CN104588081B - The preparation method of the hydrocracking catalyst containing rare earth - Google Patents

Abstract

The invention discloses the preparation method of a kind of hydrocracking catalyst containing rare earth.The method prepares nickel, aluminum precipitation thing by using positive addition, cocurrent process prepares tungsten, silicon and aluminum precipitation thing, above two precipitate is mixed, after hydrothermal treatment, add Y type molecular sieve suspension, then soak with containing in rare earth ion and organic mixed solution, then molding, it is dried and roasting, prepares the hydrocracking catalyst containing rare earth.Hydrocracking catalyst prepared by the method is particularly suitable as medium oil type hydrocracking catalyst, has both had high hydrogenation cracking activity, has again high middle distillates oil selectivity, the most also has the good serviceabilities such as stronger resistance to nitrogen ability.

Description

The preparation method of the hydrocracking catalyst containing rare earth

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.

The preparation side of the open hydrocracking catalyst containing rare earth of CN1400287A, CN1400286A, CN102247881A Method, adds rare earth component, the preparation hydrocracking catalyst containing rare earth by kneading or similar kneading method.These preparation methoies Rare earth skewness in the catalyst can be caused, between rare earth component and hydrogenation cracking activity metal can not be the most abundant Contact, therefore have impact on the activity of catalyst hydrogenation cracking.

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 containing rare earth. The method improves the distribution of hydrogenation active metals in catalyst, improves the utilization rate of hydrogenation active metals, improves hydrogenation activity gold Between genus and and carrier between cooperation effect, make 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, the serosity obtained is entered Row hydrothermal treatment consists, adds the suspension of Y type molecular sieve, stirs after hydrothermal treatment consists；

(4) material step (3) obtained is after filtering, washing, by filter cake containing rare earth ion (RE³⁺) and organic Mixed solution soaks, then filters, be dried；

(5), step (4) gained material after molding, then drying and roasting, prepare the hydrocracking catalyst containing rare earth Agent.

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 ethyl ammonium metatungstate, in one or more；Silicon source can be one or more in Ludox, sodium silicate；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), the temperature of hydrothermal treatment consists can be 40～220 DEG C, preferably 70～150 DEG C.Hydrothermal treatment consists pressure is Not less than 1MPa, preferably 1MPa～3MPa.During hydrothermal treatment consists serosity, pH value controls is 6.0 ~ 10.0, preferably 6.5 ~ 9.0.Water Heat treatment time is 0.5 ~ 30 hour, preferably 1.0 ~ 24 hours.Hydrothermal treatment consists is carried out in airtight environment.

One or more in oxygen-containing organic compound and organic compounds containing nitrogen of step (4) described Organic substance.Its Middle oxygen-containing organic compound is preferably one or more in Organic Alcohol, aldehyde and ester, such as: ethylene glycol, glycerol, diethyl two One or more in alcohol, butanediol, dodecanol, hexadecanol, methylglyoxal, diglyceride, triglyceride etc., nitrogenous organic The preferred organic amine of compound, such as: one or both in ethylenediamine, nitrilotriacetic acid (NTA).Described rare earth be lanthanum, cerium, One or more in praseodymium, rubidium.RE³⁺With in organic mixed solution, RE³⁺Weight concentration be 0.01%～4.0%, best Being 0.5%～3.0%, organic concentration is 0.05～5.0 mol/L, preferably 0.5～3.0mol/L.

Rare earth ion (RE³⁺) and organic mixed liquor volume and catalyst feed volume ratio be 1.0～2.0, preferably 1.0～1.5.The mol ratio of Organic substance and the vib metals in terms of oxide and group VIII metal sum is 0.1 ~ 3.0, preferably 0.3 ~ 2.0.Soak time is 1.0～28.0h, preferably 3.0～20.0h, and the temperature of mixed solution is 20～90 Between DEG C, preferably 30～70 DEG C.

