CN106179467B - A kind of sulfurized hydrogenation Cracking catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of sulfurized hydrogenation Cracking catalyst and preparation method thereof.The catalyst is body phase hydrocracking catalyst, and composition includes the sulfide of hydrogenation active metal component W and Ni, aluminium oxide, silica and molecular sieve；Wherein the sulfide of table phase active metal component W is with WS₂The sulfide of the weight content of meter and active metal component W in body phase are with WS₂The ratio of the weight content of meter is 2.0:1~7.0:The ratio of weight content of the sulfide of weight content of the sulfide of 1, table phase active metal component Ni in terms of NiS and body phase active metal component Ni in terms of NiS is 1.5:1~5.5:1.The catalyst is especially suitable in single-stage hydrocracking technical process, having many advantages, such as liquid yield height, good product quality.

Description

A kind of sulfurized hydrogenation Cracking catalyst and preparation method thereof

Technical field

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

Background technology

Currently, worldwide petroleum resources are insufficient, crude quality is deteriorated year by year, and intermediate oil demand increases, Petroleum chemicals upgrade and environmental regulation is 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, 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 products（Such as gasoline, jet fuel, diesel oil, profit Lubricant base oil etc.）With high-quality industrial chemicals（Such as benzene,toluene,xylene, ethylene production raw material）.

It is hydrocracked and carries out at elevated pressures, hydrocarbon molecules carry out cracking and adding hydrogen in catalyst surface with hydrogen Reaction generates the conversion process of lighter molecule, while the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs.Hydro carbons exists Cracking reaction in hydrocracking process is carried out on the acid centre of catalyst, it then follows carbon ion reaction mechanism, add hydrogen, With the generation of hydro carbons isomerization reaction while cracking reaction.Hydrocracking catalyst is made of hydrogenation component and acidic components , the two is added by a certain percentage as needed, makes that hydrogen and cracking performance is added to reach balance, effect is that hydrocarbon mixture is abundant Add hydrogen, cracking and isomerization orientation reaction.Therefore, the catalyst that distillate hydrocracking process needs should have stronger plus hydrogen There is moderate acid centre in activated centre again.

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 Afterwards again plus metal, and coprecipitated rule to be 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 prepare 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.

Current industrialized hydrocracking catalyst, it is all to exist in the form of an oxide that active metal component is most of, And need that metal sulfide on catalyst is just had to hydrogenation sites in actual use, therefore, catalyst is needed before use It will be through over cure or presulfurization.Conventional catalyst vulcanization process uses " in device " presulfurization, i.e., first by the catalyst of oxidation state It is packed into reactor, is then passed through hydrogen to reactor during continuous heating and vulcanizing agent carries out presulfurization, this side Method brings following problem：（1）Special and vulcanizing equipment is set up on hydrogenation plant；（2）The vulcanization being added in sulfidation The water and hydrogen sulfide that agent and reaction generate easily cause high-pressure reactor and the corrosion in relation to equipment, cause equipment damage and safety Hidden danger；（3）Sulfidation is longer, is delayed on-stream time.（4）Vulcanizing agent used is inflammable toxic, is caused to environment in sulfidation Pollution；（5）The cost of in-situ presulfurization is higher.

The outer pre-curing technology in scene（Or " outside device " presulfurization）It is anti-that the presulfurization of catalyst is transferred to special vulcanization Answer carried out on device or manufactured catalyst be sulphided state catalyst, catalyst is fitted into hydrogenation reactor i.e. usable. Such vulcanization process is simple, efficient, pollution-free and at low cost, has become the development of hydrocracking catalyst technology of preparing in recent years Trend.

US6299760, US6156695, US6537442, US6440888, US6652738 disclose containing group VIII/ VI B races 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, between the distribution and different activities metal to influence different hydrogenation active metals and Interaction relationship between active metal and carrier, to prevent hydrogenation activity with cracking activity from being coordinated 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, which are hydrocracked, disclosed in CN101239324A 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 and interactively coordinates bad problem between carrier.

CN103055923A discloses a kind of preparation method of hydrocracking catalyst.Using containing hydrogenation active metals acidity Solution, sodium metaaluminate alkaline solution and gas CO₂Plastic in the retort equipped with water purification is added in cocurrent；Then Y type molecules are 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, machinery Strength reduction, and lead to active metal localized clusters, the metal active position being exposed is limited.

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, to 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 relatively low, 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.

Invention content

In view of the deficiencies of the prior art, the present invention provides a kind of sulfurized hydrogenation Cracking catalyst and preparation method thereof. The distribution of hydrogenation active metals in the catalyst, improve hydrogenation active metals between and between carrier cooperation effect, Catalyst surface active bit density is improved, improves the utilization rate of hydrogenation active metals, while catalyst pore structure is reasonable, activity gold Belong to dispersion evenly, makes catalyst that there is higher performance.

