CN107971034A

CN107971034A - A kind of sulfurized hydrogenation catalyst and its preparation method and application

Info

Publication number: CN107971034A
Application number: CN201610921080.3A
Authority: CN
Inventors: 韩伟; 龙湘云; 李明丰; 杨清河; 聂红; 邵志才
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-21
Filing date: 2016-10-21
Publication date: 2018-05-01
Anticipated expiration: 2036-10-21
Also published as: CN107971034B

Abstract

The present invention relates to hydrofinishing field, discloses a kind of sulfurized hydrogenation catalyst and its preparation method and application, this method includes：(1) dispersant is mixed with the solution A containing vib metals salt, group VIII metal salt and sulphur source, the solution A is in acidity, the dispersant is the water-miscible organic solvent that boiling point is 15 90 DEG C, and the sulphur source is can be in 50 100 DEG C, the sulphur-containing substance of hydrolyzed under acidic conditions；(2) mixture obtained by step (1) is contacted at 60 150 DEG C in confined conditions with catalyst carrier 5 30 it is small when；(3) solid material of gained roasts in inertia or reducing atmosphere after step (2) is contacted.Method provided by the invention introduces host agent component and one step of auxiliary component, and prepared catalyst activity component not only high degree of dispersion, but also full cure, has finally been obviously improved catalyst hydrogenation performance.

Description

A kind of sulfurized hydrogenation catalyst and its preparation method and application

Technical field

The present invention relates to hydrofinishing field, and in particular, to a kind of preparation method of sulfurized hydrogenation catalyst and Sulfurized hydrogenation catalyst obtained by this method and its application in hydrodesulfurization and/or hydrodenitrogeneration.

Background technology

Hydrogen addition technology is the production most important means of clear gusoline, and wherein efficient hydrogenation catalyst is then the core of hydrogen addition technology Heart technology.Using group vib metal W or Mo as main active component, using group VIII metal Ni or Co as active ingredient is helped, with γ-A1₂O₃ Or modified γ-A1₂O₃Loaded catalyst for carrier is current industrial widely used hydrogenation catalyst.It is prepared by tradition The oxidized form presoma of active component is mainly introduced to carrier duct by technology using dipping means, by aging, drying, roasting Obtain hydrogenation catalyst.Wherein, Co, Ni, Mo and W active component exist in the form of an oxide.But hydrogenation is urged in actual use The existence form of agent active component is the oxide morphology of Co, Ni, Mo and W, and therefore, hydrogenation catalyst must pass through before use Vulcanization activation, is referred to as presulfurization.

Although conventional fabrication techniques obtain large-scale industrial application because of the easy to operate, advantage such as cost is low, it is still deposited In a series of problems.On the one hand, when using oxidized form active component as presoma, no matter in dipping ageing process or in drying Roasting process, itself and Al₂O₃Surface often has strong interaction, is not only easy to cause active component in carrier surface point It is scattered uneven, the generation of excessive Al-O-Mo chemical bonds is also resulted in, then causes active component vulcanization to be difficult to completely while formed Excessive low activity I class activity phases, active metal utilization rate are low (referring to CN 103143365A).In addition, with Mo base catalyst preparations Exemplified by, the presoma ion Mo of generally use₇O₂₄ ^6-Often induce Al₂O₃Surface dissociation produces Al³⁺, then react shape Into Anderson type heteropolyanion Al (OH)₆Mo₆O₁₈ ^3-, it is fired generation be difficult to by full cure so as to be unfavorable for catalysis live Property improve big crystal grain MoO₃And Al₂(MoO₄)₃Species are (referring to J.A.Bergwerff et al., Journal of the American Chemical Society 2004,126:14548；J.A.Bergwerff et al.,Catalysis Today 2008,130:117.) hydrogenation catalyst, therefore, is difficult to realize using traditional dipping technique and has high active component dispersion degree concurrently With high sulphidity, cause catalytic activity preferable not to the utmost.On the other hand, in conventional fabrication techniques pre-vulcanization process using " in device " sulfurization technology, i.e., first load oxidized catalyst in hydrogenation reactor, then to anti-during continuous heating Answer and hydrogen is passed through in device and vulcanizing agent is vulcanized, although this technology is still the technology being most widely used at present, it is still There are a series of problems：1) vulcanization time is long, and delay goes into operation；2) sulfidation easily causes corrosion of equipment, aging；3) vulcanize Agent is inflammable, poisonous, and easily environment is polluted；4) cost is higher etc..For " in device " sulfurization technology there are the problem of, CN1861258A、CN1861260A、CN101088619A、CN101088620A、CN1994567A、CN101279296A、 CN101491725A, US6365542 develop a series of " outside device " sulfurization technologies, and such technology mainly includes two lines：The A kind of technology path is first by vulcanizing agent (elementary sulfur, vegetable oil, organic sulfur compound, organic polysulfide, sulfone and sulfoxide etc.) In the gap for the hydrogenation catalyst for introducing oxidation state using the method for distillation, melting or dipping, then exist in inert gas Under thermally treated make catalyst vulcanization；Second of technology path be in special prevulcanisation-devices, in hydrogen and hydrogen sulfide or The presulfurization of oxidized catalyst is completed in the presence of labile organic sulfurizing agent.Vulcanize however, no matter using " in device ", also Be " outside device " vulcanization, be required to catalyst and first pass through oxidation state presulfurization again, cause catalyst preparation process complicated, economy compared with Difference.

To realize that Hydrobon catalyst has greater activity component dispersion degree, and ensure active component full cure, together When avoid the problem that " in device " sulfidation exists, simplify " outside device " vulcanize route, sulfurized hydrogenation catalyst was straight in recent years Connect syntheti c route and obtain more and more concerns and exploration.

Thio molybdic acid is dissolved in organic solvent by US6451729, and the non-negative of high-ratio surface is produced in the presence of high-temperature hydrogen Load type MoS₂Catalyst, the hydrogenation cracking activity of the catalyst are high.The shortcomings that such method is that catalyst preparation is of high cost, and only Powder catalyst can be prepared, it is impossible to be used in large-scale hydrogenation plant.

