heating rate be raised to 600 DEG C, then 600 DEG C constant temperature 4 hours, after roasting the weight of product and roast before the oxidation The percentage of the weight ratio of aluminium hydrate, the weight of the hydrated alumina before the weight ÷ of product is roasted after butt=roasting Amount × 100%.

In the present invention, the closed reactor can be arbitrary the reactor that the hydro-thermal reaction can be achieved, for example, Autoclave etc., the reaction can be to be carried out under static conditions, is also carried out under stirring, preferably under stirring Carry out hydro-thermal process.

In the present invention, the first organic compound R is contained in the aluminium oxide molding₁R₂R₃R₄N⁺X^-, it is with the carrier Benchmark, the R₁R₂R₃R₄N⁺X^-Mass fraction be 0.1%-10%, preferably 0.3%-5%.R therein₁R₂R₃R₄N⁺X^-Choosing From one or more of primary amine salt, secondary amine salt, tertiary ammonium salt or quaternary ammonium salt.For example, being selected from cetyl trimethylammonium bromide, ten Six alkyl trimethyl ammonium chlorides, dodecyl amine hydrochloride, octadecyl amine hydrochloride, tetradecyltrimethylammonium bromide, ten Tetraalkyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyltrimethylammonium chloride, didecyl Dimethy It is ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double dodecyl dimethyl ammonium chlorides, double Dodecyldimethylamine base ammonium bromide, double dodecyldimethylamine ammonium chlorides, dioctadecyldimethylammonium bromide, double octadecyls The one or more of alkyl dimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride, or it is selected from second Alcohol amine salt and dococylpyridinium hydrochloride and their mixture etc..

Wherein, as the R₁R₂R₃R₄N⁺X^-When for primary amine salt, the R₁、R₂、R₃Or R₄One of selected from hydrocarbon substituent or The substituent group of hydrocarbon derivative, other are hydrogen；As the R₁R₂R₃R₄N⁺X^-When for secondary amine salt, the R₁、R₂、R₃Or R₄In two kinds Substituent group selected from hydrocarbon substituent and/or hydrocarbon derivative, other are hydrogen；As the R₁R₂R₃R₄N⁺X^-When for tertiary ammonium salt, the R₁、 R₂、R₃Or R₄In three kinds of substituent groups selected from hydrocarbon substituent and/or hydrocarbon derivative, another is hydrogen；As the R₁R₂R₃R₄N⁺X^- When for quaternary amine, the R₁、R₂、R₃Or R₄In four kinds of substituent groups selected from hydrocarbon substituent and/or hydrocarbon derivative.Wherein, when There are two types of the above are when the derivative of hydrocarbon substituent and/or hydrocarbon substituent in R1, R2, R3 and R4, they can it is identical can also be with It is different.

The hydrocarbon substituent is selected from the linear or branched alkyl group of C1-C20, the linear chain or branched chain alkane of preferably C1-C18 Base, for example, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide, the tetradecane Base trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, octadecyl trimethyl bromination Ammonium, octadecyltrimethylammonium chloride, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, double dodecyls Ditallowdimethyl ammonium bromide, double dodecyl dimethyl ammonium chlorides, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine base chlorine Change ammonium, dioctadecyldimethylammonium bromide, dioctadecyl dimethyl ammonium chloride；It is either selected from the naphthenic base of C3-C20, The preferably naphthenic base of C6-C18, for example, naphthenic base imidazoline quaternary ammonium salt；Either it is selected from the aryl of C6-C20, preferably C6- The aryl of C18, for example, dodecyl benzyl dimethyl ammonium chloride, lauryl isoquinolinium bromide salt；The derivative of the hydrocarbon Substituent group be selected from the alkyl with hydroxyl and/or heterocyclic substituent, the example of the substituent group of the derivative as hydrocarbon, such as 12 Alkyl pyridine hydrochloride, glycidyl dodecyl dimethyl ammonium chloride, benzethonium chloride.

The X is selected from iodine, preferably chlorine or bromine.

It is being enough to make to contain in the molding 0.1%-10%, the preferably R of 0.3%-5%₁R₂R₃R₄N⁺X^-Premise Under, there is no limit for the method that the present invention introduces it.

In a specific embodiment, R is introduced in the molding₁R₂R₃R₄N⁺X^-Method, comprising: (1) use Containing R₁R₂R₃R₄N⁺X^-Solution impregnate the molding, the ratio between the volume of the maceration extract and the pore volume of the molding are 0.5-20, preferably 1-15；(2) mixture that dipping obtains is heat-treated in closed reactor, heat treatment temperature is Room temperature is to 250 DEG C, and preferably 60 DEG C -220 DEG C, the time is -48 hours 0.5 hour, preferably -36 hours 1 hour；(3) dry The product of step (2), the drying condition include: that temperature is 40 DEG C -250 DEG C, and preferably 100 DEG C -180 DEG C, the time is 1 small When -24 hours, preferably -18 hours 2 hours.

In the present invention, room temperature can be the room temperature in each season in throughout the year, generally 5-40 DEG C.

In the present invention, the solvent of the maceration extract is selected from water and/or alcohol (such as ethyl alcohol).

It is being enough to make R in the final molding₁R₂R₃R₄N⁺X^-Content meet the requirements under the premise of, the present invention is to dipping R in liquid₁R₂R₃R₄N⁺X^-Content and dipping time be not particularly limited.

In the case where being enough to ensure that the heat treatment carries out under air tight condition, the present invention does not have the closed reactor There are special limitation, common such as autoclave high-pressure reactor.

