CN106179464B - A kind of preparation method of hydrocracking catalyst - Google Patents

Abstract

The invention discloses a kind of preparation methods of hydrocracking catalyst.The catalyst is body phase hydrocracking catalyst, its composition includes hydrogenation active metal component W and Ni, aluminium oxide, silica and molecular sieve, preparation method is utilized in the method for carrying out ammonia still process precipitation in the presence of organic compound and prepares nickeliferous, aluminum precipitation object slurries I, tungstenic, silicon, aluminum precipitation object slurries II are prepared using cocurrent plastic method, urea is added simultaneously using hydro-thermal process in aging after the two is mixed, be added molecular sieve when being then beaten, then through molding and etc. catalyst is made.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 preparation method of hydrocracking catalyst

Technical field

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

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.

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 preparation methods of body phase hydrocracking catalyst.The party Method improves the distribution of hydrogenation active metals in catalyst, improves between hydrogenation active metals and cooperation between carrier is made With, catalyst surface active bit density is improved, improves the utilization rate of hydrogenation active metals, while catalyst pore structure is reasonable, it is living Property metal dispersion evenly, make catalyst have higher performance.

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

（1）, prepare the mixed solution A containing Ni, Al component salt and organic compound, ammonium hydroxide be added solution A make reactant Solution A is heated carry out ammonia still process generation precipitation under agitation by the pH value of system 10 or more, until slurry pH value is less than 10, it is raw At nickeliferous, aluminum precipitation object slurries I；

（2）, prepare the component saline solution B containing W, Si, Al, ammonium hydroxide and material B cocurrents generate tungstenic, silicon, aluminum precipitation object slurry Liquid 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 filters, obtains material through drying, molding, washing；

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

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.

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%~50%, W/Ni atomic ratio are 0.05~1.0, preferably 0.1~0.7, the content of silica is 1%~ 40%, preferably 5%~35%, the content of aluminium oxide are 10%~40%, preferably 15%~40%, the content of molecular sieve be 5wt%~ 20wt%, preferably 5wt%~15wt%.

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 2~60g/L, preferably 8~40g/L.Step（2）In mixed solution B, W is with WO₃The weight of meter is dense Degree is 10~100g/L, and preferably 20~90g/L, Si is with SiO₂Weight concentration be 10~120g/L, preferably 20~80g/L, Al is with Al₂O₃The weight concentration of meter is 2~60g/L, preferably 8~40g/L.When preparing mixed solution A, the nickel that generally uses 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）In, organic compound is the macromolecular compound for being dissolved in water, in polyethylene glycol, polyvinyl alcohol etc. It is one or more, wherein the molecular weight of polyethylene glycol be 200 ~ 10000, preferably 1000 ~ 8000, the molecular weight of polyvinyl alcohol It is 5000 ~ 25000, preferably 12000 ~ 20000.The dosage of the organic compound accounts for step（1）The nickeliferous, aluminum precipitation of middle generation Object（In terms of nickel oxide and aluminium oxide）5wt% ~ 70wt% of weight, preferably 10wt% ~ 60wt%.

Step（1）When solution A is added in middle ammonium hydroxide, system temperature control is 30~70 DEG C, and preferably 40~60 DEG C, ammonia is added The pH value of reaction system is controlled after water in 10 or more, preferably 10~13, ammonia still process makes the pH value of reaction system be less than 10, preferably 7.5~9.5, ammonia still process temperature is 80~150 DEG C, and preferably 80~120 DEG C, time of ammonia distillation is controlled at 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.Step（1）In ammonium hydroxide used weight concentration be 15%~28%.

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（2）In ammonium hydroxide used Weight concentration is 5%~15%.

Step（2）Weight contents of Si, the Al of middle introducing in terms of oxide in the catalyst is 5wt%~70wt%, preferably 10wt%~90wt% of the total weight of Si, Al in terms of oxide is accounted in terms of silica for 10wt%~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（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 drying, molding and washing may be used this field conventional method and carry out.The drying is general It is 1 ~ 48 hour dry at 50 ~ 200 DEG C.In forming process, it can be added conventional shaping assistant as needed, such as peptizing agent, It is one or more in extrusion aid etc..The peptizing agent is one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., The extrusion aid refer to be conducive to one kind in the substance of extrusion forming, such as sesbania powder, carbon black, graphite powder, citric acid or Several, the dosage of auxiliary agent accounts for 1wt%~10wt% of total material butt.Washing is usually used deionized water or contains decomposable asymmetric choice net salt Class（Such as ammonium acetate, ammonium chloride, ammonium nitrate）Solution washs, and is washed till neutrality.The shape of the molding, catalyst can be according to need To be sheet, spherical, cylindrical bars and irregular bar（Clover, bunge bedstraw herb）, preferably cylindrical bars and irregular bar（Clover, four leaves Grass）.The diameter of carrier can be the slice of 0.8 ~ 2.0mm and the thick item of > 2.5mm.

