CN106179461B - A kind of preparation method of hydrocracking catalyst - Google Patents

Abstract

The invention discloses a kind of preparation methods of body phase hydrocracking catalyst.The composition of the catalyst includes hydrogenation active metal component W and Ni, aluminium oxide, silica and molecular sieve, preparation method is that sodium aluminate solution progress plastic is added in the saline solution of component containing Ni A to react to obtain slurries I, cocurrent plastic is carried out with sodium aluminate solution react to obtain slurries II containing W, Si component saline mixed solution B, slurries I and slurries II is uniformly mixed, hydro-thermal process is carried out after aging, wherein hydro-thermal process when urea is added, then through mashing be added molecular sieve, then through molding and etc. hydrocracking 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 body phase 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）.

The petroleum refining industry of 21st century must comply with the strategy of sustainable development, it is necessary to while paying attention to economic benefit, protection Environment and the principle to economize on resources.Therefore, become more important using the preparation method of non-environmental-pollution production bulk phase catalyst. Existing coprecipitation method prepares catalyst technology, uses NH mostly₃·H₂For O as precipitating reagent, this will generate the largely waste water containing ammonia, nitrogen, It pollutes the environment.

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 body phase hydrocracking catalyst of the present invention, including：

（1）, prepare the solution A of the component containing Ni, sodium metaaluminate alkaline solution is added dropwise to solution A and carries out plastic reaction, it is raw At nickeliferous, aluminum precipitation object slurries I；

（2）, prepare the mixed solution B containing W, Si component, it is anti-that sodium metaaluminate alkaline solution and solution B cocurrent are carried out plastic It answers, generates 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 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.

Body phase 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 is 5~80g/L, preferably 10~60g/L.It is described Sodium metaaluminate alkaline solution in contain Al₂O₃A concentration of 5 ~ 70g/L, preferably 5 ~ 50g/L.When preparing mixed solution A, generally The nickel source used can be one or more of nickel sulfate, nickel nitrate, basic nickel carbonate, nickel chloride.

Step（2）In mixed solution B, W is with WO₃The weight concentration of meter is 10~100g/L, preferably 20~90g/L.Si With SiO₂Weight concentration is 10~120g/L, preferably 20~80g/L.Contain Al in the sodium metaaluminate alkaline solution₂O₃It is dense Degree is 5 ~ 60g/L, preferably 5 ~ 40g/L.When preparing mixed solution B, the tungsten source that generally uses can for ethyl ammonium metatungstate, partially One or more of ammonium tungstate；Silicon source can be one or more in Ludox, sodium metasilicate.

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 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（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 drying, molding, 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.Washing is usually used deionized water or contains There is decomposable asymmetric choice net salt（Such as ammonium acetate, ammonium chloride, ammonium nitrate）Solution washs, and is washed till neutrality.

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 the method for the present invention, adjuvant component can be contained as needed, adjuvant component is in silicon, phosphorus, titanium, zirconium, boron etc. One or more, preferably titanium and/or zirconium, weight content of the adjuvant component in hydrocracking catalyst is 0 ~ 20% based on the element, Preferably 1% ~ 10%.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 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 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.

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%.

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 the preparation method of catalyst of the present invention, the sodium metaaluminate alkaline solution containing Al is used to avoid use for precipitating reagent NH₃·H₂O generates the largely waste water containing ammonia, nitrogen, simultaneous reactions precipitate particles are uniform, are more advantageous in W, Ni as precipitating reagent Active metal is distributed in table phase, and W, Ni active metal are distributed more uniformly in table phase, is conducive to raising catalyst and is added Hydrogen activity.