Step (4) and (5) described being dried can use this area conventional method to carry out with molding.In forming process, permissible Add the shaping assistant of routine, one or more in such as peptizer, binding agent, extrusion aid etc. as required.Described helps Crowded agent refers to the most extruded material, such as one or more in sesbania powder, white carbon black, graphite powder, citric acid etc., helps crowded The consumption of agent accounts for 1wt%～10wt% of total material butt.Drying condition described in step (4) is as follows: 50 ~ 200 DEG C be dried 1 ~ 48 hours.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.

Washing described in step (4) 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.

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 and rare earth oxide.On the basis of the weight of catalyst, WO₃Content be 10wt%～ 50wt%, preferably 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 that rare earth metal is counted with oxide as 1wt%～20wt%, preferably 3wt%～ 15wt%, the content of amorphous silica-alumina is 10wt%～80wt%, preferably 20wt%～60wt%, the content of molecular sieve be 0wt%～ 40wt%, preferably 5wt%～30wt%, alumina content is 5wt%～45wt%, preferably 10wt%～30wt%.Amorphous silica-alumina In, the content of silicon oxide is 10wt%～90wt%, preferably 30wt%～80wt%, and the content of aluminium oxide is 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.

Catalyst prepared by the inventive method uses and once passes through or complete alternation technique, and reaction temperature is 300～500 DEG C, More preferably 350～450 DEG C；Pressure is 6～20MPa, more preferably 13～17MPa；During liquid, volume space velocity is 0.5～3.0 h^-1, It is well 0.8～1.5 h^-1；Hydrogen to oil volume ratio is 400～2000:1, preferably 800～1500:1.Catalyst of the present invention has very High hydrogenation activity and intermediate oil selectivity.

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, then both are mixed warp After hydrothermal treatment consists, add molecular sieve suspension, then with rare earth and Organic substance mixed liquid dipping, make hydrocracking catalyst.This Invent by use positive addition prepare the relatively large nickel of crystal grain, aluminum precipitation thing, cocurrent process prepare the relatively small tungsten of crystal grain, silicon and Aluminum precipitation thing, mixes above two precipitate, mix slurry is carried out hydrothermal treatment consists, and the filter cake after hydrothermal treatment consists is containing There is rare earth ion (RE³⁺) and organic mixed solution in soak, it is possible to be precipitated granule not only have good pore structure and Pattern, and promote the distribution of different hydrogenation active metals, beneficially form high activity phase between active metal tungsten, nickel, make simultaneously Rare earth metal is fully contacted with hydrogenation active metals, improves the interaction between active metal and carrier, makes the hydrogenation of gained split The hydrogenation activity changing catalyst obtains good coordinating with cracking activity, makes hydrocracking catalyst have good usability Energy.

The rare earth contained hydrocracking catalyst that the present invention uses preferred Y type molecular sieve to make is particularly suitable as senior middle school's oil Type hydrocracking catalyst, had both had high hydrogenation cracking activity, has again high middle distillates oil selectivity, the most also has the most resistance to The good serviceabilities such as nitrogen ability.

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.Wt% is matter Amount mark, v% is volume fraction.