CN1557917A discloses a kind of sulfurized hydrogenation catalyst and preparation method thereof, the preparation method master of the catalyst If to the carrier of conventional catalyst by using soluble Thiomolybdate and thiqtung state solution by vib metals Mo Be incorporated into the presoma of W in the gap of catalyst carrier for hydrgenating, under nitrogen protection 350 DEG C roasting 4 it is small when, then with contain Ni, The solution dipping of Co, when 350 DEG C of roastings 4 are small under nitrogen protection, so as to prepare the supported sulfide catalysis of Mo, W, Co, Ni Agent.Although the method can the excellent hydrogenation catalyst of processability, host agent component and auxiliary component impregnate successively, and make The synthesis technique of standby complex process, especially vulcanization type presoma is complicated, causes catalyst preparation cost very high, is not suitable for big Technical scale application.

CN102039147A discloses a kind of preparation method of sulfide type catalyst, using the alkyl containing metal Mo or W The inorganic salts and organic additive of molybdenum sulfide (tungsten) acid ammonium salt, Ni or Co are maceration extract, by impregnating the catalyst carrier needed, Again sulfide type catalyst is directly obtained through drying.This method preparation process is relatively simple, and preparation process is not required to inert gas shielding, Be easily formed the high II class activity phases of catalytic activity at the same time, catalyst performance is high, but due to equally employ more difficult synthesis, The very expensive molybdenum dithiophosphate of price (tungsten) hydrochlorate is active precursor, finally so that the manufacturing cost of catalyst is very high, application Possibility is smaller.

To sum up, the catalyst activity that the preparation method of the sulfurized hydrogenation catalyst provided by the prior art obtains has Improved, but improve limitation, and the preparation method of sulfurized hydrogenation catalyst in the presence of needing respectively lead into carrier by introducing The defects of agent component and auxiliary component, syntheti c route are complex, controllability is poor and cost is higher, therefore, in certain journey The commercial Application of these methods is limited on degree.

The content of the invention

It is relatively low for prior art sulfurized hydrogenation catalyst activity, preparation process is complex, controllability is poor and The defects of cost is higher, the present invention provide the vulcanization that a kind of preparation method of new sulfurized hydrogenation catalyst and this method obtain The application of type hydrogenation catalyst and above-mentioned sulfurized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogeneration, the present invention carry The method of confession introduces host agent component and one step of auxiliary component, and prepared catalyst activity component not only high degree of dispersion, and And full cure, finally it has been obviously improved catalyst hydrogenation performance.

The present invention provides a kind of preparation method of sulfurized hydrogenation catalyst, this method comprises the following steps：

(1) dispersant is mixed with the solution A containing vib metals salt, group VIII metal salt and sulphur source, it is described molten Liquid A is the water-miscible organic solvent that boiling point is 15-90 DEG C in acidity, the dispersant, the sulphur source for can 50-100 DEG C, The sulphur-containing substance of hydrolyzed under acidic conditions；

(2) that mixture obtained by step (1) is contacted 5-30 at 60-150 DEG C in confined conditions with catalyst carrier is small When；

(3) solid material of gained roasts in inertia or reducing atmosphere after step (2) is contacted.

Present invention also offers the sulfurized hydrogenation catalyst as made from the above method and its in hydrodesulfurization and/or hydrogenation Application in denitrogenation.

The method provided according to the present invention, prepared catalyst are sulphided state in itself, when in use without sulphur again Change.At present, most research results are thought directly in host agent MoS₂/WS₂On the basis of introduce auxiliary agent Co or Ni, be more advantageous to shape Into Co (Ni)-Mo (W)-S active phases, so that catalyst hydrogenation performance is more preferably (referring to Okamoto et al.Journal of Catalysis 2004 222:143).Therefore, when the prior art prepares sulfurized hydrogenation catalyst, more first by group VIB After metal salt enters carrier, then group VIII metal introduced, for example, the system of sulfurized hydrogenation catalyst disclosed in CN1557917A Vib metals Mo and W first are introduced to carrier in Preparation Method, group VIII metal Co and Ni are introduced after roasting.And the present invention Inventor is found surprisingly that in the course of the research, in sulfurized hydrogenation catalyst preparation process, by vib metals salt and Group VIII metal salt is collectively incorporated into carrier in the presence of sulphur source and dispersant equally can be made the preferable catalyst of Hydrogenation.Study carefully Its reason, it may be possible to because the present invention directly by containing vib metals salt, the sulphur source of group VIII metal salt solution with point Powder mixes, and is then contacted under given conditions with catalyst carrier, vib metals pass through trisulfide form of nanoparticles Diffusion-deposition is to carrier surface, and group VIII metal is by form diffusion-deposition to carrier surface of hydrated cation, by There is certain electronegativity in aqueous in trisulfide nano-particle, once therefore its nano particle generate, must be by week The group VIII metal hydrated cation enclosed is equably adsorbed to its surface, so as to promote group VIB and group VIII metal Synchronous, equably diffusion-deposition to carrier channel surfaces, this for promote as auxiliary agent atom group VIII metal more More Co (Ni)-Mo (W)-S, which are formed, into the Section VI B metal sulfides corner position as host agent atom creates condition.Therefore Effectively prevent in conventional manufacturing process causes assistant effect not because auxiliary agent group viii metal vulcanizes prior to host agent vib metal Preferable situation, it is ensured that sulfurized hydrogenation catalyst maintains higher activity.In the preferred case, the present invention uses water solubility two Valency metal salt is modified catalyst carrier in the aqueous solution containing urea, can not only improve the activity of catalyst, and And the high activity of catalyst can be effectively kept for a long time, so as to greatly improve the service life of catalyst.Speculate its reason It is probably this part aqueous divalent metal salt because by introducing water-soluble divalent metal in the aqueous solution containing urea In addition to it can be used as active component, regulating catalyst carrier surface structure is also can be used to, carrier surface is formed and is beneficial to efficiently divide Dissipate " netted " structure (as shown in Figure 2) with anchoring activity component.And after subsequently metal hydrogenation active component is introduced, catalysis The surface of agent still maintains this " netted " structure (as shown in Figure 3).This " netted " structure not only contributes to active metal The loading of component, disperse and grappling, also effectively reduces the strong interaction between active component and carrier.

