CN106179391B

CN106179391B - Hydrocracking catalyst and preparation method thereof

Info

Publication number: CN106179391B
Application number: CN201510212540.0A
Authority: CN
Inventors: 王海涛; 刘东香; 徐学军; 冯小萍
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: 2019-01-25
Anticipated expiration: 2035-04-30
Also published as: CN106179391A

Abstract

The invention discloses a kind of hydrocracking catalysts and preparation method thereof.The catalyst is body phase hydrocracking catalyst, and composition includes hydrogenation active metal component W and Ni, aluminium oxide and silica；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 ratio of the weight content of table phase active metal component NiO and the weight content of body phase active metal component NiO is 1.2:1 ~ 5.0:1.The catalyst is especially suitable in single-stage hydrocracking technical process, having many advantages, such as liquid yield height, good product quality.

Description

Hydrocracking catalyst and preparation method thereof

Technical field

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

Background technique

Currently, worldwide petroleum resources are insufficient, crude quality is deteriorated year by year, and intermediate oil demand increases, Petroleum chemicals upgrading and environmental regulation are more and more stringent, heavy oil lighting are greatly facilitated, and constitute accelerated development The very strong driving force of hydrogen addition technology.Be mainly characterized by adaptability to raw material strong, the products scheme, the selection of purpose product of hydrocracking technology Property high, good product quality and added value it is high, can directly produce a variety of high-quality oil product (such as gasoline, jet fuel, diesel oil, profits Lubricant base oil etc.) and high-quality industrial chemicals (such as benzene,toluene,xylene, ethylene production raw material).

It is hydrocracked and carries out at elevated pressures, hydrocarbon molecules and hydrogen carry out cracking and adding hydrogen in catalyst surface Reaction generates the conversion process of lighter molecule, while the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs.Currently, Domestic and international refined products market constantly increases intermediate oil demand, measures more intermediate oils well this requires refinery can produce matter Product, the key for being hydrocracked volume increase intermediate oil is to develop and uses suitable hydrocracking catalyst, currently, plus hydrogen Cracking catalyst is mostly using molecular sieve as Cracking Component, although the activity of catalyst is higher, middle distillates oil selectivity is poor, especially It is even more serious to operate the decline of latter stage middle distillates oil selectivity, using amorphous silica-alumina as the catalyst of Cracking Component, although activity is lower, Middle distillates oil selectivity is high, and middle oil yield is also relatively stable in entire use process.

In general, following method can be used to prepare for hydrocracking catalyst, such as: infusion process, kneading method, beating method, altogether The precipitation method may use ion-exchange for noble metal.Infusion process and kneading method are all made of first by carrier and acidic components Add metal again afterwards, and coprecipitated rule is that acidic components and metal coprecipitation get off, and metal loading is unrestricted.It is such The hydrogenation sites of catalyst be on the catalyst channel surfaces that reactant molecule can approach, and coprecipitation method preparation urge Agent active metal is not fully present in catalyst channel surfaces, and amount of activated metal is present in caltalyst phase, coprecipitated The tenor that method prepares catalyst table phase decides catalyst activity.

US6299760, US6156695, US6537442, US6440888, US6652738 disclose containing group VIII/ VI B race active metal component is used 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 is prepared using coprecipitation method.US Hydrocracking catalyst disclosed in 3954671, hydrogenation conversion catalyst disclosed in US 4313817 are 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 are prepared using coprecipitation method, since the deposition condition of different hydrogenation active metals is different, cause different plus hydrogen The distribution of active metal is not easily controlled, thus influence between the distribution and different activities metal of different hydrogenation active metals and Interaction relationship between active metal and carrier, thus prevent hydrogenation activity with cracking activity from being cooperated well, Meanwhile these caltalyst phase active metallic contents are more, table phase active metallic content is relatively fewer, hydrogenation sites density Smaller, final influence catalyst is hydrocracked performance.High activity, High middle distillate disclosed in CN101239324A, which are hydrocracked, urges Agent is the addition precipitating reagent alkalescent ammoniac compounds into the slurries that amorphous silica-alumina, auxiliary agent and active metal are made into, and is carried out Then precipitation reaction is added molecular sieve suspension and is made.This method is also to be prepared using coprecipitation method, however it remains table is mutually lived Property tenor it is relatively fewer, hydrogenation sites density is smaller, and different hydrogenation active metals are unevenly distributed, hydrogenation activity gold Belong to the interactively between carrier and coordinates bad problem.

CN103055923A discloses a kind of preparation method of hydrocracking catalyst.Using acid containing hydrogenation active metals Solution, sodium metaaluminate alkaline solution and gas CO₂Plastic in the reactor tank equipped with water purification is added in cocurrent；Then Y type molecule is added The suspension of sieve is uniformly mixed, and hydrocracking catalyst is made through filtering, drying, molding, then washed, dry, roasting.The party Method increases Kong Rong, the specific surface area of catalyst, makes using the releasing of gas in roasting process under the percussion of gas More metal active positions are exposed to the surface of catalyst, but such method can make cell channels collapse, pore size distribution disperse, mechanical Strength reduction, and lead to active metal localized clusters, the metal active position being exposed is limited.

