CN106179462A

CN106179462A - A kind of hydrocracking catalyst and preparation method thereof

Info

Publication number: CN106179462A
Application number: CN201510212113.2A
Authority: CN
Inventors: 冯小萍; 王海涛; 徐学军; 刘东香
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2015-04-30
Filing date: 2015-04-30
Publication date: 2016-12-07
Anticipated expiration: 2035-04-30
Also published as: CN106179462B

Abstract

The invention discloses a kind of hydrocracking catalyst and preparation method thereof.This catalyst is body phase hydrocracking catalyst, and its composition includes hydrogenation active metals component W and Ni, aluminium oxide, silicon oxide and molecular sieve；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃The ratio of weight content be 1.2:1 ~ 6.0:1, the weight content of table phase active metal component NiO is 1.2:1 ~ 5.0:1 with the ratio of the weight content of body phase active metal component NiO.The advantages such as this catalyst is particularly well-suited in single-stage hydrocracking technical process, has liquid yield high, good product quality.

Description

A kind of hydrocracking catalyst and preparation method thereof

Technical field

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

Background technology

At present, worldwide petroleum resources are not enough, and crude quality is deteriorated year by year, intermediate oil demand increases, petroleum chemicals upgrading and environmental regulation are more and more strict, heavy oil lighting is all greatly facilitated, and constitutes the very strong driving force of accelerated development hydrogen addition technology.Hydrocracking technology to be mainly characterized by adaptability to raw material strong, products scheme, purpose product selectivity height, good product quality and added value are high, can be directly produced multiple high-quality oil product (such as gasoline, jet fuel, diesel oil, lube 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 carries out cracking and the conversion process of the hydrogenation reaction lighter molecule of generation with hydrogen at catalyst surface, and the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs simultaneously.Hydro carbons cracking reaction in hydrocracking process is to carry out on the acid centre of catalyst, it then follows carbon ion reaction mechanism, with the generation of hydro carbons isomerization reaction while hydrogenation, cracking reaction.Hydrocracking catalyst is made up of hydrogenation component and acidic components, and both add the most by a certain percentage, makes hydrogenation and cracking performance reach balance, its effect be hydrocarbon mixture be fully hydrogenated with, cracking and isomerization orienting response.Therefore, the catalyst that distillate hydrocracking process needs should possess stronger hydrogenation sites moderate acid centre again.

In general, hydrocracking catalyst can be prepared using the following, such as: infusion process, kneading method, beating method, coprecipitation, may use ion exchange for noble metal.Infusion process and kneading method be all first carrier and acidic components are made after add metal again, and coprecipitated rule is acidic components and metal coprecipitation gets off, and metal loading is unrestricted.The hydrogenation sites of this type of catalyst be reactant molecule can be close catalyst channel surfaces on, and catalyst activity metal prepared by coprecipitation method does not exist entirely in catalyst channel surfaces, amount of activated metal be present in caltalyst mutually in, coprecipitation method is prepared the tenor of catalyst table phase and is decide catalyst activity.

US6299760、US6156695、US6537442、US6440888、US6652738 Disclose containing group VIII/VI B race active metal component for the bulk phase catalyst and preparation method thereof of hydrotreating.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.nullHydrocracking catalyst disclosed in US 3954671，Hydrogenation conversion catalyst disclosed in US 4313817，The hydrocracking catalyst of nitrogen-resistant type fecund intermediate oil disclosed in CN1253988A，Heavy hydrocarbons hydrocraking catalyst disclosed in CN1253989A，These catalyst use coprecipitation method to prepare，Owing to the deposition condition of different hydrogenation active metals is different，The distribution causing different hydrogenation active metals is not easily controlled，Thus affect the interaction relationship between distribution and the different activities metal of different hydrogenation active metals and between active metal and carrier，So that hydrogenation activity can not well be coordinated with cracking activity，Simultaneously，These caltalyst phase active metallic contents are more，Table phase active metallic content is relatively fewer，Hydrogenation sites density is less，Finally affect catalyst is hydrocracked performance.Disclosed in CN101239324A, high activity, medium oil type hydrocracking catalyst are addition precipitant alkalescence ammoniac compounds in the serosity that amorphous silica-alumina, auxiliary agent and active metal are made into, and carry out precipitation, are subsequently adding molecular sieve suspension and make.The method also uses coprecipitation method to prepare, however it remains table phase active metallic content is relatively fewer, and hydrogenation sites density is less, different hydrogenation active metals skewness, hydrogenation active metals and and carrier between act on the problem that harmonious relations are bad.

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；Being subsequently adding the suspension mix homogeneously of Y type molecular sieve, through filtration, dry, molding more scrubbed, dry, roasting prepares hydrocracking catalyst.The method utilizes the releasing of gas in roasting process, under the percussion of gas, increase the pore volume of catalyst, specific surface area, more metal active position is made to be exposed to the surface of catalyst, but this kind of method can make cell channels collapse, pore size distribution disperse, mechanical strength reduces, and causing active metal localized clusters, the metal active position come out is limited.

