CN104588085B - The method preparing hydrocracking catalyst - Google Patents

Abstract

The invention discloses the preparation method of a kind of hydrocracking catalyst.The method prepares nickel by using positive addition, aluminum precipitation thing, cocurrent process prepares tungsten, silicon and aluminum precipitation thing, organic amine is added during any of the above-described step or two step plastics, above two precipitate is mixed, add molecular sieve suspension, through aging, catalyst is made in molding etc., so can control the distribution of different hydrogenation active metals, be conducive to active metal tungsten, high activity phase is formed between nickel, and improve the interaction between active metal and carrier, the hydrogenation activity making the hydrocracking catalyst of gained obtains good coordinating with cracking activity, improve the serviceability of hydrocracking catalyst.

Description

The method preparing hydrocracking catalyst

Technical field

The present invention relates to the preparation method of the hydrocracking catalyst of a kind for the treatment of of heavy hydrocarbon class.

Background technology

At present, worldwide petroleum resources are not enough, and crude quality is deteriorated year by year, and intermediate oil demand increases, Petroleum chemicals upgrading and environmental regulation are more and more strict, heavy oil lighting is all greatly facilitated, and constitutes accelerated development The very strong driving force of hydrogen addition technology.Hydrocracking technology to be mainly characterized by adaptability to raw material strong, products scheme, purpose product select Property high, good product quality and added value high, multiple high-quality oil product can be directly produced (such as gasoline, jet fuel, diesel oil, profit Lubricant base oil etc.) and high-quality industrial chemicals (such as the production raw material such as benzene,toluene,xylene, ethylene).

Being hydrocracked and carry out at elevated pressures, hydrocarbon molecules cracks with hydrogen at catalyst surface and is hydrogenated with Reaction generates the conversion process of lighter molecule, and the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs simultaneously.Hydro carbons exists Cracking reaction in hydrocracking process is to carry out on the acid centre of catalyst, it then follows carbon ion reaction mechanism, hydrogenation, With the generation of hydro carbons isomerization reaction while cracking reaction.Hydrocracking catalyst is made up of hydrogenation component and acidic components , both add the most by a certain percentage, make hydrogenation and cracking performance reach balance, and its effect is that hydrocarbon mixture is abundant Hydrogenation, cracking and isomerization orienting response.Therefore, the catalyst that distillate hydrocracking process needs should possess stronger hydrogenation Active center has moderate acid centre again.

In general, hydrocracking catalyst can be prepared using the following, such as: infusion process, kneading method, beating method, altogether The sedimentation method, may use ion exchange for noble metal.Infusion process and kneading method are all first carrier and acidic components to be made After add metal again, and coprecipitated rule is acidic components and metal coprecipitation gets off, and metal loading is unrestricted.

US6299760, US6156695, US6537442, US6440888, US6652738 disclose containing group VIII/ VI B race active metal component is used for bulk phase catalyst of hydrotreating and preparation method thereof.Catalyst metal content can reach 50wt%~100wt%.Active metal component can be Ni-Mo or Ni-Mo-W.Above-mentioned catalyst uses coprecipitation method to prepare.US Hydrocracking catalyst disclosed in 3954671, hydrogenation conversion catalyst disclosed in US 4313817, resistance to disclosed in CN1253988A The hydrocracking catalyst of nitrogen type fecund intermediate oil, heavy hydrocarbons hydrocraking catalyst disclosed in CN1253989A, this A little catalyst use coprecipitation method to prepare, and owing to the deposition condition of different hydrogenation active metals is different, cause different hydrogenation The distribution of active metal is not easily controlled, thus affect between distribution and the different activities metal of different hydrogenation active metals and Interaction relationship between active metal and carrier, so that hydrogenation activity can not well be coordinated with cracking activity, Finally affect catalyst is hydrocracked performance.High activity, medium oil type hydrocracking catalyst disclosed in CN101239324A It is that the serosity being made into amorphous silica-alumina, auxiliary agent and active metal adds precipitant alkalescence ammoniac compounds, carries out precipitation anti- Should, it is subsequently adding molecular sieve suspension and makes.The method also uses coprecipitation method to prepare, however it remains different hydrogenation activities Metal Distribution, hydrogenation active metals and and carrier between act on the bad problem of harmonious relations.

CN103055923A discloses the preparation method of a kind of hydrocracking catalyst.Use containing hydrogenation active metals acid Solution, sodium metaaluminate alkaline solution and gas CO₂And stream is equipped with plastic in the retort of water purification；It is subsequently adding Y type molecule The suspension mix homogeneously of sieve, through filtration, dry, molding more scrubbed, dry, roasting prepares hydrocracking catalyst.The party Method utilizes the releasing of gas in roasting process, improves the pore structure of catalyst and the dispersion of active metal, but not from root The problem that the active metal distribution solving to produce during precipitation in basis is not easy regulation and control.