Sulfurized hydrogenation Cracking catalyst of the present invention is vulcanization type body phase hydrocracking catalyst, and composition includes plus hydrogen is lived The sulfide of property metal component W and Ni, silica and aluminium oxide and molecular sieve；The wherein sulfide of table phase active metal component W With WS₂The sulfide of the weight content of meter and active metal component W in body phase are with WS₂The ratio of the weight content of meter is 2.0:1~ 7.0:1, preferably 3.0:1~6.0:Weight content of the sulfide of 1, table phase active metal component Ni in terms of NiS is mutually active with body The ratio of weight content of the sulfide of metal component Ni in terms of NiS is 1.5:1~5.5:1, preferably 1.8 ~ 4.5:1.

Sulfurized hydrogenation Cracking catalyst of the present invention, hydrogenation active metals W, Ni therein

It is to be present in catalyst with sulphided form, usually with WS₂, NiS form exist.

In the present invention, the weight content of the sulfide of table phase active metal component W is the sulfide of W in table phase with WS₂Meter Weight content, the weight content of the sulfide of body phase active metal component W is the sulfide of W in catalyst with WS₂The weight of meter Measure content；The weight content of the sulfide of table phase active metal component Ni is that weight of the sulfide of Ni in table phase in terms of NiS contains The weight content of amount, the sulfide of body phase active metal component Ni is weight content of the sulfide of Ni in catalyst in terms of NiS.

In hydrocracking catalyst of the present invention, on the basis of the weight of catalyst, the sulfide of W and Ni are with WS₂, NiS meter Total content be 20%~65%, preferably 30%~50%, W/Ni atomic ratios be 0.05~1.0, preferably 0.1~0.7, silica Content be 1wt%~40wt%, preferably 5wt%~35wt%, the content of aluminium oxide is 10wt%~40wt%, preferably 15wt% The content of~40wt%, molecular sieve are 5wt%~20wt%, preferably 5wt%~15wt%.

In hydrocracking catalyst of the present invention, adjuvant component can also be contained, the adjuvant component is the IVth B races metal, The content in hydrocracking catalyst is 1wt%~10wt% to IVth B races metal based on the element.IVth B races metal is preferred For 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, precipitating reagent, which is added dropwise to solution A, carries out plastic reaction, and generation contains Nickel, aluminum precipitation object slurries I；

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

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

（4）, step（3）The suspension of molecular sieve, stirring is added after being beaten uniformly in obtained material under stirring condition Uniformly, it is filtered, washed, it is dry,

（5）, to step（4）ATS (Ammonium thiosulphate) and adjuvant kneading, molding, drying are added in obtained material, then It is heat-treated in the presence of an inert gas, obtains sulfurized hydrogenation Cracking catalyst.

The preferred Y type molecular sieve of institute's addition molecular sieve in the method for the present invention.Y type molecular sieve is usually with molecular sieve suspension Form is added, i.e., molecular sieve is ground to the mesh of 80 mesh ~ 140, and the mesh of preferably 100 mesh ~ 120, then plus suspension is made in water.Described Y type molecular sieve is the Y type molecular sieve used in conventional hydrocracking catalyst.

Step（1）Or step（2）Described in precipitating reagent be sodium carbonate, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, hydroxide It is one or more in potassium, potassium carbonate, saleratus, preferably ammonium hydroxide, weights of ammonia a concentration of 5%~15%.

Step（1）In mixed solution A, weight concentrations 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.Step（2）In mixed solution B, W is with WO₃The weight of meter A concentration of 10~100g/L, preferably 20~90g/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 or more in Ludox, sodium metasilicate；Silicon source can be with For one or more of aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc..

Step（1）Middle reaction temperature is 20~90 DEG C, preferably 30~70 DEG C.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.

Step（2）Weight contents of Si, the Al of middle introducing in terms of oxide in the catalyst is 10wt%~70wt%, preferably 10wt%~90wt% of the total weight of Si, Al in terms of oxide is accounted in terms of silica for 20wt%~55wt%, wherein Si, preferably 30wt%~80wt%；Step（1）Weight contents of the Al of middle introducing in terms of oxide in the catalyst is 5wt%~45wt%, compared with It is 10wt%~30wt% well.

Step（2）Middle reaction temperature is 30~90 DEG C, preferably 40~80 DEG C.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.

Step（1）And step（2）Middle gelling temperature and time can be the same or different.Step（1）And step（2）It can It can not also be carried out simultaneously with being carried out at the same time.

Step（3）Middle aging temperature is 40~90 DEG C, preferably 50~80 DEG C.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.

Step（3）Described in hydrothermal conditions it is as follows：It is carried out under closed container, temperature is 200 ~ 300 DEG C, excellent 210 ~ 260 DEG C are selected as, pressure is 1.0 ~ 8.0MPa, and preferably 3.0 ~ 6.0MPa, processing time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours.

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

Step（4）The washing, dry this field conventional method that may be used carry out.Deionization is usually used in washing Water contains decomposable asymmetric choice net salt（Such as ammonium acetate, ammonium chloride, ammonium nitrate）Solution washs, and is washed till neutrality.The drying is general It is 1 ~ 48 hour dry at 50 ~ 200 DEG C.