Step（5）This field normal condition may be used in the drying and roasting, and such as at 50 ~ 200 DEG C, drying 1 ~ 48 is small When, 1 ~ 24 hour, preferably 2 ~ 8 hours are roasted 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 races metal, Content of the IVth B family metal oxides in hydrocracking catalyst is 1wt%~10wt%.IVth B races metal is preferably Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, group containing auxiliary agent is added during preparing mixed solution A The compound divided, i.e. titanium source and/or zirconium source.One or more in Titanium Nitrate, titanium sulfate, titanium chloride etc., zirconium can be used in titanium source 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 is 0.30mL/g~0.55mL/g, opposite to crystallize Degree is 90%~130%, SiO₂/Al₂O₃Molar ratio is 30~150, preferably 50~150, and cell parameter is 2.425~2.445nm, Meleic acid amount is 0.1~1.0mmol/g, and B Suan ∕ L acid is 7.0 or more, preferably 8.0 or more, sodium oxide content≤0.05wt%, Preferably≤0.01wt%.

Hydrocracking catalyst prepared by the method for the present invention is body phase hydrocracking catalyst, and composition includes hydrogenation activity Metal component W and Ni, aluminium oxide, silica and molecular sieve；Wherein table phase active metal component WO₃Weight content mutually live with body Property metal component WO₃Weight content ratio be 1.2:1~6.0:1, preferably 1.8:1~4.5:1, table phase active metal component The ratio of the weight content of NiO and the weight content of body phase active metal component NiO is 1.2:1~5.0:1, preferably 1.5 ~ 3.5: 1。

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 prepared by the method for the present invention is as follows：Specific surface area is 250~650m²/ g, Kong Rong For 0.35~0.80mL/g, pore-size distribution is as follows：Kong Rong shared by a diameter of holes below 4nm accounts for the 1% ~ 20% of total pore volume, directly It is 55% ~ 80% that diameter, which is that Kong Rong accounts for total pore volume shared by the hole of 4 ~ 8nm, and the Kong Rong shared by the hole of a diameter of 8 ~ 15nm accounts for total pore volume It is 0.1% ~ 5.0% that the Kong Rong of 2% ~ 20%, a diameter of 15nm or more, which account for total pore volume, and preferred pore-size distribution is as follows：A diameter of 4nm Kong Rong shared by hole below accounts for the 5% ~ 17% of total pore volume, Kong Rong shared by the hole of a diameter of 4 ~ 8nm account for total pore volume be 61% ~ 75%, the Kong Rong shared by the hole of a diameter of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume, and the Kong Rong of a diameter of 15nm or more accounts for total pore volume It is 0.5% ~ 5.0%.

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 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 the method for being added to ammonium hydroxide and then carrying out ammonia still process in acid metal salt solution, and crystalline substance can be obtained Grain is relatively large and evengranular nickel, aluminum precipitation object, while the introducing of organic compound, it is therefore prevented that in ammonia still process reaction process The aggregation of nickel, aluminum precipitation object is more advantageous to active metal nickel and is present in carbon monoxide-olefin polymeric table phase；Cocurrent process prepares crystal grain phase To smaller tungsten, silicon, aluminum precipitation object, above two sediment is mixed, the distribution of different hydrogenation active metals, table can be controlled Tungsten, nickel active metal can better contact in phase, be conducive to form high activity phase between active metal tungsten, nickel, and improve activity Interaction between metal and carrier makes the hydrogenation activity of the hydrocracking catalyst of gained obtain good match with cracking activity It closes, 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.

