CN106179378B - The preparation method of hydrotreating catalyst - Google Patents

Abstract

The invention discloses a kind of preparation methods of hydrotreating catalyst.The catalyst is bulk phase catalyst, and composition includes hydrogenation active metal component W, Ni and Mo, aluminium oxide；Its preparation process is as follows: nickeliferous, aluminum precipitation object slurries are prepared using the method for ammonia still process, cocurrent process prepares tungstenic, aluminum precipitation object slurries, the two is uniformly mixed, after aging, carry out hydro-thermal process with water vapour and urea be added, then with MoO₃Be mixed with beating, through molding and etc. obtain hydrotreating catalyst.The catalyst is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

Description

The preparation method of hydrotreating catalyst

Technical field

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

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 can make catalyst surface active in this way, reduce the activity of catalyst.

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 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 how to improve the distribution of hydrogenation active metals, so that more active metals is distributed in channel surfaces and formed plus The activated centre density on bulk phase catalyst surface is improved at hydrogen activity center, and the utilization rate for improving hydrogenation active metal component is to work as Preceding 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 hydrotreating catalyst hydrogenation performance.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of preparation methods of hydrotreating catalyst.This method obtains The catalyst arrived, active metal tungsten and nickel active site density are big in table phase, can be cooperated well with active metal molybdenum, Hydrogenation active metals utilization rate is high, while catalyst pore structure is reasonable, and active metal disperses more evenly, high mechanical strength, especially It is suitable for being applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

The preparation method of hydrotreating catalyst 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, Al component is prepared, ammonium hydroxide and material B cocurrent generate tungstenic, aluminum precipitation object slurries II；

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

(4), the resulting mixtures of materials of step (3) and MoO₃Mashing is uniformly mixed, filtering, dry, molding, washing；

(5), step (4) resulting material obtains final hydrotreating catalyst through drying, roasting.

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

Hydrotreating catalyst of the invention, on the basis of the weight of hydrotreating catalyst, NiO, WO₃And MoO₃It is total Weight content is 40% ~ 95%, preferably 50% ~ 85%, and alumina content is 5% ~ 60%, preferably 15% ~ 50%.Of the invention plus hydrogen It handling in catalyst, the molar ratio of Ni/W is 1:8 ~ 8:1, and 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, Al is with Al₂O₃The weight concentration of meter is 2~60g/L, preferably 8~40g/ L.When preparing mixed solution A, the nickel source generally used can be one in nickel sulfate, nickel nitrate, basic nickel carbonate, nickel chloride Kind is several, and silicon source can be one or more of aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc..Preparing, mixing is molten When liquid B, the tungsten source generally used can be one or more of ethyl ammonium metatungstate, ammonium metatungstate；Silicon source can be nitric acid One or more of aluminium, aluminum sulfate, aluminium chloride or 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, the molar ratio of active metal (tungsten, nickel) atom total amount in the additional amount and catalyst of urea 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.

Drying described in step (5) and roasting can use this field normal condition, and drying condition is as follows: at 50 ~ 250 DEG C 1 ~ 48 hour dry, roasting condition is as follows: roasting 1 ~ 24 hour at 350 ~ 650 DEG C, preferably drying condition is as follows: at 80 ~ 180 DEG C 4 ~ 36 hours dry, roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.

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

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

The method of the present invention preparation body phase hydrotreating catalyst, composition include hydrogenation active metal component W, Ni and Mo, aluminium oxide；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃Weight content ratio For 2.0:1 ~ 7.0:1, preferably 2.5:1 ~ 5.0:1, weight content and the body phase active metal group of table phase active metal component NiO The ratio of the weight content of point NiO is 1.2:1 ~ 4.5:1, preferably are as follows: 1.8 ~ 3.0:1, MoO in table phase₃Weight content and body phase Middle MoO₃Weight content ratio be 0.95:1 ~ 1.2:1, preferably 1.0:1 ~ 1.1:1.