The preparation method of sulfurized hydrogenation catalyst provided by the invention, by vib metals and group VIII metal In the case that one step introduces, the defects of assistant effect is undesirable is effectively prevent, operating process is easy, and has active component concurrently High degree of dispersion and high curing degree, improve the Hydrogenation of catalyst.Mention at the same time in CN1557917A, be loaded with Mo, W, Co, The catalyst of the lower valency sulfide of Ni is safe, non-hypergolic and nonflammable in room temperature and relatively dry air, Therefore, according to the catalyst prepared by the method for the invention, as long as by inert gas treatment, and using room temperature is closed and lucifuge Packaging, it is ensured that catalyst storage, transport and the security for loading process.

Compared with prior art, the preparation method of sulfurized hydrogenation catalyst provided by the invention is easy to operate, is easy to weight Multiple, catalyst preparation cost is low, and obtained catalyst hydrogenation performance is good, and is not required to presulfurization, saves on-stream time, to environment friend It is good.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Brief description of the drawings

Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1 is unmodified γ-Al in embodiment 1₂O₃The SEM figures of carrier surface；

Fig. 2 is the SEM figures on the alumina support Z-1 surfaces that Co is modified in embodiment 1；

Fig. 3 is the SEM figures on sulfurized hydrogenation catalyst S-1 surfaces in embodiment 1.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more New number range, these number ranges should be considered as specific open herein.

The present invention provides a kind of preparation method of sulfurized hydrogenation catalyst, and this method comprises the following steps：

In the present invention, under preferable case, the group VIII metal is cobalt and/or nickel, and the vib metals are molybdenum And/or tungsten.

In the present invention, under preferable case, the vib metals salt is selected from sodium molybdate, sodium tungstate, ammonium tungstate, metamolybdic acid One or more in ammonium, ammonium metatungstate, ammonium phosphomolybdate and ammonium phosphotungstate；The group VIII metal salt is selected from water soluble cobalt And/or the one or more in the nitrate of nickel, carbonate, chlorate, sulfate and acetate.

In the case of, according to the invention it is preferred to, concentration of the vib metals salt in solution A is 0.005-5mol/L, preferably For 0.05-0.3mol/L, more preferably 0.15-0.3mol/L.

In the present invention, it is preferred to group VIII metallic element and the molar ratio of vib metals element are 0.1-1.5, More preferably 0.15-0.5.It is relatively beneficial to play group VIII metal and group VIB gold using this kind of preferred embodiment The synergistic effect of category, and it is relatively beneficial to the formation of active phase.

According to the present invention, the dispersant can be the water-miscible organic solvent that various boiling points are 15-90 DEG C, be preferably selected from One or more in methanol, ethanol, propyl alcohol and acetone, more preferably ethanol.

The present invention is wider to the range of choice of the addition of dispersant, it is preferable that the addition of dispersant and the body of solution A Product ratio is 0.1-10：1, more preferably 0.5-2：1.

According to the present invention, the sulphur source can be it is various can in 50-100 DEG C, the sulphur-containing substance of hydrolyzed under acidic conditions, It is preferred that the sulphur source is thio selected from the thioamides shown in following formula (1), single monothioester shown in formula (2) and two shown in formula (3) At least one of ester,

In formula (1), R¹For NH₂-、CH₃-、CH₃CH₂-、CH₃NH- or (CH₃)₂N-, R²And R³It is each independently H or C1- C4 alkyl；In formula (2), R⁴For H or C1-C4 alkyl, R⁵For C1-C4 alkyl；In formula (3), R⁶For H or C1-C4 alkyl, R⁷For C1- C4 alkyl, the C1-C4 alkyl can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group or the tert-butyl group.R²And R³ Can be identical or different.The further preferred sulphur source is the thioamides shown in formula (1), and still more preferably described sulphur source is Thiocarbamide and/or thioacetamide, most preferably described sulphur source are thioacetamide.

In the present invention, the addition of the sulphur source is to meet to make vib metals and group VIII metal full cure Subject to condition, under preferable case, the sulphur source and the molar ratio of group vib metallic element are 1-9：1, more preferably 3-5：1, Most preferably 3：1.

In the present invention, acidity refers to that pH value is less than 7.According to the present invention it is possible to make solution A be in acidity by various modes, Such as realized by adding organic acidic substances and/or inorganic acidic materials, it is preferably added to hydrochloric acid and/or nitric acid.

In the present invention, although as long as making solution A be in acid, under preferable case, it is no more than the pH value of solution A 5, more preferably 2-5.For hydrochloric acid and nitric acid, by controlling the addition of acid and the molar ratio 0.5-3 of vib metals By pH value control within the above range.

In the present invention, it is preferred to the solvent for forming solution A is water.

Under preferable case, step (1) mixing carries out under agitation, so that vib metals salt, group VIII The mixing of metal salt and sulphur source is more fully, uniformly.The speed of stirring can be 10-500rpm.

Dispersant is preferably with the mode that the solution A containing vib metals salt, group VIII metal salt and sulphur source mixes Dispersant is added dropwise in solution A.Relative to 0.1 mole of vib metals salt, the speed of addition is preferably 1-5ml/ min。

A preferred embodiment of the invention, before step (2), is modified the catalyst carrier, Modified method includes：Catalyst carrier is impregnated in the mixture containing urea, water-soluble divalent metal and water, then It is heat-treated, filtered successively, being washed, dry and roasting.

Cause carrier surface that there is net structure using this kind of preferred embodiment, beneficial to high efficiency dispersion and anchoring activity group Point, and subsequently by after the introducing of metal hydrogenation active component, the surface of catalyst still maintains this " netted " structure, this " netted " structure not only contributes to the loading of active metal component, disperses and grappling, also effectively reduces active component with carrying Strong interaction between body.

According to the present invention, in the mixture used in modification procedure, the concentration of water-soluble divalent metal is preferably 0.01mol/L-1mol/L, more preferably 0.1mol/L-0.5mol/L.

In accordance with the present invention it is preferred that the water-soluble divalent metal is selected from nitrate, sulfate and the chlorine of divalent metal One or more in salt dissolving.

The divalent metal can be selected from group VIII metal, the IIth A races metal, the Ith B races metal and II B-group metal In one or more.

In the present invention, the group VIII metallic element can be in iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum element One or more.

IIth A races metallic element can be the one or more in calcium, magnesium, strontium and barium element.

Ith B races metallic element can be copper and/or gold element.