CN1302850A discloses a kind of middle oil type hydrocracking catalyst and preparation method thereof, and carrier is unformed silicon Aluminium, aluminium oxide and auxiliary agent phosphorus.Further hydro-thermal process after carrier molding, drying.Infusion process supports active metal component W and Ni, WO in catalyst₃Content is 15.0% ~ 25.0w%, and NiO content is 4.0 ~ 5.5w%, and phosphorus content is 1.5% ~ 10.0%, specific surface area For 200 ~ 350m²/ g, hole hold 0.30 ~ 0.50cm3/g.It is intermediate that the catalyst can be used for the production of high-sulfur high nitrogen heavy oil hydrocracking Distillate.Catalyst middle distillates oil selectivity increases, but reactivity increase rate is little.

Coprecipitation method prepares catalyst technology, can be to duct table in catalyst using different coprecipitation modes, Gelation Conditions etc. On face between active metallic content and activated centre density, the distribution of different hydrogenation active metals and difference hydrogenation active metals Interaction relationship between hydrogenation active metals and carrier has a great impact.The coprecipitation method of above-mentioned use can make different plus hydrogen The distribution of active metal is not easily controlled, thus influence different hydrogenation active metals distribution and different hydrogenation active metals it Between interaction relationship between active metal and carrier, to prevent hydrogenation activity with cracking activity from being matched well It closes, meanwhile, table phase active metallic content is smaller in catalyst and activated centre density is lower, and final influence catalyst adds hydrogen to split Change performance.Therefore, the distribution for how regulating and controlling hydrogenation active metals, makes between hydrogenation active metal component and hydrogenation active metals There is suitable mating reaction between component and carrier, it is close how to increase table phase active metallic content and activated centre in catalyst Degree, improves the utilization rate of hydrogenation active metal component, is the key that improve coprecipitation method to prepare hydrocracking catalyst Hydrogenation.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of body phase hydrocracking catalysts and preparation method thereof.It should Method improve catalyst in hydrogenation active metals distribution, improve hydrogenation active metals between and the cooperation between carrier Effect improves catalyst surface active bit density, improves the utilization rate of hydrogenation active metals, while catalyst pore structure is reasonable, Active metal disperses more evenly, to make catalyst service performance with higher.

Hydrocracking catalyst of the present invention is body phase hydrocracking catalyst, and composition includes hydrogenation active metal component W And Ni, aluminium oxide and silica；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃Weight The ratio for measuring content is 1.2:1 ~ 6.0:1, the weight content and body phase of preferably 1.8:1 ~ 4.5:1, table phase active metal component NiO The ratio of the weight content of active metal component NiO is 1.2:1 ~ 5.0:1, preferably 1.5 ~ 3.5:1.

In hydrocracking catalyst of the present invention, on the basis of the weight of catalyst, WO₃With the total content of NiO be 20%~ 65%, preferably 30%~60%, W/Ni atomic ratio is 0.05~1.0, preferably 0.1~0.7, the content of silica be 5wt%~ 40wt%, preferably 5wt%~35wt%, the content of aluminium oxide are 5wt%~40wt%, preferably 10wt%~40wt%, SiO₂/ Al₂O₃Weight ratio is 0.1~2.0, preferably 0.3~1.5.

In the present invention, table phase active metal component WO₃Weight content be table phase in WO₃Weight content, body mutually activity gold Belong to component WO₃Weight content be catalyst in WO₃Weight content；The weight content of table phase active metal component NiO is table phase The weight content of middle NiO, the weight content of body phase active metal component NiO are the weight content of NiO in catalyst.

The property of hydrocracking catalyst of the present invention is as follows: specific surface area is 250~650m²/ g, Kong Rongwei 0.35~ 0.80mL/g, pore-size distribution are as follows: diameter is that Kong Rong shared by the hole below 4nm accounts for the 1% ~ 20% of total pore volume, and diameter is 4 ~ 8nm Hole shared by Kong Rong to account for total pore volume be 55% ~ 80%, diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume, directly It is 0.1% ~ 5.0% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume, and preferred pore-size distribution is as follows: diameter is the hole below 4nm Shared Kong Rong accounts for the 5% ~ 17% of total pore volume, and it is 61% ~ 75% that Kong Rong shared by hole of the diameter for 4 ~ 8nm, which accounts for total pore volume, diameter 8 Kong Rong shared by the hole of ~ 15nm accounts for the 4% ~ 17% of total pore volume, the Kong Rong that diameter is 15nm or more account for total pore volume be 0.5% ~ 5.0%。

In hydrocracking catalyst of the present invention, adjuvant component can also be contained, the adjuvant component is the IVth B race metal, Content of the IVth B family metal oxide in hydrocracking catalyst is 1wt%~10wt%.IVth B race metal is preferably Ti and/or Zr.

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

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

(2), the mixed solution B containing W, Si, Al component is prepared, precipitating reagent and solution B cocurrent are subjected to plastic reaction, generated Tungstenic, silicon, aluminum precipitation object slurries II；

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

(4), step (3) resulting material is through drying, molding and washing；

(5), hydrocracking catalyst is made through dry and roasting in step (4) resulting material.