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 the hydrotreating catalyst of the method for the present invention preparation is as follows: specific surface area is 180 ~ 450m²/ g, Kong Rongwei 0.20 ~ 0.80ml/g, pore-size distribution are as follows: diameter is that Kong Rong shared by the hole below 4nm accounts for the 1% ~ 20% of total pore volume, and diameter is Kong Rong shared by the hole of 4 ~ 8nm accounts for the 55% ~ 80% of total pore volume, diameter be Kong Rong shared by the hole of 8 ~ 15nm account 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 be 4nm with Under hole shared by Kong Rong account for the 5% ~ 17% of total pore volume, diameter is that account for total pore volume be 61% ~ 75% to Kong Rong shared by the hole of 4 ~ 8nm, Diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, and the Kong Rong that diameter is 15nm or more accounts for total pore volume and is 0.5%~5.0%。

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

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

In hydrotreating catalyst of the present invention, active metal tungsten and nickel active site density are big in table phase, can be with activity Metal molybdenum is cooperated well, and hydrogenation active metals utilization rate is high, while catalyst pore structure is reasonable, and active metal disperses more Uniformly, high mechanical strength, it is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

It is heavy that the method for the present invention carries out ammonia still process method after using ammonium hydroxide to be added to acid metal salt solution prepares the mixing of nickel aluminium Starch prepares tungstenic, aluminium mixed sediment using parallel flow precipitation, then aging after the two is mixed.The present invention is by using steaming The method of ammonia makes the variation from high to low of sediment slurry pH value prepare relatively large crystal grain and evengranular nickel, aluminum precipitation object, Cocurrent process prepares the relatively small tungsten of crystal grain and aluminum precipitation object, and above two sediment is mixed, and it is living can to control different plus hydrogen Property metal distribution, tungsten, nickel active metal can better contact in table phase, be conducive to be formed between active metal tungsten, nickel high living Property phase, and improve the interaction between active metal, improve the ultra-deep hydrodesulfuration of body phase hydrotreatment catalyst composition Performance.

In the preparation method of catalyst of the present invention, the material obtained after the co-precipitation of W, Ni, Al component is under appropriate conditions Simultaneously urea is added in steam treatment, and urea is decomposed into NH under high temperature environment₃And CO₂, NH₃And CO₂Water vapour there are the case where Lower generation NH₄ ⁺And HCO₃ ^-Ion, NH₄ ⁺And HCO₃ ^-Ion at high temperature under high pressure has a significant impact the micromorphology of material, hydro-thermal Material phase structure is in cylinder before handling, and what material phase structure was changed into that irregular sheet is piled into from cylinder after hydro-thermal process does not advise The transformation of then body, this structure obviously increases distribution of the active metal in table phase, and disperses more evenly, is conducive to mention The density of high surface position, and promote the active metal MoO of W, Ni Yu subsequent addition₃Contact probability, improve its coordination and match It is right.In addition, urea is added in steam treatment, the transformation of material form is made to collect the pore size distribution of catalyst more In, it is more uniform, be conducive to the mechanical strength for improving catalyst.Hydrotreating catalyst of the invention is de- for distillate oil deep In sulphur and denitrification process, have excellent hydrodenitrogenationactivity activity, the reduction of nitrogen content, be more advantageous to hydrodesulfurization reaction into Row, so when hydrotreating catalyst is used for working process nitrogen content high heavy distillate, with excellent ultra-deep plus hydrogen It is desulphurizing activated.