The II B-group metal element can be zinc and/or cadmium element.

Under preferable case, the one kind or more of the divalent metal element in cobalt, nickel, iron, calcium, magnesium, copper and Zn-ef ficiency Kind.

According to the present invention, in the mixture, the molar ratio of the urea and water-soluble divalent metal is preferably 2-10: 1。

According to the present invention, in the mixture, the molar ratio of the catalyst carrier and water-soluble divalent metal is 3- 20：1, more preferably 4-10：1.

In accordance with the present invention it is preferred that it is 60-140 DEG C that the condition of the heat treatment, which includes heat treatment temperature, more preferably 70-90 DEG C, when heat treatment time is 2-60 small, when more preferably 12-24 is small.

There is no particular limitation to condition dry described in catalyst carrier modifying process by the present invention, can be this area Common various drying conditions, for example, it is 100-250 DEG C that the condition of the drying, which includes drying temperature, it is preferably 100-130 DEG C, when drying time is 1-12 small, when being preferably 2-6 small.

There is no particular limitation to the condition that is roasted described in catalyst carrier modifying process by the present invention, can be this area Common various roasting conditions, for example, it can be 400-600 DEG C that the condition of roasting, which includes calcination temperature, it is preferably 450-550 DEG C, when roasting time can be 2-10 small, when being preferably 2-6 small.

There is no particular limitation to the catalyst carrier by the present invention, can be porous oxide carrier, such as can be γ-Al₂O₃、SiO₂、TiO₂、SBA-15、ZrO₂And SiO₂-γ-Al₂O₃In one or more.The particularly preferred carrier is straight γ-Al of the footpath in 2mm to 5mm₂O₃The SiO of particle or diameter in 2mm to 5mm₂-γ-Al₂O₃Particle.Above-mentioned carrier can be commercially available Obtain, can also be prepared using existing method.

In the present invention, for the addition of catalyst carrier in step (2), there is no particular limitation, people in the art Member can make choice according to actual conditions, and details are not described herein.Preferably, the addition of the catalyst carrier causes made Standby hydrogenation catalyst, on the basis of the total amount of catalyst, the content of vib metals is 5-35 weight %, more preferably 10-30 weight %, the content of group VIII metal is 1-11 weight %, and more preferably 2-5 weight %, the content of carrier are 60-90 weight %, more preferably 65-85 weight %.

In the present invention, step (2) contact carries out preferably in autoclave.The present invention, the autoclave refers to can Bear 10⁹The kettle of the pressure of Pa.

In preferred steps (2), by mixture obtained by step (1) and catalyst carrier in confined conditions at 80-120 DEG C When contact 8-24 is small.

Further preferred step (2) contact carries out under agitation.It can be dried by the way that autoclave is placed in rotation Stirring is realized by the rotation of rotary oven in case.The rotating speed of rotary oven can be 30-200rpm.

The present invention is preferably by filtering, washing, drying steps (2) contact resulting material and obtain solid material.

The present invention is to the filtering, washing, there is no particular limitation for dry condition, can be commonly used in the art Various modes, those skilled in the art can be made choice by concrete condition.

The drying can be that room temperature dries or dries (preferably carry out under an inert atmosphere) in an oven, Can be by way of vacuum be drained.

According to the present invention, the inert atmosphere can be preferably nitrogen selected from the one or more in nitrogen, argon gas and helium Gas.

According to the present invention, the reducing atmosphere can be selected from the gas containing hydrogen and/or hydrogen sulfide.

Inert gas can be contained in the reducing atmosphere, when containing inert gas in the reducing atmosphere, hydrogen and/ Or the volume content of hydrogen sulfide is not less than 5%.

Solid material after preferably step (3) is impregnated according to the present invention roasts in a reducing atmosphere, most preferably in hydrogen Roasted in atmosphere.The preferred embodiment is more advantageous to improving the activity of catalyst.

The present invention has no particular limits the condition roasted described in step (3), and the condition of preferably described roasting includes： Calcination temperature is 300-800 DEG C, when roasting time is 2-6 small；It is further preferred that calcination temperature is 400-600 DEG C, during roasting Between for 3-5 it is small when.

The sulfurized hydrogenation catalyst as made from above-mentioned preparation method has excellent hydrodesulfurization and denitrification activity, therefore Present invention also offers the sulfurized hydrogenation catalyst as made from above-mentioned preparation method and its in hydrodesulfurization and/or hydrodenitrogeneration In application.

Sulfurized hydrogenation catalyst according to the present invention, in terms of respective metal oxide, using the total amount of catalyst as base Standard, the content of vib metals is 5-35 weight %, is preferably 10-30 weight %, the content of group VIII metal is 1-11 weights % is measured, is preferably 2-5 weight %, the content of carrier is 60-90 weight %, is preferably 65-85 weight %.

A preferred embodiment of the invention, the sulfurized hydrogenation catalyst surface have net structure, institute The mesh-density for stating net structure is 0.5-50/square micron, and the mesh-density is by least 20 scanning electrons The lattice number being distributed in microphotograph in every micrometer square region calculates the method measure of average value.

, according to the invention it is preferred to the mesh-density of the net structure is 5-20/square micron.

There is no particular limitation for shooting number of the present invention for electron scanning micrograph, preferably described mesh-density It is by calculating average value to the lattice number being distributed in every micrometer square region in 30-50 electron scanning micrographs Method measure.

In the present invention, stereoscan photograph is obtained using S250MK3 types scanning electron microscope, and operating condition is 20kV, sample current 100mA, operating distance 24mm.

The preparation method of sulfurized hydrogenation catalyst provided by the invention can be construed to first by containing Section VIII Using the trithio of chemical deposition synthesis vib metals such as Mo and/or W in the solution of race's metal such as Co and/or Ni cations The solid-liquid mixture that the trisulfide nano particle of compound nano particle, acquisition Co and/or Ni cations and Mo and/or W coexist System, it is then at a certain temperature that they are co-deposited to carrier channel surfaces, filtered, drying and in inertia or reducing gas In thermally treated be converted into corresponding sulfide.