Precipitating reagent described in step (1) or step (2) is sodium carbonate, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, hydroxide One of potassium, potassium carbonate, saleratus are a variety of, preferably ammonium hydroxide.

In step (1) mixed solution A, weight concentration of the Ni in terms of NiO be 5~80g/L, preferably 10~60g/L, Al with Al₂O₃The weight concentration of meter is 10~80g/L, preferably 20~60g/L.In step (2) mixed solution B, W is with WO₃The weight of meter Concentration is 10~100g/L, preferably 20~80g/L.Si is with SiO₂Weight concentration is 10~120g/L, 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, generally use Nickel source can be one or more of nickel sulfate, nickel nitrate, basic nickel carbonate, nickel chloride, and silicon source can be aluminum nitrate, sulfuric acid One or more of aluminium, aluminium chloride or aluminium acetate etc..When preparing mixed solution B, the tungsten source generally used can be ethyl One or more of ammonium metatungstate, ammonium metatungstate；Silicon source can be one of silica solution, sodium metasilicate or a variety of；Silicon source can be with For one or more of aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc..

Reaction temperature is 20~90 DEG C, preferably 30~70 DEG C in step (1).When cemented into bundles pH value control for 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

Weight content of Si, the Al introduced in step (2) in terms of oxide in the catalyst is 10wt%~70wt%, preferably For 20wt%~55wt%, wherein Si accounts for 10wt%~90wt% of the total weight of Si, Al in terms of oxide in terms of silica, preferably 30wt%~80wt%；Weight content of the Al introduced in step (1) in terms of oxide in the catalyst is 5wt%~45wt%, compared with It is well 10wt%~30wt%.

Reaction temperature is 30~90 DEG C, preferably 40~80 DEG C in step (2).When cocurrent plastic pH value control for 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.

Gelling temperature and time can be the same or different in step (1) and step (2).Step (1) and step (2) can Can also be different when progress simultaneously.

Aging temperature is 40~90 DEG C, preferably 50~80 DEG C in step (3).PH value control is 6.0 ~ 10.0 when aging, Preferably 6.5 ~ 9.0.Ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.

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

In step (3), when hydro-thermal process, active metal (tungsten, nickel) atom total amount in the additional amount and catalyst of urea Molar ratio is 0.5:1 ~ 10.0:1, preferably 2.0:1 ~ 8.0:1.

Drying described in step (4), molding can be carried out using conventional method in that art.The drying generally 50 ~ 200 DEG C drying 1 ~ 48 hour.In forming process, it can according to need and conventional shaping assistant, such as peptizing agent, extrusion aid is added Deng one of or it is a variety of.The peptizing agent is one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., described Extrusion aid refers to one or more of the substance for being conducive to extrusion forming, such as sesbania powder, carbon black, graphite powder, citric acid, helps The dosage of agent accounts for 1wt%~10wt% of total material butt.Washing is usually used deionized water or containing decomposable salt (such as vinegar Sour ammonium, ammonium chloride, ammonium nitrate etc.) solution washing, it is washed till neutrality.The molding, the shape of catalyst can according to need as piece Shape, spherical, cylindrical bars and irregular bar (clover, bunge bedstraw herb), preferably cylindrical bars and irregular bar (clover, bunge bedstraw herb).It carries The diameter of body can be the slice of 0.8 ~ 2.0mm and the thick item of > 2.5mm.

Drying described in step (5) and roasting can use this field normal condition, such as small in 50 ~ 200 DEG C of dryings 1 ~ 48 When, it is roasted 1 ~ 24 hour, preferably 2 ~ 8 hours at 450 ~ 600 DEG C.

In hydrocracking catalyst of the present invention, adjuvant component can also be contained, the adjuvant component is the IVth B race metal, Content of the IVth B family metal oxide in hydrocracking catalyst is 1wt%~10wt%.IVth B race metal is preferably Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, preferably it is added to contain during preparing mixed solution A and helps The compound of agent component, i.e. titanium source and/or zirconium source.One of Titanium Nitrate, titanium sulfate, titanium chloride etc. or more can be used in titanium source Kind, one of zirconium nitrate, zirconium chloride, zirconium oxychloride etc. or a variety of can be used in zirconium source.

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

The heavy charge range that the catalyst of the method for the present invention preparation is applicable is very wide, 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, can also group It closes and uses, the hydro carbons that raw material is usually 250~550 DEG C containing boiling point, nitrogen content can be in 50~2500 μ g/g.

Using positive addition, (the acid precipitation method, that is, alkaline precipitating agent is added in acid metal salt solution and carries out the method for the present invention Precipitating) nickel aluminium mixed sediment is prepared, tungsten, silicon and aluminium mixed sediment are prepared using parallel flow precipitation, then after the two is mixed Aging.The present invention prepares the relatively large nickel of crystal grain, aluminum precipitation object by using positive addition, and it is relatively small that cocurrent process prepares crystal grain Tungsten, silicon and aluminum precipitation object, above two sediment is mixed, and can control the distribution of different hydrogenation active metals, is conducive to live Property tungsten, nickel between form high activity phase, and improve the interaction between active metal and carrier, urge resulting be hydrocracked The hydrogenation activity and cracking activity of agent obtain good cooperation, improve the service performance of hydrocracking catalyst.