Step（5）Described in ATS (Ammonium thiosulphate) addition with element sulphur be calculated as catalyst theory need sulfur content 100%~ 200%, preferably 105%~160%, the adjuvant are unsaturated hydro carbons, including one kind or more in alkene, alkadienes, alkynes Kind, or the mixture containing unsaturated hydro carbons（A concentration of 30v%~60v% of unsaturated hydro carbons）, including coking vapour One or more in oil, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil, the boiling point of adjuvant is 110~370 DEG C, The addition of adjuvant is calculated as step with unsaturated hydro carbons（4）The 3%~50% of gained dried material weight.

Step（5）The molding, dry this field conventional method that may be used carry out.It, can basis in forming process It needs to be added one or more in conventional shaping assistant, such as peptizing agent, extrusion aid etc..The peptizing agent be hydrochloric acid, One or more of in nitric acid, sulfuric acid, acetic acid, oxalic acid etc., the extrusion aid refers to the substance for being conducive to extrusion forming, such as sesbania One or more of powder, carbon black, graphite powder, citric acid etc., the dosage of auxiliary agent account for 1wt%~10wt% of total material butt.Institute Molding is stated, the shape of catalyst can be as needed for sheet, spherical, cylindrical bars and irregular bar（Clover, bunge bedstraw herb）, best It is cylindrical bars and irregular bar（Clover, bunge bedstraw herb）.The diameter of carrier can be 0.8 ~ 2.0mm slice and ＞ 2.5mm it is thick Item.The drying is generally 1 ~ 48 hour dry at 50 ~ 200 DEG C.

Step（5）The heat treatment is carried out in the presence of inert gas, hydrogen at least one gas, and treatment temperature is 200~600 DEG C, preferably 350~500 DEG C, processing time are 2~12 hours, preferably 4~10 hours.

In hydrocracking catalyst of the present invention, adjuvant component can also be contained, the adjuvant component is the IVth B races metal, The content in hydrocracking catalyst is 1wt%~10wt% to IVth B races metal based on the element.IVth B races metal is preferred For Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, it is added during preparing mixed solution A and contains auxiliary agent The compound of component, i.e. titanium source and/or zirconium source.Titanium source can be used it is one or more in Titanium Nitrate, titanium sulfate, titanium chloride etc., Zirconium source can be used one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride etc..

In hydrocracking catalyst of the present invention, all in the prior art can be used for plus hydrogen can be used in Y type molecular sieve used Y type molecular sieve in Cracking catalyst, such as：CN101343068A、CN1508228A、CN101450319A、CN 1209357A Disclosed in Y type molecular sieve.Y type molecular sieve disclosed in the preferred CN101343068A of the present invention, property are as follows：Compare table Area is 700m²/ g~950m²/ g, preferably 800~950m²/ g, total pore volume 0.30mL/g~0.55mL/g, relative crystallinity 90%~130%, SiO₂/Al₂O₃Molar ratio 30~150, preferably 50~150, cell parameter are 2.425~2.445nm, meleic acid 0.1~1.0mmol/g is measured, B Suan ∕ L acid is 7.0 or more, preferably 8.0 or more, sodium oxide content≤0.05wt%, preferably≤ 0.01wt%。

The heavy charge range that catalyst prepared by the method for the present invention is applicable in 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.

The method of the present invention uses positive addition（The acid precipitation method, that is, alkaline precipitating agent is added in acid metal salt solution and carries out Precipitation）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, being hydrocracked for gained made to urge The hydrogenation activity of agent obtains good cooperation with cracking activity, improves the performance of hydrocracking catalyst.

In the preparation method of catalyst of the present invention, steam treatment is simultaneously under appropriate conditions for the material that is 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 microscopic pattern 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 makes distribution of the active metal in table phase obviously increase, and disperses evenly, is conducive to improve surface work 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 More uniformly, be conducive to improve the mechanical strength of 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, makes gained The hydrogenation activity of hydrocracking catalyst obtains good cooperation with cracking activity, while catalyst pore structure is reasonable, and machinery is strong Degree is high, has excellent hydrogenation cracking activity.

Catalyst of the present invention be complete cure type catalyst, directly in presence of hydrogen heating go into operation, empty calory and Hydrogen sulfide gas release, effectively prevent ex situ presulfiding catalyst bed be easy to temperature runaway and heating initial stage device it is airtight the problems such as.

The present invention adds hydrogen using hydrocracking catalyst made of preferred Y type molecular sieve particularly suitable as High middle distillate Cracking catalyst not only has high hydrogenation cracking activity, but also has high middle distillates oil selectivity, while also having relatively strong resistance to nitrogen ability Etc. good performance.Catalyst of the present invention is suitable for single hop once by hydrocracking process, hydrocracking operation Condition is as follows：Reaction temperature is 300~500 DEG C, more preferably 350~450 DEG C；Pressure be 6~20MPa, more preferably 13~ 17MPa；Volume space velocity is 0.5~3 h when liquid^-1, preferably 0.8~1.5 h^-1；Hydrogen to oil volume ratio is 400~2000:1, it is best It is 800~1500:1.The catalyst is used in single-stage hydrocracking technical process, has liquid yield height, good product quality etc. Advantage.

