CN106179480B - A kind of Hydrobon catalyst composition and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of Hydrobon catalyst compositions and preparation method thereof.The carbon monoxide-olefin polymeric is body phase Hydrobon catalyst, its composition includes hydrogenation active metal component W, Ni and Mo, 11 molecular sieves of SAPO and aluminium oxide, its table phase active metallic content is high, active site density is big, active metal disperses evenly, cooperation between active metal is good, active metal utilization rate is high, catalyst pore structure is reasonable simultaneously, high mechanical strength has higher hydrodesulfurization and hydrodenitrogeneration reactivity worth, particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

Description

A kind of Hydrobon catalyst composition and preparation method thereof

Technical field

The present invention relates to the bodies of a kind of Hydrobon catalyst composition and preparation method thereof, especially high activity to be added hydrogen Handle carbon monoxide-olefin polymeric and preparation method thereof.

Background technology

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.Severity is reacted as improved by increase using traditional Hydrobon catalyst Reaction temperature, hydrogen partial pressure or reduction reaction velocity etc. can also realize the deep desulfuration even ultra-deep desulfurization of diesel oil, but anti- Answer the rising of temperature that the variation of product colour and catalyst life can be caused to shorten, 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.

The sulfur-containing compound containing various structures and different molecular weight in petroleum distillate, but in the ultra-deep desulfurization stage （Sulfur content is less than 50 μ g/g）, mainly remove the sulfur-containing compound of the substituted bases such as 4,6- dimethyl Dibenzothiophene classes.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 reaction rate is caused significantly to decline.

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 be distributed to the number amount and type in activated centre 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, it is difficult to meet the needs of refinery is to V diesel product of producing country.Hydrogenation catalyst prepared by body phase method is most of by active gold Belong to component to constitute, the limitation of tenor can be broken away from, can in arbitrary 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, original device can improve the processing of device without transformation 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 that a certain amount of adhesive component is added, generally meets the requirement of mechanical strength, and the addition 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 generates Ni with precipitating reagent co-precipitation_xW_yO_zIt is molten aluminium salt can be added in above process in composite oxides precursor Liquid can also be directly added into aluminium hydroxide after plastic, then with MoO₃Mashing mixing, filtering, molding, activation are final catalysis Agent.When bulk phase catalyst prepared by this method reaches the requirement for meeting mechanical strength, surface-active bit density is relatively low, 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.Catalyst obtained by this method without high-temperature roasting, Contain organic additive in final catalyst, so that the mechanical strength of catalyst is met requirement, need that more bondings are added Agent component can influence the distribution of different hydrogenation active metals, catalyst surface active is made to reduce in this way.

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 be reacted under urea melting state, and it is extra to remove Urea obtains catalyst particles, can be molded by the way that adhesive is added.Urea is added as precipitating reagent in this method , it needs heating to remove extra urea after reaction, adhesive is then added and is molded, 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.

Hydrogenation catalyst prepared by body phase method, 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 lived 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 are current important research topics.

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 pair present in distillate plus hydrogen are de- 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 production super-low sulfur product when, catalyst needs the hydrodenitrogenationactivity activity for having 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 improving body The ultra-deep hydrodesulfuration activity of phase catalyst has extremely important effect.

The petroleum refining industry of 21st century must comply with the strategy of sustainable development, it is necessary to while paying attention to economic benefit, protection Environment and the principle to economize on resources.Therefore, become more important using the preparation method of non-environmental-pollution production bulk phase catalyst. Existing coprecipitation method prepares catalyst technology, uses NH mostly₃·H₂For O as precipitating reagent, this will generate the largely waste water containing ammonia, nitrogen, It pollutes the environment.

Coprecipitation method prepares bulk phase catalyst technology, can be to catalyst mesoporous using different coprecipitation modes, Gelation Conditions etc. Active metallic content and activated centre density, the distribution of different hydrogenation active metals and 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 relatively low, 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.

Invention content

In view of the deficiencies of the prior art, the present invention provides a kind of Hydrobon catalyst compositions and preparation method thereof. The catalyst table phase active site density is big, and hydrogenation active metals utilization rate is high, improves hydrogenation active metals in carbon monoxide-olefin polymeric Distribution, improve mating reaction between hydrogenation active metals, while carbon monoxide-olefin polymeric pore structure is reasonable, and active metal disperses more Uniformly, high mechanical strength, it is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

Hydrobon catalyst composition of the present invention is body phase Hydrobon catalyst composition, and composition includes plus hydrogen is lived Property metal component W, Ni and Mo, SAPO-11 molecular sieves and aluminium oxide；Wherein table phase active metal component WO₃Weight content with Body phase active metal component WO₃Weight content ratio be 2.0:1~7.0:1, preferably 2.5:1~5.0:1, table phase active metal The ratio of the weight content of component NiO and the weight content of body phase active metal component NiO is 1.2:1~4.5:1, preferably：1.8 ~3.0:1, table phase active metal component MoO₃Weight content and body phase active metal component MoO₃The ratio of weight content be 1.8:1~6:1, preferably 2.0:1~4.5:1.