Coprecipitation method prepares catalyst technology, uses different coprecipitation mode, Gelation Conditions etc., all can be to different hydrogenation activity gold Interaction relationship between the distribution and the different hydrogenation active metals that belong to and between hydrogenation active metals and carrier has the biggest Impact.The coprecipitation method of above-mentioned employing can make the distribution of different hydrogenation active metals be not easily controlled, thus affect different hydrogenation and live Property metal distribution and different hydrogenation active metals between and active metal and carrier between interaction relationship so that adding Hydrogen activity can not well be coordinated with cracking, and finally affect catalyst is hydrocracked performance.Therefore, how hydrogenation is regulated and controled The distribution of active metal, make between hydrogenation active metals component and have between hydrogenation active metals component and carrier suitable Mating reaction, improves the utilization rate of hydrogenation active metals component, is to improve coprecipitation method to prepare hydrocracking catalyst Hydrogenation Key.

Summary of the invention

For the deficiencies in the prior art, the invention provides the preparation method of a kind of hydrocracking catalyst.The method changes The distribution of hydrogenation active metals in kind catalyst, improves the utilization rate of hydrogenation active metals, improve between hydrogenation active metals and And the cooperation effect between carrier, makes catalyst have higher serviceability.

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

(1), preparing the mixed solution A containing Ni, Al component, precipitant is added dropwise to solution A and carries out plastic reaction, generation contains Nickel, aluminum precipitation thing serosity I；

(2), preparation containing the mixed solution B of W, Si, Al component, precipitant and solution B stream are carried out plastic reaction, generate Tungstenic, silicon, aluminum precipitation thing serosity II；

(3), by the serosity I of step (1) gained and the serosity II mix homogeneously of step (2) gained, Y type molecular sieve is added Suspension is the most aging；

(4), material drying obtained by step (3), molding, washing；

(5), step (4) gained material drying again and roasting, prepared hydrocracking catalyst.

Wherein in step (1) or/and add organic amine during step (2) plastic, organic amine can be individually added into, it is possible to Together add with same precipitant.

The boiling point of described organic amine is higher than gelling temperature, typically at 50 DEG C～350 DEG C, preferably 70 DEG C～350 DEG C, such as Hexamethylenetetramine, pyridine, aniline, phenylhydrazine, benzylamine, methyl diethanolamine, N methyldiethanol amine, ethanolamine, dimethyl second Hydramine, n-butylamine, cyclohexylamine, phenethylamine, phenylpropanolamine, triethylenediamine (TEDA) diethylenetriamines (DETA), methyl One or more in diethanolamine (MDEA), isobutyl amine, sec-butylamine, preferably benzylamine and/or ethanolamine.The weight of described organic amine Amount concentration is 1%～40%, preferably 3%～20%.In step (1), the addition of organic amine and the mol ratio of Ni are 0.1～3.0, excellent Select 0.3～2.0.In step (2), the addition of organic amine and the mol ratio of W are 0.1～2.0, preferably 0.2～1.5.

In the inventive method, Y type molecular sieve is usually and adds with the form of molecular sieve suspension, will be ground to by molecular sieve 80 mesh ~ 140 mesh, preferably 100 mesh ~ 120 mesh, then add water and make suspension.Described Y type molecular sieve is conventional being hydrocracked Y type molecular sieve used by catalyst.

Precipitant described in step (1) or step (2) is sodium carbonate, sodium bicarbonate, ammonia, sodium hydroxide, hydroxide One or more in potassium, potassium carbonate, potassium bicarbonate, preferably ammonia.

In step (1) mixed solution A, Ni weight concentration in terms of NiO is 20～80g/L, preferably 30～60g/L, Al With Al₂O₃The weight concentration of meter is 60～200g/L, preferably 90～150g/L.In step (2) mixed solution B, W is with WO₃Meter Weight concentration is 50～120g/L, and preferably 70～100g/L, Si is with SiO₂Weight concentration is 80～250g/L, preferably 100 ～180g/L, Al is with Al₂O₃The weight concentration of meter is 60～200g/L, preferably 90～150g/L.In preparation mixed solution A Time, the general nickel source used can be one or more in nickel sulfate, nickel nitrate, basic nickel carbonate, Nickel dichloride., and aluminum source is permissible For one or more in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate etc..When preparing mixed solution B, the general tungsten used Source can be one or more in ethyl ammonium metatungstate, ammonium metatungstate；Silicon source can be the one in Ludox, sodium silicate or many Kind；Aluminum source can be one or more in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate etc..

In step (1), reaction temperature is 20～90 DEG C, preferably 30～70 DEG C.During cemented into bundles, pH value controls is 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

Si, the Al introduced in step (2) counts weight content in the catalyst as 10wt%～80wt% with oxide, preferably For 20wt%～60wt%, wherein Si accounts for 10wt%～90wt% of Si, Al gross weight in terms of oxide in terms of silicon oxide, preferably 30wt%～80wt%；The Al introduced in step (1) counts weight content in the catalyst as 5wt%～45wt% with oxide, relatively It is well 10wt%～30wt%.

