CN106179386B - The preparation method of Hydrobon catalyst - Google Patents

Abstract

The invention discloses a kind of preparation methods of Hydrobon catalyst.This method prepares nickel, aluminum precipitation object by using positive addition, and cocurrent process prepares tungsten, molybdenum and aluminum precipitation object, and organic amine is added during any of the above-described step or two step plastics, above two sediment is mixed, after aging, carries out hydro-thermal process and urea is added simultaneously, then catalyst is made through molding etc..The catalyst of this method preparation is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, has higher hydrodesulfurization and hydrodenitrogenationactivity activity.

Description

The preparation method of Hydrobon catalyst

Technical field

The present invention relates to the body phase hydrorefining catalysts of a kind of preparation method of Hydrobon catalyst, especially high activity The preparation method of agent.

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.

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 preparation methods of Hydrobon catalyst.Party's legal system Standby catalyst table phase active site density is big, and hydrogenation active metals utilization rate is high, improves point of hydrogenation active metals in catalyst Cloth improves mating reaction between hydrogenation active metals, while catalyst pore structure is reasonable, and active metal disperses evenly, machinery Intensity is high, particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

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

（1）, prepare the component saline mixed solution A containing Ni and Al, by precipitating reagent be added dropwise to solution A carry out plastic reaction, give birth to At nickeliferous, aluminum precipitation object slurries I；

（2）, prepare the component saline mixed solution B containing W, Mo and Al, by solution B and precipitating reagent progress cocurrent plastic reaction, Generate 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）, step（3）Resulting material is through drying, molding, washing, then obtains final hydrofinishing through drying, roasting and be catalyzed Agent；

In step（1）Or/and step（2）Organic amine is added during plastic, organic amine can be individually added into, can also be same Precipitating reagent is added together.

Hydrobon catalyst prepared by the method for the present invention, containing tri- kinds of active metal components of W, Ni, Mo, with hydrofinishing On the basis of the weight of catalyst, NiO, WO₃And MoO₃Total weight content be 40% ~ 95%, preferably 50% ~ 85%, alumina content It is 5% ~ 60%, preferably 15% ~ 50%.In the Hydrobon catalyst of the present invention, 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.

The boiling point of the organic amine is higher than gelling temperature, generally at 50 DEG C~350 DEG C, preferably 70 DEG C~350 DEG C, such as Hexa, pyridine, aniline, phenylhydrazine, benzylamine, methyl diethanolamine, N methyldiethanol amine, ethanol amine, dimethyl second Hydramine, n-butylamine, cyclohexylamine, phenyl ethylamine, phenylpropanolamine, triethylenediamine（TEDA）, diethylenetriamines（DETA）, methyl Diethanol amine（MDEA）, isobutyl amine, one or more in sec-butylamine, preferably benzylamine and/or ethanol amine.Step（1）In it is organic The addition of amine and the molar ratio of Ni are 0.1~3.0, preferably 0.3~2.0.Step（2）The addition of middle organic amine and rubbing for W You are than being 0.1~3.0, preferably 0.2~2.0.

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., preferably titanium and/or zirconium, based on the element weight of the adjuvant component in Hydrobon catalyst Content is 0 ~ 20%, preferably 1% ~ 15%.

Step（1）Or step（2）Described in precipitating reagent be sodium carbonate, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, hydroxide It is one or more in potassium, potassium carbonate, saleratus, preferably ammonium hydroxide, weights of ammonia a concentration of 5%~15%.

Step（1）In mixed solution A, weight concentrations 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.Step（2）In 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 be aluminum nitrate, aluminum sulfate, aluminium chloride or One or more of aluminium acetate etc..

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 catalyst of urea（Tungsten, molybdenum, nickel）Mole of atom total amount Than being 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（4）This field normal condition may be used in used drying and roasting after formation, and drying condition is such as Under：1 ~ 48 hour dry at 50 ~ 250 DEG C, roasting condition is as follows：Roast 1 ~ 24 hour at 350 ~ 650 DEG C, preferably drying condition is such as Under：4 ~ 36 hours dry at 80 ~ 180 DEG C, roasting condition is as follows：It is roasted 2 ~ 12 hours at 400 ~ 600 DEG C.