Specific implementation mode

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, sodium content to use plasma emission spectrometry, and mutually activity is golden for catalyst table Belong to content and uses x-ray photoelectron spectroscopy（XPS）It measures, caltalyst phase active metallic content uses inductively coupled plasma Body atomic emission spectrum（ICP-AES）It measures, transmission electron microscope（TEM catalyst surface WS) is measured₂Density.Mechanical strength is to use What side pressure method measured.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Nickel chloride, liquor alumini chloridi are dissolved in water purification respectively, are configured to mixed solution A, the weight of NiO in mixed solution A A concentration of 23g/L, Al₂O₃Weight concentration be 5g/L, ammonium metatungstate, liquor alumini chloridi are dissolved in water purification respectively, dilute water glass is added Glass solution, is configured to mixed solution B, WO in mixed solution B₃Weight concentration be 20g/L, Al₂O₃Weight concentration be 18g/ L, SiO₂Weight concentration be 30g/L.Solution A is added in a concentration of 10% ammonium hydroxide under stiring, gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.1000mL is net Water is added in retort, and a concentration of 10% ammonium hydroxide and solution B cocurrent are added in retort, and gelling temperature is maintained at 55 DEG C, and Flowing pH value control in plastic reaction process, 7.6, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries at 60 minutes II.Aging after above two is mixed containing sediment slurry, ageing time 2 hours, 75 DEG C of aging temperature, pH value control at the end of aging Then system filters, filter cake carries out hydro-thermal process under the water vapour containing urea, and the condition of hydro-thermal process is 7.6：Urea and The molar ratio of active metal atom total amount is 6:1, temperature is 230 DEG C, pressure 4.5MPa, and processing time is 4 hours, after processing Filter cake is beaten, the Y type molecular sieve suspension for accounting for catalyst weight 10wt% is added into mix slurry in terms of butt（It presses It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property is shown in Table 6, it made to be dispersed in mixed serum, filters, only Water washing 3 times, it is 8 hours dry at 100 DEG C, by material, ATS (Ammonium thiosulphate)（ATS (Ammonium thiosulphate) addition is calculated as being catalyzed with element sulphur Agent theory needs the 120% of sulfur content）And laurylene（Laurylene addition accounts for the 10% of weight of material）It is rolled after mixing, extruded moulding. It is 10 hours dry at 80 DEG C.It is heat-treated in the presence of hydrogen gas, 450 DEG C of constant temperature 4 hours obtains catalyst A.Catalyst group It is shown in Table 1 at, pore size distribution and main character.

Embodiment 2

According to the method for embodiment 1, is matched by the constituent content of the catalyst B in table 1, nitric acid is added into dissolving tank 1 Nickel, aluminum nitrate solution prepare working solution A, and after addition aluminum nitrate, ammonium metatungstate are dissolved in water purification into dissolving tank 2, dilute water is added Glass prepares working solution B.Solution A is added in a concentration of 15% ammonium hydroxide under stiring, gelling temperature is maintained at 45 DEG C, terminates When pH value control 8.0, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.800mL water purifications are added anti- It answers in tank, a concentration of 15% ammonium hydroxide and solution B cocurrent is added in retort, gelling temperature is maintained at 50 DEG C, and cocurrent plastic is anti- 8.2, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control during answering.It will be above-mentioned Two kinds containing aging after sediment slurry mixing, ageing time 3 hours, 70 DEG C of aging temperature, at the end of aging pH value control 8.0, Then it filters, filter cake carries out hydro-thermal process under the water vapour containing urea, and the condition of hydro-thermal process is：Urea and active metal The molar ratio of atom total amount is 5:1, temperature is 250 DEG C, pressure 3.5MPa, and processing time is 3 hours, plays filter cake after processing The Y type molecular sieve suspension for accounting for total catalyst weight 15wt% is added in terms of butt to slurries in slurry（Implement by CN101343068A It is prepared by example 7）, Y type molecular sieve property is shown in Table 6, it is made to be dispersed in the mixed serum that plastic obtains, filters, dry at 80 DEG C Dry 10 hours, by material, ATS (Ammonium thiosulphate)（ATS (Ammonium thiosulphate) addition is calculated as catalyst theory with element sulphur needs sulfur content 130%）And catalytic gasoline（Presence of unsaturates is 52.8v%）（In terms of unsaturated hydrocarbons weight, catalytic gasoline addition accounts for material The 12% of weight）It is rolled after mixing, extruded moulding.It is 7 hours dry at 120 DEG C.It is heat-treated in the presence of hydrogen gas, 400 DEG C Constant temperature 6 hours, obtains catalyst B.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, 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 after addition aluminium chloride, ammonium metatungstate are dissolved in water purification into dissolving tank 2, dilute water is added Glass prepares working solution B.Solution A is added in a concentration of 10% ammonium hydroxide under stiring, gelling temperature is maintained at 55 DEG C, terminates When pH value control 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 90 minutes.It is added in retort and is equipped with A concentration of 10% ammonium hydroxide and solution B cocurrent are added in retort for 900mL water purifications, and gelling temperature is maintained at 45 DEG C, cocurrent at 8.0, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control in glue reaction process.It will Above two is mixed containing sediment slurry.Aging after above two is mixed containing sediment slurry, ageing time 2.5 hours, aging temperature 72 DEG C of degree, pH value is controlled 7.8 at the end of aging, is then filtered, and filter cake carries out hydro-thermal process under the water vapour containing urea, The condition of hydro-thermal process is：The molar ratio of urea and active metal atom total amount is 4:1, temperature is 240 DEG C, and pressure is 6.0MPa, processing time are 4 hours, are beaten filter cake after processing, account for total catalyst weight 12wt%'s to the addition of sediment slurries Y type molecular sieve suspension is in terms of butt（It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property is shown in Table 6, makes it Even to be scattered in the mixed serum that plastic obtains, filtering is 9 hours dry at 110 DEG C, by material, ATS (Ammonium thiosulphate)（Thiosulfuric acid Ammonium addition is calculated as catalyst theory with element sulphur needs the 115% of sulfur content）And hexene（Hexene addition accounts for the 10% of weight of material） It is rolled after mixing, extruded moulding.It is 7 hours dry at 120 DEG C.It is heat-treated in the presence of hydrogen gas, 350 DEG C of constant temperature hours, Obtain catalyst C.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