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 and zirconium oxychloride are dissolved in water purification respectively, are configured to mixed solution A, the weight concentration of NiO is in solution A 21g/L, ZrO₂Weight concentration 5g/L.Ammonium metatungstate is dissolved in water purification, dilute water glass solution is added, is configured to mixed solution B, WO in solution B₃Weight concentration be 25g/L, SiO₂Weight concentration be 20g/L.Al will be contained₂O₃The sodium metaaluminate of 10g/L is molten Solution A is added in 600 milliliters of liquid under stiring, and gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, gelation time control System generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.1000mL water purifications are added in retort, Al will be contained₂O₃20g/L's is inclined 800 milliliters of sodium aluminate solution and solution B cocurrent are added in retort, and gelling temperature is maintained at 55 DEG C, cocurrent plastic reaction process 7.6, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 60 minutes for middle pH value control.Above two is contained Aging after sediment slurry mixing, ageing time 2 hours, 75 DEG C of aging temperature, pH value control is 7.6 at the end of aging, then mistake Filter, 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 are total The molar ratio of amount is 7:1, temperature is 230 DEG C, pressure 4.5MPa, and processing time is 3 hours, is beaten filter cake after processing, to The Y type molecular sieve suspension for accounting for total catalyst weight 10wt% is added in mix slurry in terms of butt（By CN101343068A realities Apply the preparation of example 7）, Y type molecular sieve property is shown in Table 6, it is made to be dispersed in mixed serum, filters, 8 hours dry at 100 DEG C, 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, obtain catalyst 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 prepare working solution A, after addition ammonium metatungstate is dissolved in water purification into dissolving tank 2, dilute waterglass are added and prepares work Make solution B.Al will be contained₂O₃Solution A is added in 400 milliliters of the sodium aluminate solution of 15g/L under stiring, and gelling temperature is maintained at 45 DEG C, at the end of pH value control 8.0, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 60 minutes.800mL is net Water is added in retort, will contain Al₂O₃800 milliliters of the sodium aluminate solution of 20g/L and solution B cocurrent are added in retort, plastic Temperature is maintained at 50 DEG C, in cocurrent plastic reaction process pH value control 8.2, gelation time control at 60 minutes, generate tungstenic, Silicon, aluminum precipitation object slurries II.Aging after above two is mixed containing sediment slurry, ageing time 3 hours, 70 DEG C of aging temperature, At the end of aging then pH value control is filtered 8.0, and filter cake carries out hydro-thermal process under the water vapour containing urea, at hydro-thermal The condition of reason is：The molar ratio of urea and active metal atom total amount is 6:1, temperature is 250 DEG C, pressure 3.5MPa, processing Time be 3 hours, filter cake is beaten after processing, to slurries addition account for the Y type molecular sieve suspension of total catalyst weight 12wt% with Butt meter（It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property is shown in Table 6, it made to be dispersed in what plastic obtained In mixed serum, filtering is 7 hours dry at 120 DEG C, rolls, extruded moulding.It is washed at room temperature with water purification.Then it is done at 100 DEG C Dry 12 hours, 500 DEG C roasted 5 hours, obtain catalyst B.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, is matched by the constituent content of the catalyst C in table 1, chlorination is added into dissolving tank 1 Nickel prepares working solution A, after addition ammonium metatungstate is dissolved in water purification into dissolving tank 2, dilute waterglass is added and prepares working solution B. Al will be contained₂O₃Solution A is added in 300 milliliters of the sodium aluminate solution of 20g/L under stiring, and gelling temperature is maintained at 55 DEG C, at the end of 7.6, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 90 minutes for pH value control.It is added in retort and is equipped with 900mL water purifications will contain Al₂O₃700 milliliters of the sodium aluminate solution of 25g/L and solution B cocurrent are added in retort, gelling temperature Be maintained at 45 DEG C, in cocurrent plastic reaction process pH value control 8.0, gelation time control at 60 minutes, generate tungstenic, silicon, Aluminum precipitation object slurries II.Above two is mixed containing sediment slurry.Aging after above two is mixed containing sediment slurry, when aging Between 2.5 hours, 72 DEG C of aging temperature, at the end of aging pH value control 7.8, then filter, filter cake containing urea water steam Hydro-thermal process is carried out under vapour, 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, pressure 6.0MPa, processing time is 4 hours, is beaten filter cake after processing, and catalyst is accounted for the addition of sediment slurries The Y type molecular sieve suspension of total weight 15wt% is in terms of butt（It is prepared by CN101343068A embodiments 7）, Y type molecular sieve property 6 are shown in Table, it is made to be dispersed in the mixed serum that plastic obtains, is filtered, it is 10 hours dry at 70 DEG C, it rolls, extruded moulding. It is washed at room temperature with water purification.Then 8 hours dry at 80 DEG C, 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, preparating acid sex work solution A after addition ammonium metatungstate is dissolved in water purification into dissolving tank 2, is added dilute waterglass and prepares acid work Make solution B.Al will be contained₂O₃Solution A is added in 320 milliliters of the sodium aluminate solution of 20g/L under stiring, and 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 be equipped with 1000mL water purifications, Al will be contained₂O₃720 milliliters of the sodium aluminate solution of 20g/L and solution B cocurrent are added in retort, at Glue temperature is maintained at 55 DEG C, and pH value control is 8.0 in cocurrent plastic reaction process, and at 60 minutes, generation contained gelation time control Tungsten, silicon, aluminum precipitation object slurries II.Above two is mixed containing sediment slurry.Aging after above two is mixed containing sediment slurry, Ageing time 2 hours, 75 DEG C of aging temperature, pH value is controlled 7.8 at the end of aging, is then filtered, filter cake is containing urea Hydro-thermal process is carried out under water vapour, the condition of hydro-thermal process is：The molar ratio of urea and active metal atom total amount is 3.0:1, Temperature is 260 DEG C, pressure 5.0MPa, and processing time is 5 hours, is beaten filter cake after processing, is added to the mixing of sediment slurries Enter to account for the Y type molecular sieve suspension of total catalyst weight 8wt% in terms of butt（It is prepared by CN101343068A embodiments 7）, Y types Molecular sieve property is shown in Table 6, it is made to be dispersed in the mixed serum that plastic obtains, filtering, 10 hours dry at 80 DEG C, grinds Pressure, extruded moulding.It is washed at room temperature with water purification, then 10 hours dry at 110 DEG C, 480 DEG C roast 6 hours, obtain catalyst D.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