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

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 prepared by the method for the present invention is body phase Hydrobon catalyst, and composition includes hydrogenation activity Metal component W, Ni and Mo, aluminium oxide；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃ Weight content ratio be 2.0:1~7.0:1, preferably 2.5:1~5.0:1, the weight content of table phase active metal component NiO with The ratio of 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 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 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 property of Hydrobon catalyst prepared by the method for 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 Kong Rong shared by the hole of 4 ~ 8nm accounts for the 55% ~ 80% of total pore volume, the Kong Rong shared by the hole of a diameter of 8 ~ 15nm account for total pore volume 2% ~ It is 0.1% ~ 5.0% that the Kong Rong of 20%, a diameter of 15nm or more, which account for total pore volume, and preferred pore-size distribution is as follows：A diameter of 4nm with Under hole shared by Kong Rong account for the 5% ~ 17% of total pore volume, it is 61% ~ 75% that Kong Rong, which accounts for total pore volume, shared by the hole of a diameter of 4 ~ 8nm, Kong Rong shared by the hole of a diameter of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, and the Kong Rong of a diameter of 15nm or more accounts for total pore volume and is 0.5%~5.0%。

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

Hydrobon catalyst prepared by the method for the present invention, surface-active bit density is big, and active metal disperses evenly, living Property intermetallic cooperation it is good, active metal utilization rate is high, while catalyst pore structure is reasonable, high mechanical strength, have compared with High 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 positive addition（The acid precipitation method, that is, alkaline precipitating agent is added in acid metal salt solution and carries out Precipitation）Nickel aluminium mixed sediment is prepared, tungsten, molybdenum and aluminium mixed sediment are prepared using parallel flow precipitation, then after the two is mixed Aging.The present invention prepares the relatively large nickel of crystal grain, aluminum precipitation object by using positive addition, and it is relatively small that cocurrent process prepares crystal grain Tungsten, molybdenum and aluminum precipitation object, above two sediment is mixed, and can control the distribution of different hydrogenation active metals, is conducive to live Property tungsten, molybdenum, high activity phase is formed between nickel, and improve the interaction between active metal, improve body and be added hydrogen refining catalytic The ultra-deep hydrodesulfuration performance of agent.

The method of the present invention can make sediment crystal grain more uniform during plastic, particularly with the addition of organic amine, increase table Metal active content in phase has good coordinative role between hydrogenation active metals, improves the hydrogenation activity of catalyst.

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

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. Catalyst table phase active metallic content uses x-ray photoelectron spectroscopy（XPS）It measures, caltalyst phase active metallic content is adopted Use inductively coupled plasma atomic emission spectrum（ICP-AES）It measures, transmissioning electric mirror determining catalyst surface WS₂/MoS₂Density That is WS₂And MoS₂Density.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Nickel chloride and liquor alumini chloridi are dissolved in water purification respectively, are configured to mixed solution A, the weight of NiO in mixed solution A A concentration of 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 Measure a concentration of 13g/L.Benzylamine and ammonium hydroxide are added solution A under stiring, the molar ratio of benzylamine and active metal Ni are 0.7, at Glue temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control generated nickeliferous, aluminum precipitation object slurry at 60 minutes Liquid I.1000mL water purifications are added in retort, benzylamine, ammonium hydroxide, solution B cocurrent are added in retort, benzylamine and active metal The molar ratio of W is 1.1, and gelling temperature is maintained at 60 DEG C, and pH value control is 7.8 in cocurrent plastic reaction process, gelation time control System generated tungstenic, molybdenum, aluminum precipitation object slurries II at 60 minutes.Aging after above two is mixed containing sediment slurry, ageing time 2 hours, 75 DEG C of aging temperature, pH value was controlled 7.6 at the end of aging, is then filtered, filter cake is under the water vapour containing urea Hydro-thermal process is carried out, the condition of hydro-thermal process is：The molar ratio of urea and active metal atom total amount is 7:1, temperature 250 DEG C, pressure 4.0MPa, processing time is 4 hours, and filter cake is 8 hours dry at 100 DEG C, rolls, extruded moulding.It uses at room temperature net Water washing.Then 10 hours dry at 80 DEG C, 530 DEG C roast 4 hours, obtain catalyst A.Catalyst composition, pore size distribution and master Property is wanted to be shown in Table 1.

