CN106179389B - Hydrobon catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of Hydrobon catalysts and preparation method thereof.The catalyst is body phase Hydrobon catalyst, it includes hydrogenation active metal component W, Ni and Mo that it, which is formed, and magnesia and aluminium oxide, table phase active metallic content are high, active site density is big, active metal disperses more evenly, and the cooperation between active metal is good, and active metal utilization rate is high, catalyst pore structure is reasonable simultaneously, high mechanical strength, hydrodesulfurization and hydrodenitrogeneration reactivity worth with higher are particularly suitable to apply in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

Description

Hydrobon catalyst and preparation method thereof

Technical field

The present invention relates to the body phase hydrotreatings of a kind of Hydrobon catalyst and preparation method thereof, especially high activity to urge Agent and preparation method thereof.

Background technique

At present worldwide, crude oil heaviness and in poor quality increasingly, the in addition sustainable development and environmental protection of world economy Regulation it is increasingly strict, need to produce a large amount of light clean fuels.Exploitation and the use of super-low sulfur without sulphur vapour, diesel oil is even current The trend that clean fuel develops in world wide.Using traditional Hydrobon catalyst by increasing reaction severity as improved The deep desulfuration even ultra-deep desulfurization of diesel oil also may be implemented in reaction temperature, hydrogen partial pressure or reduction reaction velocity etc., but anti- The rising of temperature is answered to will lead to the variation and catalyst life shortening of product colour, and reducing air speed then means subtracting for treating capacity It is few.For existing hydrogenation plant, design pressure has been fixed, and the amplitude for improving hydrogen partial pressure is limited.Therefore, currently Catalyst by using more high desulfurization activity is one of the important means of deep desulfuration.

Sulfur-containing compound in petroleum distillate containing various structures and different molecular weight, but in the ultra-deep desulfurization stage (sulfur content is lower than 50 μ g/g), the mainly sulfur-containing compound of the substituted base such as removing 4,6- dimethyl Dibenzothiophene class.By Make to produce steric hindrance between sulphur atom and the activated centre of catalyst in the adjacent methyl of sulphur atom, sulphur atom is not easy to connect The activated centre of proximal response, thus lead to reaction rate sharp fall.

Conventional load type hydrogenation catalyst is limited by carrier pore structure, and active metal load capacity is usually no more than 30wt%, the activated centre quantity that loaded catalyst can be provided is limited, although can to activated centre number amount and type distribution Adjustment is optimized, but since the limit bottleneck of activated centre quantity can not be broken through, the space for increasing substantially hydrogenation activity has Limit, is difficult meet the needs of refinery is to V diesel product of producing country.The hydrogenation catalyst of body phase method preparation is most of by active gold Belong to component to constitute, the limitation of tenor can be got rid of, can in any regulating catalyst each active component ratio, improve catalysis The Hydrogenation of agent can be in the item for not improving device reaction severity since bulk phase catalyst has excellent hydrogenation activity Under part, directly production meet National V emission standard without sulfur diesel product, the processing of device can be improved without transformation in original device Amount reduces the production cost of refinery, realizes energy efficiency.

Although active metallic content is high in body phase hydrogenation catalyst, the side such as aggregation is easy by mechanical strength, active metal The limitation in face needs to be added a certain amount of adhesive component, generally meets the requirement of mechanical strength, and the additional amount of adhesive is wanted It is even more in 30wt% or more, the dosage of active metal is not only reduced in this way, and amount of activated metal can be made to enter in body phase, So that it is can't be hydrogenation sites, there is a problem of that active metal utilization rate is low, meanwhile, make different hydrogenation active metals Distribution is not easily controlled, to influence the distribution of different hydrogenation active metals.Therefore, for body phase hydrogenation catalyst, tool There is the distribution of good hydrogenation active metals, there is mating reaction between suitable hydrogenation active metal component, there is high catalysis Agent surface-active bit density has high active metal utilization rate, can significantly improve the activity of catalyst.

CN1951561A discloses the method for preparing hydrogenation catalyst using co-precipitation, and catalyst uses active metal Ni, W Component and precipitating reagent co-precipitation generate Ni_xW_yO_zIt is molten aluminium salt can be added in above process in composite oxides precursor Liquid, can also to be directly added into aluminium hydroxide after plastic, then with MoO₃Mashing mixing, filtering, molding, activation are final catalysis Agent.When the bulk phase catalyst of this method preparation reaches the requirement for meeting mechanical strength, surface-active bit density is lower, no The advantage that high-content active metal component can be given full play to reduces the utilization rate of active metal, increases the preparation of catalyst Cost.

CN101306374A discloses a kind of hydrogenating catalyst composition, which is prepared by coprecipitation method, will at least one The kind compound of metal component of group VIII, the compound of at least two metal component of group VIB, organic additive and water mixing system Standby mixed liquor uses the pH of acid or alkali adjustment mixed liquor the mixed liquor to be placed in reaction kettle, in room temperature to 250 for 7~11 DEG C reaction under confined conditions 1~24 hour, filter later simultaneously dry.The resulting catalyst of this method without high-temperature roasting, Contain organic additive in final catalyst, so that the mechanical strength of catalyst is met requirement, need to be added more bondings Agent component will affect the distribution of different hydrogenation active metals in this way, reduce catalyst surface active.

CN101255356A discloses a kind of preparation method of unsupported catalyst, is to react skill using urea melting Art will contain the VIIIth race and group VIB active metal precursor and mix with urea and react under urea melting state, and it is extra to remove Urea obtains catalyst particles, can be formed by the way that adhesive is added.Urea is added as precipitating reagent in this method , it needs to heat the extra urea of removing after reaction, adhesive is then added and is formed, such this method still has bonding The addition of agent makes being unevenly distributed for different hydrogenation active metals, while the low density problem of catalyst surface active position.

The hydrogenation catalyst of body phase method preparation, hydrogenation sites are the catalyst pores that can be approached in reactant molecule On road surface, although such catalyst activity tenor is higher, not all active metal can become plus hydrogen is living Property center therefore more active metals how to be made to be distributed in channel surfaces and form hydrogenation sites, improve body be mutually catalyzed The activated centre density on agent surface, the utilization rate for improving hydrogenation active metal component is current important research topic.