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 Hydrobon catalyst composition of the present invention is urged containing tri- kinds of active metal components of W, Ni, Mo with hydrofinishing On the basis of the weight of agent composition, NiO, WO₃And MoO₃Total weight content be 40% ~ 94%, preferably 50% ~ 80%, SAPO- The content of 11 molecular sieves is 1% ~ 20%, preferably 5% ~ 15%, and alumina content is 5% ~ 60%, preferably 15% ~ 50%.The present invention's In Hydrobon catalyst composition, the molar ratio of Ni/W is 1：8~8：1, preferably 1：4~4：1,（Ni+W）/ Mo molar ratios are 1：10~10：1, preferably 1：5~5：1.

Conventional method synthesis, such as hydro-thermal crystalline substance may be used in SAPO-11 molecular sieves used in inventive catalyst composition Change method, the preferred property of SAPO-11 molecular sieves used are as follows：SiO₂/Al₂O₃Molar ratio is 0.1~1.3, and meleic acid amount is 0.6 ~1.3mmol/g, Kong Rongwei 0.10~0.25mL/g, 150~300m of specific surface area²/g。

The property of Hydrobon catalyst composition 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：Kong Rong shared by a diameter of holes below 4nm accounts for the 1% ~ 20% of total pore volume, a diameter of 4 ~ Kong Rong shared by the hole of 8nm accounts for the 55% ~ 80% of total pore volume, and the Kong Rong shared by the hole of a diameter of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume, It is 0.1% ~ 5.0% that the Kong Rong of a diameter of 15nm or more, which accounts for total pore volume, and preferred pore-size distribution is as follows：A diameter of 4nm is below Kong Rong shared by hole accounts for the 5% ~ 17% of total pore volume, and it is 61% ~ 75% that Kong Rong, which accounts for total pore volume, shared by the hole of a diameter of 4 ~ 8nm, diameter Kong Rong shared by hole for 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, the Kong Rong of a diameter of 15nm or more account for total pore volume be 0.5% ~ 5.0%。

Can contain adjuvant component in Hydrobon catalyst composition of the present invention as needed, adjuvant component be silicon, phosphorus, One or more of titanium, zirconium, boron etc., preferably titanium and/or zirconium, adjuvant component is in Hydrobon catalyst composition based on the element In weight content be 0 ~ 20%, preferably 1% ~ 15%.

The preparation method of Hydrobon catalyst composition of the present invention, including：

（1）, prepare the saline solution A of component containing Ni, by sodium metaaluminate alkaline solution be added dropwise to solution A progress plastic reaction, Generate nickeliferous, aluminum precipitation object slurries I；

（2）, prepare the component saline mixed solution B containing W, Mo, by solution B and sodium metaaluminate alkaline solution progress cocurrent plastic Reaction generates tungstenic, molybdenum, aluminum precipitation object slurries II；

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

（4）, by step（3）The material of gained is beaten, and is added with stirring SAPO-11 molecular sieve pulps and is uniformly mixed, passes through Filter, dry, molding, washing；

（5）, by step（4）The material of gained obtains final Hydrobon catalyst composition through drying, roasting.

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..

Step（1）In mixed solution A, weight concentrations of the Ni in terms of NiO is 5~80g/L, preferably 10~60g/L.Step （1）Contain Al in the sodium metaaluminate alkaline solution₂O₃A concentration of 10 ~ 70g/L, preferably 20 ~ 50g/L.When preparing solution A, one As the nickel source that uses can be one or more of nickel sulfate, nickel nitrate, basic nickel carbonate, nickel chloride.

Step（2）In mixed solution B, W is with WO₃The weight concentration of meter is 10~100g/L, preferably 20~80g/L, Mo With MoO₃5~80g/L of weight concentration of meter, preferably 10~60g/L.Step（2）Contain in the sodium metaaluminate alkaline solution Al₂O₃A concentration of 10 ~ 60g/L, preferably 10 ~ 40g/L.When preparing mixed solution B, the tungsten source generally used can be inclined for ethyl One or more of ammonium tungstate, ammonium metatungstate；Molybdenum source is ammonium molybdate.

Step（1）Middle reaction temperature is 20~90 DEG C, preferably 30~70 DEG C.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.

Step（2）Middle reaction temperature is 30~90 DEG C, preferably 40~80 DEG C.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.

Step（1）And step（2）Middle gelling temperature and time can be the same or different.Step（1）And step（2）It can It can not also be carried out simultaneously with being carried out at the same time.

Step（3）Middle aging temperature is 40~90 DEG C, preferably 50~80 DEG C.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.

Step（3）The hydrothermal conditions are as follows：It is carried out under closed container, temperature is 200 ~ 300 DEG C, preferably It it is 210 ~ 260 DEG C, pressure is 1.0 ~ 8.0 MPa, and preferably 3.0 ~ 6.0MPa, processing time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours.When hydro-thermal process, active metal in the addition and carbon monoxide-olefin polymeric of urea（Tungsten, molybdenum, nickel）Atom total amount Molar ratio be 0.5：1~10.0：1, preferably 2.0：1~8.0:1.

Step（4）Drying, molding and the washing may be used this field conventional method and carry out.Drying condition is as follows： Dry 1 ~ 48 hour at 50 ~ 250 DEG C, preferably 80 ~ 180 DEG C dryings 4 ~ 36 hours.In forming process, it can be added as needed It is one or more in conventional shaping assistant, such as peptizing agent, extrusion aid etc..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 using deionized water or contain decomposable asymmetric choice net salt（Such as ammonium acetate, ammonium chloride, ammonium nitrate）Solution washs, and is washed till neutrality.