In step (2), reaction temperature is 30～90 DEG C, preferably 40～80 DEG C.And when flowing plastic, pH value controls is 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 (1) and step (2), gelling temperature and time can be the same or different.Step (1) and step (2) can To carry out to carry out during difference simultaneously.

In step (3), aging temperature is 40～90 DEG C, preferably 50～80 DEG C.Time aging, pH value controls is 6.0 ~ 10.0, It is preferably 6.5 ~ 9.0.Ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.

Being dried described in step (4), molding can use this area conventional method to carry out.Described be dried typically 50 ~ 200 DEG C are dried 1 ~ 48 hour.In forming process, the shaping assistant of routine, such as peptizer, bonding can be added as required One or more in agent, extrusion aid etc..Described extrusion aid refers to the most extruded material, as sesbania powder, white carbon black, One or more in graphite powder, citric acid etc., the consumption of extrusion aid accounts for 1wt%～10wt% of total material butt.

After step (4) molding preferably through washing, washing be usually use deionized water or containing decomposable asymmetric choice net salt (as Ammonium acetate, ammonium chloride, ammonium nitrate etc.) solution washing, it is washed till neutrality.

Being dried described in step (5) can use this area normal condition with roasting, as little in being dried 1 ~ 48 at 50 ~ 200 DEG C Time, 450 ~ 600 DEG C of roastings 1 ~ 24 hour, preferably 2 ~ 8 hours.

In hydrocracking catalyst of the present invention, composition includes hydrogenation active metals component W and Ni, carrier component aluminium oxide and Amorphous silica-alumina, it is also possible to containing molecular sieve.On the basis of the weight of catalyst, WO₃Content be 10wt%～50wt%, preferably For 15wt%～30wt%, the content of NiO is 1wt%～30wt%, preferably 5wt%～20wt%, W/Ni atomic ratio be 0.05～ 1.0, preferably 0.1～0.7, the content of amorphous silica-alumina is 10wt%～80wt%, preferably 20wt%～60wt%, molecular sieve Content is 0wt%～40wt%, preferably 5wt%～30wt%, alumina content be 5wt%～45wt%, preferably 10wt%～ 30wt%.In amorphous silica-alumina, the content of silicon oxide is 10wt%～90wt%, preferably 30wt%～80wt%, the content of aluminium oxide For 10wt%～90wt%, preferably 30wt%～80wt%.

The character of catalyst prepared by the inventive method is as follows: specific surface area 250～500m²/ g, pore volume 0.35～ 0.70mL/g。

In hydrocracking catalyst of the present invention, it is also possible to containing adjuvant component, described adjuvant component is the IVth B race metal, IVth B family metal oxide content in hydrocracking catalyst is 1wt%～10wt%.Described IVth B race metal is preferably Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, during preparation mixed solution A, add the group Han auxiliary agent The compound divided, i.e. titanium source and/or zirconium source.Titanium source can use one or more in Titanium Nitrate, titanium sulfate, titanium chloride etc., zirconium Source can use one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride etc..

In hydrocracking catalyst of the present invention, Y type molecular sieve used can use all can be used in prior art to be hydrogenated with Y type molecular sieve in Cracking catalyst, such as: CN102441411A, CN1508228A, CN101450319A, CN Y type molecular sieve disclosed in 96119840.0.Y type molecular sieve disclosed in preferred CN102441411A in the present invention, with The molecular sieve of CN 96119840.0 report is raw material, is 650～800 DEG C in temperature, and pressure is that normal pressure is to 0.3MPa, time Hydrothermal treatment consists is carried out deep sealumination modified in the condition and range of 20～30 hours, can be containing a small amount of in water vapour during hydrothermal treatment consists Ammonia, ammonia dividing potential drop is 50 ~ 3000Pa(absolute pressure), it is then 0.5～10.0mol/L in acid concentration, the time is 0.5～20.0 hour, Temperature is 30～80 DEG C, and acid consumption carries out acid treatment in the condition and range that ratio is 1:1～20:1 of molecular sieve, uses Mineral acid is hydrochloric acid, sulphuric acid or nitric acid etc., obtains being applicable to the Y type molecular sieve that the present invention uses after hydrothermal treatment consists and acid treatment, Its character is as follows: the bore dia pore volume more than 1.7nm accounts for more than the 45% of total pore volume, and specific surface area is 750～900m²/ g, Cell parameter is at 2.423nm～2.545nm, relative crystallinity 95%～110%, SiO₂/Al₂O₃Mol ratio is 7～60.This molecule Sieving existing high degree of crystallinity, have again low cell parameter, the secondary pore of molecular sieve is many, is conducive to improving raw material and the diffusion of product Speed, reduces the second pyrolysis of product；Big specific surface area, less acid site number, it is more favorable to raising and is hydrocracked and urges The intermediate oil selectivity of agent；High silica alumina ratio, major part is the acid centre of moderate strength, and acid site is evenly distributed journey Degree height, makes this molecular sieve have the strongest nitrogen resistance and the most broken ring ability.The above-mentioned characteristic of this molecular sieve can make catalysis Agent has the ability of preferable anti-nitride poisoning, good hydrocracking activity when the raw material that directly contact impurity content is high The stability become reconciled.This catalyst is suitable for single hop once by hydrocracking process, and hydrocracking operation condition is as follows: Reaction temperature is 300～500 DEG C, more preferably 350～450 DEG C；Pressure is 6～20MPa, more preferably 13～17MPa；Volume during liquid Air speed is 0.5～3 h^-1, preferably 0.8～1.5 h^-1；Hydrogen to oil volume ratio is 400～2000:1, preferably 800～1500:1.

