CN106179387B - The preparation method of Hydrobon catalyst composition - Google Patents

Abstract

The invention discloses a kind of preparation methods of Hydrobon catalyst composition.The carbon monoxide-olefin polymeric is body phase Hydrobon catalyst composition, it includes hydrogenation active metal component W, Ni and Mo that it, which is formed, aluminium oxide, preparation method is to prepare nickel aluminium mixed sediment using the method for ammonia still process precipitating, tungsten, molybdenum and aluminium mixed sediment are prepared using parallel flow precipitation, aging after the two is mixed, hydro-thermal process simultaneously plus urea, then through molding and etc. carbon monoxide-olefin polymeric is made.The carbon monoxide-olefin polymeric of this method preparation is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, hydrodesulfurization and hydrodenitrogeneration reactivity worth with higher.

Description

The preparation method of Hydrobon catalyst composition

Technical field

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

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 preparation methods of Hydrobon catalyst composition.It should The carbon monoxide-olefin polymeric of method preparation, table phase active site density is big, and hydrogenation active metals utilization rate is high, improves and adds hydrogen in catalyst The distribution of active metal improves mating reaction between hydrogenation active metals, while catalyst pore structure is reasonable, active metal dispersion More evenly, high mechanical strength, it is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

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

(1), the mixed solution A containing Ni, Al component salt is prepared, ammonium hydroxide, which is added in solution A, reaches the pH value of reaction system To 10 or more, solution A is heated carry out ammonia still process generation precipitating under agitation, until slurry pH value less than 10, generates nickeliferous, aluminium Sediment slurries I；

(2), the saline solution B containing W, Mo, Al component is prepared, ammonium hydroxide and material B cocurrent generate tungstenic, molybdenum, aluminum precipitation object and starch Liquid 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 composition.

Hydrobon catalyst composition of the invention, on the basis of the weight of Hydrobon catalyst composition, NiO, WO₃And MoO₃Total weight content be 40% ~ 95%, preferably 50% ~ 85%, alumina content be 5% ~ 60%, preferably 15% ~ 50%. In Hydrobon catalyst composition of the invention, the molar ratio of Ni/W is 1:8 ~ 8:1, preferably 1:4 ~ 4:1, (Ni+W)/Mo Molar ratio is 1:10 ~ 10:1, preferably 1:5 ~ 5:1.

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, preferably 8~40g/L.In step (2) mixed solution B, W is with WO₃The weight of meter is dense Degree is 10~100g/L, and preferably 20~90g/L, Mo is with MoO₃5~80g/L of weight concentration of meter, preferably 10~60g/L, Al is with Al₂O₃The weight concentration of meter is 2~60g/L, preferably 8~40g/L.When preparing mixed solution A, the nickel that generally uses Source can be one or more of nickel sulfate, nickel nitrate, basic nickel carbonate, nickel chloride, and silicon source can be aluminum nitrate, sulfuric acid One or more of aluminium, aluminium chloride or aluminium acetate etc..When preparing mixed solution B, the tungsten source generally used can be ethyl One or more of ammonium metatungstate, ammonium metatungstate；Molybdenum source is ammonium molybdate；Silicon source can for aluminum nitrate, aluminum sulfate, aluminium chloride or One or more of aluminium acetate etc..

When solution A is added in ammonium hydroxide in step (1), system temperature control is 30~70 DEG C, and preferably 40~60 DEG C, ammonia is added The pH value of reaction system is controlled after water 10 or more, preferably 10~13, ammonia still process makes the pH value of reaction system less than 10, preferably 7.5~9.5, ammonia still process temperature is 80~150 DEG C, and preferably 80~120 DEG C, time of ammonia distillation is controlled at 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.The weight concentration of ammonium hydroxide used is 15%~28% in step (1).

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.In step (2), ammonium hydroxide used Weight concentration be 5%~15%.

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.

Dry and roasting used by after step (4) molding can use this field normal condition, and drying condition is as follows: 1 ~ 48 hour dry at 50 ~ 250 DEG C, roasting condition is as follows: it is roasted 1 ~ 24 hour at 350 ~ 650 DEG C, preferably drying condition is as follows: 4 ~ 36 hours dry at 80 ~ 180 DEG C, roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.