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

（1）By Al₂O₃220 milliliters of the liquor alumini chloridi of a concentration of 120g/L, containing 18 milli of nickel chloride solution that NiO is 44g/L It rises, contains ZrO₂50 milliliters of 100g/L zirconyl chloride solutions are mixed in the container of a 5L, and 2000 milliliters of water purification dilutions are added；

(2) dilute water glass solution is prepared, SiO is contained₂310 milliliters of the water glass solution of 100g/L, under agitation by (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 it is added to (1)+(2)+(3) under agitation Mixture in；

(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 to account for before aging and urge The Y type molecular sieve suspension of agent total weight 10wt% is in terms of butt（It is prepared by CN101343068A embodiments 7）, Y type molecular 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 that addition accounts for total catalyst weight 10wt% is outstanding Turbid 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 plastic In obtained mixed serum, 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	16	18	14	20
						WO3, wt%	24	28	22	26	24
SiO2, wt%	19	20	15	24	19
						Al2O3, wt%	22	24	30	28	22
Y molecular sieve, wt%	10	12	15	8	10
						Other/wt%	ZrO2/5.0	TiO2/7.0	-	-	ZrO2/5.0
Catalyst property
						Specific surface area, m2/g	392	395	388	399	288
Kong Rong, mL/g	0.406	0.385	0.382	0.418	0.285
						Mechanical strength, N/mm	22.1	23.2	22.5	23.4	19.7
Pore size distribution, %
						＜ 4nm	15.37	16.54	15.56	14.57	52.33
4nm~8nm	66.01	65.85	66.23	67.58	44.15
						8nm~15nm	15.54	14.33	15.65	15.39	1.41
＞ 15nm	3.08	3.28	2.56	2.46	2.11