Step（5）This field normal condition may be used in the drying and roasting, and drying condition is as follows：At 50 ~ 250 DEG C 1 ~ 48 hour dry, roasting condition is as follows：It is roasted 1 ~ 24 hour at 350 ~ 650 DEG C, preferably drying condition is as follows：At 80 ~ 180 DEG C 4 ~ 36 hours dry, roasting condition is as follows：It is roasted 2 ~ 12 hours at 400 ~ 600 DEG C.

In Hydrobon catalyst composition of the present invention, adjuvant component preferred Ti and/or Zr.It is urged in hydrofinishing of the present invention In agent composition preparation process, the compound containing adjuvant component, i.e. titanium source are preferably added during preparing mixed solution A The zirconium source and/or.Titanium source can be used one or more in Titanium Nitrate, titanium sulfate, titanium chloride etc., and zirconium nitrate, chlorine can be used in zirconium source Change one or more in zirconium, zirconium oxychloride etc..

In the method for the present invention, the shape of catalyst can be as needed for 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 composition of the present invention is the body phase Hydrobon catalyst composition of oxidation state, before use Conventional method can be used and carry out presulfurization.

In Hydrobon catalyst composition of the present invention, surface-active bit density is big, and active metal disperses evenly, activity Intermetallic cooperation is good, and active metal utilization rate is high, while carbon monoxide-olefin polymeric pore structure is reasonable, high mechanical strength, tool There are higher hydrodesulfurization and hydrodenitrogeneration reactivity worth, it is particularly suitable in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction Using.

The method of the present invention uses positive addition（The acid precipitation method, that is, alkaline precipitating agent is added in acid metal salt solution and carries out Precipitation）Nickeliferous, aluminium mixed sediment is prepared, tungsten, molybdenum and aluminium mixed sediment are prepared using parallel flow precipitation, then the two is mixed Aging afterwards.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, the distribution of different hydrogenation active metals can be controlled, be conducive to High activity phase is formed between active metal tungsten, molybdenum, nickel, and improves the interaction between active metal, is improved body phase hydrofinishing and is urged The ultra-deep hydrodesulfuration performance of agent composition.

In the preparation method of inventive catalyst composition, the material obtained after the co-precipitation of W, Ni, Mo, Al component is suitable Under conditions of steam treatment and urea is added, urea is decomposed into NH under high temperature environment₃And CO₂, NH₃And CO₂It is deposited in water vapour NH is generated in case₄ ⁺And HCO₃ ^-Ion, NH₄ ⁺And HCO₃ ^-Ion at high temperature under high pressure has significantly the microscopic pattern of material It influences, material phase structure is in cylinder before hydro-thermal process, and material phase structure is changed into irregular sheet heap from cylinder after hydro-thermal process The irregular body of product, the transformation of this structure makes distribution of the active metal in table phase obviously increase, and disperses more equal It is even, be conducive to the density for improving Adsorption.Simultaneously in addition, urea is added in steam treatment, make turning for material form Change can also be such that the pore size distribution of carbon monoxide-olefin polymeric more concentrates, and more uniformly, be conducive to the machinery for improving carbon monoxide-olefin polymeric Intensity.The Hydrobon catalyst composition of the present invention is in deeply desulfurizing fractional oil and denitrification process, having excellent add Hydrogen denitrification activity, the reduction of nitrogen content are more advantageous to the progress of hydrodesulfurization reaction, so Hydrobon catalyst composition is used When working process nitrogen content high heavy distillate, there is excellent ultra-deep hydrodesulfuration activity.

In the preparation method of inventive catalyst composition, the sodium metaaluminate alkaline solution containing Al is used to be avoided for precipitating reagent Use NH₃·H₂O generates the largely waste water containing ammonia, nitrogen, simultaneous reactions precipitate particles are uniform, are more advantageous to as precipitating reagent W, Ni, Mo active metal are distributed in table phase, and W, Ni, Mo active metal are distributed more uniformly in table phase, are conducive to carry Ultra-deep hydrodesulfuration, the denitrification activity of high bulk phase catalyst composition.Meanwhile during diesel oil distillate ultra-deep desulfurization, Due to 4,6- dimethyl Dibenzothiophene class sulfides desulfurization when, can occur methyl transfer, methyl removing and C-C keys fracture Reaction, and the SAPO-11 molecular sieves that the present invention selects have suitable acidity, can be effectively performed above-mentioned reaction, and with table phase Middle hydrogenation active metals match, and achieve the purpose that Ultra-deep Desulfurization of Diesel Fuels.

Specific implementation mode

In the present invention, specific surface area and Kong Rong use low temperature liquid nitrogen determination of adsorption method, mechanical strength to be measured using side pressure method. Carbon monoxide-olefin polymeric table phase active metallic content uses x-ray photoelectron spectroscopy（XPS）It measures, catalyst combination object is mutually lived Property tenor use inductively coupled plasma atomic emission spectrum（ICP-AES）It measures, transmissioning electric mirror determining catalyst group Close object surface WS₂/MoS₂Density, that is, WS₂And MoS₂Density.In the present invention, wt% is mass fraction, and v% is volume fraction.