Ammonium hydrogen carbonate is added in body phase hydrogenation catalyst disclosed in CN102049265A during coprecipitated, Carbon dioxide is added in body phase hydrogenation catalyst disclosed in CN102451703A during coprecipitated, generates carbonate or bicarbonate Salt, the above method is that a certain amount of gas is released in roasting process using it, under the percussion of gas, increases catalysis The Kong Rong of agent, specific surface area make more metal active positions be exposed to the surface of catalyst, but such method can make cell channels Collapse, pore size distribution disperse, mechanical strength reduces, and leads to active metal localized clusters, and the metal active position being exposed is It is limited.

Under distillate ultra-deep hydrodesulfuration reaction environment, nitrogen-containing organic compound present in distillate is de- to hydrogen is added Reaction of Salmon-Saxl generates apparent inhibiting effect, and hydrodesulfurization activity is reduced as the nitrogen content in raw material increases, this is because evaporating Competitive Adsorption occurs on catalyst activity position for the nitrogenous compound and sulfide divided in oil, and the adsorption capacity of nitride is stronger, The active sites on catalyst are occupied, sulfide is made to be difficult to approach, it is suppressed that hydrodesulfurization reaction, so high in processing nitrogen content Heavy diesel produce super-low sulfur product when, the hydrodenitrogenationactivity activity that catalyst needs to have excellent, the hydrodenitrogeneration of catalyst Activity improves, and after nitrogen content reduces, the nitride that competitive Adsorption occurs with sulfide is reduced, and sulfide is easier, also more It is adsorbed on catalyst activity position, promotes hydrodesulfurization reaction.Therefore the hydrodenitrogenationactivity activity of catalyst is improved to raising body The ultra-deep hydrodesulfuration activity of phase catalyst has extremely important effect.

Coprecipitation method prepares bulk phase catalyst technology, can be to catalyst mesoporous using different coprecipitation modes, Gelation Conditions etc. The distribution and different hydrogenation active metals of active metallic content and activated centre density, different hydrogenation active metals on road surface Between interaction relationship have a great impact.The coprecipitation method of above-mentioned use can be such that the distribution of different hydrogenation active metals is not easy Control reduces the mutual cooperation effect between active metal to influence the distribution of different hydrogenation active metals, meanwhile, it urges Table phase active metallic content is smaller in agent and activated centre density is lower, the final ultra-deep hydrodesulfuration for influencing catalyst Energy.Therefore, the distribution for how regulating and controlling hydrogenation active metals makes have suitable mating reaction between hydrogenation active metal component, How to increase table phase active metallic content and activated centre density in catalyst, improve the utilization rate of hydrogenation active metal component, It is the key that improve body phase Hydrobon catalyst Hydrogenation.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of Hydrobon catalysts and preparation method thereof.The catalysis Agent table phase active site density is big, and hydrogenation active metals utilization rate is high, improves the distribution of hydrogenation active metals in catalyst, improves and adds Mating reaction between hydrogen activity metal, while catalyst pore structure is reasonable, active metal disperses more evenly, and high mechanical strength is special It is not suitable for being applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

Hydrobon catalyst of the present invention be body phase Hydrobon catalyst, composition include hydrogenation active metal component W, Ni, Mo, magnesia and aluminium oxide；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃'s The ratio of weight content is 2.0:1 ~ 7.0:1, preferably 2.5:1 ~ 5.0:1, the weight content and body of table phase active metal component NiO The ratio of the weight content of phase active metal component NiO is 1.2:1 ~ 4.5:1, preferably 1.8 ~ 3.0:1, table phase active metal group Divide MoO₃Weight content and body phase active metal component MoO₃Weight content ratio be 1.8:1 ~ 6.0:1, preferably 2.0:1 ~ The weight content of 4.5:1, table phase MgO and table phase WO₃Weight content ratio be 0.02~0.5, preferably 0.05~0.3.

Hydrobon catalyst of the invention, on the basis of the weight of Hydrobon catalyst, NiO, WO₃、 MoO₃And MgO Total weight content be 40% ~ 95%, preferably 50% ~ 85%, alumina content be 5% ~ 60%, preferably 15% ~ 50%.Of the invention In Hydrobon catalyst, the molar ratio of Ni/W is 1:8 ~ 8:1, preferably 1:4 ~ 4:1, (Ni+W)/Mo molar ratio be 1:10 ~ 10:1, preferably 1:5 ~ 5:1, the molar ratio of Mg/W are 0.3~3.0, preferably 0.5~2.0.

In the present invention, table phase active metal component WO₃Weight content be table phase in WO₃Weight content, body mutually activity gold Belong to component WO₃Weight content be catalyst in WO₃Weight content；The weight content of table phase active metal component NiO is table phase The weight content of middle NiO, the weight content of body phase active metal component NiO are the weight content of NiO in catalyst；Table is mutually active Metal component MoO₃Weight content be table phase in MoO₃Weight content, body phase active metal component MoO₃Weight content be MoO in catalyst₃Weight content；The weight content of table phase MgO is the weight content of MgO in table phase.

The property of Hydrobon catalyst of the present invention is as follows: specific surface area is 180 ~ 450m²/ g, Kong Rongwei 0.20 ~ 0.80ml/g, pore-size distribution are as follows: diameter is that Kong Rong shared by the hole below 4nm accounts for the 1% ~ 20% of total pore volume, and diameter is 4 ~ 8nm Hole shared by Kong Rong account for the 55% ~ 80% of total pore volume, diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume, diameter For the Kong Rong of 15nm or more, to account for total pore volume be 0.1% ~ 5.0%, and preferred pore-size distribution is as follows: diameter is 4nm hole institute below The Kong Rong accounted for accounts for the 5% ~ 17% of total pore volume, and diameter is that account for total pore volume be 61% ~ 75% to Kong Rong shared by the hole of 4 ~ 8nm, and diameter is 8 ~ Kong Rong shared by the hole of 15nm accounts for the 4% ~ 17% of total pore volume, and it is 0.5% ~ 5.0% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume,.