In the present invention, R is introduced in the aluminium oxide molding₁R₂R₃R₄N⁺X^-Method in, the dry purpose of step (3) It is to remove the solvent in impregnation product, under the premise of being enough to realize the purpose, the present invention does not have the method for the drying Limitation, such as the method that can be heat drying, are also possible to vacuum drying method.

In the present invention, the aluminium oxide can be containing selected from silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, oxygen Change one or more of beryllium adjuvant component, on the basis of the carrier, the mass fraction of the adjuvant component be 10% hereinafter, It is preferably 0.3%-5%.

When in the molding containing in silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide one Kind or when several adjuvant components, in the preparation process of the molding include introduce selected from silica, titanium oxide, magnesia, The step of one or more of zirconium oxide, thorium oxide, beryllium oxide adjuvant component, the method for introducing adjuvant component are conventional Method.For example, it may be will contain selected from one of silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide or several The mixture warp of one or more of hibbsite, monohydrate alumina and the amorphous hydroted alumina of kind adjuvant component It is made after forming and roasting.Be also possible to mix aluminium oxide and/or its precursor with the compound containing adjuvant component, after pass through Molding, drying and roasting obtain.

In the present invention, clay and/or molecular sieve can be contained in the molding, it is described viscous on the basis of the carrier The mass fraction of soil and/or molecular sieve is 35% hereinafter, preferably 1%-20%.

It include introducing in the preparation process of the molding when containing clay and/or molecular sieve in the molding The step of clay and/or molecular sieve, the method object conventional method for introducing clay and/or molecular sieve.For example, by the clay And/or molecular sieve is selected from one or more of hibbsite, monohydrate alumina and amorphous hydroted alumina with described Mixture after molding and roasting be made.

In the present invention, the clay can selected from kaolin, halloysite, montmorillonite, diatomite, galapectite, saponite, One of rectorite, sepiolite, attapulgite, hydrotalcite and bentonite are a variety of.The molecular sieve can be zeolite molecules Sieve and/or non-zeolite molecular sieve.The zeolite molecular sieve can for erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, zeolite L, y-type zeolite, X-type zeolite, ZSM-3 molecule Sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, Beta One of zeolite and omega zeolite are a variety of.The non-zeolite molecular sieve can be phosphate aluminium molecular sieve, Titanium Sieve Molecular Sieve and phosphoric acid One of sial (that is, SAPO) molecular sieve is a variety of.According to the present invention, the molecular sieve is preferably hydrogen type molecular sieve.It is described Hydrogen type molecular sieve can be commercially available, can also be using conventional method preparation.For example, can be conventional by sodium form molecular sieve Ammonium ion exchange process carries out ion exchange and drying, forms ammonium type molecular sieve, then be fired and to form hydrogen type molecular sieve.

The second organic compound organic carboxyl acid and its ammonium salt are selected from trans- 1,2-cyclohexanediaminetetraacetic acid, ethylenediamine tetraacetic Acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and malic acid and its ammonium salt One of or it is a variety of.

In the present invention, the hydrogenation catalyst can be Hydrobon catalyst, hydrotreating catalyst or hydrocracking Catalyst.The metal component selected from group VIII and selected from group VIB in the catalyst is conventional selection, for example, described Group VIII metal component is selected from cobalt and/or nickel, and vib metals group is selected from molybdenum and/or tungsten.

It in the present invention, is counted by oxide and on the basis of the catalyst, the catalyst preferably comprises 50-90 weight % Carrier, the group VIII metal component of 1-10 weight %, the vib metals component of 5-40 weight %；Further preferably urge Agent contains the carrier of 60-85 weight %, the group VIII metal component of 1.5-6 weight %, the group VIB of 10-35 weight % Metal component.

In the present invention, at least one group VIII and at least one vib metals component are introduced in Xiang Suoshu carrier Method is method customary in the art, for example, it may be will be containing at least one group VIII and at least one selected from group VIB gold Belong to compound to be configured to impregnate the method for the carrier after mixed solution；Can be will containing at least one group VIII and at least A method of selected from vib metals compound individually prepare solution after impregnated carrier.Wherein, by metallic components The regulation and control of the concentration of solution, dosage or carrier dosage, can prepare the catalyst of specified content, this is ability Field technique personnel are readily appreciated by.

According to the present invention, after the impregnation steps are completed, it the step such as can optionally be dried, roast or do not roast Suddenly, it preferably only dries, roast.The condition of the drying and roasting is conventional, for example, drying temperature is 100-300 DEG C, Preferably 100-280 DEG C, drying time is 1-12 hours, preferably 2-8 hours；Maturing temperature is 350-550 DEG C, preferably 400-500 DEG C, calcining time is 1-10 hours, preferably 2-8 hours.

The group VIII metallic compound is selected from one or more of the soluble compound of these metals, for example, It can be one or more of the nitrate of these metals, acetate, carbonate, chloride, soluble complexes.

Described vib metals compound is selected from one or more of the soluble compound of these metals, for example, It can be one or more of molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.

According to catalyst provided by the invention, before the use preferably in presence of hydrogen, at a temperature of 140-370 DEG C Carry out presulfurization with sulphur, hydrogen sulfide or containing sulfur feedstock, this presulfurization can be carried out outside device it is also In-situ sulphiding in device, by it The active metal component loaded is converted into metal sulfide component.