Coprecipitation method prepares catalyst technology, use different coprecipitation mode, Gelation Conditions etc., all active metallic content on channel surfaces in catalyst and the interaction relationship between active center density, the distribution of different hydrogenation active metals and different hydrogenation active metals and between hydrogenation active metals and carrier can be had a great impact.The coprecipitation method of above-mentioned employing can make the distribution of different hydrogenation active metals be not easily controlled, thus affect the interaction relationship between distribution and the different hydrogenation active metals of different hydrogenation active metals and between active metal and carrier, so that hydrogenation activity can not well be coordinated with cracking activity, simultaneously, in catalyst, table phase active metallic content is less and active center density is relatively low, and finally affect catalyst is hydrocracked performance.Therefore, how to regulate and control the distribution of hydrogenation active metals, make to have between hydrogenation active metals component and between hydrogenation active metals component and carrier suitable mating reaction, how to increase table phase active metallic content and active center density in catalyst, improve the utilization rate of hydrogenation active metals component, be to improve coprecipitation method to prepare the key of hydrocracking catalyst Hydrogenation.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of body phase hydrocracking catalyst and preparation method thereof.The method improves the distribution of hydrogenation active metals in catalyst, improve between hydrogenation active metals and and carrier between cooperation effect, improve catalyst surface active bit density, improve the utilization rate of hydrogenation active metals, catalyst pore structure is reasonable simultaneously, active metal disperses evenly, makes catalyst have higher serviceability.

Hydrocracking catalyst of the present invention is body phase hydrocracking catalyst, and its composition includes hydrogenation active metals component W and Ni, aluminium oxide, silicon oxide and molecular sieve；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃The ratio of weight content be 1.2:1 ~ 6.0:1, preferably 1.8:1 ~ 4.5:1, the weight content of table phase active metal component NiO is 1.2:1 ~ 5.0:1, preferably 1.5 ~ 3.5:1 with the ratio of the weight content of body phase active metal component NiO.

In hydrocracking catalyst of the present invention, on the basis of the weight of catalyst, WO₃It is 20%～65% with the total content of NiO, it is preferably 30%～50%, W/Ni atomic ratio is 0.05～1.0, preferably 0.1～0.7, the content of silicon oxide is 1%～40%, preferably 5%～35%, the content of aluminium oxide is 10%～40%, being preferably 15%～40%, the content of molecular sieve is 5wt%～20wt%, preferably 5wt%～15wt%.

In the present invention, table phase active metal component WO₃Weight content be table mutually in WO₃Weight content, body phase active metal component WO₃Weight content be WO in catalyst₃Weight content；The weight content of table phase active metal component NiO is the weight content of table middle NiO mutually, and the weight content of body phase active metal component NiO is the weight content of NiO in catalyst.

The character of hydrocracking catalyst of the present invention is as follows: specific surface area is 250～650m²null/g，Pore volume is 0.35～0.80mL/g，Pore-size distribution is as follows: the pore volume shared by the hole of a diameter of below 4nm accounts for the 1% ~ 20% of total pore volume，Pore volume shared by the hole of a diameter of 4 ~ 8nm account for total pore volume for 55% ~ 80%，Pore volume shared by the hole of a diameter of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume，The pore volume of a diameter of more than 15nm account for total pore volume for 0.1% ~ 5.0%，Preferably pore-size distribution is as follows: the pore volume shared by the hole of a diameter of below 4nm accounts for the 5% ~ 17% of total pore volume，Pore volume shared by the hole of a diameter of 4 ~ 8nm account for total pore volume for 61% ~ 75%，Pore volume shared by the hole of a diameter of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume，The pore volume of a diameter of more than 15nm account for total pore volume for 0.5% ~ 5.0%.

In hydrocracking catalyst of the present invention, it is also possible to containing adjuvant component, described adjuvant component is the IVth B race metal, and the IVth B family metal oxide content in hydrocracking catalyst is 1wt%～10wt%.Described IVth B race metal is preferably Ti and/or Zr.

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

(1), prepare the mixed solution A containing 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, 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 most aging, after aging end, filter, the material water vapour obtained carries out hydrothermal treatment consists, wherein adds carbamide during hydrothermal treatment consists；

(4) material, obtained by step (3), after making beating uniformly, adds the suspension of molecular sieve, stirs under stirring condition, filter, obtain material drying, molding, washing；

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

The preferred Y type molecular sieve of institute's addition molecular sieve in the inventive method.Y type molecular sieve is usually and adds with the form of molecular sieve suspension, will be ground to 80 mesh ~ 140 mesh, preferably 100 mesh ~ 120 mesh by molecular sieve, then add water and make suspension.Described Y type molecular sieve is the conventional Y type molecular sieve used by hydrocracking catalyst.