The heavy charge scope that catalyst prepared by the inventive method is suitable for is the widest, and they include vacuum gas oil (VGO), coking The various hydrocarbon ils such as gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, catalytic cracking recycle oil, it is also possible to group Closing and use, raw material is generally containing the hydro carbons that boiling point is 250～550 DEG C, and nitrogen content can be at 50～2500 g/g.

The inventive method uses positive addition, and (the acid sedimentation method i.e. alkaline precipitating agent is added in the metal salt solution of acidity carry out Precipitation) prepare nickel aluminum mixed sediment, use parallel flow precipitation to prepare tungsten, silicon and aluminum mixed sediment, simultaneously in preparation precipitation Add organic amine during thing, then both are mixed addition molecular sieve suspension, the most aging, make hydrocracking catalyst. The present invention is by using positive addition to prepare the relatively large nickel of crystal grain, aluminum precipitation thing, and cocurrent process prepares the relatively small tungsten of crystal grain, silicon With aluminum precipitation thing, precipitate crystal grain can be made more uniform particularly with the addition of organic amine, above two precipitate be mixed, it is possible to control The distribution of the different hydrogenation active metals of system, beneficially forms more high activity phase, and improves activity gold between active metal tungsten, nickel Interaction between genus and carrier, makes the hydrogenation activity of the hydrocracking catalyst of gained obtain good joining with cracking activity Close, improve the serviceability of hydrocracking catalyst.

The hydrocracking catalyst that the present invention uses preferred Y type molecular sieve to make is particularly suitable as High middle distillate hydrogenation Cracking catalyst, had both had high hydrogenation cracking activity, had again high middle distillates oil selectivity, the most also had stronger resistance to nitrogen ability Etc. good serviceability.This catalyst, in single-stage hydrocracking technical process, has liquid yield high, good product quality Etc. advantage.

Detailed description of the invention

In the present invention, specific surface area and pore volume use low temperature liquid nitrogen physisorphtion, and relative crystallinity and cell parameter are adopted With x-ray diffraction method, silica alumina ratio uses chemical method, and sodium content uses plasma emission spectrometry, catalyst surface active gold Belonging to concentration uses chemical analysis electron spectrum (ESCA) to measure.Transmissioning electric mirror determining catalyst surface WS₂Density.The present invention In, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

By containing the nickel chloride solution that NiO is 45g/L 480 milliliters, containing Al₂O₃The liquor alumini chloridi of 130g/L 350 milliliters, contains ZrO₂100g/L zirconyl chloride solution 150 milliliters, is mixed in NaOH solution tank NaOH 1, adds 800 milliliters of water purification dilutions, is configured to solution A.WO will be contained₃ The ammonium metatungstate of 88g/L 950 milliliters and containing Al₂O₃ The liquor alumini chloridi of 130g/L 400 milliliters, is mixed in solution In tank 2, add 800 milliliters of water purification dilutions, add 600 milliliters under agitation containing SiO₂Dilute water glass solution of 100g/L, Configuration solution B.Benzylamine and ammonia under agitation add solution A, and benzylamine is 0.8 with the mol ratio of active metal Ni, plastic temperature Degree be maintained at 50 DEG C, at the end of pH value control 7.6, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I. 1000mL water purification is added in retort, by benzylamine, ammonia, solution B and flow in addition retort, benzylamine and active metal W Mol ratio is 1.0, and gelling temperature is maintained at 50 DEG C, and flows pH value in plastic course of reaction and control 7.6, and gelation time control exists 60 minutes, generate tungstenic, silicon, aluminum precipitation thing serosity II.Above two is mixed containing sediment slurry, in situation about being stirred continuously Under, the Y type molecular sieve accounting for total catalyst weight 15wt% to two kinds of mixing addition hydrothermal treatment modifications containing precipitate serosity is suspended Liquid (is prepared by CN102441411A embodiment 3), and Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixing that plastic obtains In serosity, aging 2.0 hours at 70 DEG C, filter, be dried 9 hours at 80 DEG C, roll, extruded moulding.Wash with water purification under room temperature. Then it is dried 8 hours at 120 DEG C, 530 DEG C of roastings 4 hours, obtains catalyst A.Catalyst composition and main character are shown in Table 1.