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 and zirconium oxychloride are dissolved in water purification respectively, addition accounts in solution nickel and aluminium with nickel oxide The polyethylene glycol for being 6000 with the molecular weight of aluminium oxide weight calculation amount 15wt%, is configured to mixed solution A, NiO in mixed solution A Weight concentration is 21g/L, Al₂O₃Weight concentration be 5g/L, ZrO₂Weight concentration 5g/L.Respectively by ammonium metatungstate, aluminium chloride Solution 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 be 25g/ L, Al₂O₃Weight concentration be 18g/L, SiO₂Weight concentration be 20g/L.Solution temperature is raised to 40 DEG C in retort 1, Xiang Rong The ammonium hydroxide of a concentration of 25wt% is added in liquid A until forming dark blue solution, solution ph 10.5 continues solution being warming up to 100 DEG C, ammonia still process 2 hours, pH value 7.8 obtains nickeliferous, aluminium sediment slurries I.1000mL water purifications are added in retort 2, A concentration of 10 wt % ammonium hydroxide and solution B cocurrent are added in retort 2, gelling temperature is maintained at 55 DEG C, and cocurrent plastic was reacted 7.6, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control in journey.By above two Aging after being mixed containing sediment slurry, ageing time 2 hours, 75 DEG C of aging temperature, pH value control is 7.6 at the end of aging, then Filtering, filter cake carry out hydro-thermal process under the water vapour containing urea, and the condition of hydro-thermal process is：Urea and active metal atom The molar ratio of total amount is 7:1, temperature is 230 DEG C, pressure 4.5MPa, and processing time is 3 hours, is beaten filter cake after processing, The Y type molecular sieve suspension for accounting for total catalyst weight 10wt% is added into mix slurry in terms of butt（By CN101343068A It is prepared by embodiment 7）, Y type molecular sieve property is shown in Table 6, it made to be dispersed in mixed serum, filters, and at 100 DEG C, dry 8 is small When, it rolls, extruded moulding.It is washed at room temperature with water purification.Then 10 hours dry at 80 DEG C, 550 DEG C roast 4 hours, are urged Agent A.Catalyst composition, pore size distribution and main character are shown in Table 1.