Specifically, when sulphur source (by taking thioacetamide as an example), molybdenum salt or tungsten salt (by taking sodium molybdate as an example), nickel salt or cobalt salt (by taking nickel nitrate as an example), H⁺(by taking nitric acid as an example) and carrier are (with γ-Al₂O₃Exemplified by) when coexisting in same solution, utilize sulphur For acetamide, slowly hydrolysis produces H under low temperature, acid condition₂The characteristic of S, by controlling solution temperature, makes it constantly occur Chemical reaction generation MoS₃Crystal grain, obtains Ni²⁺With MoS₃The suspended system of solid-liquid that crystal grain coexists, due to electrostatic adsorption, leads Cause the MoS of each electronegativity₃Some Ni are adsorbed around nanocrystal²⁺Form Ni-MoS₃Compound particle, afterwards Ni²⁺-MoS₃It is multiple Close particle and obtain catalyst precursor-Ni-MoS through spreading, depositing to carrier channel surfaces₃/γ-Al₂O₃, finally by it lazy Property or reducing gas (be preferably reducing gas) in thermally treated be converted into corresponding sulfide-NiMoS₂/γ-Al₂O₃Side Method.This process can represent as follows：

3CH₃CSNH₂+6H₂O→3CH₃COONH₄+3H₂S↑ (1)

Ni²⁺+MoO₄ ^2-+3H₂S+2H⁺+γ-Al₂O₃→Ni-MoS₃/γ-Al₂O₃↓+4H₂O (2)

The method provided according to the present invention, the addition of dispersant are to realize one of key of the object of the invention.It is former to study carefully it Cause, it may be possible to because low-boiling dispersant (such as methanol, ethanol or acetone) on the one hand can be adsorbed by van der Waals interaction power To MoS₃Grain surface, suppresses its growth, so as to control MoS₃The scale of particle, this be its can diffuse to carrier duct and then Deposit to the premise of channel surfaces；Another aspect dispersant is combined with water, can reduce the boiling point of reaction solution so that its Also " class hydro-thermal " environment can be reached under relatively low reaction temperature, so as to promote Ni-MoS₃Diffusion, deposition into duct.

Below by way of the specific embodiment implementation process that the present invention will be described in detail and caused beneficial effect, it is intended to help Where reader more clearly understands the Spirit Essence of the present invention, but any restriction cannot be formed to the practical range of the present invention.

In following embodiments, tenor is measured using X-ray fluorescence spectra (XRF) method in catalyst, wherein, X is penetrated Line fluorescence spectrum (XRF) method uses ZSX-100e type Xray fluorescence spectrometers, using Rh targets, in electric current 50mA, voltage 50kV's Under the conditions of measure.

The mesh-density of catalyst and carrier surface passes through to dividing in 50 stereoscan photographs in every micrometer square region The lattice number of cloth calculates the method measure of average value, wherein, stereoscan photograph uses S250MK3 type scanning electron microscope Obtain, operating condition 20kV, sample current 100mA, operating distance 24mm.

The dispersion degree of host agent Mo (or W) and sulphidity are analyzed (XPS) by x-ray photoelectron spectroscopy and are measured in catalyst, its In, dispersion degree represents that sulphidity is by XPS data as the surface metal atoms ratio (Mo (W)/Al) given by XPS analysis result Processing obtains, and specific processing method can be found in document Han et al., Journal of Materails Chemistry 2012,22:25340, wherein, x-ray photoelectron spectroscopy analyzes (XPS) in ESCA Lab 250 model x-ray photoelectron spectroscopies Carried out on (Britain's VG Products), use radiation source as Al K α, resolution ratio 0.5eV, be inside designated as the knot of the C1s of pollution carbon The condition for closing energy (Eb=285.0eV) obtains.

Embodiment 1

Prepare the sodium molybdate containing 0.15mol/L, the nickel nitrate of 0.06mol/L, 0.45mol/L thioacetamides it is water-soluble Liquid, in whipping process, is added dropwise 2.4mol/L hydrochloric acid 4.0mL, obtains 40mL solution As, pH value 5.0；

20mL absolute ethyl alcohols are measured, are added dropwise to the speed of 1mL/min absolute ethyl alcohol during being stirred continuously molten In liquid A, solution B is formed；

By 4.0g diameters 2-5mm γ-Al₂O₃Particle (surface SEM figures are shown in Fig. 1) is dipped in 20.0mL nitre containing 0.2mol/L Sour cobalt, 1.0mol/L urea mixed aqueous solution in, in 80 DEG C heat treatment 24 it is small when, filtering, washing then in 120 DEG C of dryings 4 it is small when, the SEM figures of the alumina support Z-1, Z-1 of Co modifications are obtained when 500 DEG C of roastings 4 are small in the air draught of 100mL/min As shown in Figure 2.Figure it is seen that the alumina carrier surface that Co is modified has substantial amounts of net structure, mesh-density is listed in In table 2；

Solution B is transferred in the autoclave for filling alumina support Z-1 obtained above, then by autoclave place to 24h is contacted at 85 DEG C in rotary oven (rotating speed 100rpm), then suspension is filtered, is washed, room temperature is dried, in 500 DEG C in H₂4h is roasted in atmosphere, obtains sulfide type catalyst S-1.Its SEM is schemed as shown in figure 3, Fig. 3 and Fig. 2 can relatively be seen Go out, " netted " structure of the two is essentially identical, and after illustrating supported active metals component, catalyst has still maintained the " net of carrier Shape " structure, tenor, dispersion degree and sulphidity analysis result are listed in Table 1 below in catalyst.Catalyst mesh-density is listed in table In 2.

Embodiment 2

The sodium tungstate containing 0.20mol/L, the nickel acetate of 0.1mol/L, the aqueous solution of 0.60mol/L thioacetamides are prepared, In whipping process, 2.4mol/L hydrochloric acid 4.5mL are added dropwise, obtain 30mL solution As, pH value 4.5；

30mL absolute ethyl alcohols are measured, are added dropwise to the speed of 1mL/min absolute ethyl alcohol during being stirred continuously molten In liquid A, solution B is formed；

By 4.0g diameters 2-5mm γ-Al₂O₃Particle is dipped in the urine of 13.0mL nickel nitrates containing 0.1mol/L, 0.4mol/L In plain mixed aqueous solution, when 70 DEG C of heat treatments 18 are small, filtering, wash and then when 130 DEG C of dryings 2 are small, 100mL/min's The mesh-density that the alumina support Z-2, Z-2 of Ni modifications are obtained when 550 DEG C of roastings 2 are small in air draught is listed in Table 2 below；

Solution B is transferred in the autoclave for filling alumina support Z-2 obtained above, then by autoclave place to 24h is contacted at 85 DEG C in rotary oven (rotating speed 80rpm), then suspension is filtered, is washed, vacuum is drained, in 500 DEG C In H₂4h is roasted in atmosphere, obtains sulfide type catalyst S-2.