Embodiment 2

According to the method for embodiment 1, by the constituent content proportioning of the catalyst B in table 1, in dissolving tank 1, add nitric acid Nickel, titanium chloride, aluminum nitrate solution, prepare working solution A, adds aluminum nitrate, ammonium metatungstate and dilute waterglass and join in dissolving tank 2 Working solution B processed, the dilutest waterglass is containing SiO₂Dilute water glass solution of 110g/L 500 milliliters.Phenethylamine and ammonia are existed Adding solution A under stirring, phenethylamine is 1.2 with the mol ratio of active metal Ni, and gelling temperature is maintained at 60 DEG C, at the end of pH value Controlling 7.8, gelation time control, at 50 minutes, generates nickeliferous, aluminum precipitation thing serosity I.1200mL water purification is added retort In, by phenethylamine, ammonia, solution B and flow in addition retort, the mol ratio of phenethylamine and active metal W is 1.4, plastic temperature Degree is maintained at 60 DEG C, and flows pH value in plastic course of reaction and control 7.8, gelation time control at 50 minutes, generate tungstenic, Silicon, aluminum precipitation thing serosity II.Above two is mixed containing sediment slurry, in the case of being stirred continuously, to two kinds containing precipitate Serosity mixing adds hydrothermal treatment modification and accounts for the Y type molecular sieve suspension of total catalyst weight 12wt% (by CN102441411A Prepared by embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains, aging at 70 DEG C 2.5 hours, filter, be dried 5 hours at 100 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried at 120 DEG C 10 hours, 500 DEG C of roastings 4 hours, obtain catalyst B.Catalyst composition and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, by the constituent content proportioning of the catalyst C in table 1, in dissolving tank 1, add chlorination Nickel, liquor alumini chloridi, prepare working solution A, adds aluminum chloride, ammonium molybdate, dilute waterglass preparation working solution in dissolving tank 2 B, the dilutest waterglass is containing SiO₂Dilute water glass solution of 100g/L 600 milliliters.Ethanolamine and ammonia are under agitation added Solution A, the mol ratio of ethanolamine and active metal Ni is 1.5, and gelling temperature is maintained at 40 DEG C, at the end of pH value control 8.0, Gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.Add in retort equipped with 1200mL water purification, by ethanol Amine, ammonia, solution B also flow in addition retort, and ethanolamine is 0.5 with the mol ratio of active metal W, and gelling temperature is maintained at 55 DEG C, and flow pH value in plastic course of reaction and control 7.8, gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing Serosity II.Above two is mixed containing sediment slurry.In the case of being stirred continuously, add to two kinds of mixing containing precipitate serosity Hydrothermal treatment modification accounts for the Y type molecular sieve suspension of total catalyst weight 10wt% and (makes by CN102441411A embodiment 3 Standby), Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains, aging 2 hours at 72 DEG C, mistake Filter, is dried 8 hours at 80 DEG C, rolls, extruded moulding.Wash with water purification under room temperature.Then 90 DEG C be dried 12 hours, 600 DEG C Roasting 4 hours, obtains catalyst C.Catalyst composition and main character are shown in Table 1.

Embodiment 4

According to the method for embodiment 1, by the constituent content proportioning of the catalyst D in table 1, in dissolving tank 1, add chlorination Nickel, zirconium oxychloride, liquor alumini chloridi, preparating acid sex work solution A, in dissolving tank 2, add aluminum chloride, ammonium molybdate, dilute water glass Glass preparating acid sex work solution B, the dilutest waterglass is containing SiO₂Dilute water glass solution of 125g/L 380 milliliters.By benzylamine and Ammonia under agitation adds solution A, and benzylamine is 0.8 with the mol ratio of active metal Ni, and gelling temperature is maintained at 50 DEG C, at the end of PH value controls 7.4, and gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.Add in retort equipped with 1200mL water purification, by ethanolamine, ammonia spirit B and flow in addition retort, the mol ratio of ethanolamine and active metal W is 0.8, Gelling temperature is maintained at 65 DEG C, and flows pH value in plastic course of reaction and control 7.8, and gelation time control, at 60 minutes, generates Tungstenic, silicon, aluminum precipitation thing serosity II.Above two is mixed containing sediment slurry.In the case of being stirred continuously, to two kinds containing heavy Shallow lake thing serosity mixing addition hydrothermal treatment modification accounts for the Y type molecular sieve suspension of total catalyst weight 12wt% and (presses Prepared by CN102441411A embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains In, aging 2 hours at 70 DEG C, filter, be dried 10 hours at 80 DEG C, roll, extruded moulding.Wash, then with water purification under room temperature It is dried 8 hours at 110 DEG C, 500 DEG C of roastings 4 hours, obtains catalyst D.Catalyst composition and main character are shown in Table 1.