Specific embodiment

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

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 and liquor alumini chloridi are dissolved in water purification respectively, are configured to mix Close solution B, WO in mixed solution B₃Weight concentration be 39g/L, Al₂O₃Weight concentration be 13g/L.Solution in reactor tank 1 Temperature is raised to 40 DEG C, into solution A be added concentration be 25wt% ammonium hydroxide until formed dark blue solution, solution ph 10.5, Continue for solution to be warming up to 100 DEG C, ammonia still process 2 hours, pH value 7.8 obtained nickeliferous, aluminium sediment slurries I.1000mL is net Water is added in reactor tank 2, is that 10wt% ammonium hydroxide and solution B cocurrent are added in reactor tank 2 by concentration, and gelling temperature is maintained at 60 DEG C, 7.8, gelation time control generated tungstenic, aluminum precipitation object slurries II at 60 minutes for pH value control in cocurrent plastic reaction process. By aging after the above two mixing containing sediment slurry, ageing time 2 hours, 75 DEG C of aging temperature, pH value was controlled at the end of aging It 7.6, then filters, filter cake carries out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urea and work Property tungsten nickle atom total amount molar ratio be 7:1, temperature be 250 DEG C, pressure 4.0MPa, processing the time be 4 hours, hydro-thermal After mixing evenly, molybdenum trioxide is added in the mashing of treated material, and filtering, filter cake is 6 hours dry at 90 DEG C, then extrusion at Type is washed 3 times with water purification, and wet bar is 5 hours dry at 120 DEG C, is roasted 4 hours at 500 DEG C, and final catalyst A is obtained, form, Pore size distribution and main character are 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 into dissolving tank 2, addition aluminum nitrate, ammonium metatungstate preparation work are molten Liquid B.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 formation navy blue is molten Liquid, 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, it was nickeliferous, aluminium heavy to obtain Starch slurries I.1000mL water purification is added in reactor tank 2, is that 8wt% ammonium hydroxide and solution B cocurrent are added in reactor tank 2 by concentration, Gelling temperature is maintained at 55 DEG C, and 7.6, gelation time control was generated at 60 minutes for pH value control in cocurrent plastic reaction process Tungstenic, aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 3 hours, aging temperature 72 DEG C, at the end of aging then pH value control is filtered, filter cake carries out hydro-thermal process, hydro-thermal under the water vapour containing urea 8.0 Treatment conditions: the molar ratio of urea and active metal tungsten nickle atom total amount is 3:1, and temperature is 230 DEG C, pressure 3.5MPa, place Managing the time is 3 hours, and after mixing evenly, molybdenum trioxide is added, filtering, filter cake is in 90 DEG C of dryings in the material mashing after hydro-thermal process 10 hours, then extruded moulding, was washed 2 times with water purification, and wet bar is 5 hours dry at 100 DEG C, is roasted 6 hours, is obtained at 450 DEG C Final catalyst B, composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, it is matched by the constituent content of the catalyst C in table 1, chlorination is added into dissolving tank 1 Nickel, aluminium chloride, phosphoric acid solution prepare working solution A, aluminium chloride are added into dissolving tank 2, ammonium metatungstate prepares working 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 formation dark blue solution, molten Liquid pH value is 12.5, continues for solution to be warming up to 110 DEG C, 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 12wt% ammonium hydroxide and solution B cocurrent are added in reactor tank by concentration, plastic 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, Aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 2 hours, 70 DEG C of aging temperature, aging At the end of pH value control 7.6, then filter, filter cake carries out hydro-thermal process, hydro-thermal process item under the water vapour containing urea Part: the molar ratio of urea and active metal tungsten nickle atom total amount is 6:1, and temperature is 220 DEG C, pressure 5.0MPa, handles the time It is 5 hours, the material mashing after hydro-thermal process after mixing evenly, is added molybdenum trioxide, filters, and filter cake is small in 130 DEG C of dryings 8 When, then extruded moulding, is washed with water 1 time, and wet bar is 5 hours dry at 120 DEG C, roasts 3 hours at 600 DEG C, is finally urged Agent C, composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

According to the method for embodiment 1, it is matched by the constituent content of the catalyst D in table 1, chlorination is added into dissolving tank 1 Nickel, aluminium chloride, titanium chloride solution prepare working solution A, aluminum nitrate are added into dissolving tank 2, ammonium metatungstate prepares working solution B.Solution temperature is raised to 45 DEG C in reactor tank 1, and it is the ammonium hydroxide of 20wt% up to forming dark blue solution that concentration is added into solution A, Solution ph is 11.0, continues for solution to be warming up to 105 DEG C, 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 10wt% ammonium hydroxide and solution B cocurrent are added in reactor tank 2 by concentration, at Glue temperature is maintained at 45 DEG C, and pH value control is 7.8 in cocurrent plastic reaction process, and at 60 minutes, generation contained gelation time control Tungsten, aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 3 hours, 70 DEG C of aging temperature, At the end of aging then pH value control is filtered 8.2, and filter cake carries out hydro-thermal process under the water vapour containing urea, at hydro-thermal Manage bar part: the molar ratio of urea and active metal tungsten nickle atom total amount is 4:1, and temperature is 250 DEG C, pressure 3.0MPa, processing Time is 6 hours, and after mixing evenly, molybdenum trioxide is added, filtering, filter cake is at 80 DEG C dry 10 in the material mashing after hydro-thermal process Hour, then extruded moulding, is washed 4 times with water purification, and wet bar is 6 hours dry at 100 DEG C, is roasted 3 hours, is obtained most at 550 DEG C Whole catalyst D, composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