Embodiment 1

By containing the nickel chloride solution that NiO is 52g/L 520 milliliters, containing Al₂O₃The liquor alumini chloridi of 114g/L 500 milliliters, contains ZrO₂80g/L zirconyl chloride solution 200 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 1095 milliliters and containing Al₂O₃ The liquor alumini chloridi of 114g/L 400 milliliters, is mixed in solution In tank 2, add 800 milliliters of water purification dilutions, add 510 milliliters under agitation containing SiO₂Dilute water glass solution of 102g/L, Configuration solution B.Ammonia under agitation adds solution A, and gelling temperature is maintained at 52 DEG C, at the end of pH value control 7.6, plastic Time controls at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.1000mL water purification is added in retort, by ammonia and solution B also flows in addition retort, and gelling temperature is maintained at 52 DEG C, at the end of pH value control 7.6, gelation time control is at 60 points Clock, generates tungstenic, silicon, aluminum precipitation thing serosity II.After above two being mixed containing sediment slurry, slurry pH value controls, 7.6, to put Entering autoclave and carry out hydrothermal treatment consists, temperature is 80 DEG C, and pressure is 1.2MPa, and hydrothermal treatment consists is after 20 hours, in the feelings being stirred continuously Under condition, the precipitate serosity mixing addition after hydrothermal treatment consists accounts for the hydrothermal treatment modification Y type of total catalyst weight 10wt% and divides Son sieve suspension (preparing by CN102441411A embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is is dispersed in plastic and obtains To mixed serum in, filter, wash with water purification under room temperature, the material obtained lanthanum, cerium, praseodymium and rubidium rare earth ion (with On the basis of rare-earth oxide gross weight, La₂O₃Account for 48.3%, CeO₂Account for 35.2%, Pr₂O₅Account for 12.8%, Nd₂O₃Account for 3.7%) and The mixed liquor of methylglyoxal soaks 8 hours (RE in mixed solution³⁺Weight concentration 2.0wt%, organic concentration is 2.6 Mol/L), mixed solution temperature is 55 DEG C, and mixed solution is 1.0 with volume of material ratio, then filters, and is dried 8 at 110 DEG C little Time, roll, extruded moulding.Then it is dried 12 hours at 80 DEG C, 530 DEG C of roastings 4 hours, obtains catalyst A.Catalyst composition and Main character is 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 105g/L 495 milliliters.Ammonia is under agitation added Entering solution A, gelling temperature is maintained at 40 DEG C, at the end of pH value control 7.8, gelation time control at 50 minutes, generate nickeliferous, Aluminum precipitation thing serosity I.1000mL water purification is added in retort, by ammonia and solution B and flow in addition retort, gelling temperature Be maintained at 50 DEG C, and flow pH value in plastic course of reaction and control 7.8, gelation time control at 60 minutes, generate tungstenic, silicon, Aluminum precipitation thing serosity II.After above two being mixed containing sediment slurry, slurry pH value controls 8.2, puts into autoclave and carries out water Heat treatment, temperature is 110 DEG C, and pressure is 2.2MPa, and hydrothermal treatment consists is after 10 hours, in the case of being stirred continuously, at hydro-thermal Precipitate serosity mixing addition after reason accounts for the hydrothermal treatment Modified Zeolite Y suspension of total catalyst weight 15wt% 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, filtering, wash with water purification under room temperature, the material obtained is (total with rare-earth oxide at lanthanum and cerium, praseodymium rare earth ion On the basis of weight, La₂O₃Account for 50.3%, CeO₂Account for 42.1%, Pr₂O₅Account for 7.6%) and the mixed solution of ethylenediamine in soak 12 hours (RE in mixed solution³⁺Weight concentration 1.2wt%, organic concentration is 1.8mol/L), mixed solution temperature is 35 DEG C, mixed Closing solution is 1.2 with volume of material ratio, then filters, and