SAPO-11 molecular sieves used in the embodiment of the present invention are to be synthesized according to 4,440,871 methods of patent US, property It is as follows：SiO₂/Al₂O₃Molar ratio is 0.8, and meleic acid amount is 1.1mmol/g, Kong Rongwei 0.18mL/g, specific surface area 220m²/g。

Embodiment 1

Nickel chloride is dissolved in water purification respectively, is configured to solution A, the weight concentration of NiO is 19g/L in solution A.It respectively will be inclined Ammonium tungstate, ammonium molybdate are dissolved in water purification, are configured to mixed solution B, WO in mixed solution B₃Weight concentration be 39g/L, MoO₃Weight Measure a concentration of 16g/L.Al will be contained₂O₃Solution A is added in 500 milliliters of the sodium aluminate solution of 20g/L under stiring, and gelling temperature is protected Hold at 60 DEG C, at the end of pH value control 7.8, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.It will 1000mL water purifications are added in retort, will contain Al₂O₃Reaction is added in 500 milliliters of the sodium aluminate solution of 20g/L and solution B cocurrent In tank, gelling temperature is maintained at 60 DEG C, in cocurrent plastic reaction process pH value control 7.8, gelation time control at 60 minutes, Generate tungstenic, molybdenum, aluminum precipitation object slurries II.Aging after above two is mixed containing sediment slurry, ageing time 2 hours, aging 75 DEG C of temperature, pH value is controlled 7.6 at the end of aging, is then filtered, filter cake carries out under the water vapour containing urea at hydro-thermal Reason, the condition of hydro-thermal process are：The molar ratio of urea and active metal atom total amount is 7:1, temperature is 250 DEG C, and pressure is 4.0MPa, processing time are 4 hours, material mashing that treated, and the obtained mixture slurry of SAPO-11 molecular sieve pulps is added Liquid filters, and filter cake is 8 hours dry at 100 DEG C, rolls, extruded moulding.It is washed at room temperature with water purification.Then at 80 DEG C, drying 10 is small When, 530 DEG C roast 4 hours, obtain carbon monoxide-olefin polymeric A.Carbon monoxide-olefin polymeric composition, pore size distribution and main character are shown in Table 1.

Embodiment 2

According to the method for embodiment 1, matches by the constituent content of the carbon monoxide-olefin polymeric B in table 1, add into dissolving tank 1 Enter nickel nitrate, zirconyl chloride solution, prepare working solution A, ammonium metatungstate is added into dissolving tank 2 and ammonium molybdate preparation work is molten Liquid B.Al will be contained₂O₃Solution A is added in 600 milliliters of the sodium aluminate solution of 20g/L under stiring, and gelling temperature is maintained at 55 DEG C, knot 8.0, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 50 minutes for pH value control when beam.600mL water purifications are added In retort, Al will be contained₂O₃800 milliliters of the sodium aluminate solution of 15g/L and solution B cocurrent are added in retort, and gelling temperature is protected Holding the pH value control in 50 DEG C, cocurrent plastic reaction process, 7.8, gelation time control generated tungstenic, molybdenum, aluminium at 60 minutes Sediment slurries II.Aging after above two is mixed containing sediment slurry, ageing time 3 hours, 72 DEG C of aging temperature, aging knot When beam then pH value control is filtered, filter cake carries out hydro-thermal process, hydrothermal conditions under the water vapour containing urea 8.0： The molar ratio of urea and active metal atom total amount is 3:1, temperature is 230 DEG C, pressure 3.5MPa, and processing time is 3 hours, The obtained mix slurry filtering of SAPO-11 molecular sieve pulps is added in material mashing that treated, and filter cake is dry 12 at 70 DEG C Hour, then extruded moulding, is washed 3 times with water purification, and wet bar is 10 hours dry at 100 DEG C, roasts 5 hours, is obtained most at 480 DEG C Whole carbon monoxide-olefin polymeric B, composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, matches by the constituent content of the carbon monoxide-olefin polymeric C in table 1, add into dissolving tank 1 Enter nickel chloride, phosphoric acid solution, prepare working solution A, ammonium metatungstate is added into dissolving tank 2 and ammonium molybdate prepares working solution B. Al will be contained₂O₃Solution A is added in 500 milliliters of the sodium aluminate solution of 18g/L under stiring, and gelling temperature is maintained at 45 DEG C, at the end of 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes for pH value control.1000mL water purifications are added anti- It answers in tank, Al will be contained₂O₃1000 milliliters of the sodium aluminate solution of 10g/L and solution B cocurrent are added in retort, and gelling temperature is protected Holding the pH value control in 60 DEG C, cocurrent plastic reaction process, 8.0, gelation time control generated tungstenic, molybdenum, aluminium at 60 minutes Sediment slurries II.Aging after above two is mixed containing sediment slurry, ageing time 2 hours, 70 DEG C of aging temperature, aging knot When beam then pH value control is filtered, filter cake carries out hydro-thermal process, hydrothermal conditions under the water vapour containing urea 7.6： The molar ratio of urea and active metal atom total amount is 6:1, temperature is 220 DEG C, pressure 5.0MPa, and processing time is 5 hours, The obtained mix slurry filtering of SAPO-11 molecular sieve pulps is added in material mashing that treated, and filter cake is dry 8 at 120 DEG C Hour, then extruded moulding, is washed with water 1 time, and wet bar is 6 hours dry at 110 DEG C, is roasted 4 hours at 600 DEG C, obtains final Carbon monoxide-olefin polymeric C, composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