By method for preparing catalyst disclosed in CN102049265A, preparation and the catalyst of embodiment 1 form identical ginseng Than agent E.Aluminium chloride, nickel chloride, ammonium metatungstate 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 1 molybdenum trioxide, mashing stir evenly, and filtering, filter cake is 6 hours dry at 90 DEG C, and then extruded moulding, is washed 3 times with water purification, wet Item is 5 hours dry at 120 DEG C, roasts 4 hours at 500 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, processing temperature 240 DEG C, pressure 5MPa of degree, the time 3 hours, the molar ratio of ammonia and active metal atom total amount was 5:1, prepared reference agent G.Group 1 is shown in Table at, pore size distribution and main character.

Comparative example 4

By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but CO is added₂, processing temperature 240 DEG C, pressure 5MPa of degree, the time 3 hours, CO₂Molar ratio with active metal atom total amount is 5:1, prepares reference agent H.Group 1 is shown in Table at, pore size distribution and main character.

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 Property metallics mass ratio be 2.5) to be 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 It is stirred in 130 DEG C 4 hours, reactant is poured into cooling in pallet while hot, cooling product is crushed with pulverizer, is placed in 150 It is dried in DEG C baking oven, decomposes extra urea.Weigh the dust technology for accounting for the boehmite addition 10% of 30% weight of solid powder Aluminum sol is made in solution, solid powder is added in Aluminum sol, and urging for diameter 1.6mm is made through kneading, extrusion at paste Agent item under infrared lamp after dry 5h, puts the drying 10 hours, 400 DEG C of roasting 5h in Muffle furnace at 110 DEG C in baking oven, Reference agent I is prepared.Composition, pore size distribution and main character are shown in Table 1.

Comparative example 6

Identical ginseng is formed by the preparation of method for preparing catalyst disclosed in CN102451703A and the catalyst of embodiment 1 Than agent J.By the catalytic component content proportion in embodiment 1, nickel chloride, ammonium metatungstate and oxychlorination are added into dissolving tank 1 Then sodium metaaluminate alkalinity working solution B is added in zirconium 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 6 hours dry at 90 DEG C, and then extruded moulding, uses water purification Washing 3 times, wet bar is 5 hours dry at 120 DEG C, roasts 4 hours at 500 DEG C, obtains final catalyst J, composition, pore size distribution and master Property is wanted to be 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 120 DEG C, 500 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 3, 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 4.Hydrotreating is detected using gas chromatography-atomic emission detector device (GC-AED) Sulfur compound in oil, the results are shown in Table 5.

It can be seen that catalyst of the present invention in the case where active metal amount does not change from table 1-2, catalyst surface gold Belong to relative atomic concentration to increase, hydrogenation sites density increases, and pore size distribution$ is more concentrated, found out from evaluation result table 5 Catalyst has excellent hydrodenitrogenationactivity activity, and the work of high plus hydrogen is shown when remove 4,6-DMDBT class macromolecular sulfide Property.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	22	16	18
WO3, wt%	38	28	34	36
					MoO3, wt%	16	18	16	20
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus
					Other/wt%	Nothing	ZrO2/2.0	P 2O5/2.0	TiO2/3.0
Specific surface area, m2/g	241	225	232	202
					Kong Rong, mL/g	0.329	0.323	0.319	0.305
Mechanical strength, N/mm	22.1	23.1	22.7	23.6
					Pore size distribution, %
< 4nm	12.13	12.41	13.59	13.14
					4nm~8nm	70.56	69.27	70.11	70.62
8nm~15nm	14.87	14.28	13.09	12.97
					> 15nm	2.44	4.04	3.21	3.27