In the preparation method of catalyst of the present invention, steam treatment is simultaneously under appropriate conditions for the material obtained after co-precipitation Urea is added, urea is decomposed into NH under high temperature environment₃And CO₂, NH₃And CO₂NH is generated in the presence of water vapour₄ ⁺With HCO₃ ^-Ion, NH₄ ⁺And HCO₃ ^-Ion at high temperature under high pressure has a significant impact the micromorphology of material, material before hydro-thermal process Phase structure is in cylinder, and material phase structure is changed into the irregular body that irregular sheet is piled into from cylinder after hydro-thermal process, this The transformation of structure obviously increases distribution of the active metal in table phase, and disperses more evenly, and it is living to be conducive to raising surface The density of property position.In addition, urea is added in steam treatment, make the transformation of material form that can also make the pore size distribution of catalyst It is more uniform, be conducive to the mechanical strength for improving catalyst.

In catalyst of the present invention, different hydrogenation active metals have good distribution, and surface-active bit density is big, activity Intermetallic cooperation is good, and active metal utilization rate is high, and improves the interaction between active metal and carrier, is catalyzed simultaneously Agent pore structure is reasonable, high mechanical strength.Hydrocracking catalyst of the present invention is medium oil type hydrocracking catalyst, is had high Middle distillates oil selectivity, hydrogenation cracking activity are improved there has also been apparent.

Catalyst of the present invention is suitable for single hop and once passes through in hydrocracking process, and hydrocracking operation condition is as follows: Reaction temperature is 300~500 DEG C, more preferably 350~450 DEG C；Pressure is 6~20MPa, more preferably 13~17MPa；Volume when liquid Air speed is 0.5~3 h^-1, preferably 0.8~1.5 h^-1；Hydrogen to oil volume ratio is 400~2000:1, preferably 800~1500:1. The catalyst is in single-stage hydrocracking technical process, having many advantages, such as liquid yield height, good product quality.

Specific embodiment

In the present invention, specific surface area and Kong Rong 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, and mutually activity is golden for catalyst table Belong to content to measure using x-ray photoelectron spectroscopy (XPS), caltalyst phase active metallic content uses inductively coupled plasma Body atomic emission spectrum (ICP-AES) measurement, transmission electron microscope (TEM) measure catalyst surface WS₂Density.Mechanical strength is to use The measurement of side pressure method.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Nickel chloride, liquor alumini chloridi and zirconium oxychloride are dissolved in water purification respectively, are configured to mixed solution A, in mixed solution A The weight concentration of NiO is 19g/L, Al₂O₃Weight concentration be 10g/L, ZrO₂Weight concentration 5g/L.Respectively by ammonium metatungstate, Liquor alumini chloridi is dissolved in water purification, and dilute water glass solution is added, and is configured to mixed solution B, WO in mixed solution B₃Weight concentration For 28g/L, Al₂O₃Weight concentration be 26g/L, SiO₂Weight concentration be 15g/L.Under stiring for 10wt% ammonium hydroxide by concentration Solution A is added, gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, at 60 minutes, generation contained gelation time control Nickel, aluminum precipitation object slurries I.1000mL water purification is added in reactor tank, is that 10wt% ammonium hydroxide and solution B cocurrent are added instead by concentration It answers in tank, gelling temperature is maintained at 55 DEG C, and pH value control is 7.6 in cocurrent plastic reaction process, and gelation time control is at 60 points Clock generates tungstenic, silicon, aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 2 hours, always Change 75 DEG C of temperature, at the end of aging then pH value control is filtered, filter cake carries out hydro-thermal under the water vapour containing urea 7.6 Processing, the condition of hydro-thermal process are as follows: the molar ratio of urea and active metal atom total amount is 6:1, and temperature is 230 DEG C, and pressure is 4.5MPa, processing time are 3 hours, after processing that filter cake is 8 hours dry at 100 DEG C, are rolled, extruded moulding.At room temperature with net Water washing.Then 10 hours dry at 80 DEG C, 550 DEG C roast 4 hours, obtain catalyst A.Catalyst composition, pore size distribution and master Property is wanted to be shown in Table 1.