Embodiment 5

According to the method for embodiment 1, by the constituent content proportioning of the catalyst A in table 1, in dissolving tank 1, add chlorination Nickel, aluminum chloride, zirconyl chloride solution, prepare working solution A, and in dissolving tank 2, addition aluminum chloride, ammonium molybdate, dilute waterglass are joined Working solution B processed, the dilutest waterglass is containing SiO₂Dilute water glass solution of 100g/L 600 milliliters.Ethanolamine and ammonia are existed Adding solution A under stirring, ethanolamine is 0.8 with the mol ratio of active metal Ni, and gelling temperature is maintained at 50 DEG C, at the end of pH value Controlling 7.6, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.Add in retort equipped with 1200mL Water purification, by ammonia, solution B and flow addition retort in, gelling temperature is maintained at 50 DEG C, and flows pH value control in plastic course of reaction System is 7.6, and gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing serosity II.By above two containing sediment slurry Mixing.In the case of being stirred continuously, add hydrothermal treatment modification to two kinds of mixing containing precipitate serosity and account for overall catalyst weight The Y type molecular sieve suspension (preparing by CN102441411A embodiment 3) of amount 15wt%, Y type molecular sieve character is shown in Table 6 so that it is all Even it is scattered in the mixed serum that plastic obtains, aging 2.0 hours at 70 DEG C, filter, be dried 9 hours at 80 DEG C, roll, extrusion Molding.Wash with water purification under room temperature.Then it is dried 8 hours at 120 DEG C, 530 DEG C of roastings 4 hours, obtains catalyst E.Catalyst Composition and main character are shown in Table 1.

Comparative example 1

Preparing according to method disclosed in CN101239324A, catalyst composition is prepared catalyst A with embodiment 1 and is formed phase With, specifically comprise the following steps that

(1) preparation is containing Al₂O₃Concentration is the liquor alumini chloridi 750 milliliters of 130g/L, molten containing the Nickel dichloride. that NiO is 45g/L Liquid 480 milliliters, containing ZrO₂100g/L zirconyl chloride solution 150 milliliters, and be mixed in the container of 5 liters, add 2000 millis Rise water purification dilution.

(2) dilute water glass solution is prepared, containing SiO₂The water glass solution of 100g/L 600 milliliters, under agitation will (2) add in (1)；

(3) ammonia is added under agitation the mixture of (1) and (2) until pH value 5.2；

(4) preparation sodium tungstate solution 950 milliliters, containing WO₃For 88g/L, and join under agitation (1)+(2)+ (3) in mixture；

(5) ammonia is continuously added until pH value is 7.6；

(6) whole plastic process should be carried out at 50 DEG C；

(7) mixture stands aging 2.0 hours at 70 DEG C；Add before aging with CN102441411A embodiment 3 preparation Y type molecular sieve suspension, Y type molecular sieve accounts for the 15% of total catalyst weight, and character is shown in Table 6.

(8) filter, 80 DEG C of oven dryings 9 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters；Use under room temperature The Spirit of Mindererus. washing of pH=8.8；Then 120 DEG C of oven dryings 8 hours, 530 DEG C of roastings 4 hours, obtain reference agent F, group Become and main character is shown in Table 1.

Comparative example 2

Comparative example 2 preparation process uses two steps be cocurrent process plastic and prepare hydrocracking catalyst.Catalyst forms Prepare catalyst A composition with embodiment 1 identical, specifically comprise the following steps that

In dissolving tank 1, add Nickel dichloride., zirconium oxychloride, liquor alumini chloridi, prepare working solution A, add in dissolving tank 2 Entering aluminum chloride, ammonium metatungstate and dilute waterglass preparation working solution B, the dilutest waterglass is containing SiO₂Dilute waterglass of 100g/L Solution 600 milliliters.Just 1000mL water purification adds in retort, by benzylamine, ammonia, solution A and flow in addition retort, and benzylamine Being 0.8 with the mol ratio of active metal Ni, gelling temperature is maintained at 50 DEG C, and flows pH value in plastic course of reaction and control 7.6, Gelation time control, at 60 minutes, generates nickel-and aluminum-containing precipitate serosity I.1000mL water purification is added in retort, by benzylamine, ammonia Water, solution B also flow in addition retort, and benzylamine is 1.0 with the mol ratio of active metal W, and gelling temperature is maintained at 50 DEG C, and flows In plastic course of reaction, pH value controls 7.6, and gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing serosity II. Above two is mixed containing sediment slurry, in the case of being stirred continuously, adds through hydro-thermal to two kinds of mixing containing precipitate serosity Processing modification and account for the Y type molecular sieve suspension (preparing by CN102441411A embodiment 3) of total catalyst weight 15wt%, Y type divides Son sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains, aging 2.0 hours at 70 DEG C, filters, 80 DEG C be dried 9 hours, roll, extruded moulding.Wash with water purification under room temperature.Then being dried 8 hours at 120 DEG C, 530 DEG C of roastings 4 are little Time, obtain catalyst G.Catalyst composition and main character are shown in Table 1.