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	202	214	220	232	218	198
								Kong Rong, mL/g	0.315	0.298	0.305	0.299	0.340	0.242	0.212
Mechanical strength, N/mm	20.1	19.9	19.1	18.7	11.5	20.5	18.5
								Pore size distribution, %
< 4nm	19.23	16.14	15.25	15.48	14.25	17.25	54.45
								4nm~8nm	32.45	33.24	35.71	33.66	28.42	35.28	21.14
8nm~15nm	38.17	33.46	33.95	35.73	38.81	33.85	18.32
								> 15nm	10.15	17.16	15.09	15.13	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 number	A	B	C	D	E
						Table phase IW/ body phase IW	4.27	3.45	4.09	3.92	0.95
Table phase INi/ body phase INi	3.24	2.37	3.03	3.15	0.91
						Table phase IMo/ body phase IMo	1.01	1.02	1.00	1.01	1.01

Continued 2

Catalyst number	F	G	H	I	J	K
							Table phase IW/ body phase IW	1.12	1.12	1.13	0.99	1.42	1.04
Table phase INi/ body phase INi	1.09	1.17	1.17	0.94	1.38	0.99
							Table phase IMo/ body phase IMo	0.99	1.01	1.01	1.01	1.00	-

3 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

4 catalyst activity evaluation result of table

Catalyst number	A	B	C	D	E
						It generates oil density (20 DEG C), g/cm3	0.8399	0.8404	0.8406	0.8403	0.8534
Boiling range range, DEG C	167-367	170-367	174-368	173-369	176-376
						S, μ g/g	5.5	9.5	7.2	8.1	189.8
N, μ g/g	1.0	1.0	1.0	1.0	19.4
						Cetane number	51.3	51.5	51.2	51.6	45.6

Continued 4

Catalyst number	F	G	H	I	J	K
							It generates oil density (20 DEG C), g/cm3	0.8497	0.8512	0.8509	0.8546	0.8498	0.8516
Boiling range range, DEG C	180-374	179-372	177-374	174-372	169-373	169-374
							S, μ g/g	172.2	165.8	187.5	215.2	169.8	204.8
N, μ g/g	18.1	17.9	19.1	21.2	16.4	19.7
							Cetane number	49.5	49.7	49.4	46.1	45.6	45.9

The content of different sulfide in table 5 hydrotreating oil

Catalyst number	A	B	C	D	E
						Nitrogen content in hydrotreating oil, μ g/g	1.0	1.0	1.0	1.0	19.4
Sulfur content in hydrotreating oil, μ g/g	5.5	9.5	7.2	8.1	189.8
						C1- DBT, μ g/g	0	0	0	0	28.3
4- BMDBT, μ g/g	0.7	1.9	1.2	1.4	39.2
						6-BMDBT, μ g/g	1.1	1.7	1.9	1.7	35.6
4,6- BMDBT, μ g/g	3.7	5.9	4.1	5.0	86.7

Continued 5

Catalyst number	F	G	H	I	J	K
							Nitrogen content in hydrotreating oil, μ g/g	18.1	17.9	19.1	17.7	16.8	19.7
Sulfur content in hydrotreating oil, μ g/g	172.2	165.8	187.5	176.8	169.4	204.8
							C1- DBT, μ g/g	26.7	25.2	28.9	35.1	30.3	35.4
4- BMDBT, μ g/g	38.5	38.1	37.4	39.9	38.1	40.8
							6-BMDBT, μ g/g	39.1	36.4	39.9	36.7	34.6	44.5
4,6- BMDBT, μ g/g	67.9	66.1	81.3	103.5	66.8	84.1

Claims (19)

1. a kind of preparation method of hydrotreating catalyst, comprising:

(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, Al component is prepared, ammonium hydroxide and material B cocurrent generate tungstenic, 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), the resulting mixtures of materials of step (3) and MoO₃Mashing is uniformly mixed, filtering, dry, molding, washing；

(5), step (4) resulting material obtains hydrotreating catalyst through drying, roasting.