According to the method for embodiment 1, is matched by the constituent content of the catalyst D in table 1, chlorination is added into dissolving tank 1 Nickel, liquor alumini chloridi, preparating acid sex work solution A are added after into dissolving tank 2, addition aluminium chloride, ammonium metatungstate are dissolved in water purification Dilute waterglass preparating acid sex work solution B.Solution A is added in a concentration of 10% ammonium hydroxide under stiring, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 80 minutes.Retort is added In 1000mL water purifications are housed, a concentration of 10% ammonium hydroxide and solution B cocurrent are added in retort, gelling temperature is maintained at 60 DEG C, 8.0, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries at 60 minutes for pH value control in cocurrent plastic reaction process II.Above two is mixed containing sediment slurry.Aging after above two is mixed containing sediment slurry, ageing time 2 hours, aging 75 DEG C of temperature, pH value is controlled 7.8 at the end of aging, is then filtered, filter cake carries out under the water vapour containing urea at hydro-thermal Reason, the condition of hydro-thermal process are：The molar ratio of urea and active metal atom total amount is 3.0:1, temperature is 260 DEG C, and pressure is 5.0MPa, processing time are 5 hours, are beaten filter cake after processing, are added to the mixing of sediment slurries and account for total catalyst weight The Y type molecular sieve suspension of 8wt% is in terms of butt（It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property is shown in Table 6, So that it is dispersed in the mixed serum that plastic obtains, filters, it is 6 hours dry at 80 DEG C, by material, ATS (Ammonium thiosulphate)（Sulphur Ammonium thiosulfate addition is calculated as catalyst theory with element sulphur needs the 150% of sulfur content）And coker gasoline（Presence of unsaturates is 45.2v%）（It is calculated with the weight of unsaturated hydrocarbons, coker gasoline addition accounts for the 20% of weight of material）Rolled after mixing, extrusion at Type.It is 10 hours dry at 100 DEG C.It is heat-treated in the presence of hydrogen gas, 500 DEG C of constant temperature 4 hours obtains catalyst D.Catalysis Agent composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

It is prepared according to method disclosed in CN101239324A, catalyst composition forms identical with embodiment 1, and specific steps are such as Under：

(1) it prepares and contains Al₂O₃320 milliliters of the liquor alumini chloridi of a concentration of 120g/L, it is molten containing the nickel chloride that NiO is 44g/L 270 milliliters of liquid contains ZrO₂50 milliliters of 100g/L zirconyl chloride solutions are simultaneously mixed in one 5 liters of container, are added 2000 milliliters Water purification dilutes；

(2) dilute water glass solution is prepared, SiO is contained₂310 milliliters of the water glass solution of 100g/L under agitation will (2) it is added in (1)；

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

(4) 240 milliliters of sodium tungstate solution is 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 stands aging 2.0 hours at 75 DEG C, and pH value control is 7.6 at the end of aging；It is added and accounts for before aging The Y type molecular sieve suspension of total catalyst weight 10wt% is in terms of butt（It is prepared by CN101343068A embodiments 7）, Y type molecules Sieve property is shown in Table 6,