In the present invention, to the hydrotreating reaction condition, there is no particular limitation, and preferred reaction condition includes: anti- Answer 200-420 DEG C of temperature, further preferably 220-400 DEG C, pressure 2-18 megapascal, further preferably 2-15 megapascal, when liquid Air speed 0.3-10 hours^-1, further preferably 0.3-5 hours^-1, hydrogen to oil volume ratio 50-5000, further preferably 50- 4000。

The device of the hydrogenation reaction can be enough to urge the feedstock oil under hydrogenation conditions with described any It is carried out in the catalytic reaction dress device of agent, for example, the reaction is in fixed bed reactors, moving-burden bed reactor or ebullated bed It is carried out in reactor.

Compared with prior art, the hydrogenation activity that the present invention provides catalyst is improved, especially by containing R₁R₂R₃R₄N⁺ X^-Carrier preparation of the use through the modified hydrated alumina preparation of method provided by the invention catalyst, this modification is especially Obviously.

For example, containing R with provided by the invention respectively₁R₂R₃R₄N⁺X^-Aluminium oxide molding and conventional method preparation carrier Prepare tenor 2.4%NiO and 12%MoO₃Hydrobon catalyst C and DC (reference agent).To contain 4,6- dimethyl two The mixed solution of the n-decane of 0.59 weight % of benzothiophene (4,6-DMDBT) is raw material, the hydrodesulfurization to two kinds of catalyst Activity is evaluated.With the activity of catalyst DC for 100, the hydrodesulfurization activity of catalyst C is 114.The result shows that with existing The catalyst for having technology to provide carrier preparation is compared, and is obviously mentioned by the hydrodesulfurization activity that present invention offer carrier prepares catalyst It is high.

All kinds of hydrocarbon oil crude materials can be processed using catalyst provided by the invention.For example, the hydrocarbon oil crude material can be respectively Kind heavy mineral oil or synthetic oil or their mixed fraction oil, for example it is selected from crude oil, distillate, solvent-refined oil, slack wax, wax One or more of lower oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.

Specific embodiment

The present invention will be further illustrated in following example, but not thereby limiting the invention.

In following embodiment, analysis measurement is carried out using content of the x-ray fluorescence method to each element in catalyst (RIPP132-90, referring to: petrochemical egineering analysis method (RIPP test methods), Yang Cui is surely equal to be compiled, Science Press, and 1990, 371-375).X-ray fluorescence test before first by catalyst sample in air atmosphere 450 DEG C roast 6 hours.

The measurement of sample crystal phase, relative crystallinity and mean grain size is referring to " solid catalyst Practical Research method " (Liu The big volume of Wei Qiao, Sun Gui, Sinopec publishing house, 2000,57-89) and " petrochemical egineering analysis method (RIPP test methods) " (poplar Kingfisher is fixed, and Gu Kanying, Wu Wenhui are compiled, Science Press, 1990,394-405) in X-ray diffraction method carry out.

Modified boehmite and/or false boehmite used in embodiment 1-10 declaratives carrier, preparation Method and the alumina support thus prepared.

Hydrated alumina used in experiment are as follows:

CL-A powder (false boehmite powder), relative crystallinity 100%, grain size 2.9nm, 70 weight % of butt, Purchased from middle petrochemical industry Chang Ling catalyst branch.

CL-B powder (boehmite), relative crystallinity 100%, grain size 5.2nm, 78 weight % of butt are purchased from Middle petrochemical industry Chang Ling catalyst branch).

CL-C powder (gibbsite (α-Al₂O₃·3H₂O)), relative crystallinity 100%, grain size 156nm, butt 65 Weight % is purchased from middle petrochemical industry Chang Ling catalyst branch.

Wherein, 10000 grams of CL-A powder are weighed, with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, type Number: F-26 (III)) it is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in sky Under gas atmosphere in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-A-Al₂O₃.Pass through X-ray diffraction method table Its crystal phase, crystallinity and grain size are levied, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and Kong Rong, The results are shown in Table 2.

10000 grams of CL-B powder are weighed, with banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F- 26 (III)) it is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere Under in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support CL-B-Al₂O₃.Its crystalline substance is characterized by X-ray diffraction method Phase, crystallinity and grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and Kong Rong, as a result arranges In table 2.

It is obtained according to the step (1) in the method for modified boehmite of the present invention and/or false boehmite Product of roasting are as follows:

CL-A-600: 10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter CL-A-600 is obtained within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.

CL-A-450: 10000 grams of CL-A powder are weighed in air atmosphere in Muffle furnace with 3 DEG C/min of heating rate liter CL-A-450 is obtained within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.

CL-A-400: 10000 grams of CL-A powder are weighed in a nitrogen atmosphere in Muffle furnace with 5 DEG C/min of heating rate liter CL-A-400 is obtained within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.

CL-A-350: 10000 grams of CL-A powder are weighed and are raised in a nitrogen atmosphere with 3 DEG C/min of heating rate in baking oven 350 DEG C, and CL-A-350 is obtained within constant temperature 4 hours at 350 DEG C.

CL-B-600: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter CL-B-600 is obtained within constant temperature 4 hours to 600 DEG C, and at 600 DEG C.

CL-B-450: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter CL-B-450 is obtained within constant temperature 4 hours to 450 DEG C, and at 450 DEG C.

CL-B-400: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter CL-B-400 is obtained within constant temperature 4 hours to 400 DEG C, and at 400 DEG C.

CL-B-350: 10000 grams of CL-B powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating rate liter CL-B-350 is obtained within constant temperature 4 hours to 350 DEG C, and at 350 DEG C.

CL-C-600: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed Rate is raised to 600 DEG C, and obtains CL-C-600 within constant temperature 4 hours at 600 DEG C.