2. according to the method for claim 1, it is characterised in that: on the basis of the weight of hydrotreating catalyst, NiO, WO₃ And MoO₃Total weight content be 40% ~ 95%, alumina content be 5% ~ 60%, wherein the molar ratio of Ni/W be 1:8 ~ 8:1, (Ni + W)/Mo molar ratio be 1:10 ~ 10:1.

3. according to the method for claim 2, it is characterised in that: on the basis of the weight of hydrotreating catalyst, NiO, WO₃ And MoO₃Total weight content be 50% ~ 85%, alumina content be 15% ~ 50%, wherein the molar ratio of Ni/W be 1:4 ~ 4:1, (Ni+W)/Mo molar ratio is 1:5 ~ 5:1.

4. 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 Al is with Al₂O₃The weight concentration of meter is 2~60g/L.

5. according to the method for claim 4, it is characterised in that: in step (1) mixed solution A, weight of the Ni in terms of NiO is dense Degree is 10~60g/L, and Al is with Al₂O₃The weight concentration of meter is 8~40g/L；In step (2) mixed solution B, W is with WO₃The weight of meter Amount concentration is 20~90g/L, and Al is with Al₂O₃The weight concentration of meter is 8~40g/L.

6. 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 made as 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；The weight concentration of ammonium hydroxide used in step (1) It is 15%~28%.

7. 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 is 0.2 ~ 4.0 hour, in step (2), the weight concentration of ammonium hydroxide used is 5%~ 15%。

8. according to the method for claim 7, it is characterised in that: reaction temperature is 40~80 DEG C in step (2), cocurrent plastic When pH value control be 7.0 ~ 9.0, gelation time be 0.5 ~ 3.0 hour.

9. according to the method for claim 1, it is characterised in that: aging temperature is 40~90 DEG C in step (3), pH when aging Value control is 6.0 ~ 10.0, and ageing time is 0.5 ~ 6.0 hour.

10. according to the method for claim 9, 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.

11. according to the method for claim 1, it is characterised in that hydrothermal conditions described in step (3) are as follows: closed Container under carry out, temperature be 200 ~ 300 DEG C, pressure be 1.0 ~ 8.0 MPa, processing the time be 0.5 ~ 10.0 hour.

12. according to the method for claim 1, it is characterised in that hydrothermal conditions described in step (3) are as follows: closed Container under carry out, temperature be 210 ~ 260 DEG C, pressure be 3.0 ~ 6.0MPa, processing the time be 1.0 ~ 6.0 hours.

13. according to the method for claim 1, it is characterised in that in step (3), when hydro-thermal process, the additional amount of urea with Active metal tungsten in catalyst, nickle atom total amount molar ratio be 0.5:1 ~ 10.0:1.

14. according to the method for claim 13, it is characterised in that in step (3), when hydro-thermal process, the additional amount of urea with Active metal tungsten in catalyst, 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 condition described in step (5) is as follows: at 50 ~ 250 DEG C 1 ~ 48 hour dry, roasting condition is as follows: roasting 1 ~ 24 hour at 350 ~ 650 DEG C.

16. according to the method for claim 15, it is characterised in that drying condition described in step (5) is as follows: 80 ~ 180 DEG C dry 4 ~ 36 hours, roasting condition was as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.

17. according to the method for claim 1, it is characterised in that: molten mixing in hydrotreating 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 uses one of zirconium nitrate, zirconium chloride, zirconium oxychloride or a variety of.

18. according to the method for claim 1, it is characterised in that: in the hydrotreating catalyst, table phase active metal The ratio of the weight content of component NiO and the weight content of body phase active metal component NiO is 1.2:1 ~ 4.5:1, MoO in table phase₃ Weight content and MoO in body phase₃Weight content ratio be 0.95:1 ~ 1.2:1.

19. according to the method for claim 18, it is characterised in that: in the hydrotreating catalyst, mutually activity is golden for table The ratio of the weight content and the weight content of body phase active metal component NiO that belong to component NiO is 1.8 ~ 3.0:1, MoO in table phase₃ Weight content and MoO in body phase₃Weight content ratio be 1.0:1 ~ 1.1:1.