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

In step (1) mixed solution A, Ni weight concentration in terms of NiO is 5～80g/L, and preferably 10～60g/L, Al is with Al₂O₃The weight concentration of meter is 10～80g/L, preferably 20～60g/L.In step (2) mixed solution B, W is with WO₃The weight concentration of meter is 10～100g/L, preferably 20～90g/L.Si is with SiO₂Weight concentration is 10～120g/L, and preferably 20～80g/L, Al is with Al₂O₃The weight concentration of meter is 10～80g/L, preferably 20～60g/L.When preparing mixed solution A, the general nickel source used can be one or more in nickel sulfate, nickel nitrate, basic nickel carbonate, Nickel dichloride., and aluminum source can be one or more in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate etc..When preparing mixed solution B, the general tungsten source used can be one or more in ethyl ammonium metatungstate, ammonium metatungstate；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 5wt%～70wt% with oxide, preferably 10wt%～55wt%, wherein Si accounts for 10wt%～90wt% of Si, Al gross weight in terms of oxide, preferably 30wt%～80wt% in terms of silicon oxide；The Al introduced in step (1) counts weight content in the catalyst as 5wt%～45wt%, preferably 10wt%～30wt% with oxide.

In step (2), reaction temperature is 30～90 DEG C, preferably 40～80 DEG C.And pH value control is 6.0 ~ 11.0 when flowing plastic, 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 carry out can also carrying 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, preferably 6.5 ~ 9.0.Ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.

Hydrothermal conditions described in step (3) is as follows: carry out under airtight container, and temperature is 200 ~ 300 DEG C, preferably 210 ~ 260 DEG C, and pressure is 1.0 ~ 8.0MPa, preferably 3.0 ~ 6.0MPa, and the process time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours.

In step (3), during hydrothermal treatment consists, the addition of carbamide is 0.5:1 ~ 10.0:1, preferably 2.0:1 ~ 8.0:1 with the mol ratio of active metal (tungsten, nickel) atom total amount in catalyst.

Being dried described in step (4), molding can use this area conventional method to carry out.Described being dried typically is dried 1 ~ 48 hour at 50 ~ 200 DEG C.In forming process, the shaping assistant of routine, one or more in such as peptizer, extrusion aid etc. can be added as required.Described peptizer is one or more in hydrochloric acid, nitric acid, sulphuric acid, acetic acid, oxalic acid etc., described extrusion aid refers to the most extruded material, such as one or more in sesbania powder, white carbon black, graphite powder, citric acid etc., the consumption of auxiliary agent accounts for 1wt%～10wt% of total material butt.Washing is usually and uses deionized water or wash containing decomposable asymmetric choice net salt (such as ammonium acetate, ammonium chloride, ammonium nitrate etc.) solution, is washed till neutrality.Described molding, the shape of catalyst can be as needed for lamellar, spherical, cylindrical bars and irregular bar (Herba Trifolii Pratentis, Herba Galii Bungei), preferably cylindrical bars and irregular bar (Herba Trifolii Pratentis, Herba Galii Bungei).The diameter of carrier can be slice and the thick bar of ＞ 2.5mm of 0.8 ~ 2.0mm.

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

In hydrocracking catalyst of the present invention, it is also possible to containing adjuvant component, described adjuvant component is the IVth B race metal, and the 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, preferably during preparation mixed solution A, add the compound containing adjuvant component, 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 Y type molecular sieves that can be used in hydrocracking catalyst in prior art, such as: CN101343068A, CN1508228A, CN101450319A, CN Y type molecular sieve disclosed in 1209357A.Y type molecular sieve disclosed in the preferred CN101343068A of the present invention, its character is as follows: specific surface area is 700m²/ g～950m²/ g, preferably 800～950m²/ g, total pore volume 0.30mL/g～0.55mL/g, relative crystallinity 90%～130%, SiO₂/Al₂O₃Mol ratio 30～150, preferably 50～150, cell parameter is 2.425～2.445nm, meleic acid amount 0.1～1.0mmol/g, and B-acid L acid is more than 7.0, preferably more than 8.0, sodium oxide content≤0.05wt%, is preferably≤0.01wt%.

Hydrocracking catalyst of the present invention is the body phase hydrocracking catalyst of oxidation state, and conventional method can be used before use to carry out presulfurization.

The heavy charge scope that catalyst prepared by the inventive method is suitable for is the widest, they include the various hydrocarbon ils such as vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, catalytic cracking recycle oil, can also be applied in combination, 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 (the acid sedimentation method i.e. alkaline precipitating agent is added in the metal salt solution of acidity precipitate) to prepare nickel aluminum mixed sediment, uses parallel flow precipitation to prepare tungsten, silicon and aluminum mixed sediment, then by aging after both mixing.The present invention prepares the relatively large nickel of crystal grain, aluminum precipitation thing by using positive addition, cocurrent process prepares the relatively small tungsten of crystal grain, silicon and aluminum precipitation thing, above two precipitate is mixed, the distribution of different hydrogenation active metals can be controlled, be conducive to being formed between active metal tungsten, nickel high activity phase, and improve the interaction between active metal and carrier, make the hydrogenation activity of the hydrocracking catalyst of gained obtain good coordinating with cracking activity, improve the serviceability of hydrocracking catalyst.