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, titanium chloride, aluminum nitrate solution, addition account for nickel and aluminium in solution and are with the molecular weight of nickel oxide and aluminium oxide weight calculation amount 22wt% 18000 polyvinyl alcohol is configured to solution A after stirring evenly.Prepare working solution A, into dissolving tank 2 be added aluminum nitrate, partially After ammonium tungstate is dissolved in water purification, dilute waterglass is added and prepares working solution B.Solution temperature is raised to 50 DEG C in retort 1, to solution A Until forming dark blue solution, solution ph 13.0 continues solution being warming up to 100 the middle ammonium hydroxide that a concentration of 18wt% is added DEG C, ammonia still process 1 hour, pH value 8.2 obtains nickeliferous, aluminium slurries I.1000mL water purifications are added in retort 2, it will be a concentration of 8wt% ammonium hydroxide and solution B cocurrent are added in retort 2, and gelling temperature is maintained at 50 DEG C, pH value control in cocurrent plastic reaction process For system 7.6, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes.Above two is contained into sediment slurry Aging after mixing, ageing time 3 hours, 70 DEG C of aging temperature, pH value is controlled 8.0 at the end of aging, is then filtered, filter cake exists Hydro-thermal process is carried out under water vapour containing urea, the condition of hydro-thermal process is：Mole of urea and active metal atom total amount Than being 6:1, temperature is 250 DEG C, pressure 3.5MPa, and processing time is 3 hours, is beaten filter cake after processing, is added to slurries The Y type molecular sieve suspension of total catalyst weight 12wt% is accounted in terms of butt（It is prepared by CN101343068A embodiments 7）, Y types point Son sieve property is shown in Table 6, so that it is dispersed in the mixed serum that plastic obtains, filters, 7 hours dry at 120 DEG C, rolls, Extruded moulding.It is washed at room temperature with water purification.Then 12 hours dry at 100 DEG C, 500 DEG C roast 5 hours, obtain catalyst B.It urges Agent 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, it is 14000 to be added and account in solution nickel and aluminium with the molecular weight of nickel oxide and aluminium oxide weight calculation amount 30wt% Polyvinyl alcohol is configured to solution A after stirring evenly, prepare working solution A, and it is molten that aluminium chloride, ammonium metatungstate are added into dissolving tank 2 After water purification, dilute waterglass is added and prepares working solution B.Solution temperature is raised to 50 DEG C in retort 1, is added into solution A dense Degree is the ammonium hydroxide of 20wt% until formation dark blue solution, solution ph 12.0 continue solution being warming up to 120 DEG C, ammonia still process 1.5 hours, pH value 8.2 obtained nickeliferous, aluminium sediment slurries I.1000mL water purifications are added in retort 2, it will be a concentration of 12wt% ammonium hydroxide and solution B cocurrent are added in retort 2, and gelling temperature is maintained at 55 DEG C, pH value control in cocurrent plastic reaction process For system 7.6, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes.Above two is contained into sediment slurry Mixing.Aging after above two is mixed containing sediment slurry, ageing time 2.5 hours, 72 DEG C of aging temperature, pH at the end of aging Then value control is filtered, filter cake carries out hydro-thermal process under the water vapour containing urea, and the condition of hydro-thermal process is 7.8：Urine The molar ratio of element and active metal atom total amount is 4:1, temperature is 240 DEG C, pressure 6.0MPa, and processing time is 4 hours, place Filter cake is beaten after reason, the Y type molecular sieve suspension for accounting for total catalyst weight 15wt% is added in terms of butt to sediment slurries （It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property is shown in Table 6, it made to be dispersed in the mixing slurry that plastic obtains In liquid, filtering is 10 hours dry at 70 DEG C, rolls, extruded moulding.It is washed at room temperature with water purification.Then at 80 DEG C, drying 8 is small When, 530 DEG C roast 4.5 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, be added account for nickel and aluminium in solution with the molecular weight of nickel oxide and aluminium oxide weight calculation amount 35wt% be 4000 it is poly- Ethylene glycol is added in NaOH solution tank NaOH 1, solution A is configured to after stirring evenly, preparating acid sex work solution A is added into dissolving tank 2 After aluminium chloride, ammonium metatungstate are dissolved in water purification, dilute waterglass preparating acid sex work solution B is added.Solution temperature is raised in retort 1 45 DEG C, the ammonium hydroxide of a concentration of 20wt% is added into solution A until forming dark blue solution, solution ph 11.0, continuing will be molten Liquid is warming up to 105 DEG C, and ammonia still process 2 hours, pH value 7.8 obtains nickeliferous, aluminium sediment slurries I.1000mL water purifications are added anti- It answers in tank 2, a concentration of 10wt% ammonium hydroxide and solution B cocurrent is added in retort 2, gelling temperature is maintained at 60 DEG C, cocurrent plastic 8.0, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for pH value control in reaction process.It will be upper Two kinds are stated to mix containing sediment slurry.Aging after above two is mixed containing sediment slurry, ageing time 2 hours, aging temperature 75 DEG C, pH value is controlled 7.8 at the end of aging, is then filtered, filter cake carries out hydro-thermal process, hydro-thermal under the water vapour containing urea The condition of processing is：The molar ratio of urea and active metal atom total amount is 3.0:1, temperature is 260 DEG C, pressure 5.0MPa, Processing time is 5 hours, is beaten filter cake after processing, and the Y types for accounting for total catalyst weight 8wt% are added to the mixing of sediment slurries 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, it made uniformly to divide It dissipates in the mixed serum that plastic obtains, filters, it is 10 hours dry at 80 DEG C, it rolls, extruded moulding.It is washed at room temperature with water purification It washs, then 10 hours dry at 110 DEG C, 480 DEG C roast 6 hours, obtain catalyst D.Catalyst composition, pore size distribution and main property Matter is 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 the container of a 5L, are added 2000 milliliters only Water 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, in 100 DEG C of oven dryings 8 hours, rolls, with 3 millimeters of orifice plate extruded moulding of diameter；At room temperature It is washed with the ammonium acetate solution of pH=8.8；Then in 80 DEG C of oven dryings 10 hours, 550 DEG C roast 4 hours, obtain 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 7:1, 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 7:1, 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, the Y type molecular sieve for accounting for total catalyst weight 10wt% is added Suspension is in terms of butt（It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property is shown in Table 6, it made to be dispersed in into In the mixed serum that glue obtains, aging 2 hours are stood at 75 DEG C or so.