Embodiment 2

According to the method for embodiment 1, it is matched by the constituent content of the catalyst B in table 1, nitric acid is added into dissolving tank 1 Nickel, titanium chloride, aluminum nitrate solution prepare working solution A, and aluminum nitrate, ammonium metatungstate and dilute waterglass are added into dissolving tank 2 and matches Working solution B processed.By concentration be 15wt% ammonium hydroxide solution A is added under stiring, gelling temperature is maintained at 45 DEG C, at the end of pH value 7.8, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes for control.Reactor tank is added in 800mL water purification In, it is that 15wt% ammonium hydroxide and solution B cocurrent are added in reactor tank by concentration, gelling temperature is maintained at 50 DEG C, and cocurrent plastic was reacted 8.2, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control in journey.It will be above two Containing aging after sediment slurry mixing, ageing time 3 hours, 70 DEG C of aging temperature, pH value control was 8.0 at the end of aging, then Filtering, filter cake carry out hydro-thermal process, the condition of hydro-thermal process under the water vapour containing urea are as follows: urea and active metal atom The molar ratio of total amount is 5:1, and temperature is 250 DEG C, pressure 3.5MPa, and the processing time is 3 hours, by filter cake 120 after processing It DEG C dry 7 hours, rolls, extruded moulding.It is washed at room temperature with water purification.Then 12 hours dry at 100 DEG C, 500 DEG C of roastings 5 are small When, obtain catalyst B.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, it is matched by the constituent content of the catalyst C in table 1, chlorination is added into dissolving tank 1 Nickel, liquor alumini chloridi prepare working solution A, and into dissolving tank 2, addition aluminium chloride, ammonium metatungstate, the preparation work of dilute waterglass are molten Liquid B.By concentration be 10wt% ammonium hydroxide solution A is added under stiring, gelling temperature is maintained at 55 DEG C, at the end of pH value control exist 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 90 minutes.It is added in reactor tank and 900mL water purification is housed, it will Concentration is that 10wt% ammonium hydroxide and solution B cocurrent are added in reactor tank, and gelling temperature is maintained at 45 DEG C, in cocurrent plastic reaction process 8.0, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control.By above two containing heavy The mixing of shallow lake slurries.By it is above two containing sediment slurry mix after aging, ageing time 2.5 hours, 72 DEG C of aging temperature, aging knot When beam then pH value control is filtered, filter cake carries out hydro-thermal process, the item of hydro-thermal process under the water vapour containing urea 7.8 Part are as follows: the molar ratio of urea and active metal atom total amount is 4:1, and temperature is 240 DEG C, pressure 6.0MPa, and the processing time is 4 Hour, it is after processing that filter cake is 10 hours dry at 70 DEG C, it rolls, extruded moulding.It is washed at room temperature with water purification.Then dry at 80 DEG C Dry 8 hours, 530 DEG C roasted 4.5 hours, obtained catalyst C.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

According to the method for embodiment 1, it is matched by the constituent content of the catalyst D in table 1, chlorination is added into dissolving tank 1 Aluminium chloride, ammonium metatungstate, dilute waterglass preparating acid are added into dissolving tank 2 for nickel, liquor alumini chloridi, preparating acid sex work solution A Sex work solution B.By concentration be 15wt% ammonium hydroxide solution A is added under stiring, gelling temperature is maintained at 50 DEG C, at the end of pH value 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 80 minutes for control.It is added in reactor tank and 1000mL is housed Concentration is that 15wt% ammonium hydroxide and solution B cocurrent are added in reactor tank by water purification, and gelling temperature is maintained at 45 DEG C, the reaction of cocurrent plastic 8.0, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control in the process.By above-mentioned two Kind is mixed containing sediment slurry.By it is above two containing sediment slurry mix after aging, ageing time 2 hours, 75 DEG C of aging temperature, always At the end of change then pH value control is filtered, filter cake carries out hydro-thermal process, hydro-thermal process under the water vapour containing urea 7.8 Condition are as follows: the molar ratio of urea and active metal atom total amount be 3.0:1, temperature be 260 DEG C, pressure 5.0MPa, processing Time is 5 hours, after processing that filter cake is 10 hours dry at 80 DEG C, is rolled, extruded moulding.It is washed at room temperature with water purification, then 10 hours dry at 110 DEG C, 480 DEG C roast 6 hours, obtain catalyst D.Catalyst composition, pore size distribution and main character are shown in Table 1。

Comparative example 1

Amorphous hydrocracking catalyst is prepared according to method disclosed in CN101239324A, catalyst forms same embodiment 1 is identical, the specific steps are as follows:

(1) it prepares and contains Al₂O₃Concentration is 30 milliliters of liquor alumini chloridi of 120g/L, the nickel chloride solution for being 44g/L containing NiO 400 milliliters, contain ZrO₂50 milliliters of 100g/L zirconyl chloride solution is simultaneously mixed in one 5 liters of container, is added 2000 milliliters only Water dilution；

(2) dilute water glass solution is prepared, SiO is contained₂350 milliliters of the water glass solution of 100g/L under agitation will (2) it is added in (1)；

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

(4) 340 milliliters of sodium tungstate solution are prepared, WO is contained₃For 80g/L, and be added under agitation (1)+(2)+ (3) in mixture；

(5) ammonium hydroxide is continuously added until pH value is 7.6；

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

(7) mixture 75 DEG C standing aging 2.0 hours, at the end of aging pH value control 7.6；

(8) reactant slurries are filtered, filter cake 100 DEG C oven drying 8 hours, roll, with 3 millimeters of orifice plate of diameter Extruded moulding；It is washed at room temperature with the ammonium acetate solution of pH=8.8；Then 80 DEG C oven drying 10 hours, 550 DEG C roasting 4 Hour, reference agent E is obtained, catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 2

It is added without urea by 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, prepares reference agent F.Catalyst Composition, pore size distribution and main character are shown in Table 1.