Can according to need in Hydrobon catalyst of the present invention containing adjuvant component, adjuvant component be silicon, phosphorus, titanium, zirconium, One or more of boron etc., preferably titanium and/or zirconium, based on the element weight content of the adjuvant component in Hydrobon catalyst It is 0 ~ 20%, preferably 1% ~ 15%.

The preparation method of Hydrobon catalyst of the present invention, comprising:

(1), the saline mixed solution A containing Ni and Al component is prepared, precipitating reagent is added dropwise to solution A and carries out plastic reaction, it is raw At nickeliferous, aluminum precipitation object slurries I；

(2), the saline mixed solution B containing W, Mo and Al component is prepared, solution B and precipitating reagent are subjected to the reaction of cocurrent plastic, Generate tungstenic, molybdenum, aluminum precipitation object slurries II；

(3), the resulting slurries I of step (1) and the resulting slurries II of step (2) is uniformly mixed, under agitation always Change, after aging, filtering, obtained material carries out hydro-thermal process with water vapour, urea is wherein added when hydro-thermal process；

(4), step (3) resulting material is through drying, molding, washing, then obtains final hydrofinishing through drying, roasting and be catalyzed Agent；

Magnesium-containing compound is added when preparing mixed solution A and/or step (2) preparation mixed solution B in step (1).

In the method for the present invention, required catalyst promoter can be added according to a conventional method, adjuvant component be silicon, phosphorus, titanium, One or more of zirconium, boron etc..

Precipitating reagent described in step (1) or step (2) is sodium carbonate, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, hydroxide One of potassium, potassium carbonate, saleratus are a variety of, preferably ammonium hydroxide, and weights of ammonia concentration is 5%~15%.

In step (1) mixed solution A, weight concentration of the Ni in terms of NiO be 5~80g/L, preferably 10~60g/L, Al with Al₂O₃The weight concentration of meter is 2~60g/L, and when containing magnesium in preferably 8~40g/L step (1) mixed solution A, Mg is in terms of MgO Weight concentration be 1~30g/L, preferably 2~20g/L.In step (2) mixed solution B, W is with WO₃The weight concentration of meter is 10 ~100g/L, preferably 20~90g/L, Mo is with MoO₃5~80g/L of weight concentration of meter, preferably 10~60g/L, Al with Al₂O₃The weight concentration of meter is 2~60g/L, preferably 8~40g/L.When containing magnesium in step (2) mixed solution B, Mg is with MgO The weight concentration of meter is 1~30g/L, preferably 2~20g/L.When preparing mixed solution A, the nickel source that generally uses can be for One or more of nickel sulfate, nickel nitrate, basic nickel carbonate, nickel chloride, silicon source can be aluminum nitrate, aluminum sulfate, aluminium chloride Or one or more of aluminium acetate etc., magnesium source, that is, magnesium-containing compound can be the one of the soluble magnesium salts such as magnesium chloride, magnesium nitrate Kind is several.When preparing mixed solution B, the tungsten source generally used can be one of ethyl ammonium metatungstate, ammonium metatungstate Or it is several；Molybdenum source is ammonium molybdate；Silicon source can be one or more of aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc., magnesium Source, that is, magnesium-containing compound can be the one or more of the soluble magnesium salts such as magnesium chloride, magnesium nitrate.

Reaction temperature is 20~90 DEG C, preferably 30~70 DEG C in step (1).When cemented into bundles pH value control for 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

Reaction temperature is 30~90 DEG C, preferably 40~80 DEG C in step (2).When cocurrent plastic pH value control for 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

Gelling temperature and time can be the same or different in step (1) and step (2).Step (1) and step (2) can Can also be different when progress simultaneously.

Aging temperature is 40~90 DEG C, preferably 50~80 DEG C in step (3).PH value control is 6.0 ~ 10.0 when aging, Preferably 6.5 ~ 9.0.Ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.

Hydrothermal conditions described in step (3) are as follows: carrying out under closed container, temperature is 200 ~ 300 DEG C, preferably It is 210 ~ 260 DEG C, pressure is 1.0 ~ 8.0 MPa, preferably 3.0 ~ 6.0MPa, and the processing time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours.When hydro-thermal process, mole of active metal (tungsten, molybdenum, nickel) atom total amount in the additional amount and catalyst of urea Than for 0.5:1 ~ 10.0:1, preferably 2.0:1 ~ 8.0:1.

Drying, molding and washing described in step (4) can be carried out using conventional method in that art.Drying condition is as follows: It is 1 ~ 48 hour dry at 50 ~ 250 DEG C, preferably 80 ~ 180 DEG C drying 4 ~ 36 hours.In forming process, addition can according to need One of conventional shaping assistant, such as peptizing agent, extrusion aid etc. is a variety of.The peptizing agent is hydrochloric acid, nitric acid, sulphur One or more of in acid, acetic acid, oxalic acid etc., the extrusion aid refers to the substance for being conducive to extrusion forming, such as sesbania powder, charcoal One or more of black, graphite powder, citric acid etc., the dosage of extrusion aid account for 1wt%~10wt% of total material butt.Washing one As be to be washed till neutrality using deionized water or containing decomposable salt (such as ammonium acetate, ammonium chloride, ammonium nitrate) solution washing.

Used dry and roasting can use this field normal condition to step (4) after formation, and drying condition is such as Under: 1 ~ 48 hour dry at 50 ~ 250 DEG C, roasting condition is as follows: roasting 1 ~ 24 hour at 350 ~ 650 DEG C, preferably drying condition is such as Under: 4 ~ 36 hours dry at 80 ~ 180 DEG C, roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.

In Hydrobon catalyst of the present invention, adjuvant component preferred Ti and/or Zr.In Hydrobon catalyst system of the present invention During standby, the compound containing adjuvant component, i.e. titanium source and/or zirconium source are preferably added during preparing mixed solution A.Titanium source One of Titanium Nitrate, titanium sulfate, titanium chloride etc. or a variety of can be used, zirconium nitrate, zirconium chloride, zirconium oxychloride etc. can be used in zirconium source One of or it is a variety of.

In the method for the present invention, the shape of catalyst be can according to need as sheet, spherical, cylindrical bars and irregular bar (three leaves Grass, bunge bedstraw herb), preferably cylindrical bars and irregular bar (clover, bunge bedstraw herb).The diameter of carrier can be the thin of 0.8 ~ 2.0mm The thick item of item and > 2.5mm.