Embodiment 2

According to the method for embodiment 1, 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.Ethanol amine and ammonium hydroxide are added solution A under stiring, the molar ratio of ethanol amine and active metal Ni are 1.5, Gelling temperature is maintained at 50 DEG C, at the end of pH value control 8.0, gelation time control generated nickeliferous, aluminum precipitation object at 50 minutes Slurries I.600mL water purifications are added in retort, ethanol amine, ammonium hydroxide, solution B cocurrent are added in retort, ethanol amine and work Property metal W molar ratio be 0.5, gelling temperature is maintained at 50 DEG C, and pH value control is 7.8 in cocurrent plastic reaction process, plastic Time control generated tungstenic, molybdenum, aluminum precipitation object slurries II at 60 minutes.Aging after above two is mixed containing sediment slurry, always Change 3 hours time, 72 DEG C of aging temperature, pH value is controlled 8.0 at the end of aging, is then filtered, filter cake is in the water containing urea Hydro-thermal process, hydrothermal conditions are carried out under steam：The molar ratio of urea and active metal atom total amount is 3:1, temperature 230 DEG C, pressure 3.5MPa, processing time is 4 hours, and material after hydro-thermal process is 12 hours dry at 70 DEG C, then extrusion at Type is washed 3 times with water purification, and wet bar is 10 hours dry at 100 DEG C, is roasted 5 hours at 480 DEG C, obtains final catalyst B, form, Pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, 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.Benzylamine and ammonium hydroxide are added solution A under stiring, the molar ratio of benzylamine and active metal Ni are 0.8, gelling temperature Be maintained at 45 DEG C, at the end of pH value control 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.It will 1000mL water purifications are added in retort, and ethanol amine, ammonia spirit B cocurrents are added in retort, ethanol amine and active metal W Molar ratio is 0.8, and gelling temperature is maintained at 55 DEG C, and 8.0, gelation time control exists for pH value control in cocurrent plastic reaction process 60 minutes, generate tungstenic, molybdenum, aluminum precipitation object slurries II.Aging after above two is mixed containing sediment slurry, ageing time 2 are small When, 70 DEG C of aging 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 Hydro-thermal process, hydrothermal conditions：The molar ratio of urea and active metal atom total amount is 6:1, temperature is 220 DEG C, and pressure is 5.0MPa, processing time are 4 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 bar is 6 hours dry at 110 DEG C, is roasted 4 hours at 600 DEG C, obtains final catalyst C, composition, pore size distribution and main property Matter is shown in Table 1.

Embodiment 4

According to the method for embodiment 1, 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.Phenyl ethylamine and ammonium hydroxide are added solution A under stiring, the molar ratio of phenyl ethylamine and active metal Ni are 1.0, at Glue temperature is maintained at 40 DEG C, at the end of pH value control 7.8, gelation time control generated nickeliferous, aluminum precipitation object slurry at 60 minutes Liquid I.800mL water purifications are added in retort, phenyl ethylamine, ammonium hydroxide, solution B cocurrent are added in retort, phenyl ethylamine and activity The molar ratio of metal W is 1.3, and gelling temperature is maintained at 50 DEG C, and pH value control is at 8.0, plastic in cocurrent plastic reaction process Between control at 60 minutes, generate tungstenic, molybdenum, aluminum precipitation object slurries II.Aging after above two is mixed containing sediment slurry, aging 3 hours time, 70 DEG C of aging temperature, pH value is controlled 8.2 at the end of aging, is then filtered, and filter cake is steamed in the water containing urea Hydro-thermal process, hydrothermal conditions are carried out under vapour：The molar ratio of urea and active metal atom total amount is 4:1, temperature 250 DEG C, pressure 3.0MPa, processing time is 6 hours, and the material after hydro-thermal process is 6 hours dry at 80 DEG C, then extruded moulding, It is washed 4 times with water purification, wet bar is 8 hours dry at 100 DEG C, is roasted 5 hours at 550 DEG C, obtains final catalyst D, composition, hole point Cloth and main character are shown in Table 1.