In the preparation method of catalyst of the present invention, the material obtained after co-precipitation steam treatment under appropriate conditions also adds carbamide, and carbamide is decomposed into NH in high temperature environments₃And CO₂, NH₃And CO₂NH is generated in the presence of water vapour₄ ⁺And HCO₃ ^-Ion, NH₄ ⁺And HCO₃ ^-The microscopic pattern of material is had a significant impact by ion at high temperature under high pressure, before hydrothermal treatment consists, material phase structure is cylinder, after hydrothermal treatment consists, material phase structure is changed into, from cylinder, the irregular body that irregular lamellar is piled into, the transformation of this structure make active metal table mutually in distribution substantially increase, and disperse evenly, be conducive to improving the density of Adsorption.Additionally, add carbamide when steam treatment, make the transformation of material form can also make the pore size distribution of catalyst more uniformly, be conducive to improving the mechanical strength of catalyst.

In catalyst of the present invention, different hydrogenation active metals there is good distribution, surface activity bit density is big, cooperation between active metal is good, and active metal utilization rate is high, and improves the interaction between active metal and carrier, the hydrogenation activity making the hydrocracking catalyst of gained obtains good coordinating with cracking activity, catalyst pore structure is reasonable simultaneously, and mechanical strength is high, has the hydrogenation cracking activity of excellence.

The hydrocracking catalyst that the present invention uses preferred Y type molecular sieve to make is particularly suitable as medium oil type hydrocracking catalyst, both there is high hydrogenation cracking activity, there is again high middle distillates oil selectivity, the most also there is the good serviceabilities such as stronger resistance to nitrogen ability.Catalyst of the present invention 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；During liquid, volume space velocity 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 advantages such as this catalyst, in single-stage hydrocracking technical process, has liquid yield high, good product quality.

Detailed description of the invention

In the present invention, specific surface area and pore volume use low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter use x-ray diffraction method, silica alumina ratio uses chemical method, sodium content uses plasma emission spectrometry, catalyst table phase active metallic content uses x-ray photoelectron spectroscopy (XPS) to measure, and caltalyst phase active metallic content uses inductively coupled plasma atomic emission spectrum (ICP-AES) to measure, and transmission electron microscope (TEM) measures catalyst surface WS₂Density.Mechanical strength is to use side pressure method to measure.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Respectively Nickel dichloride., liquor alumini chloridi and zirconium oxychloride being dissolved in water purification, be configured to mixed solution A, in mixed solution A, the weight concentration of NiO is 21g/L, Al₂O₃Weight concentration be 5g/L, ZrO₂Weight concentration 5g/L.Respectively ammonium metatungstate, liquor alumini chloridi are dissolved in water purification, add dilute water glass solution, be configured to mixed solution B, WO in mixed solution B₃Weight concentration be 25g/L, Al₂O₃Weight concentration be 18g/L, SiO₂Weight concentration be 20g/L.The ammonia that concentration is 10wt% is under agitation added solution A, and gelling temperature is maintained at 55 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 ammonia that concentration is 10wt% and solution B and flow in addition retort, gelling temperature is maintained at 55 DEG C, and flows 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.By above two containing aging after sediment slurry mixing, ageing time 2 hours, aging temperature 75 DEG C, at the end of aging, pH value controls 7.6, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, the condition of hydrothermal treatment consists is: the mol ratio of carbamide and active metal atom total amount is 7:1, temperature is 230 DEG C, pressure is 4.5MPa, the process time is 3 hours, after process, filter cake is pulled an oar, the Y type molecular sieve suspension (in terms of butt) (preparing by CN101343068A embodiment 7) accounting for total catalyst weight 10wt% is added in mix slurry, Y type molecular sieve character is shown in Table 6, it is made to be dispersed in mixed serum, filter, it is dried 8 hours at 100 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 10 hours at 80 DEG C, 550 DEG C of roastings 4 hours, obtains catalyst A.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 2

Method according to embodiment 1, by the constituent content proportioning of the catalyst B in table 1, in dissolving tank 1, add nickel nitrate, titanium chloride, aluminum nitrate solution, prepare working solution A, after addition aluminum nitrate, ammonium metatungstate are dissolved in water purification in dissolving tank 2, add dilute waterglass preparation working solution B.The ammonia that concentration is 15wt% is under agitation added solution A, and gelling temperature is maintained at 45 DEG C, at the end of pH value control 8.0, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.800mL water purification is added in retort, by ammonia that concentration is 15wt% and solution B and flow in addition retort, gelling temperature is maintained at 50 DEG C, and flows pH value in plastic course of reaction and control 8.2, gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing serosity II.By above two containing aging after sediment slurry mixing, ageing time 3 hours, aging temperature 70 DEG C, at the end of aging, pH value controls 8.0, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, the condition of hydrothermal treatment consists is: the mol ratio of carbamide and active metal atom total amount is 6:1, temperature is 250 DEG C, pressure is 3.5MPa, the process time is 3 hours, after process, filter cake is pulled an oar, the Y type molecular sieve suspension (in terms of butt) (preparing by CN101343068A embodiment 7) accounting for total catalyst weight 12wt% is added to serosity, Y type molecular sieve character is shown in Table 6, it is made to be dispersed in the mixed serum that plastic obtains, filter, it is dried 7 hours at 120 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 12 hours at 100 DEG C, 500 DEG C of roastings 5 hours, obtains catalyst B.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