In the preparation process of Hydrobon catalyst composition of the present invention, required catalyst can be added according to a conventional method Auxiliary agent, adjuvant component are one or more of silicon, phosphorus, titanium, zirconium, boron etc., preferably titanium and/or zirconium.The dosage of auxiliary agent accounts for plus hydrogen The 0% ~ 20% of catalyst for refining composition weight, preferably 1% ~ 15%.It was prepared in Hydrobon catalyst composition of the present invention The compound containing adjuvant component, i.e. titanium source and/or zirconium source is preferably added in Cheng Zhong during preparing mixed solution A.Titanium source can adopt With one of Titanium Nitrate, titanium sulfate, titanium chloride etc. or a variety of, zirconium source be can be used in zirconium nitrate, zirconium chloride, zirconium oxychloride etc. It is one or more.

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.

The Hydrobon catalyst composition of the method for the present invention preparation is body phase Hydrobon catalyst composition, composition Including hydrogenation active metal component W, Ni and Mo, aluminium oxide；Wherein table phase active metal component WO₃Weight content mutually live with body Property metal component WO₃Weight content ratio be 2.0:1 ~ 7.0:1, preferably 2.5:1 ~ 5.0:1, 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, preferably are as follows: 1.8 ~ 3.0:1, table phase active metal component MoO₃Weight content and body phase active metal component MoO₃Weight content ratio 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 carbon monoxide-olefin polymeric in WO₃Weight content；The weight content of table phase active metal component NiO For the weight content of NiO in table phase, the weight content of body phase active metal component NiO is the weight of NiO in carbon monoxide-olefin polymeric Content；Table phase active metal component MoO₃Weight content be table phase in MoO₃Weight content, body phase active metal component MoO₃ Weight content be carbon monoxide-olefin polymeric in MoO₃Weight content.

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

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 more evenly, activity Intermetallic cooperation is good, and active metal utilization rate is high, while catalyst pore structure is reasonable, high mechanical strength, has higher Hydrodesulfurization and hydrodenitrogeneration reactivity worth, it is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

The method of the present invention uses the method for being added to ammonium hydroxide and then carrying out ammonia still process in acid metal salt solution, prepares nickel aluminium Mixed sediment prepares tungstenic, molybdenum, aluminium mixed sediment using parallel flow precipitation, then aging after the two is mixed.The present invention is logical It crosses and relatively large crystal grain and evengranular nickel, aluminum precipitation is prepared using the variation from high to low of ammonia still process method sediment slurry pH value Object, cocurrent process prepare the relatively small tungsten of crystal grain, molybdenum and aluminum precipitation object, above two sediment are mixed, and can control difference The distribution of hydrogenation active metals, tungsten, molybdenum, nickel active metal can better contact in table phase, be conducive to active metal tungsten, molybdenum, High activity phase is formed between nickel, and improves the interaction between active metal, improves the super of body phase Hydrobon catalyst composition Deep hydrodesulfurizationof performance.

In the preparation method of inventive catalyst composition, the material obtained after the co-precipitation of W, Ni, Mo, Al component is being suitable for 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 micromorphology 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 obviously increases distribution of the active metal in table phase, and disperses more equal It is even, be conducive to the density for improving Adsorption.In addition, urea is added in steam treatment, make the transformation of material form also The pore size distribution of carbon monoxide-olefin polymeric can be made more to concentrate, it is more uniform, be conducive to the mechanical strength for improving carbon monoxide-olefin polymeric. Hydrobon catalyst composition of the invention is for having excellent hydrodenitrogeneration in deeply desulfurizing fractional oil and denitrification process Activity, the reduction of nitrogen content are more advantageous to the progress of hydrodesulfurization reaction, so Hydrobon catalyst composition is for processing When handling the high heavy distillate of nitrogen content, with excellent 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. Carbon monoxide-olefin polymeric table phase active metallic content is measured using x-ray photoelectron spectroscopy (XPS), and catalyst combination object is mutually lived Property tenor using inductively coupled plasma atomic emission spectrum (ICP-AES) measure, 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.