Comparative example 3

By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but NH is added₃, NH₃And work Property metallic atom total amount molar ratio be 6:1, temperature be 230 DEG C, pressure 4.5MPa, processing the time be 3 hours, prepare reference Agent G.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 4

By 1 catalyst of embodiment composition and preparation method, when hydro-thermal process, is added without urea, but CO is added₂, CO₂And work Property metallic atom total amount molar ratio be 6:1, temperature be 230 DEG C, pressure 4.5MPa, processing the time be 3 hours, prepare reference Agent H.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 5

Amorphous hydrocracking catalyst is prepared by method disclosed in CN103055923A, composition is with example 1 group at phase Together, the specific steps are as follows:

(1) it prepares acid solution A: being formed by 1 catalyst of embodiment, nickel chloride, ammonium metatungstate, zirconium oxychloride are mixed In one 5 liters of container, 1000 milliliters of water purification dilutions are added.It prepares containing with SiO in embodiment 1₂The identical dilute water glass of content Glass solution is added under agitation in mixing salt solution above.

(2) configure alkaline solution B: configuration is containing the same as Al in embodiment 1₂O₃The identical alkaline sodium aluminate solution of content 3000mL。

(3) by solution A, solution B and CO₂Plastic in plastic cans is added in gas cocurrent, and gelling temperature is maintained at 50 DEG C, pH Value is 7.6.Wherein CO used₂Gas concentration is 45v%, and CO is added₂Al in the total amount and alkaline solution of gas₂O₃Molar ratio 3, A, B solution flow velocity are adjusted, guarantee while being dripped off, to guarantee that it is constant that catalyst distribution uniformly forms.

(4) after cemented into bundles, 75 DEG C or so aging 2 hours, at the end of aging pH value control 7.6.

(5) reaction precipitate slurries filter, and filter cake is 8 hours dry at 100 DEG C, roll, extruded moulding.At room temperature with net Water washing.Then 10 hours dry at 80 DEG C, 550 DEG C of roastings obtain reference catalyst I in 4 hours.Catalyst composition, pore size distribution and Main character is shown in Table 1.

Embodiment 5

By middle oil type hydrocracking catalyst A, B, C, D of the invention and reference catalyst E, F, G, H, I in midget plant Upper evaluation result is compared.Evaluation condition are as follows: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity when liquid 1.0h^-1, evaluation is Iranian VGO heavy distillate with raw material, and main character is shown in Table 4, and table 5 lists evaluation result.

From table 2 and table 3 as can be seen that active metallic content is apparently higher than body in catalyst table phase prepared by the method for the present invention Active metallic content in phase, activity mutually increases considerably in catalyst.It can be seen that from the data of table 5 using prepared by the present invention The activity and middle distillates oil selectivity of catalyst A, B, C, D are better than reference agent, illustrate the catalyst activity metal benefit of this method preparation With rate height, catalyst reaction activity is significantly improved.

1 catalyst of table composition and property

Catalyst number	A	B	C	D	E
						Catalyst composition
NiO, wt%	18	18	16	22	18
						WO₃, wt%	27	20	24	20	27
SiO₂, wt%	15	25	24	24	15
						Al₂O₃, wt%	35	30	36	34	35
Other/wt%	ZrO₂/5.0	TiO₂/7.0	-	-	ZrO₂/5.0
						Catalyst property
Specific surface area, m²/g	391	389	385	397	288
						Kong Rong, mL/g	0.405	0.399	0.393	0.411	0.285
Mechanical strength, N/mm	22.8	22.4	23.3	22 .7	19.7
						Pore size distribution, %
< 4nm	15.21	14.14	14.25	14.09	52.33
						4nm~8nm	68.22	67.52	69.17	68.66	44.15
8nm~15nm	14.33	14.58	15.96	14.56	1.41
						> 15nm	2.15	3.76	2.62	2.69	2.11

Continued 1

Catalyst number	F	G	H	I
					Catalyst composition
NiO, wt%	18	18	18	18
					WO₃, wt%	27	27	27	27
SiO₂, wt%	15	15	15	15
					Al₂O₃, wt%	35	35	35	35
Other/wt%	ZrO₂/5.0	ZrO₂/5.0	ZrO₂/5.0	ZrO₂/5.0
					Catalyst property
Specific surface area, m²/g	359	361	377	312
					Kong Rong, mL/g	0.385	0.378	0.383	0.355
Intensity, N/mm	19.54	18.3	18.1	17.8
					Pore size distribution, %
< 4nm	28.42	23.56	25.02	14.25
					4nm~8nm	34.18	38.94	34.61	35.42
8nm~15nm	24.94	23.05	23.41	36.84
					> 15nm	12.46	14.45	16.96	13.49

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

Catalyst number	A	B	C	D	E
						Table phase I_W/ body phase I_W	3.91	3.85	3.54	2.99	0.99
Table phase I_Ni/ body phase I_Ni	2.98	2.84	2.71	2.45	0.94

Continued 2

Catalyst number	F	G	H	I
					Table phase I_W/ body phase I_W	1.03	1.07	1.12	1.22
Table phase I_Ni/ body phase I_Ni	1.08	1.14	1.07	1.18

3 catalyst surface WS of table₂Density

Catalyst number	A	B	C	D	E	F	G	H	I
										WS₂Density, grain/100nm	79	74	75	76	40	43	43	44	46