CL-C-450: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed Rate is raised to 450 DEG C, and obtains CL-C-450 within constant temperature 6 hours at 450 DEG C.

CL-C-400: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating speed Rate is raised to 400 DEG C, and obtains CL-C-400 within constant temperature 6 hours at 400 DEG C.

CL-C-350: 10000 grams of gibbsite-powder are weighed in air atmosphere in Muffle furnace with 4 DEG C/min of heating Rate is raised to 350 DEG C, and obtains CL-C-350 within constant temperature 6 hours at 350 DEG C.

Embodiment 1

120 grams of 350 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively The mass ratio of A powder is 0.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 160 DEG C are heated to after closed, and constant temperature 4 under stiring Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified product Q-S1.Pass through X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.

Q-S1 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support S1.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method Size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.

Embodiment 2

Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S2.Pass through X-ray Diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.

Q-S2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S2 in air atmosphere.Pass through X- Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption measurement Its specific surface area and Kong Rong, the results are shown in Table 2.

Embodiment 3

Weigh respectively in terms of butt 464 grams of 109 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt The mass ratio of CL-A powder is 4.25), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to Room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S3.Pass through X-ray Diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.

Formed alumina provided by the invention and its preparation:

Q-S3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S3 in air atmosphere.Pass through X- Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption measurement Its specific surface area and Kong Rong, the results are shown in Table 2.

Embodiment 4

150 grams of 100 grams of 84 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A-450 in terms of butt are weighed respectively (total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 250 grams of powder, 180 grams of CL-A-600 powder 8.10) they and 3600 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring, In the autoclave of stainless steel band polytetrafluoro liner, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to room temperature and after filtering, it will Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S4.Its crystalline substance is characterized by X-ray diffraction method Phase, relative crystallinity and grain size, the results are shown in Table 1.

Q-S4 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S4 in air atmosphere.Pass through X- Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption measurement Its specific surface area and Kong Rong, the results are shown in Table 2.

Embodiment 5

200 grams of 100 grams of 140 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A- in terms of butt are weighed respectively (total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 450 300 grams of powder, 10 grams of CL-A-600 powder 4.36) they and 3100 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring, In the autoclave of stainless steel band polytetrafluoro liner, 60 DEG C of constant temperature are heated to after closed 48 hours；It is down to room temperature and after filtering, it will Filter cake is 8 hours dry in 120 DEG C, obtains modified hydrated alumina Q-S5.Its crystalline substance is characterized by X-ray diffraction method Phase, relative crystallinity and grain size, the results are shown in Table 1.

Q-S5 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S5 in air atmosphere.Pass through X- Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption measurement Its specific surface area and Kong Rong, the results are shown in Table 2.

Embodiment 6

100 grams of 200 grams of 70 grams of CL-A powder, CL-A-350 powder, CL-A-400 powder, the CL-A-450 in terms of butt are weighed respectively (total amount of the powder of CL-A-350~600 and the mass ratio of the CL-A powder in terms of butt are for 400 grams of powder, 20 grams of CL-A-600 powder 10.29) they and 3200 grams of deionized waters, are mixed into slurries；It is 5 liters that the slurries, which are transferred to the volume with stirring, In the autoclave of stainless steel band polytetrafluoro liner, 100 DEG C of constant temperature are heated to after closed 24 hours；It is down to room temperature and after filtering, Filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina Q-S6.It is characterized by X-ray diffraction method Crystal phase, relative crystallinity and grain size, the results are shown in Table 1.

Q-S6 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S6 in air atmosphere.Pass through X- Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption measurement Its specific surface area and Kong Rong, the results are shown in Table 2.

Embodiment 7

60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder 220 Gram, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, 8 grams of CL-C-600 powder (total amount of the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 8.09), by them and 3600 grams of deionized waters It is mixed into slurries；The slurries are transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, it obtains through changing The hydrated alumina Q-S7 of property.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, is as a result arranged In table 1.

Q-S7 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support S7.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method Size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.

Embodiment 8

60 grams of 14 grams of 70 grams of CL-A powder, CL-B powder, CL-A-350 powder, the CL-B-350 powder 20 in terms of butt are weighed respectively Gram, 20 grams of CL-C-350 powder, 100 grams of CL-A-400 powder, 30 grams of CL-B-400 powder, 20 grams of CL-C-400 powder, CL-A-450 powder 220 grams, 20 grams of CL-B-450 powder, 10 grams of CL-C-450 powder, 150 grams of CL-A-600 powder, 22 grams of CL-B-600 powder, CL-C-600 powder 8 grams (total amount of the powder of CL-350~600 and the mass ratio of CL powder in terms of butt be 8.09), by them and 3600 grams of deionizations Water is mixed into slurries；The slurries are transferred to the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters In, 160 DEG C of constant temperature are heated to after closed 4 hours.It is cooled to room temperature, high pressure kettle cover is opened, 11.75 grams of biphosphates are added Ammonium continues stirring 24 hours in room temperature, after filtering, filter cake is 8 hours dry in 120 DEG C, obtains modified containing auxiliary agent The hydrated alumina Q-S8 of phosphorus.Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, is as a result arranged In table 1.

Q-S8 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support S8.Its crystal phase, relative crystallinity and crystal grain are characterized by X-ray diffraction method Size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.It is glimmering using X Light method measures the content of adjuvant component, and the mass fraction of the phosphate builder based on the element is 0.41%.