Method according to embodiment 1, by the constituent content proportioning of the catalyst C in table 1, in dissolving tank 1, add Nickel dichloride., liquor alumini chloridi, prepare working solution A, after addition aluminum chloride, ammonium metatungstate are dissolved in water purification in dissolving tank 2, add dilute waterglass preparation working solution B.The ammonia that concentration is 10wt% is under agitation added solution A, and gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, gelation time control, at 90 minutes, generates nickeliferous, aluminum precipitation thing serosity I.Add in retort equipped with 900mL water purification, by ammonia that concentration is 10wt% and solution B and flow in addition retort, gelling temperature is maintained at 45 DEG C, and flows pH value in plastic course of reaction and control 8.0, gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing serosity II.Above two is mixed containing sediment slurry.By above two containing aging after sediment slurry mixing, ageing time 2.5 hours, aging temperature 72 DEG C, at the end of aging, pH value controls 7.8, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, the condition of hydrothermal treatment consists is: the mol ratio of carbamide and active metal atom total amount is 4:1, temperature is 240 DEG C, pressure is 6.0MPa, the process time is 4 hours, after process, filter cake is pulled an oar, the Y type molecular sieve suspension (in terms of butt) (preparing by CN101343068A embodiment 7) accounting for total catalyst weight 15wt% is added to precipitate serosity, Y type molecular sieve character is shown in Table 6, it is made to be dispersed in the mixed serum that plastic obtains, filter, it is dried 10 hours at 70 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 8 hours at 80 DEG C, 530 DEG C of roastings 4.5 hours, obtains catalyst C.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

Method according to embodiment 1, by the constituent content proportioning of the catalyst D in table 1, in dissolving tank 1, add Nickel dichloride., liquor alumini chloridi, preparating acid sex work solution A, after addition aluminum chloride, ammonium metatungstate are dissolved in water purification in dissolving tank 2, add dilute waterglass preparating acid sex work solution B.The ammonia that concentration is 10wt% is under agitation added solution A, and gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, gelation time control, at 80 minutes, generates nickeliferous, aluminum precipitation thing serosity I.Add in retort equipped with 1000mL water purification, by ammonia that concentration is 10wt% and solution B and flow in addition retort, gelling temperature is maintained at 65 DEG C, and flows pH value in plastic course of reaction and control 8.0, gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing serosity II.Above two is mixed containing sediment slurry.By above two containing aging after sediment slurry mixing, ageing time 2 hours, aging temperature 75 DEG C, at the end of aging, pH value controls 7.8, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, the condition of hydrothermal treatment consists is: the mol ratio of carbamide and active metal atom total amount is 3.0:1, temperature is 260 DEG C, pressure is 5.0MPa, the process time is 5 hours, after process, filter cake is pulled an oar, the Y type molecular sieve suspension (in terms of butt) (preparing by CN101343068A embodiment 7) accounting for total catalyst weight 8wt% is added to the mixing of precipitate serosity, Y type molecular sieve character is shown in Table 6, it is made to be dispersed in the mixed serum that plastic obtains, filter, it is dried 10 hours at 80 DEG C, roll, extruded moulding.Wash with water purification under room temperature, be then dried 10 hours at 110 DEG C, 480 DEG C of roastings 6 hours, obtain catalyst D.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

Preparing according to method disclosed in CN101239324A, catalyst composition forms identical with embodiment 1, specifically comprises the following steps that

(1) by Al₂O₃Concentration is the liquor alumini chloridi 220 milliliters of 120g/L, containing the nickel chloride solution that NiO is 44g/L 18 milliliters, containing ZrO₂100g/L zirconyl chloride solution 50 milliliters is mixed in the container of a 5L, adds 2000 milliliters of water purification dilutions；

(2) dilute water glass solution is prepared, containing SiO₂(2) are added in (1) by the water glass solution of 100g/L 310 milliliters under agitation；

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

(4) preparation sodium tungstate solution 240 milliliters, containing WO₃For 80g/L, and join under agitation in the mixture of (1)+(2)+(3)；

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

(6) whole plastic process should be carried out at 55 DEG C；

(7) mixture 75 DEG C stand aging 2.0 hours, aging at the end of pH value control 7.6；Adding the Y type molecular sieve suspension (in terms of butt) (preparing by CN101343068A embodiment 7) accounting for total catalyst weight 10wt% before aging, Y type molecular sieve character is shown in Table 6,

(8) filter, 100 DEG C of oven dryings 8 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters；With the Spirit of Mindererus. washing of pH=8.8 under room temperature；Then 80 DEG C of oven dryings 10 hours, 550 DEG C of roastings 4 hours, obtain reference agent E, catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 2

By embodiment 1 catalyst composition and preparation method, it is added without carbamide during hydrothermal treatment consists, prepares reference agent F.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 3