(8) it filters, filter cake is 8 hours dry at 100 DEG C, by material, ATS (Ammonium thiosulphate)（ATS (Ammonium thiosulphate) addition is with sulphur Element, which is calculated as catalyst theory, needs the 120% of sulfur content）And laurylene（Laurylene addition accounts for the 10% of weight of material）It is ground after mixing Pressure, extruded moulding.It is 10 hours dry at 80 DEG C.It is heat-treated in the presence of hydrogen gas, 450 DEG C of constant temperature 4 hours obtains reference Agent E, 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 is 230 DEG C, pressure 4.5MPa, and processing 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 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 is 230 DEG C, pressure 4.5MPa, and processing time is 3 hours, prepares reference Agent H.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 5

It is prepared by method disclosed in CN103055923A, catalyst composition forms identical with embodiment 1, and specific steps are such as Under：

(1) acid solution A is prepared：It is formed by 1 catalyst of embodiment, nickel chloride, ammonium metatungstate, zirconium oxychloride is 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) configuration 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 55 DEG C, pH Value is 7.6.CO wherein 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, ensure while being dripped off, to ensure that it is constant that catalyst distribution uniformly forms.

(4) after cemented into bundles, in the case where being stirred continuously, hydrothermal treatment modification is added and accounts for total catalyst weight The Y type molecular sieve suspension of 10wt% is in terms of butt（It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property is shown in Table 6, So that it is dispersed in the mixed serum that plastic obtains, aging 2 hours are stood at 75 DEG C or so.

(5) it filters, filter cake is 8 hours dry at 100 DEG C, by material, ATS (Ammonium thiosulphate)（ATS (Ammonium thiosulphate) addition is with sulphur Element, which is calculated as catalyst theory, needs the 120% of sulfur content）And laurylene（Laurylene addition accounts for the 10% of weight of material）It is ground after mixing Pressure, extruded moulding.It is 10 hours dry at 80 DEG C.It is heat-treated in the presence of hydrogen gas, 450 DEG C of constant temperature 4 hours is catalyzed Agent I.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 5

By middle oil type hydrocracking catalyst A, B, C, D of the present invention and reference catalyst E, F, G, H, I in midget plant Upper evaluation result is compared.Evaluation condition is：React stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity when liquid 1.5h^-1, evaluation is Iranian VGO heavy distillates 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 prepared by the use present invention from the data of table 5 The activity and middle distillates oil selectivity of catalyst A, B, C, D are better than reference agent, illustrate catalyst activity metal profit prepared by this method With rate height, catalyst reaction activity significantly improves.

1 catalyst of table forms and property

Catalyst is numbered	A	B	C	D	E
						Catalyst forms
NiS, wt%	22	18	20	20	22
						WS2, wt%	20	26	18	24	20
SiO2, wt%	20	15	25	25	20
						Al2O3, wt%	28	36	25	23	28
Y molecular sieve, wt%	10	15	12	8	10
						Catalyst property
Specific surface area *, m2/g	385	371	389	390	281
						Hole holds *, mL/g	0.389	0.382	0.385	0.399	0.278
Intensity, N/mm	22.1	21.4	22.5	22 .1	19.3
						Pore size distribution *, %
＜ 4nm	15.01	16.02	15.42	14.25	51.30
						4nm~8nm	65.41	65.14	66.51	67.43	43.91
8nm~15nm	15.12	14.85	15.11	15.28	1.89
						＞ 15nm	4.46	3.99	2.96	3.04	2.90

Continued 1

Catalyst is numbered	F	G	H	I
					Catalyst forms
NiS, wt%	22	22	22	22
					WS2, wt%	20	20	20	20
SiO2, wt%	20	20	20	20
					Al2O3, wt%	28	28	28	28
Y molecular sieve, wt%	10	10	10	10
					Catalyst property
Specific surface area *, m2/g	345	354	362	304
					Hole holds *, mL/g	0.341	0.350	0.365	0.335
Intensity, N/mm	18.9	18.5	18.1	19.4
					Pore size distribution *, %
＜ 4nm	28.24	24.86	25.72	14.96
					4nm~8nm	34.16	38.35	33.94	35.85
8nm~15nm	24.95	23.26	24.85	36.11
					＞ 15nm	12.65	13.53	15.49	13.08

Note：The specific surface area of catalyst, Kong Rong and pore size distribution are passed through by sulfide type catalyst in Muffle furnace in table 1 Air, room temperature are warming up to 230 DEG C ~ 260 DEG C constant temperature for 3 hours 4 hours, continue to be warming up to for 3 hours 400 DEG C ~ 420 DEG C constant temperature 4 hours, It is converted into the result that oxidized catalyst measures

The weight content of 2 catalyst table phase active metal sulphides of table and the weight content of body phase active metal sulphides it Than

Catalyst is numbered	A	B	C	D	E
						Table phase IW/ body phase IW	5.25	4.97	5.07	4.19	0.99
Table phase INi/ body phase INi	3.98	3.57	3.72	2.89	0.96