Hydrobon catalyst of the present invention is the body phase Hydrobon catalyst of oxidation state, and conventional side can be used before use Method carries out presulfurization.

In Hydrobon catalyst of the present invention, surface-active bit density is big, and active metal disperses more evenly, between active metal Cooperation it is good, active metal utilization rate is high, while catalyst pore structure is reasonable, high mechanical strength, has higher plus hydrogen de- Sulphur and hydrodenitrogeneration reactivity worth, it is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

Using positive addition, (the acid precipitation method, that is, alkaline precipitating agent is added in acid metal salt solution and carries out the method for the present invention Precipitating) nickel aluminium mixed sediment is prepared, tungsten, molybdenum and aluminium mixed sediment are prepared using parallel flow precipitation, then after the two is mixed Aging.The present invention prepares the relatively large nickel of crystal grain, aluminum precipitation object by using positive addition, and it is relatively small that cocurrent process prepares crystal grain Tungsten, molybdenum and aluminum precipitation object, above two sediment is mixed, and can control the distribution of different hydrogenation active metals, is conducive to live Property tungsten, molybdenum, high activity phase is formed between nickel, and improve the interaction between active metal, improve body and be added hydrogen refining catalytic The ultra-deep hydrodesulfuration performance of agent.Mg is added in preparation process, coprecipitated active metal W, Ni, Mo can be made more uniformly to divide It is dispersed in catalyst table phase, while acting synergistically to form the higher compound of hydrogen storage capability with W, Ni, Mo metal, increase catalyst Suction take off capacity, improve the Hydrogenation of catalyst.

In the preparation method of catalyst of the present invention, the material obtained after the co-precipitation of W, Ni, Mo, Al component is in suitable condition Simultaneously urea is added in lower steam treatment, and urea is decomposed into NH under high temperature environment₃And CO₂, NH₃And CO₂The feelings existing for water vapour NH is generated under condition₄ ⁺And HCO₃ ^-Ion, NH₄ ⁺And HCO₃ ^-Ion at high temperature under high pressure has a significant impact the micromorphology of material, water Material phase structure is in cylinder before being heat-treated, and material phase structure is changed into irregular sheet from cylinder and is piled into not after hydro-thermal process The transformation of rule body, this structure obviously increases distribution of the active metal in table phase, and disperses more evenly, is conducive to Improve the density of Adsorption.In addition, urea is added in steam treatment, make the transformation of material form that can also make to be catalyzed The pore size distribution of agent is more concentrated, more uniform, is conducive to the mechanical strength for improving catalyst.Hydrobon catalyst of the invention For in deeply desulfurizing fractional oil and denitrification process, having excellent hydrodenitrogenationactivity activity, the reduction of nitrogen content is more advantageous to and adds The progress of hydrogen desulphurization reaction, so having excellent when Hydrobon catalyst is used for working process nitrogen content high heavy distillate Different ultra-deep hydrodesulfuration activity.

Specific embodiment

In the present invention, specific surface area and Kong Rong use low temperature liquid nitrogen determination of adsorption method, and mechanical strength is measured using side pressure method. Catalyst table phase active metallic content is measured using x-ray photoelectron spectroscopy (XPS), and caltalyst phase active metallic content is adopted It is measured with inductively coupled plasma atomic emission spectrum (ICP-AES), transmissioning electric mirror determining catalyst surface WS₂/MoS₂Density That is WS₂And MoS₂Density.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Nickel chloride, magnesium chloride and liquor alumini chloridi are dissolved in water purification respectively, are configured to mixed solution A, in mixed solution A The weight concentration of NiO is 20g/L, and MgO weight concentration is 4g/L, Al₂O₃Weight concentration be 12g/L.Respectively by ammonium metatungstate, Ammonium molybdate, magnesium chloride and liquor alumini chloridi are dissolved in water purification, are configured to mixed solution B, WO in mixed solution B₃Weight concentration be 39g/L, MoO₃Weight concentration is 16g/L, and MgO weight concentration is 4g/L, Al₂O₃Weight concentration be 10g/L.It is 10% by concentration Solution A is added in (weight) ammonium hydroxide under stiring, and gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control At 60 minutes, nickeliferous, aluminium, magnesium precipitate object slurries I are generated.1000mL water purification is added in reactor tank, is 10%(weight by concentration) ammonia Water and solution B cocurrent are added in reactor tank, and gelling temperature is maintained at 60 DEG C, in cocurrent plastic reaction process pH value control 7.8, Gelation time control generated tungstenic, molybdenum, aluminium, magnesium precipitate object slurries II at 60 minutes.After the above two mixing containing sediment slurry Aging, ageing time 2 hours, 75 DEG C of aging temperature, at the end of aging then pH value control was filtered 7.6, and filter cake is containing urine Hydro-thermal process, the condition of hydro-thermal process are carried out under the water vapour of element are as follows: the molar ratio of urea and active metal atom total amount is 6: 1, temperature is 230 DEG C, pressure 3.0MPa, and the processing time is 5 hours, and filter cake is 6 hours dry at 120 DEG C, is rolled, extrusion at Type.It is washed at room temperature with water purification.Then 8 hours dry at 100 DEG C, 530 DEG C roast 4 hours, obtain catalyst A.Catalyst group 1 is shown in Table at, pore size distribution and main character.