Embodiment 9

Weigh respectively in terms of butt 300 grams of 224 grams of CL-A powder, CL-A-600 powder (CL-A-600 powder in terms of butt The mass ratio of CL-A powder is 1.34), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band In the autoclave for the stainless steel band polytetrafluoro liner that the volume of stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours.It is down to After room temperature, high pressure kettle cover is opened, 84.51 grams of titanium sulfates are added, continues stirring 24 hours, then filters.By filter cake through 120 DEG C It is 8 hours dry, obtain the modified hydrated alumina Q-S9 containing auxiliary agent titanium.Its crystalline substance is characterized by X-ray diffraction method Phase, relative crystallinity and grain size, the results are shown in Table 1.

Q-S9 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S9 in air atmosphere.Pass through X- Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption measurement Its specific surface area and Kong Rong, the results are shown in Table 2.The content of adjuvant component, the titanium based on the element are measured using X-fluorescence method The mass fraction of auxiliary agent is 3.12%.

Embodiment 10

320 grams of 230 grams of CL-B powder, CL-A-450 powder (CL-A-600 powder and the CL- in terms of butt in terms of butt are weighed respectively The mass ratio of B powder is 1.39), they to be mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to band to stir In the autoclave for the stainless steel band polytetrafluoro liner that the volume mixed is 5 liters, 200 DEG C are heated to after closed, and constant temperature 4 under stiring Hour；Later, it is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified product Q-S10.It is logical It crosses X-ray diffraction method and characterizes its crystal phase, relative crystallinity and grain size, the results are shown in Table 1.

Q-S10 banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into The cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters.Wet bar is after 120 DEG C 4 hours dry, in air atmosphere in Muffle furnace 600 DEG C constant temperature 4 hours, obtain alumina support S10.Its crystal phase, relative crystallinity and crystalline substance are characterized by X-ray diffraction method Grain size, the results are shown in Table 1.Pass through N₂Absorption/desorption measures its specific surface area and Kong Rong, and the results are shown in Table 2.

What embodiment 11-13 illustrated that the present invention uses prepare boehmite by conventional method of modifying and/or a false water is soft The modifier of aluminium stone and the alumina support being prepared by the modifier.

Embodiment 11

470 grams of CL-A powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 160 DEG C of constant temperature 4 is heated to after closed Hour；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-1. Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.

QBF-1 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S11 in air atmosphere.Pass through X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption is surveyed Its fixed specific surface area and Kong Rong, the results are shown in Table 2.

Embodiment 12

470 grams of CL-A-600 powder are weighed, it is mixed into slurries with 3600 grams of deionized waters；The slurries are transferred to In the autoclave for the stainless steel band polytetrafluoro liner that volume with stirring is 5 liters, 160 DEG C of constant temperature are heated to after closed 4 hours；Drop It is to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-2.Pass through X- Diffraction characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.

QBF-2 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S12 in air atmosphere.Pass through X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption is surveyed Its fixed specific surface area and Kong Rong, the results are shown in Table 2.

Embodiment 13

470 grams of CL-B powder in terms of butt are weighed, it is mixed into slurries with 3600 grams of deionized waters；By the slurries It is transferred in the autoclave for the stainless steel band polytetrafluoro liner that the volume with stirring is 5 liters, 200 DEG C of constant temperature 4 is heated to after closed Hour；It is down to room temperature and after filtering, filter cake is 8 hours dry in 120 DEG C, obtain modified hydrated alumina QBF-3. Its crystal phase, relative crystallinity and grain size are characterized by X-ray diffraction method, the results are shown in Table 1.

QBF-3 is extruded into the cloverleaf pattern item that circumscribed circle diameter is 1.6 millimeters with banded extruder (with embodiment 1).Wet bar warp 120 DEG C after drying 4 hours, 600 DEG C constant temperature 4 hours in Muffle furnace, obtain alumina support S13 in air atmosphere.Pass through X-ray diffraction method characterizes its crystal phase, relative crystallinity and grain size, and the results are shown in Table 1.Pass through N₂Absorption/desorption is surveyed Its fixed specific surface area and Kong Rong, the results are shown in Table 2.

Table 1

Wherein, when measuring the crystallinity of false boehmite, using CL-A powder as standard specimen；Admire the knot of aluminium stone measuring a water When crystalline substance is spent, using CL-B powder as standard specimen；When measuring gama-alumina crystallinity, with CL-B-Al₂O₃For standard specimen.

Table 2

Embodiment	Aluminium oxide	Specific surface area, m2/g	Kong Rong, cm3/g
					CL-A-Al2O3	283	0.71
	CL-B-Al2O3	201	0.51
				1	S1	255	0.66
2	S2	238	0.62
				3	S3	213	0.61
4	S4	236	0.62
				5	S5	265	0.68
6	S6	258	0.66
				7	S7	216	0.60
8	S8	222	0.61
				9	S9	243	0.63
10	S10	185	0.60
				11	S11	233	0.52
12	S12	173	0.60
				13	S13	131	0.45

Embodiment 14-29 illustrates the carrier of offer of the present invention, that is, contains R₁R₂R₃R₄N⁺X^-Aluminium oxide molding and its Preparation method.