Continued 2

Catalyst is numbered	F	G	H	I
					Table phase IW/ body phase IW	1.05	1.08	1.13	1.25
Table phase INi/ body phase INi	1.07	1.13	1.10	1.19

3 catalyst surface WS of table₂Density

Catalyst is numbered	A	B	C	D	E	F	G	H	I
										WS2Density, grain/100nm	80	78	76	75	41	43	44	45	49

4 feedstock oil main character of table

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

5 evaluating catalyst result of table

Catalyst is numbered	A	B	C	D	E
						Reaction temperature, DEG C	390	391	389	391	398
Product distribution, wt%
						Light naphthar（C5~82℃）	5.5	5.4	5.9	5.6	7.0
Heavy naphtha（82~138℃）	9.5	9.3	9.0	9.4	9.8
						Jet fuel（138℃~249℃）	27.1	26.8	27.1	26.8	23.2
Diesel oil（249℃~371℃）	26.9	28.1	27.9	27.7	24.1
						Tail oil（>371℃）	31.0	30.4	30.1	30.5	35.9
Middle distillates oil selectivity, wt%	78.2	78.8	78.6	78.4	73.8

Continued 5

Catalyst is numbered	F	G	H	I
					Reaction temperature, DEG C	396	397	398	397
Product distribution, wt%
					Light naphthar（C5~82℃）	6.1	5.9	6.9	6.4
Heavy naphtha（82~138℃）	9.7	10..2	9.6	10.1
					Jet fuel（138℃~249℃）	23.5	23.3	23.2	23.4
Diesel oil（249℃~371℃）	24.7	23.8	24.2	24.3
					Tail oil（>371℃）	36.0	36.8	36.1	35.8
Middle distillates oil selectivity, wt%	75.3	74.5	74.2	74.3

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

Molecular sieve property	Y
		Relative crystallinity, %	117
Cell parameter, nm	2.429
		SiO2/Al2O3Molar ratio	80.4
Specific surface area, m2/g	876
		Kong Rong, mL/g	0.493
Infrared total acid, mmol/g	0.240
		B Suan ∕ L acid	11.36
Na2O, wt%	<0.01

Claims (30)

1. a kind of hydrocracking catalyst, which is body phase hydrocracking catalyst, and composition includes hydrogenation active metals Sulfide, aluminium oxide, silica and the molecular sieve of component W and Ni；Wherein the sulfide of table phase active metal component W is with WS₂Meter Weight content and active metal component W in body phase sulfide with WS₂The ratio of the weight content of meter is 2.0:1~7.0:1, table The sulfide of weight content of the sulfide of phase active metal component Ni in terms of NiS and body phase active metal component Ni are in terms of NiS Weight content ratio be 1.5:1~5.5:1.

2. catalyst described in accordance with the claim 1, it is characterised in that：In the hydrocracking catalyst, table phase active metal The sulfide of component W is with WS₂The sulfide of the weight content of meter and active metal component W in body phase are with WS₂The weight content of meter Than being 3.0:1~6.0:Weight content and body phase active metal component of the sulfide of 1, table phase active metal component Ni in terms of NiS The ratio of weight content of the sulfide of Ni in terms of NiS is 1.8 ~ 4.5:1.

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, the sulfide of W and Ni are with WS₂, NiS meters total content be 20%~65%, W/Ni atomic ratios be 0.05~1.0, oxygen The content of SiClx is 1wt%~40wt%, and the content of aluminium oxide is 10wt%~40wt%, and the content of molecular sieve is 5wt%~20wt%.

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, the sulfide of W and Ni are with WS₂, NiS meters total content be 30%~50%, W/Ni atomic ratios be 0.1~0.7, aoxidize The content of silicon is 5wt%~35wt%, and the content of aluminium oxide is 15wt%~40wt%, and the content of molecular sieve is 5wt%~15wt%.

5. catalyst described in accordance with the claim 1, it is characterised in that：The molecular sieve is Y type molecular sieve, and property is as follows： Specific surface area is 700m²/ g~950m²/ g, total pore volume are 0.30mL/g~0.55mL/g, and relative crystallinity is 90%~130%, SiO₂/Al₂O₃Molar ratio is 30~150, and cell parameter is 2.425~2.445nm, and meleic acid amount is 0.1~1.0mmol/g, B Suan ∕ L acid is 7.0 or more, sodium oxide content≤0.05wt%.

6. according to any catalyst of claim 1-5, it is characterised in that：In the hydrocracking catalyst, containing helping Agent component, the adjuvant component are Ti and/or Zr, and the content in hydrocracking catalyst is 1wt%~10wt% based on the element.

7. the preparation method of any catalyst of Claims 1 to 5, including：

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

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

（4）, step（3）The suspension of molecular sieve is added after being beaten uniformly in obtained material under stirring condition, stirring is equal It is even, it is filtered, washed, it is dry；

（5）, to step（4）ATS (Ammonium thiosulphate) and adjuvant kneading, molding, drying are added in obtained material, then lazy It is heat-treated in the presence of property gas, obtains sulfurized hydrogenation Cracking catalyst；

Wherein, step（5）The adjuvant is unsaturated hydro carbons, including one or more in alkene, alkynes or for containing One kind in the mixture of unsaturated hydro carbons, including coker gasoline, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil or A variety of, the boiling point of adjuvant is 110~370 DEG C, wherein a concentration of 30v%~60v% of unsaturated hydro carbons.