Comparative example 3

Comparative example 3 preparation process uses two steps be positive addition plastic and prepare hydrocracking catalyst.Catalyst forms Identical with catalyst A composition, specifically comprise the following steps that

In dissolving tank 1, add Nickel dichloride., zirconium oxychloride, liquor alumini chloridi, prepare working solution A, add in dissolving tank 2 Entering aluminum chloride, ammonium metatungstate and dilute waterglass preparation working solution B, the dilutest waterglass is containing SiO₂Dilute waterglass of 100g/L Solution 600 milliliters.Benzylamine and ammonia under agitation add solution A, and benzylamine is 0.8 with the mol ratio of active metal Ni, plastic Temperature is maintained at 50 DEG C, at the end of pH value control 7.6, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.Benzylamine and ammonia under agitation add solution B, and benzylamine is 1.0 with the mol ratio of active metal W, and gelling temperature is maintained at 50 DEG C, at the end of pH value control 7.6, gelation time control at 60 minutes, tungsten, silicon, aluminum precipitation thing serosity II.Above two is contained Sediment slurry mixes, and in the case of being stirred continuously, accounts for two kinds of mixing addition hydrothermal treatment modifications containing precipitate serosity and urges The Y type molecular sieve suspension (preparing by CN102441411A embodiment 3) of agent gross weight 15wt%, Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains, aging 2.0 hours at 70 DEG C, filter, be dried 9 hours at 80 DEG C, Roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 8 hours at 120 DEG C, 530 DEG C of roastings 4 hours, obtains catalyst H.Catalyst composition and main character are shown in Table 1.

Embodiment 5

Middle oil type hydrocracking catalyst A, B, D, E and reference catalyst F, G, H of the present invention are commented on midget plant Valency result compares.Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.5h^-1, evaluate and use Raw material is Iran's VGO heavy distillate, and its main character is shown in Table 4, and table 5 lists evaluation result.

From table 2 and table 3 it can be seen that the reunion of tungsten and nickel particles does not occurs in catalyst prepared by the inventive method, activity Metal dispersion is uniform, and can be fully contacted.From the data of table 5 can be seen that use the present invention prepare catalyst A, catalyst B, The activity of catalyst D and middle distillates oil selectivity are better than reference agent, illustrate that active metal is uniformly dispersed, and improve the activity of catalyst Rate of metal.

Table 1 catalyst composition and character

Table 2 ESCA measures catalyst surface metal relative atomic concentration (mol ratio)

Catalyst is numbered	A	B	C	D	E	F	G	H
									IW/IAl	0.18	0.17	0.18	0.19	0.17	0.12	0.11	0.11
INi/IAl	0.48	0.49	0.49	0.48	0.47	0.41	0.41	0.41

Table 3 transmissioning electric mirror determining catalyst surface WS₂Density

Table 4 raw oil main character

Table 5 evaluating catalyst result

The character of the modified molecular screen that table 6 the present invention relates to

Claims (24)

1. a preparation method for hydrocracking catalyst, including:

(1), preparation containing the mixed solution A of Ni, Al component, precipitant is added dropwise to solution A and carries out plastic reaction, generate nickeliferous, Aluminum precipitation thing serosity I；

(2), preparation containing the mixed solution B of W, Si, Al component, precipitant and solution B stream are carried out plastic reaction, generation contains Tungsten, silicon, aluminum precipitation thing serosity II；

(3), by the serosity I of step (1) gained and the serosity II mix homogeneously of step (2) gained, it is subsequently adding Y type molecular sieve and hangs Turbid liquid, more aging；

(4) the material drying, obtained by step (3), molding, washing,

(5), step (4) gained material drying again and roasting, prepared hydrocracking catalyst；

Wherein in step (1) or/and add organic amine during step (2) plastic.

The most in accordance with the method for claim 1, it is characterised in that: described Y type molecular sieve is with the shape of molecular sieve suspension Formula adds, and will be ground to 80 mesh ~ 140 mesh by molecular sieve, then add water and make suspension.

The most in accordance with the method for claim 1, it is characterised in that: the character of described Y type molecular sieve is as follows: bore dia is more than The pore volume of 1.7nm accounts for more than the 45% of total pore volume, and specific surface area is 750～900m²/ g, cell parameter at 2.423nm～ 2.545nm, relative crystallinity 95%～110%, SiO₂/Al₂O₃Mol ratio is 7～60.

The most in accordance with the method for claim 1, it is characterised in that: the boiling point of described organic amine is higher than gelling temperature, 50 DEG C～350 DEG C.

The most in accordance with the method for claim 1, it is characterised in that: described organic amine is hexamethylenetetramine, aniline, benzene Hydrazine, benzylamine, methyl diethanolamine, ethanolamine, dimethylethanolamine, n-butylamine, cyclohexylamine, phenethylamine, phenylpropanolamine, Sanya second One or more in base diamidogen, diethylenetriamines, isobutyl amine, sec-butylamine.

The most in accordance with the method for claim 1, it is characterised in that: described organic amine is benzylamine and/or ethanolamine.

The most in accordance with the method for claim 1, it is characterised in that: the addition of organic amine and the mol ratio of Ni in step (1) It is 0.1～3.0；In step (2), the addition of organic amine and the mol ratio of W are 0.1～2.0.