Comparative example 1

By method for preparing catalyst disclosed in CN102049265A, prepares and form identical ginseng with the catalyst of embodiment 1 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 At 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 ammonium hydroxide cocurrent addition retort, 60 DEG C of gelling temperature, at The pH value of 1.0 hours glue time, plastic slurry are 7.8.Aging 2 hours after cemented into bundles.Then it filters, obtained filter cake And molybdenum trioxide, mashing stir evenly, filtering, filter cake is 8 hours dry at 100 DEG C, rolls, extruded moulding.Water purification is used at room temperature Washing.Then 10 hours dry at 80 DEG C, 530 DEG C roast 4 hours, obtain final catalyst E, composition, pore size distribution and main property Matter is 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, processing time is 4 hours, and the molar ratio of ammonia and active metal atom total amount is 7:1, prepare 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, processing time is 4 hours, CO₂Molar ratio with active metal atom total amount is 7:1, prepare ginseng Than agent H.Composition, pore size distribution and main character are shown in Table 1.

Comparative example 5

It is prepared by method for preparing catalyst disclosed in CN101255356A and forms identical reference with the catalyst of embodiment 1 Agent I.It is matched by catalytic component content in embodiment 1, by MoO₃, wolframic acid, basic nickel carbonate, urea（The quality of urea and work Property metal quality is than 2.5）It is 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 is stirred 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, so that extra urea is decomposed.The dilute nitric acid solution for weighing the boehmite addition 10wt% for accounting for solid powder 30wt% is 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, It after drying 5h under infrared lamp, puts in baking oven and is 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

It is prepared by method for preparing catalyst disclosed in CN102451703A and forms identical reference with the catalyst of embodiment 1 Agent J.By the catalytic component content proportioning 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 retort 350mL water, temperature rise to 60 DEG C.In the case of stirring, by solution A, solution B and CO₂Plastic in retort, CO is added in cocurrent₂ The pH value of a concentration of 45v%, 60 DEG C of gelling temperature, gelation time 1 hour, plastic slurries are 7.8.CO is added during plastic₂Gas The total amount of body and the Al in alkaline working solution B₂O₃Molar ratio is 4.0.Aging 2 hours after plastic.Then it filters, filter cake is added 500mL water purifications and molybdenum trioxide, mashing stir evenly, filtering, and filter cake is 8 hours dry at 100 DEG C, rolls, extruded moulding.Room temperature It is lower to be washed with water purification.Then 10 hours dry at 80 DEG C, 530 DEG C roast 4 hours, obtain 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.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 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 devices Experiment, test raw material are Zhenghai mixed diesel (catalytic diesel oil accounts for the 40% of mixing weight of oil).Raw material main character is shown in Table 4, catalysis Agent activity rating process conditions：Hydrogen partial pressure is 6.4MPa, and reaction temperature is 360 DEG C, and volume space velocity is 2.0h when liquid^-1, hydrogen oil body Product is than being 500:1, evaluation result is shown in Table 5.Using gas chromatography-atomic emission detector device（GC-AED）Detect hydrofinishing 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, is shown 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 forms and property

Catalyst is numbered	A	B	C	D
					NiO, wt%	19	18	16	22
WO3, wt%	38	36	34	35
					MoO3, wt%	16	22	19	14
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus
					Other/wt%	Nothing	ZrO2/2.0	P2O5/3.0	TiO2/3.0
Specific surface area, m2/g	243	237	227	234
					Kong Rong, mL/g	0.336	0.325	0.332	0.329
Mechanical strength, N/mm	22.9	21.7	22.4	23.3
					Pore size distribution, %
＜ 4nm	10.36	12.27	14.06	13.53
					4nm~8nm	71.92	69.31	70.73	70.55
8nm~15nm	15.45	14.94	12.48	13.23
					＞ 15nm	2.27	3.48	2.73	2.69