Embodiment 1

Nickel chloride and liquor alumini chloridi are dissolved in water purification respectively, are configured to mixed solution A, the weight of NiO in mixed solution A Concentration is 19g/L, Al₂O₃Weight concentration be 13g/L.Ammonium metatungstate, ammonium molybdate and liquor alumini chloridi are dissolved in water purification respectively, It is configured to mixed solution B, WO in mixed solution B₃Weight concentration be 39g/L, MoO₃Weight concentration is 16g/L, Al₂O₃Weight Amount concentration is 13g/L.Solution temperature is raised to 40 DEG C in reactor tank 1, and the ammonium hydroxide that concentration is 25wt% is added into solution A until shape At dark blue solution, solution ph 10.5 continues for solution to be warming up to 100 DEG C, and ammonia still process 2 hours, pH value 7.8 was contained The sediment slurries I of nickel, aluminium.1000mL water purification is added in reactor tank 2, is that 10 wt % ammonium hydroxide and solution B cocurrent add by concentration Enter in reactor tank 2, gelling temperature is maintained at 60 DEG C, and 7.8, gelation time control exists for pH value control in cocurrent plastic reaction process 60 minutes, generate tungstenic, molybdenum, aluminum precipitation object slurries II.By aging after the above two mixing containing sediment slurry, ageing time 2 is small When, 75 DEG C of aging temperature, at the end of aging then pH value control is filtered, filter cake carries out under the water vapour containing urea 7.6 Hydro-thermal process, the condition of hydro-thermal process are as follows: the molar ratio of urea and active metal atom total amount is 7:1, and temperature is 250 DEG C, pressure Power is 4.0MPa, and the processing time is 4 hours, and filter cake is 8 hours dry at 100 DEG C, is rolled, extruded moulding.It is washed at room temperature with water purification It washs.Then 10 hours dry at 80 DEG C, 530 DEG C roast 4 hours, obtain catalyst A.Catalyst composition, pore size distribution and main property Matter is shown in Table 1.