4 feedstock oil main character of table

Project	Analyze result
		Density (20 DEG C), g/cm³	0.9225
Boiling range range, DEG C	314-538
		S, μ g/g	10800
N, μ g/g	1790
		Carbon residue, wt%	0.14
Condensation point, DEG C	35
		Cetane number	43.1

5 evaluating catalyst result of table

Catalyst number	A	B	C	D	E
						Reaction temperature, DEG C	397	399	399	398	407
Product distribution, wt%
						Light naphthar (C₅~ 82 DEG C)	5.1	5.4	4.8	5.3	5.2
Heavy naphtha (82 ~ 138 DEG C)	6.5	6.2	6.1	5.8	5.9
						Jet fuel (138 DEG C ~ 249 DEG C)	24.4	23.8	24.2	24.8	21.0
Diesel oil (249 DEG C ~ 371 DEG C)	32.9	33.2	34.1	33.9	24.5
						Tail oil (> 371 DEG C)	31.1	31.4	30.8	30.2	43.4
Middle distillates oil selectivity, wt%	83.1	83.2	84.2	84.1	80.3

Continued 5

Catalyst number	F	G	H	I
					Reaction temperature, DEG C	405	406	407	404
Product distribution, wt%
					Light naphthar (C₅~ 82 DEG C)	5.7	5.5	5.9	5.2
Heavy naphtha (82 ~ 138 DEG C)	6.1	5.9	6.3	6.3
					Jet fuel (138 DEG C ~ 249 DEG C)	21.8	21.5	20.5	21.7
Diesel oil (249 DEG C ~ 371 DEG C)	26.3	25.9	27.1	26.8
					Tail oil (> 371 DEG C)	40.1	41.2	40.2	40.0
Middle distillates oil selectivity, wt%	80.3	80.6	79.6	80.8

Claims

1. a kind of hydrocracking catalyst, which is body phase hydrocracking catalyst, and composition includes hydrogenation active metals Component W and Ni, aluminium oxide and silica；Wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃Weight content ratio be 1.2:1 ~ 6.0:1, weight content and the body phase active metal group of table phase active metal component NiO The ratio for dividing the weight content of NiO is 1.2:1 ~ 5.0:1；The pore-size distribution of the hydrocracking catalyst is as follows: diameter is 4nm or less Hole shared by Kong Rong account for the 1% ~ 20% of total pore volume, diameter is that account for total pore volume be 55% ~ 80% to Kong Rong shared by the hole of 4 ~ 8nm, directly Diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume, and it is 0.1% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume, ~5.0%。

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

3. catalyst described in accordance with the claim 1, it is characterised in that: in the hydrocracking catalyst, with the weight of catalyst On the basis of amount, WO₃Total content with NiO is 20wt%~65wt%, and W/Ni atomic ratio is 0.05~1.0, and the content of silica is 5wt%~40wt%, the content of aluminium oxide are 5wt%~40wt%, SiO₂/Al₂O₃Weight ratio is 0.1~2.0.

4. catalyst described in accordance with the claim 1, it is characterised in that: in the hydrocracking catalyst, with the weight of catalyst On the basis of amount, WO₃Total content with NiO is 30wt%~60wt%, and W/Ni atomic ratio is 0.1~0.7, and the content of silica is 5wt%~35wt%, the content of aluminium oxide are 10wt%~40wt%, SiO₂/Al₂O₃Weight ratio is 0.3~1.5.

5. according to any catalyst of claim 1-4, it is characterised in that: the property of the hydrocracking catalyst is such as Under: specific surface area is 250~650m²0.35~0.80mL/g of/g, Kong Rongwei.

6. according to any catalyst of claim 1-4, it is characterised in that: the pore-size distribution of the hydrocracking catalyst As follows: diameter is that Kong Rong shared by the hole below 4nm accounts for the 5% ~ 17% of total pore volume, and diameter is that Kong Rong shared by the hole of 4 ~ 8nm is accounted for always Kong Rong is 61% ~ 75%, and diameter is that Kong Rong shared by the hole of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, and diameter is the hole of 15nm or more It is 0.5% ~ 5.0% that appearance, which accounts for total pore volume,.

7. according to any catalyst of claim 1-4, it is characterised in that: in the hydrocracking catalyst, containing helping Agent component, the adjuvant component are Ti and/or Zr, content in terms of oxide in hydrocracking catalyst for 1wt%~ 10wt%。

8. the preparation method of any catalyst of claim 1-6, comprising:

(1), prepare the mixed solution A containing Ni, Al component, by precipitating reagent be added dropwise to solution A carry out plastic reaction, generate it is nickeliferous, Aluminum precipitation object slurries I；

(2), the mixed solution B containing W, Si, Al component is prepared, precipitating reagent and solution B cocurrent are subjected to plastic reaction, generation contains Tungsten, silicon, aluminum precipitation object slurries II；

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

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

9. according to the method for claim 8, it is characterised in that: precipitating reagent described in step (1) or step (2) is carbonic acid One of sodium, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, saleratus are a variety of.

10. according to the method for claim 9, it is characterised in that: precipitating reagent described in step (1) or step (2) is ammonia Water.