Embodiment 2

According to the method for embodiment 1, it is matched by the constituent content of the catalyst B in table 1, chlorination is added into dissolving tank 1 Nickel, magnesium chloride, aluminum nitrate, zirconyl chloride solution prepare working solution A, and aluminum nitrate, ammonium metatungstate, chlorine are added into dissolving tank 2 Change magnesium and ammonium molybdate prepares working solution B.It is 8%(weight by concentration) solution A is added in ammonium hydroxide under stiring, and gelling temperature is maintained at 55 DEG C, at the end of pH value control 8.0, gelation time control generated nickeliferous, aluminium, magnesium precipitate object slurries I at 50 minutes.It will 600mL water purification is added in reactor tank, is 8%(weight by concentration) ammonium hydroxide and solution B cocurrent be added in reactor tank, gelling temperature holding 7.8, gelation time control generated tungstenic, molybdenum, aluminium, magnesium at 60 minutes for pH value control in 60 DEG C, cocurrent plastic reaction process Sediment slurries II.By it is above two containing sediment slurry mix after aging, ageing time 2 hours, 72 DEG C of aging temperature, aging knot When beam then pH value control is filtered, filter cake carries out hydro-thermal process under the water vapour containing urea, hydrothermal conditions 8.0: The molar ratio of urea and active metal atom total amount is 5:1, and temperature is 220 DEG C, pressure 4.0MPa, and the processing time is 6 hours, Material after hydro-thermal process is 10 hours dry at 70 DEG C, and then extruded moulding, is washed 3 times with water purification, and wet bar is at 120 DEG C dry 8 Hour, it is roasted 5 hours at 500 DEG C, obtains final catalyst B, composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, it is matched by the constituent content of the catalyst C in table 1, chlorination is added into dissolving tank 1 Nickel, magnesium chloride, aluminium chloride, phosphoric acid solution prepare working solution A, and aluminium chloride, ammonium metatungstate, magnesium chloride are added into dissolving tank 2 Working solution B is prepared with ammonium molybdate.It is 10%(weight by concentration) solution A is added in ammonium hydroxide under stiring, and gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, gelation time control generated nickeliferous, aluminium, magnesium precipitate object slurries I at 60 minutes.It will 1000mL water purification is added in reactor tank, is 10%(weight by concentration) ammonium hydroxide and solution B cocurrent be added in reactor tank, gelling temperature guarantor PH value control is held in 45 DEG C, cocurrent plastic reaction process 8.2, gelation time control at 60 minutes, generate tungstenic, molybdenum, aluminium, Magnesium precipitate object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 2 hours, 75 DEG C of aging temperature, aging At the end of pH value control 7.8, then filter, filter cake carries out hydro-thermal process, hydro-thermal process item under the water vapour containing urea Part: the molar ratio of urea and active metal atom total amount is 7:1, and temperature is 240 DEG C, pressure 5.0MPa, and the processing time is 4 small When, the material after hydro-thermal process is 14 hours dry at 90 DEG C, and then extruded moulding, is washed with water 1 time, and wet bar is in 100 DEG C of dryings It 12 hours, is roasted 4 hours at 550 DEG C, obtains final catalyst C, composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

According to the method for embodiment 1, it is matched by the constituent content of the catalyst D in table 1, chlorination is added into dissolving tank 1 Nickel, magnesium chloride, aluminium chloride, titanium chloride solution prepare working solution A, and aluminum nitrate, ammonium metatungstate, chlorination are added into dissolving tank 2 Magnesium and ammonium molybdate prepare working solution B.It is 12%(weight by concentration) solution A is added in ammonium hydroxide under stiring, and gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control generated nickeliferous, aluminium, magnesium precipitate object slurries I at 60 minutes.By 800mL Water purification be added reactor tank in, by concentration be 12%(weight) ammonium hydroxide and solution B cocurrent addition reactor tank in, gelling temperature is maintained at 50 DEG C, 7.6, gelation time control generated tungstenic, molybdenum, aluminium, magnesium precipitate at 60 minutes for pH value control in cocurrent plastic reaction process Object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 2 hours, 72 DEG C of aging temperature, at the end of aging PH value is controlled 8.0, is then filtered, filter cake carries out hydro-thermal process under the water vapour containing urea, hydrothermal conditions: urea Molar ratio with active metal atom total amount is 3:1, and temperature is 260 DEG C, pressure 3.0MPa, and the processing time is 5 hours, hydro-thermal Treated, and material is 8 hours dry at 100 DEG C, and then extruded moulding, is washed 3 times with water purification, and wet bar is 8 hours dry at 80 DEG C, It is roasted 5 hours at 580 DEG C, obtains final catalyst D, composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

By method for preparing catalyst disclosed in CN102049265A, preparation and the catalyst of embodiment 1 form identical ginseng Than agent E.Aluminium chloride, nickel chloride, ammonium metatungstate, magnesium chloride preparating acid sex work solution A are added into dissolving tank, takes 100g carbonic acid Hydrogen ammonium is made into the solution that molar concentration is 2.0mol/l.500mL water is added into reactor tank, temperature rises to 60 DEG C.In stirring In the case of, by solution A, ammonium bicarbonate aqueous solution and concentration be 10%(weight) ammonium hydroxide cocurrent be added reactor tank in plastic, gelling temperature 60 DEG C, gelation time 1.0 hours, the pH value of plastic slurry was 7.8.Aging 2 hours after cemented into bundles, pH at the end of aging Value is 7.6.Then it filters, obtained filter cake and molybdenum trioxide, mashing stirs evenly, and filtering, filter cake is 6 hours dry at 120 DEG C, It rolls, extruded moulding.It is washed at room temperature with water purification.Then 8 hours dry at 100 DEG C, 530 DEG C roast 4 hours, are finally urged Agent E, composition, pore size distribution and main character are shown in Table 1.

Comparative example 2

It is added without urea by 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, prepares reference agent F.Composition, Pore size distribution and main character are shown in Table 1.

Comparative example 3

By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but NH is added₃, temperature is 230 DEG C, pressure 3.0MPa, the processing time is 5 hours, and the molar ratio of ammonia and active metal atom total amount is 6:1, preparation ginseng Than agent G.Composition, pore size distribution and main character are shown in Table 1.

Comparative example 4

By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but CO is added₂, temperature is 230 DEG C, pressure 3.0MPa, the processing time is 5 hours, and the molar ratio of ammonia and active metal atom total amount is 6:1, preparation ginseng Than agent H.Composition, pore size distribution and main character are shown in Table 1.