is dried 12 hours at 70 DEG C, rolls, extruded moulding, then does at 100 DEG C Dry 10 hours, 450 DEG C of roastings 6 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 metatungstate, dilute waterglass preparation work molten in dissolving tank 2 Liquid B, the dilutest waterglass is containing SiO₂Dilute water glass solution of 120g/L 420 milliliters.Ammonia is under agitation added solution A, Gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.8, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing Serosity I.Adding in retort equipped with 1000mL water purification, by ammonia and solution B and flow in addition retort, gelling temperature is maintained at 65 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.After above two being mixed containing sediment slurry, slurry pH value controls 7.6, puts into autoclave and carries out hydrothermal treatment consists, Temperature is 90 DEG C, pressure 1.4MPa, and hydrothermal treatment consists is after 19 hours, the precipitation in the case of being stirred continuously, after hydrothermal treatment consists The mixing addition of thing serosity accounts for the hydrothermal treatment Modified Zeolite Y 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, filter, wash with water purification under room temperature, the material obtained at lanthanum, ce metal ion (with rare-earth oxide gross weight as base Standard, La₂O₃Account for 44.6%, CeO₂Account for 55.4%) rare earth ion and triglyceride mixed solution in soak 15 hours (mixed Close RE in solution³⁺Weight concentration 2.0wt%, organic concentration is 2.4 mol/L), mixed solution temperature is 55 DEG C, mixing Solution is 1.1 with volume of material ratio, then filters, and is dried 12 hours at 80 DEG C, rolls, extruded moulding, is then dried at 100 DEG C 8 hours, 600 DEG C of roastings 4 hours, obtain 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 metatungstate, dilute water Glass preparating acid sex work solution B, the dilutest waterglass is containing SiO₂Dilute water glass solution of 122g/L 490 milliliters.By ammonia Under agitation adding solution A, gelling temperature is maintained at 60 DEG C, at the end of pH value control 8.0, gelation time control is at 60 points Clock, generates nickeliferous, aluminum precipitation thing serosity I.Add in retort equipped with 1000mL water purification, by ammonia and solution B and to flow addition anti- Answering in tank, gelling temperature is maintained at 50 DEG C, and flows pH value in plastic course of reaction and control 8.0, and gelation time control is at 60 points Clock, generates tungstenic, silicon, aluminum precipitation thing serosity II.After above two being mixed containing sediment slurry, slurry pH value controls, 7.8, to put Entering autoclave and carry out hydrothermal treatment consists, temperature is 140 DEG C, and pressure is 2.8MPa, and hydrothermal treatment consists is after 12 hours, in the feelings being stirred continuously Under condition, the precipitate serosity mixing addition after hydrothermal treatment consists accounts for the hydrothermal treatment modification Y type of total catalyst weight 18wt% and divides Son sieve suspension (preparing by CN102441411A embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is is dispersed in plastic and obtains To mixed serum in, filter, under room temperature with the Spirit of Mindererus. washing of pH=8.8, the material obtained is at lanthanum, cerium, praseodymium, rubidium gold Genus ion (on the basis of the gross weight of rare-earth oxide, La₂O₃Account for 42.2%, CeO₂Account for 36.5%, Pr₂O₅Account for 14.1%, Nd₂O₃Account for 7.2%) and the mixed solution of nitrilotriacetic acid soak 12 hours (RE in mixed solution³⁺Weight concentration 1.8wt%, have The concentration of machine thing is 2.4 mol/L), mixed solution temperature is 65 DEG C, and mixed solution is 1.3 with volume of material ratio, then filters, It is dried 11 hours at 95 DEG C, rolls, extruded moulding, be then dried 10 hours at 100 DEG C, 530 DEG C of roastings 5 hours, it is catalyzed Agent D.Catalyst composition and main character are shown in Table 1.