By embodiment 1 catalyst composition and preparation method, it is added without carbamide during hydrothermal treatment consists, but adds NH₃, NH₃Being 7:1 with the mol ratio of active metal atom total amount, temperature is 230 DEG C, and pressure is 4.5MPa, and the process time is 3 hours, prepares reference agent G.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 4

By embodiment 1 catalyst composition and preparation method, it is added without carbamide during hydrothermal treatment consists, but adds CO₂, CO₂Being 7:1 with the mol ratio of active metal atom total amount, temperature is 230 DEG C, and pressure is 4.5MPa, and the process time is 3 hours, prepares reference agent H.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 5

As disclosed in CN103055923A prepared by method, and catalyst composition forms identical with embodiment 1, specifically comprises the following steps that

(1) the acid solution A of preparation: form by embodiment 1 catalyst, Nickel dichloride., ammonium metatungstate, zirconium oxychloride are mixed in the container of 5 liters, adds 1000 milliliters of water purification dilutions.Preparation is containing with SiO in embodiment 1₂Dilute water glass solution that content is identical, adds in mixing salt solution above under agitation.

(2) configuration alkaline solution B: configuration is containing with Al in embodiment 1₂O₃The alkaline sodium aluminate solution 3000mL that content is identical.

(3) by solution A, solution B and CO₂Gas also flows plastic in addition plastic cans, and gelling temperature is maintained at 50 DEG C, and pH value is 7.6.CO the most used₂Gas concentration is 45v%, adds CO₂The total amount of gas and the Al in alkaline solution₂O₃Mol ratio 3, adjusts A, B solution flow velocity, it is ensured that drip off simultaneously, constant to ensure that catalyst distribution uniformly forms.

(4) after cemented into bundles, in the case of being stirred continuously, add the Y type molecular sieve suspension (in terms of butt) (preparing by CN101343068A embodiment 7) accounting for total catalyst weight 10wt%, Y type molecular sieve character is shown in Table 6, make it be dispersed in the mixed serum that plastic obtains, stand aging 2 hours at about 75 DEG C.

(5) material filtering step (4) obtained, filter cake is dried 8 hours at 100 DEG C, rolls, extruded moulding.Wash with water purification under room temperature.Then it is dried 10 hours at 80 DEG C, 550 DEG C of roastings 4 hours, obtains catalyst I.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 5

Middle oil type hydrocracking catalyst A, B, C, D and reference catalyst E, F, G, H, I evaluation result on midget plant of the present invention are compared.Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.5h during liquid^-1, evaluation 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 catalyst table phase active metallic content prepared of the inventive method is apparently higher than body phase active metallic content, in catalyst, activity increases considerably mutually.Can be seen that the activity of catalyst A, B, C, D of using the present invention to prepare and middle distillates oil selectivity are better than reference agent from the data of table 5, illustrate that catalyst activity rate of metal prepared by the inventive method is high, catalyst reaction activity significantly improves.

Table 1 catalyst composition and character

Catalyst is numbered	A	B	C	D	E
						Catalyst forms
NiO, wt%	20	15	18	21	20
						WO₃, wt%	24	25	23	23	24
SiO₂, wt%	19	16	22	20	19
						Al₂O₃, wt%	22	25	22	28	22
Y molecular sieve, wt%	10	12	15	8	10
						Other/wt%	ZrO₂/5.0	TiO₂/7.0	-	-	ZrO₂/5.0
Catalyst property
						Specific surface area, m²/g	387	384	381	395	288
Pore volume, mL/g	0.408	0.392	0.397	0.401	0.285
						Mechanical strength, N/mm	22.1	22.2	23.3	22 .4	19.7
Pore size distribution, %
						＜ 4nm	13.26	14.18	12.29	13.01	52.33
4nm~8nm	67.23	67.52	69.14	68.65	44.15
						8nm~15nm	15.36	14.58	15.92	15.21	1.41
＞ 15nm	3.15	3.72	2.65	2.13	2.11

Continued 1

Catalyst is numbered	F	G	H	I
					Catalyst forms
NiO, wt%	20	20	20	20
					WO₃, wt%	24	24	24	24
SiO₂, wt%	19	19	19	19
					Al₂O₃, wt%	22	22	22	22
Y molecular sieve, wt%	10	10	10	10
					Other/wt%	ZrO₂/5.0	ZrO₂/5.0	ZrO₂/5.0	ZrO₂/5.0
Catalyst property
					Specific surface area, m²/g	345	365	337	312
Pore volume, mL/g	0.382	0.371	0.387	0.355
					Intensity, N/mm	19.4	18.3	18.7	17.8
Pore size distribution, %
					＜ 4nm	28.18	24.29	25.99	14.25
4nm~8nm	34.52	38.14	33.65	35.42
					8nm~15nm	24.48	22.92	24.23	36.84
＞ 15nm	12.82	14.65	16.13	13.49

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

Catalyst is numbered	A	B	C	D	E
						Table phase I_W/ body phase I_W	4.18	3.91	3.64	3.34	0.99
Table phase I_Ni/ body phase I_Ni	3.25	3.04	2.99	2.26	0.94