Embodiment 14

It weighs 1 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 1.36 grams of cetyl trimethylammonium bromides is added 200 milliliters of alcoholic solution, it is closed after in 90 DEG C constant temperature 24 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S1.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 15

It weighs 2 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 1.85 grams of cetyl trimethylammonium bromides is added It 200 milliliters of alcoholic solution, is placed at room temperature after closed 48 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S2.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 16

It weighs 3 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 3.81 grams of cetyl trimethylammonium bromides is added 200 milliliters of alcoholic solution, it is closed after in 60 DEG C constant temperature 18 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S3.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 17

It weighs 4 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 1.10 grams of cetyl trimethylammonium bromides is added 200 milliliters of alcoholic solution, it is closed after in 120 DEG C constant temperature 6 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S4.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 18

It weighs 5 200 grams of carrier S to be placed in autoclave, the aqueous solution for containing 0.89 gram of cetyl trimethylammonium bromide is added 200 milliliters, it is closed after in 160 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains containing R₁R₂R₃R₄N⁺ X^-Aluminium oxide molding R-S5.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 19

It weighs 6 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 4.86 grams of cetyl trimethylammonium bromides is added 200 milliliters of alcoholic solution, it is closed after in 180 DEG C constant temperature 2 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S6.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 20

It weighs 7 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 5.18 grams of cetyl trimethylammonium bromides is added 200 milliliters of alcoholic solution, it is closed after in 110 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S7.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 21

It weighs 8 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 4.56 grams of cetyl trimethylammonium bromides is added 200 milliliters of alcoholic solution, it is closed after in 120 DEG C constant temperature 4 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S8.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 22

It weighs 9 200 grams of carrier S to be placed in autoclave, the anhydrous second for containing 4.69 grams of cetyl trimethylammonium bromides is added It 200 milliliters of alcoholic solution, is handled 4 hours after closed in 130 DEG C.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S9.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 23

It weighs 10 200 grams of carrier S to be placed in autoclave, is added and contains the anhydrous of 1.02 grams of cetyl trimethylammonium bromides It 200 milliliters of ethanol solution, is handled 10 hours after closed in 80 DEG C.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S10.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 24

It weighs 11 200 grams of carrier S to be placed in autoclave, is added and contains the anhydrous of 1.36 grams of cetyl trimethylammonium bromides It 200 milliliters of ethanol solution, is handled 24 hours after closed in 90 DEG C.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S11.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 25

It weighs 12 200 grams of carrier S to be placed in autoclave, is added and contains the anhydrous of 1.36 grams of cetyl trimethylammonium bromides It 200 milliliters of ethanol solution, is handled 24 hours after closed in 90 DEG C.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S12.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 26

It weighs 13 200 grams of carrier S to be placed in autoclave, is added and contains the anhydrous of 1.36 grams of cetyl trimethylammonium bromides It 200 milliliters of ethanol solution, is handled 4 hours after closed in 90 DEG C.It is after cooling that sample is 4 hours dry in 120 DEG C, contained R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S13.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 27

Weigh support C L-A-Al₂O₃200 grams are placed in autoclave, are added and contain 1.36 grams of cetyl trimethylammonium bromides 200 milliliters of ethanol solution, it is closed after in 90 DEG C handle 24 hours.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains To containing R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S14.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 28

Then the hydrated alumina Q-S2 powder of preparation and 2 equivalent of embodiment (is purchased from middle petrochemical industry with 25 grams of silicon dioxide powders Chang Ling catalyst branch) mixing after use banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) being extruded into circumscribed circle diameter is 1.6 millimeters of cloverleaf pattern item, 4 hours dry through 120 DEG C, finally horse in air atmosphere Not be raised to 600 DEG C in furnace with 4 DEG C/min of heating rate, then 600 DEG C constant temperature 4 hours, obtain alumina support S14.

It weighs 14 200 grams of carrier S to be placed in autoclave, is added and contains 3.56 grams of cetyl trimethylammonium bromides and 3.89 200 milliliters of ethanol solution of gram dodecyl trimethyl ammonium chloride are handled 2 hours after closed in 100 DEG C.By sample after cooling Product are 4 hours dry in 120 DEG C, obtain containing R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S15.R in carrier₁R₂R₃R₄N⁺X^-Matter Amount score is listed in table 3.

Embodiment 29

Preparation and the hydrated alumina Q-S2 powder of 2 equivalent of embodiment, then with 36 grams of Hydrogen Y molecular sieve (Na₂O content 0.2%, cell parameter 2.464, relative crystallinity 88%, be purchased from middle petrochemical industry Chang Ling catalyst branch) mixing after use banded extruder (manufacturer: South China Science & Engineering University's science and technology industry head factory, model: F-26 (III)) is extruded into three that circumscribed circle diameter is 1.6 millimeters Clover shape item, it is 4 hours dry through 120 DEG C, finally 600 are raised to 4 DEG C/min of heating rate in Muffle furnace in air atmosphere DEG C, then 600 DEG C constant temperature 4 hours, obtain alumina support S15.

It weighs 15 200 grams of carrier S to be placed in autoclave, is added and contains 1.73 grams of cetyl trimethylammonium bromides, 1.12 grams Hexadecyltrimethylammonium chloride, 3.08 grams of dodecyl trimethyl ammonium bromide and 3.16 grams of dodecyl trimethyl ammonium chloride It 200 milliliters of ethanol solution, is handled 3 hours after closed in 100 DEG C.It is after cooling that sample is 4 hours dry in 120 DEG C, it obtains Contain R₁R₂R₃R₄N⁺X^-Aluminium oxide molding R-S16.R in carrier₁R₂R₃R₄N⁺X^-Mass fraction be listed in table 3.

Embodiment 30-48 illustrates catalyst provided by the invention and its preparation.