Comparative example 1

Preparing according to method disclosed in CN101239324A, catalyst composition is shown in Table 1, specifically comprises the following steps that

(1) preparation is containing Al₂O₃Concentration is the liquor alumini chloridi 900 milliliters of 114g/L, is the nickel chloride solution of 52g/L containing NiO 520 milliliters, containing ZrO₂80g/L zirconyl chloride solution 200 milliliters, and be mixed in the container of 5 liters, add 2000 milliliters only Water dilutes.

(2) dilute water glass solution is prepared, containing SiO₂The water glass solution of 102g/L 510 milliliters, under agitation by (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 1095 milliliters, containing WO₃For 88g/L, and join under agitation (1)+(2)+ (3) in mixture；

(5) ammonia is continuously added until pH value is 7.8；

(6) whole plastic process should be carried out at 52 DEG C；

(7) mixture stands aging 2.5 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 10% of total catalyst weight, and character is shown in Table 6.

(8) filter, 110 DEG C of oven dryings 8 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters；Under room temperature Wash with the Spirit of Mindererus. of pH=8.8；Then 80 DEG C of oven dryings 12 hours, 530 DEG C of roastings 4 hours, obtain reference agent E, Composition and main character are 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 Form identical with embodiment 1, specifically comprise the following steps that the method according to embodiment 1, join by the constituent content of the catalyst A in table 1 Ratio, adds chloric acid nickel, zirconium oxychloride, chlorine aluminum solutions in dissolving tank 1, prepares working solution A, adds chlorination in dissolving tank 2 Aluminum, ammonium metatungstate and dilute waterglass preparation working solution B, the dilutest waterglass is containing SiO₂Dilute water glass solution of 102g/L 510 milliliters.Just 1000mL water purification adds in retort, and by ammonia and solution A and flow in addition retort, gelling temperature keeps At 52 DEG C, and flowing 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.Being added in retort by 1000mL water purification, by ammonia and solution B and flow in addition retort, gelling temperature is maintained at 52 DEG C, and flow pH value in plastic course of reaction and control 7.6, gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing Serosity II.After above two being mixed containing sediment slurry, slurry pH value controls 7.6, puts into autoclave and carries out hydrothermal treatment consists, temperature Degree is 80 DEG C, and pressure is 1.2MPa, and hydrothermal treatment consists is after 20 hours, the precipitation in the case of being stirred continuously, after hydrothermal treatment consists The mixing addition of thing serosity accounts for the hydrothermal treatment Modified Zeolite Y suspension of total catalyst weight 10wt% 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 2.5 hours at 70 DEG C, filter, wash with water purification under room temperature, the material obtained lanthanum, cerium, praseodymium and rubidium rare earth metal from Son (on the basis of rare-earth oxide gross weight, La₂O₃Account for 48.3%, CeO₂Account for 35.2%, Pr₂O₅Account for 12.8%, Nd₂O₃Account for 3.7%) 8 hours (RE in mixed solution are soaked and in the mixed liquor of methylglyoxal³⁺Weight concentration 2.0wt%, organic concentration is 2.6 mol/L), mixed solution temperature is 55 DEG C, and mixed solution is 1.0 with volume of material ratio, then filters, and is dried 8 at 110 DEG C Hour, roll, extruded moulding.Then it is dried 12 hours at 80 DEG C, 530 DEG C of roastings 4 hours, obtains catalyst F.Catalyst forms And main character is 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 Form identical with embodiment 1, specifically comprise the following steps that

According to the method for embodiment 1, by the constituent content proportioning of the catalyst A in table 1, in dissolving tank 1, add chloric acid Nickel, zirconium oxychloride, chlorine aluminum solutions, prepare working solution A, adds aluminum chloride, 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 102g/L 510 milliliters.Ammonia is under agitation added Entering solution A, gelling temperature is maintained at 52 DEG C, at the end of pH value control 7.6, gelation time control at 60 minutes, generate nickeliferous, Aluminum precipitation thing serosity I.Ammonia under agitation adds solution B, and gelling temperature is maintained at 52 DEG C, at the end of pH value control 7.6, Gelation time control at 60 minutes, tungsten, silicon, aluminum precipitation thing serosity II.After above two is mixed containing sediment slurry, slurry pH value Controlling 7.6, put into autoclave and carry out hydrothermal treatment consists, temperature is 80 DEG C, and pressure is 1.2MPa, and hydrothermal treatment consists is after 20 hours, In the case of being stirred continuously, the mixing of precipitate serosity after hydrothermal treatment consists add account for total catalyst weight 10wt% through hydro-thermal Processing Modified Zeolite Y suspension (preparing by CN102441411A embodiment 3), 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 2.5 hours at 70 DEG C, filter, wash with water purification under room temperature.The thing obtained Expect lanthanum, cerium, praseodymium and rubidium rare earth ion (on the basis of rare-earth oxide gross weight, La₂O₃Account for 48.3%, CeO₂Account for 35.2%, Pr₂O₅Account for 12.8%, Nd₂O₃Account for 3.7%) and the mixed liquor of methylglyoxal in soak 8 hours (RE in mixed solution³⁺Weight Concentration 2.0wt%, organic concentration is 2.6 mol/L), mixed solution temperature is 55 DEG C, and mixed solution with volume of material ratio is 1.0, then filter, then filter, be dried 8 hours at 110 DEG C, roll, extruded moulding.Then 80 DEG C be dried 12 hours, 530 DEG C roasting 4 hours, obtains catalyst G.Catalyst composition and main character are shown in Table 1.