(5) it filters, it is 8 hours dry at 100 DEG C, it rolls, extruded moulding.It is washed at room temperature with water purification.Then it is done at 80 DEG C Dry 10 hours, 550 DEG C roasted 4 hours, obtain catalyst 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 catalyst table phase active metallic content prepared by the method for the present invention is apparently higher than body phase Active metallic content, activity mutually increases considerably in catalyst.It can be seen that the catalysis prepared using the present invention from the data of table 5 The activity and middle distillates oil selectivity of agent A, B, C, D are better than reference agent, illustrate catalyst activity metal profit prepared by the method for the present invention 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
NiO, wt%	20	17	24	19	20
						WO3, wt%	24	21	18	25	24
SiO2, wt%	19	17	20	22	19
						Al2O3, wt%	22	26	23	26	22
Y molecular sieve, wt%	10	12	15	8	10
						Other/wt%	ZrO2/5.0	TiO2/7.0	-	-	ZrO2/5.0
Catalyst property
						Specific surface area, m2/g	394	384	389	391	288
Kong Rong, mL/g	0.412	0.390	0.393	0.407	0.285
						Mechanical strength, N/mm	22.4	22.9	22.9	23.4	19.7
Pore size distribution, %
						< 4nm	15.32	16.85	15.69	14.55	52.33
4nm~8nm	65.17	65.63	66.19	67.51	44.15
						8nm~15nm	15.72	14.42	15.24	15.02	1.41
> 15nm	3.79	3.10	2.88	2.92	2.11

Continued 1

Catalyst is numbered	F	G	H	I
					Catalyst forms
NiO, wt%	20	20	20	20
					WO3, wt%	24	24	24	24
SiO2, wt%	19	19	19	19
					Al2O3, wt%	22	22	22	22
Y molecular sieve, wt%	10	10	10	10
					Other/wt%	ZrO2/5.0	ZrO2/5.0	ZrO2/5.0	ZrO2/5.0
Catalyst property
					Specific surface area, m2/g	379	371	382	312
Kong Rong, mL/g	0.384	0.381	0.394	0.355
					Intensity, N/mm	19.5	18.9	18.1	17.8
Pore size distribution, %
					< 4nm	28.45	24.52	25.62	14.25
4nm~8nm	34.21	38.73	33.54	35.42
					8nm~15nm	24.84	23.41	24.29	36.84
> 15nm	12.50	13.34	16.55	13.49

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

Catalyst is numbered	A	B	C	D	E
						Table phase IW/ body phase IW	4.33	3.94	3.84	2.97	0.95
Table phase INi/ body phase INi	3.55	3.11	2.94	2.53	0.91

Continued 2

Catalyst is numbered	F	G	H	I
					Table phase IW/ body phase IW	1.04	1.07	1.15	1.22
Table phase INi/ body phase INi	1.08	1.12	1.09	1.18

3 catalyst surface WS of table₂Density

Catalyst is numbered	A	B	C	D	E	F	G	H	I
										WS2Density, grain/100nm	77	74	76	72	39	43	42	43	47

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	389	390	388	389	397
Product distribution, wt%
						Light naphthar（C5~82℃）	5.8	5.9	5.5	5.6	5.9
Heavy naphtha（82~138℃）	9.1	9.4	9.2	9.6	9.9
						Jet fuel（138℃~249℃）	27.9	26.2	26.8	27.4	23.0
Diesel oil（249℃~371℃）	26.4	27.9	28.4	27.1	24.5
						Tail oil（>371℃）	30.8	30.6	30.1	30.3	36.1
Middle distillates oil selectivity, wt%	78.5	777.9	79.8	78.2	74.3

Continued 5

Catalyst is numbered	F	G	H	I
					Reaction temperature, DEG C	397	398	396	397
Product distribution, wt%
					Light naphthar（C5~82℃）	5.5	5.8	6.3	5.8
Heavy naphtha（82~138℃）	10.4	10..1	9.7	10.0
					Jet fuel（138℃~249℃）	23.4	23.8	23.4	23.1
Diesel oil（249℃~371℃）	23.5	23.1	24.1	24.2
					Tail oil（>371℃）	37.2	36.9	36.4	36.9
Middle distillates oil selectivity, wt%	74.6	74.3	74.7	73.4

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 (24)

1. a kind of preparation method of hydrocracking catalyst, including：

（1）, prepare the mixed solution A containing Ni, Al component salt and organic compound, ammonium hydroxide be added solution A make reaction system Solution A is heated carry out ammonia still process generation precipitation under agitation, until slurry pH value is less than 10, generation contains by pH value 10 or more Nickel, aluminum precipitation object slurries I；

（2）, prepare the component saline solution B containing W, Si, Al, ammonium hydroxide and material B cocurrents generation 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, 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 Even, filtering obtains material through drying, molding, washing；

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

2. according to the method for claim 1, 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.

3. according to the method for claim 2, 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.

4. according to the method for claim 1, it is characterised in that：Step（1）The weight concentration of ammonium hydroxide used is 15%~28%, Step（2）The weight concentration of ammonium hydroxide used is 5%~15%.