Comparative example 5

Identical reference is formed by the preparation of method for preparing catalyst disclosed in CN101255356A and the catalyst of embodiment 1 Agent I.It is matched by catalytic component content in embodiment 1, by MoO₃, wolframic acid, basic nickel carbonate, magnesium chloride, the urea (matter of urea Amount and active metal mass ratio 2.5) be added in three-necked flask, and a small amount of water, which is added, makes it be uniformly dispersed, be placed in oil bath in 130 DEG C are stirred 4 hours, and reactant is poured into cooling in pallet while hot, are crushed cooling product with pulverizer, are placed in 150 DEG C It is dried in baking oven, decomposes extra urea.Weigh the dust technology for accounting for the boehmite addition 10wt% of solid powder 30wt% Aluminum sol is made in solution, solid powder is added in Aluminum sol, and urging for diameter 1.6mm is made through kneading, extrusion at paste Agent item under infrared lamp after dry 5h, puts the drying 10 hours, 400 DEG C of roasting 5h in Muffle furnace at 110 DEG C in baking oven, Reference agent I is prepared.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 6

Identical ginseng is formed by the preparation of method for preparing catalyst disclosed in CN102451703A and the catalyst of embodiment 1 Than agent J.By in embodiment 1 catalytic component content proportion, into dissolving tank 1 be added nickel chloride, ammonium metatungstate, magnesium chloride and Then sodium metaaluminate alkalinity working solution B is added in zirconium oxychloride preparating acid sex work solution A into dissolving tank 2.Into reactor tank 350mL water is added, temperature rises to 60 DEG C.In the case of stirring, by solution A, solution B and CO₂Cocurrent be added reactor tank at Glue, CO₂Concentration is 45v%, and 60 DEG C of gelling temperature, gelation time 1 hour, the pH value of plastic slurries was 7.8.Add during plastic Enter CO₂Al in the total amount of gas and alkaline working solution B₂O₃Molar ratio is 4.0.Aging 2 hours after plastic.Then it filters, filters Cake is added 500ml water purification and molybdenum trioxide, mashing and stirs evenly, and filters, and filter cake is 6 hours dry at 120 DEG C, rolls, extrusion at Type.It is washed at room temperature with water purification.Then 8 hours dry at 100 DEG C, 530 DEG C roast 4 hours, obtain final catalyst J, form, Pore size distribution and main character are shown in Table 1.

Comparative example 7

By method disclosed in CN1951561A, detailed process is as follows:

It is formed by the catalyst of embodiment 1, the preparation of nickel chloride, magnesium chloride and ammonium metatungstate is dissolved in water purification, is configured to mix Solution is closed, wherein the weight concentration of NiO is 19g/L, WO₃Weight concentration be 39g/L, MgO weight concentration be 8g/L.It will be dense Degree is 10%(weight) ammonium hydroxide is added in mixed solution under stiring and carries out plastic, gelling temperature is maintained at 60 DEG C, at the end of pH value control For system 7.8, gelation time control generated nickeliferous, tungsten, magnesium precipitate object slurries at 60 minutes.Then aging, ageing time 2 are carried out Hour, 75 DEG C of aging temperature, at the end of aging pH value control after 7.6, filtering, in filter cake be added water purification, aluminium hydroxide and After mixing, extruded moulding is washed with water purification molybdenum trioxide at room temperature.Then 8 hours dry at 100 DEG C, 530 DEG C of roastings 4 Hour, obtain catalyst K.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 5

The present embodiment is catalyst activity evaluation experimental of the present invention, and is compared with comparative example catalyst.Using this hair Bright A, B, C, D catalyst and comparative example E, F, G, H, I, J, K catalyst, carry out comparative evaluation on 200mL small hydrogenation device Test, test raw material are Zhenghai mixed diesel (catalytic diesel oil account for miscella weight 40%).Raw material main character is shown in Table 4, catalysis Agent activity rating process conditions: hydrogen partial pressure 6.4MPa, reaction temperature are 360 DEG C, and volume space velocity is 2.0h when liquid^-1, hydrogen oil body Product ratio is 500:1, and evaluation result is shown in Table 5.Hydrofinishing is detected using gas chromatography-atomic emission detector device (GC-AED) Sulfur compound in oil, the results are shown in Table 6.

From table 1, table 2 and table 3 as can be seen that catalyst of the present invention is not in the case where active metal amount changes, catalysis Agent surface-active metal atomic concentration increases, and hydrogenation sites density increases, and pore size distribution$ is more concentrated, from evaluation result Table 6 finds out that catalyst has excellent hydrodenitrogenationactivity activity, shows when removing 4,6-DMDBT class macromolecular sulfide high Hydrogenation activity.Catalyst is used for working process distillate, when in particular for the high heavier diesel fraction of processing nitrogen content, has Excellent ultra-deep hydrodesulfuration activity.

1 catalyst of table composition and property

Catalyst number	A	B	C	D
					NiO, wt%	19	17	15	18
WO3, wt%	38	39	31	35
					MoO3, wt%	16	21	17	15
MgO, wt%	8	6	5	5
					Al2O3, wt%	Surplus	Surplus	Surplus	Surplus
Other/wt%	Nothing	ZrO2/2.0	P2O5/2.0	TiO2/3.0
					Specific surface area, m2/g	229	235	223	232
Kong Rong, mL/g	0.331	0.327	0.335	0.331
					Mechanical strength, N/mm	23.7	22.6	22.2	23.3
Pore size distribution, %
					< 4nm	10.32	11.20	12.09	12.76
4nm~8nm	71.11	70.26	70.21	71.19
					8nm~15nm	15.83	15.03	14.50	12.94
> 15nm	2.74	3.51	3.20	3.11

Continued 1

Catalyst number	E	F	G	H	I	J	K
								NiO, wt%	19	19	19	19	19	19	19
WO3, wt%	38	38	38	38	38	38	38
								MoO3, wt%	16	16	16	16	16	16	16
MgO, wt%	8	8	8	8	8	8	8
								Al2O3, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
Other/wt%	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing
								Specific surface area, m2/g	214	208	212	215	232	218	194
Kong Rong, mL/g	0.242	0.312	0.323	0.316	0.340	0.242	0.205
								Mechanical strength, N/mm	19.2	18.8	19.3	20.1	11.5	20.5	18.9
Pore size distribution, %
								< 4nm	19.24	16.67	15.01	14.59	14.25	17.25	53.16
4nm~8nm	32.24	32.61	36.19	33.71	28.42	35.28	22.72
								8nm~15nm	38.23	34.78	31.07	35.34	37.81	33.85	16.97
> 15nm	10.29	15.94	17.73	16.36	19.52	13.62	7.15