Embodiment 2

According to the method for embodiment 1, it is matched by the constituent content of the catalyst B in table 1, nitric acid is added into dissolving tank 1 Nickel, aluminum nitrate, zirconyl chloride solution prepare working solution A, and aluminum nitrate, ammonium metatungstate and ammonium molybdate are added into dissolving tank 2 and matches Working solution B processed.Solution temperature is raised to 50 DEG C in reactor tank 1, and the ammonium hydroxide that concentration is 20wt% is added into solution A until being formed Dark blue solution, solution ph 12.0 continue for solution to be warming up to 120 DEG C, and ammonia still process 1.5 hours, pH value 8.2 was contained The sediment slurries I of nickel, aluminium.1000mL water purification is added in reactor tank 2, is that 8 wt% ammonium hydroxide and solution B cocurrent are added by concentration In reactor tank 2, gelling temperature is maintained at 55 DEG C, and pH value control is 7.6 in cocurrent plastic reaction process, and gelation time control is 60 Minute, generate tungstenic, molybdenum, aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 3 hours, 72 DEG C of aging temperature, at the end of aging then pH value control is filtered, filter cake carries out water under the water vapour containing urea 8.0 Heat treatment, hydrothermal conditions: the molar ratio of urea and active metal atom total amount is 3:1, and temperature is 230 DEG C, and pressure is 3.5MPa, processing time are 3 hours, and the material after hydro-thermal process is 12 hours dry at 70 DEG C, and then extruded moulding, is washed with water purification It washs 3 times, wet bar is 10 hours dry at 100 DEG C, roasts 5 hours at 480 DEG C, obtains final catalyst B, composition, pore size distribution and master Property is wanted to be 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, aluminium chloride, phosphoric acid solution prepare working solution A, and aluminium chloride, ammonium metatungstate and ammonium molybdate are added into dissolving tank 2 and prepares work Make solution B.Solution temperature is raised to 55 DEG C in reactor tank 1, and the ammonium hydroxide that concentration is 18wt% is added into solution A until being formed dark blue Color solution, solution ph 12.5 continue for solution to be warming up to 110 DEG C, and ammonia still process 2.5 hours, pH value 8.0 obtained nickeliferous, aluminium Sediment slurries I.1000mL water purification is added in reactor tank, is that reaction is added in 12 wt % ammonium hydroxide and solution B cocurrent by concentration In tank, gelling temperature is maintained at 50 DEG C, in cocurrent plastic reaction process pH value control 8.0, gelation time control at 60 minutes, Generate tungstenic, molybdenum, aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 2 hours, aging Temperature 70 C, at the end of aging then pH value control is filtered, filter cake carries out at hydro-thermal under the water vapour containing urea 7.6 Reason, hydrothermal conditions: the molar ratio of urea and active metal atom total amount is 6:1, and temperature is 220 DEG C, pressure 5.0MPa, Handling the time is 3 hours, and the material after hydro-thermal process is 8 hours dry at 120 DEG C, and then extruded moulding, is washed with water 1 time, wet Item is 6 hours dry at 110 DEG C, roasts 4 hours at 600 DEG C, obtains final catalyst C, and 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, aluminium chloride, titanium chloride solution prepare working solution A, and aluminum nitrate, ammonium metatungstate and ammonium molybdate are added into dissolving tank 2 and prepares Working solution B.Solution temperature is raised to 45 DEG C in reactor tank 1, and the ammonium hydroxide that concentration is 20wt% is added into solution A until being formed deep Blue solution, solution ph 11.0 continue for solution to be warming up to 105 DEG C, and ammonia still process 2 hours, pH value 7.8 obtained nickeliferous, aluminium Sediment slurries I.1000mL water purification is added in reactor tank 2, is that reactor tank is added in 8wt% ammonium hydroxide and solution B cocurrent by concentration In 2, 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.By it is above two containing sediment slurry mix after aging, ageing time 3 hours, aging Temperature 70 C, at the end of aging then pH value control is filtered, filter cake carries out at hydro-thermal under the water vapour containing urea 8.2 Reason, hydrothermal conditions: the molar ratio of urea and active metal atom total amount is 4:1, and temperature is 250 DEG C, pressure 3.0MPa, Handling the time is 6 hours, and the material after hydro-thermal process is 6 hours dry at 80 DEG C, and then extruded moulding, is washed 4 times with water purification, wet Item is 8 hours dry at 100 DEG C, roasts 5 hours at 550 DEG C, obtains final catalyst D, and 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 preparating acid sex work solution A are added into dissolving tank, 100g ammonium hydrogen carbonate is taken to match The solution for being 2.0mol/l at molar concentration.500mL water is added into reactor tank, temperature rises to 60 DEG C.In the case of stirring, By solution A, ammonium bicarbonate aqueous solution and concentration be 10wt% ammonium hydroxide cocurrent be added reactor tank in plastic, 60 DEG C of gelling temperature, plastic Time 1.0 hours, the pH value of plastic slurry was 7.8.Aging 2 hours after cemented into bundles.Then filter, obtained filter cake and Molybdenum trioxide, mashing stir evenly, and filtering, filter cake is 8 hours dry at 100 DEG C, and then extruded moulding, is washed 3 times with water purification, wet Item is 10 hours dry at 80 DEG C, roasts 4 hours at 530 DEG C, obtains final catalyst E, and 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 250 DEG C, pressure 4.0MPa, the processing time is 4 hours, and the molar ratio of ammonia and active metal atom total amount is 7:1, 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 250 DEG C, pressure 4.0MPa, the processing time is 4 hours, CO₂Molar ratio with active metal atom total amount is 7:1, 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, the urea (quality and work of urea 2.5) property metal quality is than being added in three-necked flask, and a small amount of water, which is added, makes it be uniformly dispersed, and is placed in oil bath and stirs in 130 DEG C It mixes 4 hours, reactant is poured into cooling in pallet while hot, cooling product is crushed with pulverizer, is placed in 150 DEG C of baking ovens and dries It is dry, decompose extra urea.Weigh account for solid powder 30wt% boehmite be added 10wt% dilute nitric acid solution be made Aluminum sol solid powder is added in Aluminum sol, and the catalyst item of diameter 1.6mm is made through kneading, extrusion at paste, After drying 5h under infrared lamp, puts in baking oven and dried 10 hours at 110 DEG C, 400 DEG C of roasting 5h, are prepared ginseng in Muffle furnace Than agent I.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 6