Continued 1

Catalyst 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
								Other/wt%	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing
Specific surface area, m2/g	212	207	205	212	232	218	198
								Kong Rong, mL/g	0.315	0.302	0.312	0.313	0.340	0.242	0.212
Mechanical strength, N/mm	20.1	18.1	18.8	19.1	11.5	20.5	18.5
								Pore size distribution, %
＜ 4nm	19.23	16.14	15.75	15.06	14.25	17.25	54.45
								4nm~8nm	32.45	31.32	37.43	33.53	28.42	35.28	21.14
8nm~15nm	38.17	33.59	31.35	35.32	38.81	33.85	18.32
								＞ 15nm	10.15	18.95	15.47	16.09	19.52	13.62	6.09

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

Catalyst is numbered	A	B	C	D	E
						Table phase IW/ body phase IW	4.52	3.59	4.42	3.97	0.95
Table phase INi/ body phase INi	2.89	2.42	2.68	2.61	0.91
						Table phase IMo/ body phase IMo	4.27	3.32	4.19	3.95	-

Continued 2

Catalyst is numbered	F	G	H	I	J	K
							Table phase IW/ body phase IW	1.08	1.12	1.27	0.99	1.42	1.04
Table phase INi/ body phase INi	1.12	1.20	1.13	0.94	1.38	0.99
							Table phase IMo/ body phase IMo	1.05	1.14	1.02	-	-	-

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

Catalyst is numbered	A	B	C	D	E	F	G	H	I	J	K
												MoS2/WS2Density, grain/100nm	95	90	87	86	51	55	51	59	50	66	51

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 catalyst activity evaluation result of table

Catalyst is numbered	A	B	C	D	E
						Generate oil density (20 DEG C), g/cm3	0.8394	0.8411	0.8405	0.8416	0.8534
Boiling range range, DEG C	168-366	171-367	171-367	172-368	176-376
						S, μ g/g	8.2	8.5	9.0	9.2	189.8
N, μ g/g	1.0	1.0	1.0	1.0	19.4
						Cetane number	51.5	51.1	51.0	51.3	45.6

Continued 5

Catalyst is numbered	F	G	H	I	J	K
							Generate oil density (20 DEG C), g/cm3	0.8487	0.8504	0.8509	0.8533	0.8498	0.8516
Boiling range range, DEG C	184-372	180-373	178-374	168-376	169-373	169-374
							S, μ g/g	174.2	159.1	164.8	215.2	169.8	204.8
N, μ g/g	16.1	15.4	15.8	21.2	16.4	19.7
							Cetane number	49.2	50.1	48.8	46.1	45.6	45.9

The content of different sulfide in 6 hydrofined oil of table

Catalyst 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	8.2	8.5	9.0	9.2	189.8
						C1- DBT, μ g/g	0	0	0	0	28.3
4- BMDBT, μ g/g	1.4	1.6	1.7	1.6	39.2
						6-BMDBT, μ g/g	1.2	1.4	1.5	1.2	35.6
4,6- BMDBT, μ g/g	5.6	5.5	5.8	6.4	86.7

Continued 6

Catalyst is numbered	F	G	H	I	J	K
							Nitrogen content in hydrofined oil, μ g/g	16.1	15.4	15.8	21.2	16.4	19.7
Sulfur content in hydrofined oil, μ g/g	174.2	159.1	164.8	215.2	169.8	204.8
							C1- DBT, μ g/g	22.7	23.1	28.1	35.1	30.3	35.4
4- BMDBT, μ g/g	33.9	35.2	34.3	39.9	38.1	40.8
							6-BMDBT, μ g/g	36.4	30.9	31.4	36.7	34.6	44.5
4,6- BMDBT, μ g/g	81.2	69.9	71.0	103.5	66.8	84.1

Claims (24)

1. a kind of preparation method of Hydrobon catalyst, including：

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

（2）, prepare the component saline mixed solution B containing W, Mo and Al, solution B and precipitating reagent are subjected to cocurrent plastic reaction, generation 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）, step（3）Resulting material obtains Hydrobon catalyst through drying, molding, washing, then through drying, roasting；

In step（1）Or/and step（2）Organic amine is added during plastic.