Tenor, dispersion degree and sulphidity analysis result are listed in Table 1 below in catalyst.Catalyst mesh-density is listed in table In 2.

Embodiment 3

The sodium molybdate containing 0.20mol/L, the nickel nitrate of 0.09mol/L, the aqueous solution of 0.60mol/L thiocarbamides are prepared, is being stirred During mixing, 2.4mol/L hydrochloric acid 4.5mL are added dropwise, obtain 30mL solution As, pH value 4.5；

By 4.0g diameters 2-5mm γ-Al₂O₃Particle is dipped in the urine of 20.0mL magnesium nitrates containing 0.5mol/L, 1.0mol/L In plain mixed aqueous solution, when 90 DEG C of heat treatments 12 are small, filtering, wash and then when 100 DEG C of dryings 6 are small, 100mL/min's The mesh-density that the alumina support Z-3, Z-3 of Mg modifications are obtained when 450 DEG C of roastings 6 are small in air draught is listed in Table 2 below.

Solution A is transferred in the autoclave for filling alumina support Z-3 obtained above, then by autoclave place to 24h is contacted at 85 DEG C in rotary oven (rotating speed 100rpm), then suspension is filtered, is washed, room temperature is dried, in 500 DEG C in H₂4h is roasted in atmosphere, obtains sulfide type catalyst S-3.

Embodiment 4

The sodium molybdate containing 0.30mol/L, the cobalt nitrate of 0.05mol/L, the aqueous solution of 0.90mol/L thiocarbamides are prepared, is being stirred During mixing, 2.4mol/L hydrochloric acid 4.5mL are added dropwise, obtain 20mL solution As, pH value 5.0；

40mL absolute ethyl alcohols are measured, are added dropwise to the speed of 1mL/min absolute ethyl alcohol during being stirred continuously molten In liquid A, solution B is formed；

Solution B is transferred to the γ-Al for filling 4.0g diameters in 2-5mm₂O₃In the autoclave of particle, then by autoclave Placement contacts 24h into rotary oven (rotating speed 150rpm) at 85 DEG C, then filters suspension, washes, and room temperature is dried, In 500 DEG C in H₂4h is roasted in atmosphere and obtains sulfide type catalyst S-4.

Tenor, dispersion degree and sulphidity analysis result are listed in Table 1 below in catalyst.SEM figures show, catalyst surface Without net structure.

Embodiment 5

Prepare the sodium molybdate containing 0.30mol/L, the cobalt acetate of 0.08mol/L, 0.90mol/L thioacetamides it is water-soluble Liquid, in whipping process, is added dropwise 2.4mol/L hydrochloric acid 9.0mL, obtains 30mL solution As, pH value 2.5；

The solution B is transferred to the γ-Al for filling 8.0g diameters in 2-5mm₂O₃In the autoclave of particle, then by high pressure Kettle is placed contacts 24h into rotary oven (rotating speed 50rpm) at 85 DEG C, then filters suspension, washes, room temperature is dried in the air It is dry, in 500 DEG C in H₂4h is roasted in atmosphere, obtains sulfide type catalyst S-5.

Embodiment 6

Prepare the sodium molybdate containing 0.20mol/L, the nickel nitrate of 0.05mol/L, 0.60mol/L thioacetamides it is water-soluble Liquid, in whipping process, is added dropwise 2.4mol/L hydrochloric acid 3.0mL, obtains 30mL solution As, pH value 5.0；

The solution B is transferred to the γ-Al for filling 2.0g diameters in 2-5mm₂O₃In the autoclave of particle, then by high pressure Kettle is placed contacts 24h into rotary oven (rotating speed 60rpm) at 85 DEG C, then filters suspension, washes, room temperature is dried in the air It is dry, in 500 DEG C in H₂4h is roasted in atmosphere, obtains sulfide type catalyst S-6.

Embodiment 7

The sodium molybdate containing 0.20mol/L, 0.06mol/L nickel nitrates, the aqueous solution of 0.60mol/L thiocarbamides are prepared, is being stirred During, 2.4mol/L hydrochloric acid 5.0mL are added dropwise, obtain 30mL solution As, pH value 4.0；

30mL absolute ethyl alcohols are measured, are added dropwise to the speed of 2mL/min absolute ethyl alcohol during being stirred continuously molten In liquid A, solution B is formed；

Solution B is transferred to the γ-Al for filling 5.0g diameters in 2-5mm₂O₃In the autoclave of particle, then by autoclave Placement contacts 20h into rotary oven (rotating speed 200rpm) at 105 DEG C, then filters suspension, washes, room temperature is dried in the air It is dry, in 500 DEG C in H₂4h is roasted in S atmosphere, obtains sulfide type catalyst S-7.

Embodiment 8

The sodium molybdate containing 0.20mol/L, the nickel nitrate of 0.05mol/L, the aqueous solution of 0.60mol/L thiocarbamides are prepared, is being stirred During mixing, 2.4mol/L hydrochloric acid 5.0mL are added dropwise, obtain 30mL solution As, pH value 4.0；

30mL absolute ethyl alcohols are measured, are added dropwise to the speed of 3mL/min absolute ethyl alcohol during being stirred continuously molten In liquid A, solution B is formed；

Solution B is transferred to the γ-Al for filling 4.0g diameters in 2-5mm₂O₃-SiO₂In the autoclave of particle, then by height Pressure kettle is placed contacts 24h into rotary oven (rotating speed 100rpm) at 80 DEG C, then filters suspension, washes, room temperature Dry, in 500 DEG C in H₂/H₂4h is roasted in S atmosphere, obtains sulfide type catalyst S-8.