Identical reference is formed by the preparation of method for preparing catalyst disclosed in CN102451703A and the catalyst of embodiment 1 Agent J.By the catalytic component content proportion in embodiment 1, nickel chloride, ammonium metatungstate and zirconium oxychloride are added into dissolving tank 1 Then sodium metaaluminate alkalinity working solution B is added in preparating acid sex work solution A into dissolving tank 2.It is added into reactor tank 350mL water, temperature rise to 60 DEG C.In the case of stirring, by solution A, solution B and CO₂Plastic in reactor tank, CO is added in cocurrent₂ Concentration is 45v%, and 60 DEG C of gelling temperature, gelation time 1 hour, the pH value of plastic slurries was 7.8.CO is added during plastic₂Gas Al in the total amount of body and alkaline working solution B₂O₃Molar ratio is 4.0.Aging 2 hours after plastic.Then it filters, filter cake is added 500ml water purification and molybdenum trioxide, mashing stir evenly, and filtering, filter cake is 8 hours dry at 100 DEG C, then extruded moulding, with net Water washing 3 times, wet bar is 10 hours dry at 80 DEG C, roasts 5 hours at 450 DEG C, obtains final catalyst J, composition, pore size distribution and Main character is 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.It is 10%(weight by concentration) 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 is carried out, ageing time 2 hours, 75 DEG C of aging temperature, at the end of aging PH value controls after 7.6, filtering, and water purification, aluminium hydroxide and molybdenum trioxide is added after mixing in filter cake, extruded moulding, It is washed at room temperature with water purification.Then 10 hours dry at 80 DEG C, 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 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	18	14	22
WO3, wt%	38	35	40	34
					MoO3, wt%	16	20	12	16
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus
					Other/wt%	Nothing	ZrO2/2.0	P2O5/2.0	TiO2/3.0
Specific surface area, m2/g	242	231	225	236
					Kong Rong, mL/g	0.339	0.318	0.327	0.331
Mechanical strength, N/mm	23.2	22.8	22.7	22.9
					Pore size distribution, %
< 4nm	11.45	11.25	13.41	13.34
					4nm~8nm	71.62	69.95	70.04	71.18
8nm~15nm	14.15	14.33	13.27	12.47
					> 15nm	2.78	4.47	3.28	3.01

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
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
								Other/wt%	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing
Specific surface area, m2/g	212	211	213	219	232	218	198
								Kong Rong, mL/g	0.315	0.301	0.305	0.310	0.340	0.242	0.212
Mechanical strength, N/mm	20.1	18.9	19.6	18.7	11.5	20.5	18.5
								Pore size distribution, %
< 4nm	19.23	17.33	15.41	15.52	14.25	17.25	54.45
								4nm~8nm	32.45	32.14	37.86	33.41	28.42	35.28	21.14
8nm~15nm	38.17	34.68	32.35	34.03	38.81	33.85	18.32
								> 15nm	10.15	15.85	14.38	17.04	19.52	13.62	6.09

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

Carbon monoxide-olefin polymeric number	A	B	C	D	E
						Table phase IW/ body phase IW	4.52	3.35	4.18	3.96	0.95
Table phase INi/ body phase INi	2.89	2.43	2.87	2.96	0.91
						Table phase IMo/ body phase IMo	4.28	3.43	4.05	3.86	-

Continued 2

Carbon monoxide-olefin polymeric number	F	G	H	I	J	K
							Table phase IW/ body phase IW	1.03	1.10	1.18	0.99	1.42	1.04
Table phase INi/ body phase INi	1.08	1.17	1.09	0.95	1.38	0.99
							Table phase IMo/ body phase IMo	1.02	1.11	1.07	-	-	-

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

Carbon monoxide-olefin polymeric number	A	B	C	D	E	F	G	H	I	J	K
												MoS2/WS2Density, grain/100nm	93	90	89	86	51	55	56	57	50	66	51

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 carbon monoxide-olefin polymeric Activity evaluation of table

Carbon monoxide-olefin polymeric number	A	B	C	D	E
						It generates oil density (20 DEG C), g/cm3	0.8399	0.8401	0.8405	0.8406	0.8534
Boiling range range, DEG C	169-366	171-367	171-368	171-368	176-376
						S, μ g/g	7.9	8.4	8.7	9.6	189.8
N, μ g/g	1.0	1.0	1.0	1.0	19.4
						Cetane number	51.5	51.8	51.4	51.2	45.6

Continued 5

Carbon monoxide-olefin polymeric number	F	G	H	I	J	K
							It generates oil density (20 DEG C), g/cm3	0.8494	0.8500	0.8509	0.8546	0.8498	0.8516
Boiling range range, DEG C	178-372	174-374	167-373	168-376	169-373	169-374
							S, μ g/g	182.4	165.6	179.1	215.2	169.8	204.8
N, μ g/g	16.8	17.2	18.7	21.2	16.4	19.7
							Cetane number	49.8	49.5	48.9	46.1	45.6	45.9

The content of different sulfide in 6 hydrofined oil of table

Carbon monoxide-olefin polymeric 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	7.9	8.4	8.7	9.6	189.8
						C1- DBT, μ g/g	0	0	0	0	28.3
4- BMDBT, μ g/g	1.2	1.5	1.4	1.9	39.2
						6-BMDBT, μ g/g	1.1	1.2	2.6	1.4	35.6
4,6- BMDBT, μ g/g	5.4	5.7	5.0	6.6	86.7