The weight content of the weight content and body phase reactive metal oxides of 2 catalyst table phase reactive metal oxides of table The ratio between

Catalyst number	A	B	C	D	E
						Table phase IW/ body phase IW	4.39	3.52	4.22	3.97	0.95
Table phase INi/ body phase INi	2.82	2.25	2.69	2.51	0.91
						Table phase IMo/ body phase IMo	4.21	3.36	4.13	3.92	-

Continued 2

Catalyst number	F	G	H	I	J	K
							Table phase IW/ body phase IW	1.06	1.01	1.23	0.99	1.42	1.14
Table phase INi/ body phase INi	1.11	1.19	1.13	0.94	1.38	1.17
							Table phase IMo/ body phase IMo	0.98	1.12	1.09	-	-	-

3 transmissioning electric mirror determining catalyst surface MoS of table₂/WS₂Density

Catalyst number	A	B	C	D	E	F	G	H	I	J	K
												MoS2/WS2Density, grain/100nm	92	89	86	85	52	59	55	56	53	62	58

4 feedstock oil main character of table

Project	Analyze result
		Density (20 DEG C), g/cm3	0.8814
Boiling range range, DEG C	178-375
		S, μ g/g	13300
N, μ g/g	728
		Cetane number	41.5

5 catalyst activity evaluation result of table

Catalyst number	A	B	C	D	E
						It generates oil density (20 DEG C), g/cm3	0.8391	0.8407	0.8402	0.8405	0.8534
Boiling range range, DEG C	170-365	171-367	170-366	172-366	176-376
						S, μ g/g	7.4	9.3	8.8	8.3	189.8
N, μ g/g	1.0	1.0	1.0	1.0	19.4
						Cetane number	51.3	51.6	51.4	51.2	45.6

Continued 5

Catalyst number	F	G	H	I	J	K
							It generates oil density (20 DEG C), g/cm3	0.8493	0.8506	0.8504	0.8546	0.8498	0.8504
Boiling range range, DEG C	185-373	179-373	167-374	168-376	169-373	170-374
							S, μ g/g	162.4	152.6	157.8	215.2	169.8	219.8
N, μ g/g	13.8	15.1	14.7	21.2	16.4	23.4
							Cetane number	49.2	50.6	45.9	46.1	45.6	45.4

The content of different sulfide in 6 hydrofined oil of table

Catalyst number	A	B	C	D	E
						Nitrogen content in hydrofined oil, μ g/g	1.0	1.0	1.0	1.0	19.4
Sulfur content in hydrofined oil, μ g/g	7.5	9.3	8.8	8.4	189.8
						C1- DBT, μ g/g	0	0	0	0	28.3
4- BMDBT, μ g/g	0.9	1.6	1.2	1.4	39.2
						6-BMDBT, μ g/g	0.8	1.1	1.9	1.7	35.6
4,6- BMDBT, μ g/g	5.5	6.1	5.4	5.0	86.7

Continued 6

Catalyst number	F	G	H	I	J	K
							Nitrogen content in hydrofined oil, μ g/g	14.4	15.8	15.1	21.2	16.4	23.4
Sulfur content in hydrofined oil, μ g/g	162.4	152.6	157.8	215.2	169.8	219.8
							C1- DBT, μ g/g	20.5	23.3	27.6	35.1	30.3	34.8
4- BMDBT, μ g/g	31.4	35.7	33.8	39.9	38.1	39.7
							6-BMDBT, μ g/g	38.2	30.4	31.1	36.7	34.6	40.1
4,6- BMDBT, μ g/g	72.3	63.2	65.3	103.5	66.8	105.2

Claims (23)

1. a kind of Hydrobon catalyst, which is body phase Hydrobon catalyst, and composition includes hydrogenation active metals Component W, Ni and Mo, magnesia and aluminium oxide；Wherein table phase active metal component WO₃Weight content and body phase active metal group Divide WO₃Weight content ratio be 2.0:1 ~ 7.0:1, weight content and the body phase active metal of table phase active metal component NiO The ratio of the weight content of component NiO is 1.2:1 ~ 4.5:1, table phase active metal component MoO₃Weight content and body mutually activity gold Belong to component MoO₃Weight content ratio be 1.8:1 ~ 6:1；The weight content of table phase MgO and table phase WO₃The ratio of weight content be 0.02~0.5；The pore-size distribution of the Hydrobon catalyst is as follows: diameter is that Kong Rong shared by the hole below 4nm accounts for total pore volume 1% ~ 20%, diameter is that Kong Rong shared by the hole of 4 ~ 8nm accounts for the 55% ~ 80% of total pore volume, and diameter is Kong Rong shared by the hole of 8 ~ 15nm The 2% ~ 20% of total pore volume is accounted for, it is 0.1% ~ 5.0% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume,.

2. catalyst described in accordance with the claim 1, it is characterised in that: in the catalyst, table phase active metal component WO₃'s Weight content and body phase active metal component WO₃Weight content ratio be 2.5:1 ~ 5.0:1, table phase active metal component NiO Weight content and the weight content of body phase active metal component NiO ratio be 1.8 ~ 3.0:1, table phase active metal component MoO₃ Weight content and body phase active metal component MoO₃Weight content ratio be 2.0:1 ~ 4.5:1, the weight content of table phase MgO With table phase WO₃Weight content ratio be 0.05~0.3.

3. catalyst described in accordance with the claim 1, it is characterised in that: on the basis of the weight of Hydrobon catalyst, NiO, WO₃、MoO₃Total weight content with MgO is 40% ~ 95%, and alumina content is 5% ~ 60%.

4. catalyst described in accordance with the claim 3, it is characterised in that: on the basis of the weight of Hydrobon catalyst, NiO, WO₃、MoO₃Total weight content with MgO is 50% ~ 85%, and alumina content is 15% ~ 50%.

5. according to catalyst described in claim 1 or 3, it is characterised in that: in the Hydrobon catalyst, mole of Ni/W Than for 1:8 ~ 8:1, (Ni+W)/Mo molar ratio is 1:10 ~ 10:1, the molar ratio of Mg/W is 0.3~3.0.