Embodiment 9

Prepare the sodium molybdate containing 0.20mol/L, the nickel nitrate of 0.05mol/L, 0.60mol/L thioacetamides it is water-soluble Liquid, in whipping process, is added dropwise 2.4mol/L hydrochloric acid 4.5mL, obtains 30mL solution As, pH value 4.3；

Solution B is transferred to the SiO for filling 4.0g diameters in 2-5mm₂-γ-Al₂O₃Particle (SiO₂/γ-Al₂O₃Molar ratio For 1：5) in autoclave, then autoclave is placed into rotary oven (rotating speed 100rpm) and contacts 24h at 75 DEG C, so Suspension is filtered afterwards, is washed, room temperature is dried, in 500 DEG C in H₂4h is roasted in atmosphere, obtains sulfide type catalyst S-9.

Embodiment 10

Method according to embodiment 1 prepares sulfurized hydrogenation catalyst, unlike, not to γ-Al₂O₃Particle is changed Property, it is specially：

Solution B is transferred to the γ-Al for filling 4.0g diameters in 2-5mm₂O₃In the autoclave of particle, then by autoclave Placement contacts 24h into rotary oven (rotating speed 100rpm) at 85 DEG C, then filters suspension, washes, and room temperature is dried, In 500 DEG C in H₂4h is roasted in atmosphere, obtains sulfide type catalyst S-10.Tenor, dispersion degree and sulphidity in catalyst Analysis result is listed in Table 1 below.SEM figures show that catalyst surface does not have net structure.

Comparative example 1

NiMo/ γ-Al are prepared using room temperature equi-volume impregnating₂O₃Catalyst.Specially：Weigh Ammonium Molybdate Tetrahydrate 1.25g, is made into maceration extract about 10mL, and a small amount of hydrochloric acid is added dropwise to pH value about 4.5, this solution is added dropwise in vacuum state γ-Al of the diameter of 10g in 2-5mm₂O₃In carrier, then place at room temperature until its natural drying, then place baking oven in 120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain Mo/Al₂O₃；Nickel nitrate 0.67g is weighed, maceration extract 8mL is made into, impregnates at room temperature 12h, 120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain NiMo/ γ-Al₂O₃, then take 1g NiMo/ γ-Al₂O₃Put into miniature Hydrogenation reactor vulcanize " in device ", and conditions of vulcanization is：4.0MPa, 300 DEG C, 4h, hydrogen to oil volume ratio 300, sulfurized oil oil inlet Flow is 8mL/h, and catalyst D-1 is obtained after vulcanization, and tenor, dispersion degree and sulphidity analysis result arrange in catalyst In table 1.SEM figures show that catalyst surface does not have net structure.

Comparative example 2

CoMo/ γ-Al are prepared using room temperature equi-volume impregnating₂O₃Catalyst.Specially：Weigh Ammonium Molybdate Tetrahydrate 1.25g, is made into maceration extract about 10mL, and a small amount of hydrochloric acid is added dropwise to pH value about 4.5, this solution is added dropwise in vacuum state γ-Al of the diameter of 10g in 2-5mm₂O₃In carrier, then place at room temperature until its natural drying, then place baking oven in 120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain Mo/Al₂O₃；Cobalt nitrate 0.67g is weighed, maceration extract 8mL is made into, impregnates at room temperature 12h, 120 DEG C of dry 10h, 500 DEG C of roasting 4h, obtain CoMo/ γ-Al₂O₃, the then vulcanization process pair as described in comparative example 1 CoMo/γ-Al₂O₃Vulcanized, obtain catalyst D-2, tenor, dispersion degree and sulphidity analysis result arrange in catalyst In table 1.SEM figures show that catalyst surface does not have net structure.

Comparative example 3

NiW/ γ-Al are prepared using room temperature equi-volume impregnating₂O₃Catalyst.Specially：Sodium tungstate 4.80g is weighed, is made into This solution, is added dropwise to γ-Al of the diameter in 2-5mm of the 10g in vacuum state by maceration extract about 10mL₂O₃In carrier, then Place at room temperature until its natural drying, is then placed in 120 DEG C of dry 10h in baking oven, 500 DEG C of roasting 4h, obtain W/Al₂O₃； Nickel nitrate 0.70g is weighed, is made into maceration extract 8mL, impregnates 12h, 120 DEG C of dry 10h at room temperature, 500 DEG C of roasting 4h, obtain NiW/ γ-Al₂O₃Catalyst D-3, tenor, dispersion degree and sulphidity analysis result are listed in Table 1 below in catalyst.SEM figures show, Catalyst surface does not have net structure.

Comparative example 4

Method according to embodiment 1 prepares sulfide type catalyst, unlike, directly by solution A and the oxidation of Co modifications Alumina supporter Z-1 is contacted in autoclave, that is, is added without absolute ethyl alcohol to prepare solution B, obtains sulfide type catalyst D-4.

Comparative example 5

Method according to embodiment 1 prepares sulfide type catalyst, unlike, hydrochloric acid is added without when preparing solution A, is obtained Solution pH value be 7.0, obtain sulfide type catalyst D-5.

Tenor, dispersion degree and sulphidity analysis result in 1 catalyst of table

The mesh-density of 2 catalyst of table and carrier

Sample number into spectrum	Mesh-density (a/square micron)
		γ-Al₂O₃	0
Z-1	8.9
		Z-2	6.9
Z-3	9.6
		S-1	8.6
S-2	6.4
		S-3	9.2
D-4	6.5
		D-5	8.0

The mesh-density of carrier and catalyst means carrier and catalyst in remaining unlisted embodiment and comparative example Surface does not have net structure.

Test example

In this test example, add to what the hydrogenation catalyst and comparative example prepared using method provided by the present invention was provided The desulfurization of hydrogen catalyst and denitrification activity are evaluated in accordance with the following methods, and list result.

Hydrodesulfurization：Using the cyclohexane solution of dibenzothiophenes (DBT) mass content 1% as raw material, first weighed in Tianjin The desulphurizing activated of catalyst is evaluated on the continuous high pressure reaction assemblies of WFSP3050 of instrument company's production.It is not required to before the reaction to urging Agent S-1 to S-10 presulfurizations handle.Reaction condition is：4.0MPa, 340 DEG C, hydrogen to oil volume ratio 300, oil inlet flow is 8mL/ h.After stable reaction 3h, sampled after reaction 4h and reaction 1000h, sample is surveyed sulphur nitrogen instrument with HS-500 types high frequency-infrared and divided Analysis, activity is represented with the desulfurization degree of DBT, the results are shown in Table 3.