2. according to the method for claim 1, it is characterised in that：On the basis of the weight of Hydrobon catalyst, NiO, WO₃ And 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, NiO, WO₃ And MoO₃Total weight content be 50% ~ 85%, alumina content be 15% ~ 50%.

4. according to any methods of claim 1-3, it is characterised in that：In the Hydrobon catalyst, Ni/W's rubs You are than being 1：8~8：1,（Ni+W）/ Mo molar ratios are 1：10~10：1.

5. according to the method for claim 4, it is characterised in that：In the Hydrobon catalyst, the molar ratio of Ni/W is 1：4~4：1,（Ni+W）/ Mo molar ratios are 1：5~5：1.

6. according to the method for claim 1, it is characterised in that：The boiling point of the organic amine is higher than gelling temperature, organic amine Boiling point be 50 DEG C~350 DEG C.

7. according to the method for claim 6, it is characterised in that：The boiling point of the organic amine is higher than gelling temperature, organic amine Boiling point be 70 DEG C~350 DEG C.

8. according to the method for claim 1, it is characterised in that：The organic amine is selected from hexa, pyridine, benzene Amine, phenylhydrazine, benzylamine, methyl diethanolamine, ethanol amine, dimethylethanolamine, n-butylamine, cyclohexylamine, phenyl ethylamine, phenylpropanolamine, It is one or more in triethylenediamine, diethylenetriamines, isobutyl amine, sec-butylamine.

9. according to the method for claim 8, it is characterised in that：The organic amine is selected from benzylamine and/or ethanol amine.

10. according to the method for claim 1, it is characterised in that：Step（1）When middle addition organic amine, addition and Ni Molar ratio be 0.1~3.0；Step（2）When middle addition organic amine, the molar ratio of addition and W are 0.1~3.0.

11. according to the method for claim 10, it is characterised in that：Step（1）When middle addition organic amine, addition and Ni Molar ratio be 0.3~2.0；Step（2）When middle addition organic amine, the molar ratio of addition and W are 0.2~2.0.

12. according to the method for claim 1, it is characterised in that step（1）Or step（2）Described in precipitating reagent be carbonic acid It is one or more in sodium, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, saleratus.

13. according to the method for claim 12, it is characterised in that step（1）Or step（2）Described in precipitating reagent be ammonia Water, weights of ammonia a concentration of 5%~15%.

14. according to the method for claim 1, it is characterised in that step（1）In 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；Step（2）In mixed solution B, W is with WO₃The weight of meter A concentration of 10~100g/L, Mo is with MoO₃5~80g/L of weight concentration of meter, Al is with Al₂O₃The weight concentration of meter is 2~60g/L.

15. according to the method for claim 1, 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.

16. according to the method for claim 15, 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.

17. according to the method for claim 1, 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.

18. according to the method for claim 17, 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.

19. according to the method for claim 1, 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.

20. according to the method for claim 19, 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.

21. according to the method for claim 1, 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.

22. according to the method for claim 1, 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.

23. according to the method for claim 1, it is characterised in that：Step（4）Used drying and roasting condition after molding It is as follows：It is 1 ~ 48 hour dry at 50 ~ 250 DEG C, it is roasted 1 ~ 24 hour at 350 ~ 650 DEG C.

24. according to the method for claim 1, it is characterised in that：It is molten mixing in Hydrobon catalyst preparation process The compound containing adjuvant component, i.e. titanium source and/or zirconium source are added in liquid A, titanium source is using in Titanium Nitrate, titanium sulfate, titanium chloride One or more, zirconium source is using one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.