Embodiment 5

Middle oil type hydrocracking catalyst A, B, D and reference catalyst E, F, G of the present invention are evaluated on midget plant Result compares.Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.5h^-1, evaluate with former 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
								IW/IAl	0.18	0.18	0.17	0.17	0.10	0.12	0.12
INi/IAl	0.48	0.47	0.47	0.48	0.41	0.42	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 (25)

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, the serosity obtained is carried out water Heat treatment, adds the suspension of Y type molecular sieve, stirs after hydrothermal treatment consists；

(4) material, obtained by step (3) is through filtering, after washing, by filter cake containing rare earth ion and organic mixed solution Middle immersion, then filters, and is dried；

(5), step (4) gained material after molding, then drying and roasting, prepare the hydrocracking catalyst containing rare earth；

Wherein, one or more in oxygen-containing organic compound and organic compounds containing nitrogen of step (4) described Organic substance.

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: 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.

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 15wt%～30wt%, the content of NiO is 5wt%～20wt%, and W/Ni atomic ratio is 0.1～0.7.

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

The most in accordance with the method for claim 1, it is characterised in that: in described hydrocracking catalyst, the content of Y type molecular sieve For 5wt%～30wt%.

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

The most 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.

The most 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 SiO₂The weight concentration of meter is 80～250g/L, and Al is with Al₂O₃The weight concentration of meter It is 60～200g/L.

11. 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 SiO₂The weight concentration of meter is 100～180g/L, and Al is with Al₂O₃The weight of meter is dense Degree is 90～150g/L.

12. 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.

13. 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.

14. 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.

15. in accordance with the method for claim 1, it is characterised in that: in step (3), the temperature of hydrothermal treatment consists is 40～220 DEG C, Hydrothermal treatment consists pressure is 1MPa～3MPa, and during hydrothermal treatment consists serosity, pH value controls is 6.0 ~ 10.0, hydrothermal conditions is 0.5 ~ 30 hours.

16. in accordance with the method for claim 1, it is characterised in that: in step (3), the temperature of hydrothermal treatment consists is 70～150 DEG C,

Hydrothermal treatment consists pressure is 1MPa～3MPa, and during hydrothermal treatment consists serosity, pH value controls is 6.5 ~ 9.0, and hydrothermal conditions is 1.0 ~ 24 hours.

17. in accordance with the method for claim 1, it is characterised in that: the rare earth described in step (4) is in lanthanum, cerium, praseodymium, neodymium One or more.

18. in accordance with the method for claim 17, it is characterised in that: step (4) described oxygen-containing organic compound be Organic Alcohol, One or more in aldehyde and ester, organic compounds containing nitrogen is organic amine.

19. in accordance with the method for claim 17, it is characterised in that: step (4) described oxygen-containing organic compound be ethylene glycol, One or many in glycerol, diethylene glycol, butanediol, dodecanol, hexadecanol, methylglyoxal, diglyceride, triglyceride Kind, organic compounds containing nitrogen is one or both in ethylenediamine, nitrilotriacetic acid.

20. in accordance with the method for claim 1, it is characterised in that: step (4) described rare earth ion and organic mixing are molten In liquid, the weight concentration of rare earth ion is 0.01%～4.0%, and organic concentration is 0.05～5.0 mol/L, rare earth ion and Organic mixed liquor volume and step (4) filter cake volume ratio are 1.0～2.0；Soak time is 1.0～28.0h, mixes molten The temperature of liquid is 20～90 DEG C.

21. in accordance with the method for claim 1, it is characterised in that: in step (4), Organic substance and W and Ni in terms of oxide The mol ratio of sum is 0.1 ~ 3.0.

22. in accordance with the method for claim 1, it is characterised in that: in step (4), introduce the amount of rare earth metal with oxide Meter content in hydrocracking catalyst is 1wt%～20wt%.

23. 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.

24. 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.

25. in accordance with the method for claim 24, 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.