According to the method for embodiment 1, matches by the constituent content of the carbon monoxide-olefin polymeric D in table 1, add into dissolving tank 1 Enter nickel chloride, titanium chloride solution, prepare working solution A, ammonium metatungstate is added into dissolving tank 2 and ammonium molybdate prepares working solution B.Al will be contained₂O₃Solution A is added in 400 milliliters of the sodium aluminate solution of 25g/L under stiring, and gelling temperature is maintained at 40 DEG C, terminates When pH value control 7.8, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.800mL water purifications are added anti- It answers in tank, Al will be contained₂O₃1000 milliliters of the sodium aluminate solution of 12g/L and solution B cocurrent are added in retort, and gelling temperature is protected Holding the pH value control in 60 DEG C, cocurrent plastic reaction process, 8.0, gelation time control generated tungstenic, molybdenum, aluminium at 60 minutes Sediment slurries II.Aging after above two is mixed containing sediment slurry, ageing time 3 hours, 70 DEG C of aging temperature, aging knot When beam then pH value control is filtered, filter cake carries out hydro-thermal process, hydrothermal conditions under the water vapour containing urea 8.2： The molar ratio of urea and active metal atom total amount is 4:1, temperature is 250 DEG C, pressure 3.0MPa, and processing time is 6 hours, The obtained mix slurry filtering of SAPO-11 molecular sieve pulps is added in material mashing that treated, and filter cake is dry 6 at 80 DEG C Hour, then extruded moulding, is washed 4 times with water purification, and wet bar is 8 hours dry at 100 DEG C, roasts 5 hours, is obtained most at 550 DEG C Whole carbon monoxide-olefin polymeric D, composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

By carbon monoxide-olefin polymeric preparation method disclosed in CN102049265A, the carbon monoxide-olefin polymeric with embodiment 1 is prepared Form identical reference agent E.Aluminium chloride, nickel chloride, ammonium metatungstate preparating acid sex work solution A are added into dissolving tank, takes 100g ammonium hydrogen carbonate is made into the solution that molar concentration is 2.0mol/l.500mL water is added into retort, temperature rises to 60 DEG C. In the case of stirring, by solution A, ammonium bicarbonate aqueous solution and a concentration of 10%（Weight）Plastic in retort is added in ammonium hydroxide cocurrent, The pH value of 60 DEG C of gelling temperature, gelation time 1.0 hours, plastic slurry is 7.8.Aging 2 hours after cemented into bundles.Then Filtering is added molybdenum trioxide and SAPO-11 molecular sieve pulps, stirs evenly, filter, filter cake is 100 after obtained filter cake mashing DEG C dry 8 hours, then extruded moulding, wash 3 times with water purification, and wet bar is dried 10 hours at 80 DEG C, is roasted 4 hours at 530 DEG C, Final carbon monoxide-olefin polymeric E is obtained, composition, pore size distribution and main character are shown in Table 1.

Comparative example 2

It is added without urea by 1 carbon monoxide-olefin polymeric 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 carbon monoxide-olefin polymeric of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but NH is added₃, Temperature is 250 DEG C, pressure 4.0MPa, and processing time is 4 hours, and the molar ratio of ammonia and active metal atom total amount is 7:1, Prepare reference agent G.Composition, pore size distribution and main character are shown in Table 1.

Comparative example 4

By 1 carbon monoxide-olefin polymeric of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but CO is added₂, Temperature is 250 DEG C, pressure 4.0MPa, and processing time is 4 hours, CO₂Molar ratio with active metal atom total amount is 7:1, Prepare reference agent H.Composition, pore size distribution and main character are shown in Table 1.

Comparative example 5

The carbon monoxide-olefin polymeric group with embodiment 1 is prepared by carbon monoxide-olefin polymeric preparation method disclosed in CN101255356A At identical reference agent I.It is matched by catalyst composition component content in embodiment 1, by MoO₃, wolframic acid, basic nickel carbonate, SAPO-11 molecular sieves, urea（The quality of urea and active metal mass ratio 2.5）It is added in three-necked flask, and is added a small amount of Water makes it be uniformly dispersed, and is placed in oil bath and is stirred in 130 DEG C 4 hours, reactant is poured into cooling in pallet while hot, uses pulverizer Cooling product is crushed, is placed in 150 DEG C of baking ovens and dries, extra urea is made to decompose.It weighs and accounts for the quasi- of solid powder 30wt% Aluminum sol is made in the dilute nitric acid solution that 10wt% is added in boehmite, and solid powder is added in Aluminum sol, and at paste, through mixed It pinches, extrusion, the catalyst item of diameter 1.6mm is made, under infrared lamp after dry 5h, it is small to put in baking oven at 110 DEG C dry 10 When, 400 DEG C of roasting 5h, are prepared reference agent I in Muffle furnace.Carbon monoxide-olefin polymeric composition, pore size distribution and main character are shown in Table 1.