Hydrodenitrogeneration：Using the n-heptane solution of quinoline (Q) mass content 1% as raw material, in Tianjin Xian Quan instrument companies The denitrification activity of catalyst is evaluated on the continuous high pressure reaction assemblies of WFSP3050 of production.It is not required to before the reaction to catalyst S-1 Handled to S-10 presulfurizations.Reaction condition is：4.0MPa, 340 DEG C, hydrogen to oil volume ratio 400, oil inlet flow is 8mL/h.Reaction is steady After determining 3h, sampled after reaction 4h and reaction 1000h, sample is surveyed sulphur nitrogen instrument with HS-500 types high frequency-infrared and analyzed, activity Q Denitrification percent represent, the results are shown in Table 3.

Reaction desulfuration (nitrogen) rate X is calculated as follows：

The hydrodesulfurization of 3 catalyst of table, denitrification activity evaluation result

Note："-" represents not to be detected.

It can be illustrated by the result of table 1, table 2 and table 3, the hydrogenation catalyst prepared than conventional method, is carried with the present invention For the sulfurized hydrogenation catalyst of preparation, not only with preferable active component dispersion degree, higher sulphidity, substantially increase The utilization rate of active metal, and under preferable case, catalyst surface has net structure, it is even more important that although two classes Catalyst composition is similar, but catalyst provided by the invention has considerably better hydrodesulfurization and denitrification activity.Above-mentioned knot Fruit fully shows, provided by the present invention to prepare with the incomparable superiority of conventional impregnation method.In addition, pass through comparative example 4 and comparative example 5 understand that in the present invention, dispersant and acid solution are to ensure that the catalyst preparation technology route success is real The key factor applied.The side of being preferable to carry out using the present invention can be seen that by the comparing result of embodiment 1 and embodiment 10 Formula, can effectively extend catalyst service life.In addition method provided by the invention draws host agent component and one step of auxiliary component Enter simplified preparation process, solve the defects of prior art preparation process is complex, controllability is poor and cost is higher.

The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of preparation method of sulfurized hydrogenation catalyst, this method comprise the following steps：

(1) dispersant is mixed with the solution A containing vib metals salt, group VIII metal salt and sulphur source, the solution A In acidity, the dispersant is the water-miscible organic solvent that boiling point is 15-90 DEG C, and the sulphur source is can be in 50-100 DEG C, acid The sulphur-containing substance hydrolyzed under the conditions of property；

(2) mixture obtained by step (1) is contacted at 60-150 DEG C in confined conditions with catalyst carrier 5-30 it is small when；

2. preparation method according to claim 1, wherein, the addition of dispersant and the volume ratio of solution A are 0.1-10： 1；

Preferably, one or more of the dispersant in methanol, ethanol, propyl alcohol and acetone.

3. preparation method according to claim 1 or 2, wherein, the pH value of the solution A is 2-5, vib metals salt Concentration in solution A is 0.005-5mol/L.

4. preparation method according to claim 1, wherein, in terms of element sulphur, the sulphur source and vib metals element Molar ratio is 1-9：1, it is preferably 3-5：1；Group VIII metallic element and the molar ratio of vib metals element are 0.1-1.5, Preferably 0.15-0.5.

5. the preparation method according to claim 1 or 4, wherein, the sulphur source be selected from thioamides shown in following formula (1), At least one of dithioesters shown in single monothioester and formula (3) shown in formula (2),

In formula (1), R¹For NH₂-、CH₃-、CH₃CH₂-、CH₃NH- or (CH₃)₂N-, R²And R³It is each independently H or C1-C4 alkane Base；

In formula (2), R⁴For H or C1-C4 alkyl, R⁵For C1-C4 alkyl；

In formula (3), R⁶For H or C1-C4 alkyl, R⁷For C1-C4 alkyl；

Preferably, the sulphur source is the thioamides shown in formula (1), more preferably thiocarbamide and/or thioacetamide.

6. preparation method according to claim 1, wherein, before step (2), the catalyst carrier is changed Property, modified method includes：

Catalyst carrier is impregnated in the mixture containing urea, water-soluble divalent metal and water, then carries out heat successively Processing, filtering, washing, dry and roasting.

7. preparation method according to claim 6, wherein, the molar ratio of the urea and water-soluble divalent metal is 2- 10：1；

Preferably, the catalyst carrier and the molar ratio of water-soluble divalent metal are 3-20：1, more preferably 4-10： 1。

8. the preparation method according to claim 6 or 7, wherein, in the mixture used in modification procedure, watersoluble divalent gold The concentration for belonging to salt is 0.01mol/L-1mol/L, and the water-soluble divalent metal is selected from nitrate, the sulfate of divalent metal With the one or more in chlorate, the divalent metal be selected from group VIII metal, the IIth A races metal, the Ith B races metal and One or more in II B-group metal, are preferably the one or more in cobalt, nickel, iron, calcium, magnesium, copper and zinc.

9. according to the preparation method described in any one in claim 6-8, wherein, the condition of the heat treatment includes heat treatment Temperature is 60-140 DEG C, is preferably 70-90 DEG C, when heat treatment time is 2-60 small, when being preferably 12-24 small；The drying It is 100-250 DEG C that condition, which includes drying temperature, is preferably 100-130 DEG C, when drying time is 1-12 small, when being preferably 2-6 small； It is 400-600 DEG C that the condition of the roasting, which includes calcination temperature, is preferably 450-550 DEG C, when roasting time is 2-10 small, preferably For 2-6 it is small when.

10. preparation method according to claim 1, wherein, in step (2), by mixture obtained by step (1) and catalyst Carrier in confined conditions at 80-120 DEG C contact 8-24 it is small when.

11. according to the preparation method described in any one in claim 1-10, wherein, the condition bag of step (3) described roasting Include：Calcination temperature is 300-800 DEG C, when roasting time is 2-6 small.

12. the sulfurized hydrogenation catalyst as made from the preparation method described in any one in claim 1-11.

13. application of the sulfurized hydrogenation catalyst in hydrodesulfurization and/or hydrodenitrogeneration described in claim 12.