Embodiment 30-45

Respectively with the ammonium hydroxide containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of ethylenediamine tetra-acetic acids 199 milliliters of solution dipping embodiments 14~29 be prepared R-S1, R-S2, R-S3, R-S4, R-S5, R-S6, R-S7, R-S8, R-S9, R-S10, R-S11, R-S12, R-S13, R-S14, R-S15 and R-S16, dip time 2 hours, later impregnation product in 120 DEG C drying 4 hours, obtain catalyst C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 and C16。

Embodiment 46

With containing 34.96 grams of ammonium heptamolybdates, 1.28 grams of trans- 1,2-cyclohexanediaminetetraacetic acid, 3.56 grams of ethylenediamine tetra-acetic acids, 199 milliliters of dipping embodiments 14 of ammonia spirit of 2.58 grams of malic acid, 1.69 grams of tartaric acid and 2.31 grams of ammonium citrates are prepared into The R-S1 arrived, impregnation product is 4 hours dry in 120 DEG C later；Then again with containing 22.62 grams of Nickelous nitrate hexahydrates, 12.27 grams of second 199 milliliters of the ammonia spirit above-mentioned carriers of dipping of ethylenediamine tetraacetic acid (EDTA) and 3.26 grams of ammonium oxalate, dip time 2 hours, impregnate later Product is 4 hours dry in 120 DEG C, obtains catalyst C17.

Embodiment 47

With containing 34.96 grams of ammonium heptamolybdates, 0.15 gram of glyoxalic acid, 1.23 grams of hydroxyacetic acids, 1.56 grams of formic acid, 6.98 grams of lemons The R-S1 that 199 milliliters of ammonia spirit dipping embodiments 14 of sour ammonium and 36.23 grams of citric acids are prepared, later impregnation product in 120 DEG C drying 4 hours；Then again with containing 22.62 grams of Nickelous nitrate hexahydrates, 21.27 grams of ethylenediamine tetra-acetic acids and 1.86 grams of amino 199 milliliters of the ammonia spirit above-mentioned carriers of dipping of triacetic acid, dip time 2 hours, impregnation product was small in 120 DEG C of dryings 4 later When, obtain catalyst C18.

Embodiment 48

It is prepared into 199 milliliters of dipping embodiments 14 of ammonia spirit containing 34.96 grams of ammonium heptamolybdates and 22.51 grams of citric acids The R-S1 arrived, impregnation product is 4 hours dry in 120 DEG C later；Then again with containing 22.62 grams of Nickelous nitrate hexahydrates and 23.27 grams 199 milliliters of the ammonia spirit above-mentioned carriers of dipping of ethylenediamine tetra-acetic acid, dip time 2 hours, impregnation product was dry in 120 DEG C later Dry 4 hours, obtain catalyst C19.

Comparative example 1-5 illustrates comparative catalyst and its preparation.

Comparative example 1

11 200 grams of carrier S are weighed, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of second two 199 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of amine tetraacethyl, it is then 4 hours dry at 120 DEG C, obtain catalyst D1.

Comparative example 2

12 200 grams of carrier S are weighed, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of second two 199 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of amine tetraacethyl, it is then 4 hours dry at 120 DEG C, obtain catalyst D2.

Comparative example 3

13 200 grams of carrier S are weighed, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 grams of second two 199 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of amine tetraacethyl, it is then 4 hours dry at 120 DEG C, obtain catalyst D3.

Comparative example 4

Weigh support C L-A-Al₂O₃200 grams, with containing 34.96 grams of ammonium heptamolybdates, 22.62 grams of Nickelous nitrate hexahydrates and 8.15 199 milliliters of ammonia spirit dippings above-mentioned carrier 2 hours of gram ethylenediamine tetra-acetic acid, it is then 4 hours dry at 120 DEG C, it is urged Agent D4.

Comparative example 5

With the 199 milliliters of dipping embodiments 14 of ammonia spirit for containing 34.96 grams of ammonium heptamolybdates and 22.62 grams of Nickelous nitrate hexahydrates The R-S1 being prepared 2 hours, it is then 4 hours dry at 120 DEG C, obtain catalyst D5.

Catalyst performance evaluation:

It evaluates embodiment 30-48 and the hydrodesulfurization performance for the comparative catalyst that catalyst and comparative example 1-5 are provided is provided, As a result it is listed in table 3.

Evaluating catalyst is with the mixing of the n-decane containing 4,6- dimethyl Dibenzothiophene (4,6-DMDBT) 0.59 weight % Solution is raw material, evaluates and urges in high-pressure micro-device (manufacturer: Beijing petrochemical industry information automation company, model: DADI) Catalyst breakage is the particle of 40-60 mesh at diameter by the hydrodesulfurization activity of agent, and the loadings of catalyst are 0.15 gram. Before formal charging, presulfurization, pre- sulphur first are carried out to catalyst respectively using the hexamethylene containing 6 weight % carbon disulfide as sulfurized oil The condition of change include: pressure be 4.14MPa, temperature be 362 DEG C, the time be 3.5 hours, sulfurized oil feed rate be 0.2 milliliter/ Minute.After vulcanization, being cooled to reaction temperature is 280 DEG C, cuts raw material.Reaction condition includes: that raw material feed rate is 0.2 Ml/min, pressure 4.14MPa, hydrogen to oil volume ratio 900.It is sampled after reaction 3 hours in high-pressure separator exit.Institute Sample is obtained to be analyzed with Agilent6890N gas chromatograph.Wherein, the hydrodesulfurization activity A of 4,6-DMDBT is counted as the following formula It calculates:

A=ln [100/ (100-X)],

In formula, the desulfurization degree of X 4,6-DMDBT (circular of X referring to " catalysis journal) ", 2002,23 (3): 271-275)。

The hydrodesulfurization activity for taking 4, the 6-DMDBT of comparative catalyst D1 is 100, then opposite the 4,6- of other catalyst The hydrodesulfurization activity of DMDBT can be represented by the formula:

Relative activity=(A_QT/A_D1) × 100%, A in formula_QTFor the activity of other catalyst, A_D1For the work of reference catalyst Property.