Comparative example 6

The carbon monoxide-olefin polymeric with embodiment 1 is prepared by carbon monoxide-olefin polymeric preparation method disclosed in CN102451703A Form identical reference agent J.By the catalyst composition component content proportioning in embodiment 1, chlorination is added into dissolving tank 1 Then it is molten that the work of sodium metaaluminate alkalinity is added in nickel, ammonium metatungstate and zirconium oxychloride preparating acid sex work solution A into dissolving tank 2 Liquid B.350mL water is added into retort, temperature rises to 60 DEG C.In the case of stirring, by solution A, solution B and CO₂Cocurrent Plastic in retort, CO is added₂A concentration of 45v%, 60 DEG C of gelling temperature, gelation time 1 hour, the pH value of plastic slurries are 7.8.CO is added during plastic₂The total amount of gas and the Al in alkaline working solution B₂O₃Molar ratio is 4.0.Aging 2 after plastic Hour.Then it filters, after obtained filter cake mashing, molybdenum trioxide and SAPO-11 molecular sieve pulps is added, stirs evenly, filters, Filter cake is 8 hours dry at 100 DEG C, rolls, extruded moulding.It is washed at room temperature with water purification.Then 10 hours dry at 80 DEG C, 530 DEG C roasting 4 hours, obtains final carbon monoxide-olefin polymeric J, composition, 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, nickel chloride and ammonium metatungstate preparation is dissolved in water purification, are configured to mixed solution, Wherein the weight concentration of NiO is 19g/L, WO₃Weight concentration be 39g/L.By a concentration of 10%（Weight）Ammonium hydroxide adds under stiring Enter and carry out plastic in mixed solution, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control is 60 Minute, generate nickeliferous, tungsten sediment slurries.Then aging, ageing time 2 hours, 75 DEG C of aging temperature, at the end of aging are carried out PH value controls after 7.6, filtering, and the obtained mix slurry filtering of SAPO-11 molecular sieve pulps, filter cake are added in filter cake After mixing, extruded moulding is washed with water purification at room temperature for middle addition water purification, aluminium hydroxide and molybdenum trioxide.Then at 80 DEG C 10 hours dry, 530 DEG C roast 4 hours, obtain catalyst K.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 5

The present embodiment is inventive catalyst composition active appraisal experiment, and is carried out pair with comparative example carbon monoxide-olefin polymeric Than.It is small-sized in 200mL using A, B, C, D carbon monoxide-olefin polymeric of the present invention and comparative example E, F, G, H, I, J, K carbon monoxide-olefin polymeric Comparative evaluation's experiment is carried out on hydrogenation plant, test raw material is Zhenghai mixed diesel (catalytic diesel oil accounts for the 40% of mixing weight of oil). Raw material main character is shown in Table 4, carbon monoxide-olefin polymeric activity rating process conditions：Hydrogen partial pressure is 6.4MPa, reaction temperature 360 DEG C, volume space velocity is 2.0h when liquid^-1, hydrogen to oil volume ratio 500:1, evaluation result is shown in Table 5.Using gas-chromatography-atomic emissions Spectroscopic detector（GC-AED）Sulfur compound in hydrofined oil is detected, the results are shown in Table 6.

From table 1, table 2 and table 3 as can be seen that inventive catalyst composition is not the case where active metal amount changes Under, carbon monoxide-olefin polymeric surface-active metal atomic concentration increases, and hydrogenation sites density increases, and pore size distribution$ more collects In, find out that carbon monoxide-olefin polymeric has excellent hydrodenitrogenationactivity activity from evaluation result table 6, divides greatly in removing 4,6-DMDBT classes High hydrogenation activity is shown when sub- sulfide.Carbon monoxide-olefin polymeric is used for working process distillate, contains in particular for processing When the high heavier diesel fraction of nitrogen quantity, there is excellent ultra-deep hydrodesulfuration activity.

1 carbon monoxide-olefin polymeric of table forms and property

Carbon monoxide-olefin polymeric is numbered	A	B	C	D
					NiO, wt%	19	18	16	22
WO3, wt%	38	36	30	34
					MoO3, wt%	16	20	22	18
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus
					SAPO-11, wt%	10	8	12	5
Other/wt%	Nothing	ZrO2/2.0	P/2.0	TiO2/3.0
					Specific surface area, m2/g	245	234	221	228
Kong Rong, mL/g	0.354	0.335	0.329	0.322
					Mechanical strength, N/mm	23.1	22.8	22.7	23.5
Pore size distribution, %
					＜ 4nm	11.45	12.05	12.36	13.23
4nm~8nm	71.89	69.75	71.45	71.69
					8nm~15nm	14.65	14.32	13.81	12.72
＞ 15nm	2.11	3.88	2.38	2.36

Continued 1

Carbon monoxide-olefin polymeric is numbered	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
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
								SAPO-11, wt%	10	10	10	10	10	10	10
Other/wt%	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing
								Specific surface area, m2/g	212	222	213	216	232	218	197
Kong Rong, mL/g	0.315	0.314	0.327	0.303	0.340	0.242	0.194
								Mechanical strength, N/mm	20.1	18.3	19.7	19.2	11.5	20.5	18.5
Pore size distribution, %
								＜ 4nm	19.23	17.36	15.25	15.47	14.25	17.25	56.17
4nm~8nm	32.45	32.45	37.18	33.86	28.42	35.28	18.84
								8nm~15nm	38.17	34.82	31.68	35.25	38.81	33.85	18.91
＞ 15nm	10.15	15.37	15.89	15.42	19.52	13.62	6.08

The ratio between the weight content of the weight content and body phase active metal of 2 carbon monoxide-olefin polymeric table phase active metal of table

Carbon monoxide-olefin polymeric is numbered	A	B	C	D	E
						Table phase IW/ body phase IW	4.27	3.59	4.141	3.94	0.95
Table phase INi/ body phase INi	3.11	3.45	3.21	2.53	0.91
						Table phase IMo/ body phase IMo	4.29	3.98	4.04	3.99	-

Continued 2

Carbon monoxide-olefin polymeric is numbered	F	G	H	I	J	K
							Table phase IW/ body phase IW	1.12	1.08	1.24	0.99	1.42	1.13
Table phase INi/ body phase INi	1.16	1.22	1.16	0.94	1.38	1.08
							Table phase IMo/ body phase IMo	0.94	1.11	1.05	-	-	-