Continued 6

Carbon monoxide-olefin polymeric number	F	G	H	I	J	K
							Nitrogen content in hydrofined oil, μ g/g	16.8	17.2	18.7	21.2	16.4	19.7
Sulfur content in hydrofined oil, μ g/g	182.4	165.6	179.1	215.2	169.8	204.8
							C1- DBT, μ g/g	21.8	24.8	29.6	35.1	30.3	35.4
4- BMDBT, μ g/g	43.6	37.3	34.2	39.9	38.1	40.8
							6-BMDBT, μ g/g	47.9	35.1	35.6	36.7	34.6	44.5
4,6- BMDBT, μ g/g	69.1	68.4	79.7	103.5	66.8	84.1

Claims (16)

1. a kind of preparation method of Hydrobon catalyst composition, it is characterised in that:

(1), the mixed solution A containing Ni, Al component salt is prepared, ammonium hydroxide, which is added in solution A, makes the pH value of reaction system reach 10 More than, solution A is heated carry out ammonia still process generation precipitating under agitation, until slurry pH value less than 10, generates nickeliferous, aluminum precipitation Object slurries I；

(2), the saline solution B containing W, Mo, Al component is prepared, ammonium hydroxide and material B cocurrent 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, 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 combination through drying, molding, washing, then through drying, roasting Object.

2. according to the method for claim 1, it is characterised in that: on the basis of the weight of Hydrobon catalyst composition, NiO、WO₃And MoO₃Total weight content be 40% ~ 95%, alumina content be 5% ~ 60%.

3. according to the method for claim 2, it is characterised in that: on the basis of the weight of Hydrobon catalyst composition, NiO、WO₃And MoO₃Total weight content be 50% ~ 85%, alumina content be 15% ~ 50%.

4. according to the method for claim 1, it is characterised in that: in the Hydrobon catalyst composition, Ni/W's rubs , than being 1:8 ~ 8:1, (Ni+W)/Mo molar ratio is 1:10 ~ 10:1 for you.

5. according to the method for claim 4, it is characterised in that: in the Hydrobon catalyst composition, Ni/W's rubs , than being 1:4 ~ 4:1, (Ni+W)/Mo molar ratio is 1:5 ~ 5:1 for you.

6. according to the method for claim 1, it is characterised in that the weight concentration of ammonium hydroxide used in step (1) is 15%~28%, The weight concentration of ammonium hydroxide used in step (2) is 5%~15%.

7. according to the method for claim 1, it is characterised in that in step (1) mixed solution A, weight of the Ni in terms of NiO is dense Degree 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 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.

8. according to the method for claim 1, it is characterised in that when solution A is added in ammonium hydroxide in step (1), system temperature control Be 30~70 DEG C, being added after ammonium hydroxide and controlling the pH value of reaction system is 10~13, ammonia still process make the pH value 7.5 of reaction system~ 9.5, ammonia still process temperature is 80~150 DEG C, and time of ammonia distillation was controlled at 0.2 ~ 4.0 hour.

9. according to the method for claim 1, it is characterised in that: reaction temperature is 30~90 DEG C in step (2), cocurrent plastic When pH value control be 6.0 ~ 11.0, gelation time be 0.2 ~ 4.0 hour.

10. according to the method for claim 9, 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.

11. according to the method for claim 1, 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.

12. according to the method for claim 11, 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.

13. according to the method for claim 1, 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 carbon monoxide-olefin polymeric of urea, molybdenum, nickle atom total amount molar ratio be 0.5:1 ~ 10.0:1.

14. according to the method for claim 1, 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 carbon monoxide-olefin polymeric of urea, molybdenum, nickle atom total amount molar ratio be 2.0:1 ~ 8.0: 1。

15. according to the method for claim 1, it is characterised in that: drying and roasting condition after step (4) molding are such as Under: it is 1 ~ 48 hour dry at 50 ~ 250 DEG C, it is roasted 1 ~ 24 hour at 350 ~ 650 DEG C.

16. according to the method for claim 1, 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 uses Titanium Nitrate, titanium sulfate, chlorination One of titanium is a variety of, and zirconium source uses one of zirconium nitrate, zirconium chloride, zirconium oxychloride or a variety of.