Continued 2

Catalyst is numbered	F	G	H	I
					Table phase I_W/ body phase I_W	1.02	1.09	1.10	1.22
Table phase I_Ni/ body phase I_Ni	1.05	1.10	1.04	1.18

Table 3 catalyst surface WS₂Density

Catalyst is numbered	A	B	C	D	E	F	G	H	I
										WS₂Density, grain/100nm	75	72	73	74	39	42	41	42	47

Table 4 raw oil main character

Project	Analysis result
		Density (20 DEG C), g/cm³	0.9113
Boiling range scope, DEG C	314-539
		S, g/g	9800
N, g/g	1710
		Carbon residue, wt%	0.14
Condensation point, DEG C	34
		Cetane number	43.9

Table 5 evaluating catalyst result

Catalyst is numbered	A	B	C	D	E
						Reaction temperature, DEG C	389	389	390	391	397
Product slates, wt%
						Light naphthar (C₅~ 82 DEG C)	5.3	5.6	5.5	5.3	6.9
Heavy naphtha (82 ~ 138 DEG C)	9.0	9.1	9.0	9.2	9.9
						Jet fuel (138 DEG C ~ 249 DEG C)	27.4	27.8	26.8	27.3	23.0
Diesel oil (249 DEG C ~ 371 DEG C)	26.9	27.5	27.1	26.9	24.5
						Tail oil (> 371 DEG C)	31.4	30.0	31.6	31.3	35.7
Middle distillates oil selectivity, wt%	79.1	79.0	78.8	78.5	73.8

Continued 5

Catalyst is numbered	F	G	H	I
					Reaction temperature, DEG C	394	395	395	397
Product slates, wt%
					Light naphthar (C₅~ 82 DEG C)	5.7	5.8	5.9	5.8
Heavy naphtha (82 ~ 138 DEG C)	9.8	9.6	9.7	10.0
					Jet fuel (138 DEG C ~ 249 DEG C)	23.7	22.8	23.3	23.1
Diesel oil (249 DEG C ~ 371 DEG C)	24.1	23.7	24.4	24.2
					Tail oil (> 371 DEG C)	36.7	38.1	36.7	36.9
Middle distillates oil selectivity, wt%	75.5	75.1	75.3	74.9

The character of Y type molecular sieve used by table 6 embodiment of the present invention and comparative example

Molecular sieve character	Y
		Relative crystallinity, %	117
Cell parameter, nm	2.429
		SiO₂/Al₂O₃Mol ratio	80.4
Specific surface area, m²/g	876
		Pore volume, mL/g	0.493
Infrared total acid, mmol/g	0.240
		B-acid L acid	11.36
Na₂O, wt%	<0.01

Claims

1. a hydrocracking catalyst, this catalyst is body phase hydrocracking catalyst, and its composition includes hydrogenation active metals component W and Ni, aluminium oxide, silicon oxide and molecular sieve；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃The ratio of weight content be 1.2:1 ~ 6.0:1, the weight content of table phase active metal component NiO is 1.2:1 ~ 5.0:1 with the ratio of the weight content of body phase active metal component NiO.

2. according to the catalyst described in claim 1, it is characterised in that: in described hydrocracking catalyst, table phase active metal component WO₃Weight content and body phase active metal component WO₃The ratio of weight content be 1.8:1 ~ 4.5:1, the weight content of table phase active metal component NiO is 1.5 ~ 3.5:1 with the ratio of the weight content of body phase active metal component NiO.

3. according to the catalyst described in claim 1, it is characterised in that: in described hydrocracking catalyst, on the basis of the weight of catalyst, WO₃Being 20%～65% with the total content of NiO, W/Ni atomic ratio is 0.05～1.0, and the content of silicon oxide is 1wt%～40wt%, and the content of aluminium oxide is 10wt%～40wt%, and the content of molecular sieve is 5wt%～20wt%.

4. according to the catalyst described in claim 1, it is characterised in that: in described hydrocracking catalyst, on the basis of the weight of catalyst, WO₃Being 30%～50% with the total content of NiO, W/Ni atomic ratio is 0.1～0.7, and the content of silicon oxide is 5wt%～35wt%, and the content of aluminium oxide is 15wt%～40wt%, and the content of molecular sieve is 5wt%～15wt%.

5. according to the catalyst described in claim 1,3 or 4, it is characterised in that: described molecular sieve is Y type molecular sieve, and its character is as follows: specific surface area is 700m²/ g～950m²/ g, total pore volume 0.30mL/g～0.55mL/g, relative crystallinity 90%～130%, SiO₂/Al₂O₃Mol ratio 30～150, cell parameter is 2.425～2.445nm, meleic acid amount 0.1～1.0mmol/g, and B-acid L acid is more than 7.0, sodium oxide content≤0.05wt%.

6. according to the arbitrary described catalyst of claim 1-5, it is characterised in that: the character of described hydrocracking catalyst is as follows: specific surface area is 250～650m²/ g, pore volume is 0.35～0.80mL/g, pore-size distribution is as follows: the pore volume shared by the hole of a diameter of below 4nm accounts for the 1% ~ 20% of total pore volume, pore volume shared by the hole of a diameter of 4 ~ 8nm account for total pore volume for 55% ~ 80%, pore volume shared by the hole of a diameter of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume, the pore volume of a diameter of more than 15nm account for total pore volume for 0.1% ~ 5.0%.