3 transmissioning electric mirror determining carbon monoxide-olefin polymeric surface MoS of table₂/WS₂Density

Carbon monoxide-olefin polymeric is numbered	A	B	C	D	E	F	G	H	I	J	K
												MoS2/WS2Density, grain/100nm	92	90	89	89	51	55	57	58	50	66	55

4 feedstock oil main character of table

Project	Analysis 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 carbon monoxide-olefin polymeric Activity evaluation of table

Carbon monoxide-olefin polymeric is numbered	A	B	C	D	E
						Generate oil density (20 DEG C), g/cm3	0.8398	0.8401	0.8404	0.8407	0.8534
Boiling range range, DEG C	167-367	171-367	171-368	174-367	176-376
						S, μ g/g	5.8	6.4	7.1	7.7	189.8
N, μ g/g	1.0	1.0	1.0	1.0	19.4
						Cetane number	51.3	51.8	51.2	51.4	45.6

Continued 5

Carbon monoxide-olefin polymeric is numbered	F	G	H	I	J	K
							Generate oil density (20 DEG C), g/cm3	0.8491	0.8509	0.8506	0.8541	0.8498	0.8514
Boiling range range, DEG C	177-373	178-372	169-373	169-375	169-373	172-374
							S, μ g/g	177.2	166.1	151.7	215.2	169.8	220.6
N, μ g/g	15.3	16.6	18.7	21.2	16.4	21.9
							Cetane number	49.1	50.4	45.9	46.1	45.6	45.5

The content of different sulfide in 6 hydrofined oil of table

Carbon monoxide-olefin polymeric is numbered	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	5.8	6.4	7.1	7.7	189.8
						C1- DBT, μ g/g	0	0	0	0	28.3
4- BMDBT, μ g/g	0.8	1.0	1.3	1.7	39.2
						6-BMDBT, μ g/g	0.6	0.9	1.2	1.1	35.6
4,6- BMDBT, μ g/g	4.4	4.5	4.8	4.9	86.7

Continued 6

Carbon monoxide-olefin polymeric is numbered	F	G	H	I	J	K
							Nitrogen content in hydrofined oil, μ g/g	15.3	16.6	18.7	21.2	16.4	21.9
Sulfur content in hydrofined oil, μ g/g	177.2	166.1	151.7	215.2	169.8	220.6
							C1- DBT, μ g/g	20.5	24.2	27.2	35.1	30.3	38.6
4- BMDBT, μ g/g	32.3	36.3	31.6	39.9	38.1	40.1
							6-BMDBT, μ g/g	38.9	31.2	32.6	36.7	34.6	37.7
4,6- BMDBT, μ g/g	85.5	74.4	60.3	103.5	66.8	104.2

Claims (22)

1. a kind of Hydrobon catalyst composition, which is body phase Hydrobon catalyst composition, group At including hydrogenation active metal component W, Ni and Mo, SAPO-11 molecular sieves and aluminium oxide；Wherein table phase active metal component WO₃ Weight content and body phase active metal component WO₃Weight content ratio be 2.0:1~7.0:1, table phase active metal component The ratio of the weight content of NiO and the weight content of body phase active metal component NiO is 1.2:1~4.5:1, table phase active metal group Divide MoO₃Weight content and body phase active metal component MoO₃Weight content ratio be 1.8:1~6:1；The hydrofinishing is catalyzed The pore-size distribution of agent composition is as follows：Kong Rong shared by a diameter of holes below 4nm accounts for the 1% ~ 20% of total pore volume, a diameter of 4 ~ Kong Rong shared by the hole of 8nm accounts for the 55% ~ 80% of total pore volume, and the Kong Rong shared by the hole of a diameter of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume, It is 0.1% ~ 5.0% that the Kong Rong of a diameter of 15nm or more, which accounts for total pore volume,.

2. carbon monoxide-olefin polymeric described in accordance with the claim 1, it is characterised in that：In the carbon monoxide-olefin polymeric, table is mutually active Metal component WO₃Weight content and body phase active metal component WO₃Weight content ratio be 2.5:1~5.0:1, table is mutually active The ratio of the weight content of metal component NiO and the weight content of body phase active metal component NiO is 1.8 ~ 3.0:1, table is mutually active Metal component MoO₃Weight content and body phase active metal component MoO₃Weight content ratio be 2.0:1~4.5:1.

3. carbon monoxide-olefin polymeric described in accordance with the claim 1, it is characterised in that：With the weight of Hydrobon catalyst composition On the basis of, NiO, WO₃And MoO₃Total weight content be 40% ~ 94%, SAPO-11 molecular sieve contents be 1% ~ 20%, alumina content It is 5% ~ 60%.

4. carbon monoxide-olefin polymeric described in accordance with the claim 3, it is characterised in that：With the weight of Hydrobon catalyst composition On the basis of, NiO, WO₃And MoO₃Total weight content be 50% ~ 80%, SAPO-11 molecular sieve contents be 5% ~ 15%, alumina content It is 15% ~ 50%.

5. according to the carbon monoxide-olefin polymeric described in claim 1 or 3, it is characterised in that：The Hydrobon catalyst composition In, the molar ratio of Ni/W is 1：8~8：1,（Ni+W）/ Mo molar ratios are 1：10~10：1.