8. according to the method for claim 7, it is characterised in that：Institute's addition molecular sieve is Y type molecular sieve, molecular sieve suspension Molecular sieve is ground to the mesh of 80 mesh ~ 140, then plus suspension is made in water.

9. according to the method for claim 8, it is characterised in that：Institute's addition molecular sieve is Y type molecular sieve, molecular sieve suspension Molecular sieve is ground to the mesh of 100 mesh ~ 120, then plus suspension is made in water.

10. according to the method for claim 7, it is characterised in that：Step（1）Or step（2）Described in precipitating reagent be carbon It is one or more in sour sodium, sodium bicarbonate, ammonium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, saleratus.

11. according to the method for claim 10, it is characterised in that：Step（1）Or step（2）Described in precipitating reagent be ammonia Water, weights of ammonia a concentration of 5%~15%.

12. according to the method for claim 7, it is characterised in that：Step（1）In mixed solution A, weight of the Ni in terms of NiO A concentration of 5~80g/L, Al is with Al₂O₃The weight concentration of meter is 10~80g/L.

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

14. according to the method for claim 7, it is characterised in that：Step（2）In 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.

15. according to the method for claim 14, it is characterised in that：Step（2）In mixed solution B, W is with WO₃The weight of meter is dense Degree is 20~90g/L, and Si is with SiO₂Weight concentration is 20~80g/L, and Al is with Al₂O₃The weight concentration of meter is 20~60g/L.

16. according to the method for claim 7, it is characterised in that：Step（1）Middle reaction temperature is 20~90 DEG C, when plastic Between be 0.2 ~ 4.0 hour, pH value control is 6.0 ~ 11.0 when cemented into bundles.

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

18. according to the method for claim 7, it is characterised in that：Step（2）Si, Al of middle introducing are 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 10wt%~90wt%；Step（1）Weight contents of the Al of middle introducing in terms of oxide in the catalyst is 5wt%~45wt.

19. according to the method for claim 18, it is characterised in that：Step（2）Si, Al of middle introducing are 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 30wt%~80wt%；Step（1）Weight contents of the Al of middle introducing in terms of oxide in the catalyst is 10wt%~30wt%.

20. according to the method for claim 7, it is characterised in that：Step（2）Middle reaction temperature be 30~90 DEG C, cocurrent at PH value control is 6.0 ~ 11.0 when glue, and gelation time is 0.2 ~ 4.0 hour.

21. according to the method for claim 20, it is characterised in that：Step（2）Middle reaction temperature be 40~80 DEG C, cocurrent at PH value control is 7.0 ~ 9.0 when glue, and gelation time is 0.5 ~ 3.0 hour.

22. according to the method for claim 7, it is characterised in that：Step（3）Middle aging temperature is 40~90 DEG C, when aging PH value control is 6.0 ~ 10.0, and ageing time is 0.5 ~ 6.0 hour.

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

24. according to the method for claim 7, it is characterised in that：Step（3）Described in hydrothermal conditions it is as follows： It is carried out under closed container, temperature is 200 ~ 300 DEG C, and pressure is 1.0 ~ 8.0MPa, and 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 in the addition and catalyst of urea：1~10.0： 1。

25. the method described in claim 24, it is characterised in that：Step（3）Described in hydrothermal conditions it is as follows：Closed Container under carry out, temperature be 210 ~ 260 DEG C, pressure be 3.0 ~ 6.0MPa, processing time be 1.0 ~ 6.0 hours；Step（3） In, when hydro-thermal process, the molar ratio of active metal atom total amount is 2.0 in the addition and catalyst of urea：1~8.0:1.

26. according to the method for claim 7, it is characterised in that：Step（5）Described in ATS (Ammonium thiosulphate) addition with Element sulphur, which is calculated as catalyst theory, needs the 100%~200% of sulfur content.

27. according to the method for claim 7, it is characterised in that：Step（5）Described in ATS (Ammonium thiosulphate) addition with Element sulphur, which is calculated as catalyst theory, needs the 105%~160% of sulfur content.

28. according to the method for claim 7, it is characterised in that：Step（5）The addition of middle adjuvant is with unsaturated hydro carbons It is calculated as step（4）The 3%~50% of gained dried material weight.

29. according to the method for claim 7, it is characterised in that：Step（4）The heat treatment is in inert gas, hydrogen It is carried out in the presence of gas at least one gas, treatment temperature is 200~600 DEG C, and processing time is 2~12 hours.

30. according to the method for claim 29, it is characterised in that：Step（4）The heat treatment, treatment temperature 350 ~500 DEG C, processing time is 4~10 hours.