7. according to the arbitrary described catalyst of claim 1-5, it is characterized in that: the pore-size distribution of described hydrocracking catalyst is as follows: the pore volume shared by the hole of a diameter of below 4nm accounts for the 5% ~ 17% of total pore volume, pore volume shared by the hole of a diameter of 4 ~ 8nm account for total pore volume for 61% ~ 75%, pore volume shared by the hole of a diameter of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, the pore volume of a diameter of more than 15nm account for total pore volume for 0.5% ~ 5.0%.

8. according to the arbitrary described catalyst of claim 1-5, it is characterised in that: in described hydrocracking catalyst, containing adjuvant component, described adjuvant component is Ti and/or Zr, counts the content in hydrocracking catalyst as 1wt%～10wt% with oxide.

9. the preparation method of the arbitrary described catalyst of claim 1～7, including:

The most in accordance with the method for claim 9, it is characterised in that: institute's addition molecular sieve is Y type molecular sieve, and molecular sieve suspension will be ground to 80 mesh ~ 140 mesh, preferably 100 mesh ~ 120 mesh by molecular sieve, then adds water and makes suspension.

11. in accordance with the method for claim 9, it is characterized in that: the precipitant described in step (1) or step (2) is one or more in sodium carbonate, sodium bicarbonate, ammonia, sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, preferably ammonia.

12. in accordance with the method for claim 9, it is characterised in that: in step (1) mixed solution A, Ni weight concentration in terms of NiO is 5～80g/L, and preferably 10～60g/L, Al is with Al₂O₃The weight concentration of meter is 10～80g/L, preferably 20～60g/L.

13. in accordance with the method for claim 9, it is characterised in that: in step (2) mixed solution B, W is with WO₃The weight concentration of meter is 10～100g/L, and preferably 20～90g/L, Si is with SiO₂Weight concentration is 10～120g/L, and preferably 20～80g/L, Al is with Al₂O₃The weight concentration of meter is 10～80g/L, preferably 20～60g/L.

14. in accordance with the method for claim 9, it is characterised in that: in step (1), reaction temperature is 20～90 DEG C, preferably 30～70 DEG C, gelation time is 0.2 ~ 4.0 hour, being preferably 0.5 ~ 3.0 hour, during cemented into bundles, pH value controls is 6.0 ~ 11.0, preferably 7.0 ~ 9.0.

15. in accordance with the method for claim 9, it is characterized in that: Si, the Al introduced in step (2) counts weight content in the catalyst as 10wt%～70wt% with oxide, preferably 20wt%～55wt%, wherein Si accounts for 10wt%～90wt% of Si, Al gross weight in terms of oxide, preferably 30wt%～80wt% in terms of silicon oxide；The Al introduced in step (1) counts weight content in the catalyst as 5wt%～45wt%, preferably 10wt%～30wt% with oxide.

16. in accordance with the method for claim 9, it is characterised in that: in step (2), reaction temperature is 30～90 DEG C, preferably 40～80 DEG C, and pH value control is 6.0 ~ 11.0 when flowing plastic, being preferably 7.0 ~ 9.0, gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

17. in accordance with the method for claim 9, it is characterised in that: 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, being preferably 6.5 ~ 9.0, ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.

18. in accordance with the method for claim 9, it is characterized in that: the hydrothermal conditions described in step (3) is as follows: carry out under airtight container, temperature is 200 ~ 300 DEG C, it is preferably 210 ~ 260 DEG C, pressure is 1.0 ~ 8.0MPa, preferably 3.0 ~ 6.0MPa, the process time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours；In step (3), during hydrothermal treatment consists, the addition of carbamide is 0.5:1 ~ 10.0:1, preferably 2.0:1 ~ 8.0:1 with the mol ratio of active metal atom total amount in catalyst.

19. in accordance with the method for claim 9, it is characterised in that: being dried described in step (5) is as follows with roasting condition: be dried 1 ~ 48 hour at 50 ~ 200 DEG C, 450 ~ 600 DEG C of roastings 1 ~ 24 hour.

20. in accordance with the method for claim 9, it is characterized in that: in hydrocracking catalyst preparation process, the compound containing adjuvant component is added in mixed solution A, i.e. titanium source and/or zirconium source, titanium source uses one or more in Titanium Nitrate, titanium sulfate, titanium chloride, and zirconium source uses one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.

21. 1 kinds of method for hydrogen cracking, it is characterised in that use the arbitrary described catalyst of claim 1～8.

22. in accordance with the method for claim 21, it is characterised in that: using single hop once by hydrocracking process, hydrocracking operation condition is as follows: reaction temperature is 300～500 DEG C, and pressure is 6～20MPa, and during liquid, volume space velocity is 0.5～3.0h^-1, hydrogen to oil volume ratio is 400～2000:1.