6. carbon monoxide-olefin polymeric according to claim 5, it is characterised in that：In the Hydrobon catalyst composition, The molar ratio of Ni/W is 1：4~4：1,（Ni+W）/ Mo molar ratios are 1：5~5：1.

7. carbon monoxide-olefin polymeric described in accordance with the claim 1, it is characterised in that：The property of the Hydrobon catalyst composition Matter is as follows：Specific surface area is 180 ~ 450m²0.20 ~ 0.80mL/g of/g, Kong Rongwei.

8. carbon monoxide-olefin polymeric described in accordance with the claim 1, it is characterised in that：The hole of the Hydrobon catalyst composition Diameter distribution is as follows：Kong Rong shared by a diameter of holes below 4nm accounts for the 5% ~ 17% of total pore volume, hole shared by the hole of a diameter of 4 ~ 8nm To account for total pore volume be 61% ~ 75% to appearance, and the Kong Rong shared by the hole of a diameter of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, a diameter of 15nm with On Kong Rong to account for total pore volume be 0.5% ~ 5.0%.

9. carbon monoxide-olefin polymeric described in accordance with the claim 1, it is characterised in that：The property of SAPO-11 molecular sieves used is as follows： SiO₂/Al₂O₃Molar ratio is 0.1~1.3, and meleic acid amount is 0.6~1.3mmol/g, and 0.10~0.25mL/g of Kong Rongwei compare table 150~300m of area²/g。

10. carbon monoxide-olefin polymeric described in accordance with the claim 1, it is characterised in that：Contain in the Hydrobon catalyst and helps Agent component, adjuvant component are one or more of silicon, phosphorus, titanium, zirconium, boron, and adjuvant component is in hydrofinishing catalysis based on the element Weight content in agent is 1% ~ 15%.

11. the preparation method of any carbon monoxide-olefin polymeric of claim 1~9, including：

（1）, prepare the saline solution A of component containing Ni, by sodium metaaluminate alkaline solution be added dropwise to solution A carry out plastic reaction, generation Nickeliferous, aluminum precipitation object slurries I；

（2）, prepare the component saline mixed solution B containing W, Mo, by solution B and sodium metaaluminate alkaline solution progress cocurrent plastic it is anti- It answers, generates tungstenic, molybdenum, aluminum precipitation object slurries II；

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

（4）, by step（3）The material of gained is beaten, and is added with stirring SAPO-11 molecular sieve pulps and is uniformly mixed, through filtering, doing Dry, molding, washing,

（5）, by step（4）The material of gained obtains Hydrobon catalyst composition through drying, roasting.

12. according to the method for claim 11, it is characterised in that step（1）In mixed solution A, weight of the Ni in terms of NiO A concentration of 5~80g/L, step（1）Contain Al in the sodium metaaluminate alkaline solution used₂O₃A concentration of 10 ~ 70g/L；Step （2）In mixed solution B, W is with WO₃The weight concentration of meter is 10~100g/L, and Mo is with MoO₃5~80g/L of weight concentration of meter, step Suddenly（2）Contain Al in the sodium metaaluminate alkaline solution used₂O₃A concentration of 10 ~ 60g/L.

13. according to the method for claim 11, it is characterised in that：Step（1）Middle reaction temperature is 20~90 DEG C；At cementing PH value control is 6.0 ~ 11.0 when beam；Gelation time is 0.2 ~ 4.0 hour.

14. according to the method for claim 13, it is characterised in that：Step（1）Middle reaction temperature is 30~70 DEG C；At cementing PH value control is 7.0 ~ 9.0 when beam；Gelation time is 0.5 ~ 3.0 hour.

15. according to the method for claim 11, it is characterised in that：Step（2）Middle 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.

16. according to the method for claim 15, it is characterised in that：Step（2）Middle 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.

17. according to the method for claim 11, it is characterised in that：Step（3）Middle aging temperature is 40~90 DEG C, when aging PH value control is 6.0 ~ 10.0, and ageing time is 0.5 ~ 6.0 hour.

18. according to the method for claim 17, it is characterised in that：Step（3）Middle aging temperature is 50~80 DEG C, when aging PH value control is 6.5 ~ 9.0, and ageing time is 1.0 ~ 4.0 hours.

19. according to the method for claim 11, it is characterised in that：Step（3）The hydrothermal conditions 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 processing time is 0.5 ~ 10.0 hour；Hydro-thermal When processing, active metal tungsten in the addition and catalyst of urea, molybdenum, nickle atom total amount molar ratio be 0.5：1~10.0：1.

20. according to the method for claim 11, it is characterised in that：Step（3）The hydrothermal conditions 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 processing time is 1.0 ~ 6.0 hours；At hydro-thermal When reason, active metal tungsten in the addition and catalyst of urea, molybdenum, nickle atom total amount molar ratio be 2.0：1~8.0:1.

21. according to the method for claim 11, it is characterised in that：Step（5）The drying and roasting condition is as follows： 50 ~ 250 DEG C of dryings 1 ~ 48 hour, roast 1 ~ 24 hour at 350 ~ 650 DEG C.

22. according to the method for claim 11, it is characterised in that：In Hydrobon catalyst composition preparation process, The compound containing adjuvant component, i.e. titanium source and/or zirconium source are added in mixed solution A, titanium source is using Titanium Nitrate, titanium sulfate, chlorine One or more in change titanium, zirconium source is using one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.