5. according to the method for claim 1, it is characterised in that：In the hydrocracking catalyst, with the weight of catalyst On the basis of, WO₃Total content with NiO is 20wt%~65wt%, and W/Ni atomic ratios are 0.05~1.0, and the content of silica is The content of 1wt%~40wt%, aluminium oxide are 10wt%~40wt%, and the content of molecular sieve is 5wt%~20wt%.

6. according to the method for claim 1, it is characterised in that：In the hydrocracking catalyst, with the weight of catalyst On the basis of, WO₃Total content with NiO is 30wt%~50wt%, and W/Ni atomic ratios are 0.1~0.7, and the content of silica is 5wt% The content of~35wt%, aluminium oxide are 15wt%~40wt%, and the content of molecular sieve is 5wt%~15wt%.

7. according to the method for claim 1, it is characterised in that：The molecular sieve is Y type molecular sieve, and property is as follows：Than 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%.

8. according to the method for claim 1, it is characterised in that：Step（1）In mixed solution A, weight of the Ni in terms of NiO is dense Degree is 5~80g/L, and Al is with Al₂O₃The weight concentration of meter is 2~60g/L.

9. according to the method for claim 8, it is characterised in that：Step（1）In mixed solution A, weight of the Ni in terms of NiO is dense Degree is 10~60g/L, and Al is with Al₂O₃The weight concentration of meter is 8~40g/L.

10. according to the method for claim 1, 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 2~60g/L.

11. according to the method for claim 10, 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 8~40g/L.

12. according to the method for claim 1, it is characterised in that step（1）Organic compound used be selected from polyethylene glycol, One or more in polyvinyl alcohol, wherein the molecular weight of polyethylene glycol is 200 ~ 10000, and the molecular weight of polyvinyl alcohol is 5000 ~25000；The dosage of the organic compound accounts for step（1）Nickeliferous, the aluminum precipitation object of middle generation is with nickel oxide and aluminium oxide weight calculation amount 5wt% ~ 70wt%.

13. according to the method for claim 12, it is characterised in that step（1）Organic compound used is selected from poly- second two One or more in alcohol, polyvinyl alcohol, wherein the molecular weight of polyethylene glycol is 1000 ~ 8000, and the molecular weight of polyvinyl alcohol is 12000~20000；The dosage of the organic compound accounts for step（1）Nickeliferous, the aluminum precipitation object of middle generation is with nickel oxide and aluminium oxide 10wt% ~ 60wt% of weight calculation amount.

14. according to the method for claim 1, it is characterised in that：Step（1）When solution A is added in middle ammonium hydroxide, system temperature control Be made as 30~70 DEG C, the pH value that control reaction system after ammonium hydroxide is added is 10~13, ammonia still process make the pH value of reaction system be 7.5~ 9.5, ammonia still process temperature is 80~150 DEG C, and time of ammonia distillation was controlled at 0.2 ~ 4.0 hour.

15. according to the method for claim 1, 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%.

16. according to the method for claim 15, 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%.

17. according to the method for claim 1, it is characterised in that：Step（2）Middle reaction temperature is 30~90 DEG C；Cocurrent at PH value control is 6.0 ~ 11.0 when glue；Gelation time is 0.2 ~ 4.0 hour.

18. according to the method for claim 17, it is characterised in that：Step（2）Middle reaction temperature is 40~80 DEG C；Cocurrent at PH value control is 7.0 ~ 9.0 when glue；Gelation time is 0.5 ~ 3.0 hour.

19. according to the method for claim 1, 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；Ageing time is 0.5 ~ 6.0 hour.

20. according to the method for claim 19, 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；Ageing time is 1.0 ~ 4.0 hours.

21. according to the method for claim 1, 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。

22. according to the method for claim 21, it is characterised in that：Step（3）Described in hydrothermal conditions it is as follows：? It is carried out under closed container, temperature is 210 ~ 260 DEG C, and pressure is 3.0 ~ 6.0MPa, and 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 in the addition and catalyst of urea：1~8.0:1.

23. according to the method for claim 1, it is characterised in that：Step（5）The drying and roasting condition is as follows：? 50 ~ 200 DEG C of dryings 1 ~ 48 hour, roast 1 ~ 24 hour at 450 ~ 600 DEG C.

24. according to the method for claim 1, it is characterised in that：It is 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 is using one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.