11. according to the method for claim 8, it is characterised in that: in step (1) mixed solution A, weight of the Ni in terms of NiO Concentration is 5~80g/L, and Al is with Al₂O₃The weight concentration of meter is 10~80g/L.

12. according to the method for claim 11, it is characterised in that: in step (1) mixed solution A, weight of the Ni in terms of NiO Concentration is 10~60g/L, and Al is with Al₂O₃The weight concentration of meter is 20~60g/L.

13. according to the method for claim 8, it is characterised in that: in step (2) mixed solution B, W is with WO₃The weight of meter is dense Degree is 10~100g/L, and Si is with SiO₂Weight concentration is 10~120g/L, and Al is with Al₂O₃The weight concentration of meter is 10~80g/L.

14. according to the method for claim 13, it is characterised in that: in step (2) mixed solution B, W is with WO₃The weight of meter is dense Degree is 20~80g/L, and Si is with SiO₂Weight concentration is 20~80g/L, and Al is with Al₂O₃The weight concentration of meter is 20~60g/L.

15. according to the method for claim 8, it is characterised in that: reaction temperature is 20~90 DEG C, when plastic in step (1) Between be 0.2 ~ 4.0 hour, pH value control is 6.0 ~ 11.0 when cemented into bundles.

16. according to the method for claim 15, it is characterised in that: reaction temperature is 30~70 DEG C, when plastic in step (1) Between be 0.5 ~ 3.0 hour, pH value control is 7.0 ~ 9.0 when cemented into bundles.

17. according to the method for claim 8, it is characterised in that: Si, the Al introduced in step (2) is being urged in terms of oxide Weight content in agent is 10wt%~70wt%, and wherein Si accounts for the total weight of Si, Al in terms of oxide in terms of silica The weight content of 10wt%~90wt%, the middle Al introduced of step (1) in terms of oxide in the catalyst is 5wt%~45wt%.

18. according to the method for claim 17, it is characterised in that: Si, the Al introduced in step (2) is being urged in terms of oxide Weight content in agent is 20wt%~55wt%, and wherein Si accounts for the total weight of Si, Al in terms of oxide in terms of silica The weight content of 30wt%~80wt%, the middle Al introduced of step (1) in terms of oxide in the catalyst is 10wt%~30wt%.

19. according to the method for claim 8, it is characterised in that: reaction temperature is 30~90 DEG C in step (2)；Cocurrent at PH value control is 6.0 ~ 11.0 when glue；Gelation time is 0.2 ~ 4.0 hour.

20. according to the method for claim 19, it is characterised in that: reaction temperature is 40~80 DEG C in step (2)；Cocurrent at PH value control is 7.0 ~ 9.0 when glue；Gelation time is 0.5 ~ 3.0 hour.

21. according to the method for claim 8, it is characterised in that: aging temperature is 40~90 DEG C, when aging in step (3) PH value control is 6.0 ~ 10.0, and ageing time is 0.5 ~ 6.0 hour.

22. according to the method for claim 21, it is characterised in that: aging temperature is 50~80 DEG C, when aging in step (3) PH value control is 6.5 ~ 9.0, and ageing time is 1.0 ~ 4.0 hours.

23. according to the method for claim 8, it is characterised in that: hydrothermal conditions described in step (3) are as follows: It is carried out under closed container, temperature is 200 ~ 300 DEG C, and pressure is 1.0 ~ 8.0MPa, and the processing time is 0.5 ~ 10.0 hour；Step (3) in, when hydro-thermal process, the molar ratio of active metal atom total amount is 0.5:1 ~ 10.0 in the additional amount and catalyst of urea: 1。

24. according to the method for claim 23, it is characterised in that: hydrothermal conditions described in step (3) are as follows: It is carried out under closed container, temperature is 210 ~ 260 DEG C, and pressure is 3.0 ~ 6.0MPa, and the processing time is 1.0 ~ 6.0 hours；Step (3) in, when hydro-thermal process, the molar ratio of active metal atom total amount is 2.0:1 ~ 8.0:1 in the additional amount and catalyst of urea.

25. according to the method for claim 8, it is characterised in that: molten mixing in hydrocracking catalyst preparation process The compound containing adjuvant component, i.e. titanium source and/or zirconium source are added in liquid A, titanium source is using in Titanium Nitrate, titanium sulfate, titanium chloride One or more, zirconium source uses one of zirconium nitrate, zirconium chloride, zirconium oxychloride or a variety of.

26. according to the method for claim 8, it is characterised in that: drying described in step (5) and roasting condition are as follows: 50 ~ 200 DEG C drying 1 ~ 48 hour, 450 ~ 600 DEG C roast 1 ~ 24 hour.

27. a kind of method for hydrogen cracking, it is characterised in that use any catalyst of claim 1-7.

28. according to the method for claim 27, it is characterised in that: once passed through in hydrocracking process using single hop, added Hydrogen cracking operation condition is as follows: reaction temperature is 300~500 DEG C, and pressure is 6~20MPa, when liquid volume space velocity be 0.5~ 3.0h^-1, hydrogen to oil volume ratio is 400~2000:1.