Table 3

By table 3 the results show that hydrogenation catalyst according to the present invention shows higher hydrodesulfurization activity.

Claims (16)

1. a kind of hydrogenation catalyst, containing carrier and at least one it is selected from group VIII and at least one gold selected from group VIB Belonging to component, which is characterized in that the carrier is the aluminium oxide molding containing R1R2R3R4N+X-, on the basis of the carrier, The mass fraction of the R1R2R3R4N+X- is 0.1%-10%, and the R1R2R3R4N+X- is selected from primary amine salt, secondary amine salt, tertiary ammonium salt Or one or more of quaternary ammonium salt, wherein described R1, R2, R3, R4 are selected from hydrogen, hydrocarbon substituent and its derivative；The catalysis Agent also contains the second organic matter in addition to R1R2R3R4N+X-, on the basis of catalyst, the mass fraction of second organic matter For 0.1-30%；

Second organic matter is selected from one or more of organic carboxyl acid and its ammonium salt；

The method of R1R2R3R4N+X- is introduced in the molding, comprising: (1) impregnate institute with the solution containing R1R2R3R4N+X- Molding is stated, the ratio between the volume of the maceration extract and the pore volume of the molding are 0.5-20；(2) mixing for obtaining dipping Object is heat-treated in closed reactor, and heat treatment temperature is room temperature to 250 DEG C, and the time is -48 hours 0.5 hour；(3) it does The product of dry step (2), the drying condition include: that temperature is 40 DEG C -250 DEG C, and the time is -24 hours 1 hour.

2. catalyst according to claim 1, which is characterized in that on the basis of the carrier, the R1R2R3R4N+X- Mass fraction be 0.3%-5%, on the basis of catalyst, the mass fraction of second organic matter is 1-22%.

3. catalyst according to claim 1, which is characterized in that the hydrocarbon substituent is selected from the linear chain or branched chain of C1-C20 Alkyl, or the naphthenic base selected from C3-C20, or the aryl selected from C6-C20；The derivative of the hydrocarbon substituent is selected from Alkyl with hydroxyl and/or heterocyclic substituent.

4. catalyst according to claim 3, which is characterized in that the hydrocarbon substituent is selected from the straight chain or branch of C1- C18 Alkyl group；Either it is selected from the naphthenic base of C6-C18；Either it is selected from the aryl of C6-C18.

5. according to claim 1,2 or 3 described in any item catalyst, which is characterized in that the X is selected from chlorine, bromine or iodine.

6. catalyst according to claim 5, which is characterized in that the X is selected from chlorine or bromine.

7. according to claim 1,2 or 3 described in any item catalyst, which is characterized in that the R1R2R3R4N+X- is selected from ten Six alkyl trimethyl ammonium bromides, hexadecyltrimethylammonium chloride, dodecyl amine hydrochloride, octadecyl amine hydrochloride, ten Tetraalkyl trimethylammonium bromide, tetradecyl trimethyl ammonium chloride, Cetyltrimethylammonium bromide, octadecyl trimethyl chlorine Change ammonium, didecyl Dimethy ammonium bromide, didecyl Dimethy ammonium chloride, didodecyldimethylammbromide bromide, double 12 Alkyl dimethyl ammonium chloride, double dodecyldimethylamine base ammonium bromides, double dodecyldimethylamine ammonium chlorides, double hexadecyldimethylamines Base ammonium bromide, dioctadecyl dimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium chloride It is one or more.

8. according to claim 1,2 or 3 described in any item catalyst, which is characterized in that the R1R2R3R4N+X- is selected from second Alcohol amine salt, dococylpyridinium hydrochloride.

9. catalyst according to claim 1, which is characterized in that the organic carboxyl acid is selected from trans- 1,2- cyclohexanediamine Tetraacethyl, ethylenediamine tetra-acetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxalic acid, hydroxyacetic acid, tartaric acid and One of malic acid is a variety of.

10. catalyst according to claim 1, which is characterized in that the group VIII metal is selected from nickel and/or cobalt, institute It states vib metals and is selected from molybdenum and/or tungsten, on the basis of the catalyst, the mass fraction of the metal component of group VIII is 1-10%, the mass fraction of metal component of group VIB are 5-40%.

11. catalyst according to claim 10, which is characterized in that on the basis of the catalyst, the VIIIth race gold The mass fraction for belonging to component is 1.5-6%, and the mass fraction of metal component of group VIB is 10-35%.

12. catalyst according to claim 1, which is characterized in that in the aluminium oxide molding containing selected from silica, One or more of titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide adjuvant component, on the basis of the carrier, institute The mass fraction for stating adjuvant component is 10% or less.

13. catalyst according to claim 12, which is characterized in that on the basis of the carrier, the adjuvant component Mass fraction is 0.3%-5%.

14. according to claim 1 or catalyst described in 12, which is characterized in that in the aluminium oxide molding containing clay and/ Or molecular sieve, on the basis of the carrier, the mass fraction of the clay and/or molecular sieve is 35% or less.

15. catalyst according to claim 14, which is characterized in that on the basis of the carrier, the clay and/or point The mass fraction of son sieve is 1%-20%.

16. a kind of hydrogenation method for hydrocarbon oils, is included under hydrogenation conditions, by hydrocarbon ils and catalyst haptoreaction, feature exists In the catalyst is catalyst described in claim 1-15 any one.