The most in accordance with the method for claim 1, it is characterised in that: the addition of organic amine and the mol ratio of Ni in step (1) It is 0.3～2.0；In step (2), the addition of organic amine and the mol ratio of W are 0.2～1.5.

The most in accordance with the method for claim 1, it is characterised in that: described organic amine is individually added in reaction system, or Together add in reaction system with precipitant.

The most in accordance with the method for claim 1, it is characterised in that: in described hydrocracking catalyst, with the weight of catalyst On the basis of, WO₃Content be 10wt%～50wt%, the content of NiO is 1wt%～30wt%, and W/Ni atomic ratio is 0.05～1.0.

11. in accordance with the method for claim 1, it is characterised in that: in described hydrocracking catalyst, with the weight of catalyst On the basis of, WO₃Content be 15wt%～30wt%, the content of NiO is 5wt%～20wt%, and W/Ni atomic ratio is 0.1～0.7.

12. in accordance with the method for claim 1, it is characterised in that: Si, Al of introducing in step (2) are urging in terms of oxide Weight content in agent is 20wt%～60wt%, and wherein Si accounts for Si, Al gross weight in terms of oxide in terms of silicon oxide 30wt%～80wt%；The Al introduced in step (1) counts weight content in the catalyst as 10wt%～30wt% with oxide.

13. in accordance with the method for claim 1, it is characterised in that: in described hydrocracking catalyst, containing of Y type molecular sieve Amount is 10wt%～30wt%.

14. in accordance with the method for claim 1, it is characterised in that: the precipitant described in step (1) or step (2) is carbon One or more in acid sodium, sodium bicarbonate, ammonia, sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate.

15. in accordance with the method for claim 1, it is characterised in that: the precipitant described in step (1) or step (2) is ammonia Water.

16. in accordance with the method for claim 1, it is characterised in that: in step (1) mixed solution A, Ni weight in terms of NiO Concentration is 20～80g/L, and Al is with Al₂O₃The weight concentration of meter is 60～200g/L；In step (2) mixed solution B, W is with WO₃Meter Weight concentration be 50～120g/L, Si is with SiO₂Meter weight concentration is 80～250g/L, and Al is with Al₂O₃The weight concentration of meter is 60～200g/L.

17. in accordance with the method for claim 1, it is characterised in that: in step (1) mixed solution A, Ni weight in terms of NiO Concentration is 30～60g/L, and Al is with Al₂O₃The weight concentration of meter is 90～150g/L；In step (2) mixed solution B, W is with WO₃Meter Weight concentration be 70～100g/L, Si is with SiO₂Meter weight concentration is 100～180g/L, and Al is with Al₂O₃The weight concentration of meter It is 90～150g/L.

18. in accordance with the method for claim 1, it is characterised in that: when preparing mixed solution A, the nickel source of employing is sulphuric acid One or more in nickel, nickel nitrate, basic nickel carbonate, Nickel dichloride., aluminum source is aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate In one or more；Prepare mixed solution B time, the tungsten source of employing be the one in ethyl ammonium metatungstate, ammonium metatungstate or Several；Silicon source is one or more in Ludox, sodium silicate；Aluminum source is in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate One or more.

19. in accordance with the method for claim 1, it is characterised in that: in step (1), reaction temperature is 20～90 DEG C, becomes cementing During bundle, pH value controls is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour；In step (2), reaction temperature is 30～90 DEG C, and During stream plastic, pH value controls to be 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour.

20. in accordance with the method for claim 1, it is characterised in that: in step (1), reaction temperature is 30～70 DEG C, becomes cementing During bundle, pH value controls is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3.0 hour；In step (2), reaction temperature is 40～80 DEG C, and flows During plastic, pH value controls is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3.0 hour.

21. in accordance with the method for claim 1, it is characterised in that: in step (3), aging temperature is 40～90 DEG C, time aging It is 6.0 ~ 10.0 that pH value controls, and ageing time is 0.5 ~ 6.0 hour.

22. in accordance with the method for claim 1, it is characterised in that: the drying condition described in step (4): do at 50 ~ 200 DEG C Dry 1 ~ 48 hour；Being dried described in step (5) is as follows with roasting condition: be dried 1 ~ 48 hour at 50 ~ 200 DEG C, at 450 ~ 600 DEG C Roasting 1 ~ 24 hour.

23. in accordance with the method for claim 1, it is characterised in that: containing adjuvant component in described hydrocracking catalyst, Described adjuvant component is Ti and/or Zr, counts the content in hydrocracking catalyst as 1wt%～10wt% with oxide.

24. in accordance with the method for claim 23, it is characterised in that: in hydrocracking catalyst preparation process, in preparation The compound containing adjuvant component, i.e. titanium source and/or zirconium source is added during mixed solution A；Titanium source use Titanium Nitrate, titanium sulfate, One or more in titanium chloride, zirconium source uses one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.