6. according to catalyst described in claim 1 or 3, it is characterised in that: in the Hydrobon catalyst, mole of Ni/W Than for 1:4 ~ 4:1, (Ni+W)/Mo molar ratio is 1:5 ~ 5:1, the molar ratio of Mg/W is 0.5~2.0.

7. catalyst described in accordance with the claim 1, it is characterised in that: the property of the Hydrobon catalyst is as follows: comparing table Area is 180 ~ 450m²0.20 ~ 0.80mL/g of/g, Kong Rongwei.

8. catalyst described in accordance with the claim 1, it is characterised in that: the pore-size distribution of the Hydrobon catalyst is as follows: Diameter is that Kong Rong shared by the hole below 4nm accounts for the 5% ~ 17% of total pore volume, and diameter is that Kong Rong shared by the hole of 4 ~ 8nm accounts for total pore volume It is 61% ~ 75%, diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, and diameter is that the Kong Rong of 15nm or more is accounted for always Kong Rong is 0.5% ~ 5.0%.

9. catalyst described in accordance with the claim 1, it is characterised in that: contain adjuvant component in the Hydrobon catalyst, Adjuvant component is one or more of silicon, phosphorus, titanium, zirconium, boron, based on the element weight of the adjuvant component in Hydrobon catalyst Measuring content is 1% ~ 15%.

10. the preparation method of any catalyst of claim 1~8, comprising:

(1), the saline mixed solution A containing Ni and Al component is prepared, precipitating reagent is added dropwise to solution A and carries out plastic reaction, generation contains Nickel, aluminum precipitation object slurries I；

(2), the saline mixed solution B containing W, Mo and Al component is prepared, solution B and precipitating reagent are subjected to the reaction of cocurrent plastic, generated Tungstenic, molybdenum, aluminum precipitation object slurries II；

(3), the resulting slurries I of step (1) and the resulting slurries II of step (2) is uniformly mixed, aging under agitation, always After change, filtering, obtained material carries out hydro-thermal process with water vapour, urea is wherein added when hydro-thermal process；

(4), step (3) resulting material obtains Hydrobon catalyst through drying, molding, washing, then through drying, roasting；

Magnesium-containing compound is added when preparing mixed solution A and/or step (2) preparation mixed solution B in step (1).

11. according to the method for claim 10, it is characterised in that precipitating reagent described in step (1) or step (2) is carbon One of sour sodium, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, saleratus are a variety of.

12. according to the method for claim 11, it is characterised in that precipitating reagent described in step (1) or step (2) is ammonia Water, weights of ammonia concentration are 5%~15%.

13. according to the method for claim 10, it is characterised in that in step (1) mixed solution A, weight of the Ni in terms of NiO Concentration is 5~80g/L, and Al is with Al₂O₃The weight concentration of meter is 2~60g/L；In step (2) mixed solution B, W is with WO₃The weight of meter Amount concentration is 10~100g/L, and Mo is with MoO₃5~80g/L of weight concentration of meter, Al is with Al₂O₃The weight concentration of meter is 2~60g/ L；When containing magnesium in step (1) mixed solution A, weight concentration of the Mg in terms of MgO is 1~30g/L, in step (2) mixed solution B When containing magnesium, weight concentration of the Mg in terms of MgO is 1~30g/L.

14. according to the method for claim 10, it is characterised in that: reaction temperature is 20~90 DEG C in step (1)；At cementing PH value control is 6.0 ~ 11.0 when beam；Gelation time is 0.2 ~ 4.0 hour.

15. according to the method for claim 14, it is characterised in that: reaction temperature is 30~70 DEG C in step (1)；At cementing PH value control is 7.0 ~ 9.0 when beam；Gelation time is 0.5 ~ 3.0 hour.

16. according to the method for claim 10, it is characterised in that: in step (2) reaction temperature be 30~90 DEG C, cocurrent at PH value control is 6.0 ~ 11.0 when glue, and gelation time is 0.2 ~ 4.0 hour.

17. according to the method for claim 16, it is characterised in that: in step (2) reaction temperature be 40~80 DEG C, cocurrent at PH value control is 7.0 ~ 9.0 when glue, and gelation time is 0.5 ~ 3.0 hour.

18. according to the method for claim 10, it is characterised in that: aging temperature is 40~90 DEG C, when aging in step (3) PH value control is 6.0 ~ 10.0, and ageing time is 0.5 ~ 6.0 hour.

19. according to the method for claim 18, it is characterised in that: aging temperature is 50~80 DEG C, when aging in step (3) PH value control is 6.5 ~ 9.0, and ageing time is 1.0 ~ 4.0 hours.

20. according to the method for claim 10, it is characterised in that: hydrothermal conditions described in step (3) are as follows: close It is carried out under the container closed, temperature is 200 ~ 300 DEG C, and pressure is 1.0 ~ 8.0 MPa, and the processing time is 0.5 ~ 10.0 hour；Hydro-thermal When processing, active metal tungsten in the additional amount and catalyst of urea, molybdenum, nickle atom total amount molar ratio be 0.5:1 ~ 10.0:1.

21. according to the method for claim 10, it is characterised in that: hydrothermal conditions described in step (3) are as follows: close It is carried out under the container closed, temperature is 210 ~ 260 DEG C, and pressure is 3.0 ~ 6.0MPa, and the processing time is 1.0 ~ 6.0 hours；At hydro-thermal When reason, active metal tungsten in the additional amount and catalyst of urea, molybdenum, nickle atom total amount molar ratio be 2.0:1 ~ 8.0:1.

22. according to the method for claim 10, it is characterised in that: used drying and roasting item after step (4) molding Part is as follows: it is 1 ~ 48 hour dry at 50 ~ 250 DEG C, it is roasted 1 ~ 24 hour at 350 ~ 650 DEG C.

23. according to the method for claim 10, it is characterised in that: in Hydrobon catalyst preparation process, mixing The compound containing adjuvant component, i.e. titanium source and/or zirconium source are added in solution A, titanium source is using in Titanium Nitrate, titanium sulfate, titanium chloride It is one or more, zirconium source use one of zirconium nitrate, zirconium chloride, zirconium oxychloride or a variety of.