Continued 1

Catalyst is numbered	F	G	H	I
					Catalyst forms
NiO, wt%	20	20	20	20
					WO3, wt%	24	24	24	24
SiO2, wt%	19	19	19	19
					Al2O3, wt%	22	22	22	22
Y molecular sieve, wt%	10	10	10	10
					Other/wt%	ZrO2/5.0	ZrO2/5.0	ZrO2/5.0	ZrO2/5.0
Catalyst property
					Specific surface area, m2/g	345	369	365	312
Kong Rong, mL/g	0.335	0.342	0.356	0.355
					Intensity, N/mm	18.2	17.5	18.4	17.8
Pore size distribution, %
					＜ 4nm	28.25	24.63	25.90	14.25
4nm~8nm	35.21	38.51	33.66	35.42
					8nm~15nm	24.84	23.45	24.97	36.84
＞ 15nm	11.70	13.41	15.47	13.49

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

Catalyst is numbered	A	B	C	D	E
						Table phase IW/ body phase IW	4.24	3.84	3.81	2.47	0.95
Table phase INi/ body phase INi	3.41	3.58	3.12	2.59	0.91

Continued 2

Catalyst is numbered	F	G	H	I
					Table phase IW/ body phase IW	1.05	1.11	1.13	1.22
Table phase INi/ body phase INi	1.11	1.16	1.18	1.18

3 catalyst surface WS of table₂Density

Catalyst is numbered	A	B	C	D	E	F	G	H	I
										WS2Density, grain/100nm	84	81	78	79	39	44	43	44	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	389	390	389	397
Product distribution, wt%
						Light naphthar（C5~82℃）	5.6	5.1	6.8	5.5	5.9
Heavy naphtha（82~138℃）	7.2	8.9	7.5	7.7	9.9
						Jet fuel（138℃~249℃）	27.8	28.1	27.2	28.3	23.0
Diesel oil（249℃~371℃）	27.2	27.4	27.8	26.9	24.5
						Tail oil（>371℃）	32.2	30.5	30.7	31.6	36.1
Middle distillates oil selectivity, wt%	81.1	79.8	79.3	80.7	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℃）	6.6	7.2	6.9	5.8
Heavy naphtha（82~138℃）	9.9	10.1	9.5	10.0
					Jet fuel（138℃~249℃）	23.6	22.8	23.1	23.1
Diesel oil（249℃~371℃）	24.1	23.5	23.9	24.2
					Tail oil（>371℃）	35.8	36.4	36.6	36.9
Middle distillates oil selectivity, wt%	74.3	72.8	74.1	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 (20)

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

（1）, prepare the solution A of the component containing Ni, sodium metaaluminate alkaline solution is added dropwise to solution A and carries out plastic reaction, generation contains Nickel, aluminum precipitation object slurries I；

（2）, prepare the mixed solution B containing W, Si component, sodium metaaluminate alkaline solution and solution B cocurrent are subjected to plastic reaction, Generate 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：In the hydrocracking catalyst, with the weight of catalyst On the basis of, WO₃Total content with NiO is that 20%~65%, W/Ni atomic ratios are 0.05~1.0, the content of silica be 1wt%~ The content of 40wt%, aluminium oxide are 10wt%~40wt%, and the content of molecular sieve is 5wt%~20wt%.

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 that 30%~50%, W/Ni atomic ratios are 0.1~0.7, the content of silica be 5wt%~ The content of 35wt%, aluminium oxide are 15wt%~40wt%, and the content of molecular sieve is 5wt%~15wt%.

6. 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%.

7. according to the method for claim 1, it is characterised in that：Step（1）In the saline solution of component containing Ni A, Ni is in terms of NiO Weight concentration be 5~80g/L, Al is contained in the sodium metaaluminate alkaline solution₂O₃A concentration of 5 ~ 70g/L.

8. according to the method for claim 1, it is characterised in that：Step（2）In mixed solution B, W is with WO₃The weight concentration of meter For 10~100g/L, Si is with SiO₂Weight concentration is 10~120g/L, contains Al in the sodium metaaluminate alkaline solution₂O₃Concentration For 5 ~ 60g/L.

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

10. according to the method for claim 9, 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.

11. 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%.

12. according to the method for claim 11, 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%.

13. according to the method for claim 1, it is characterised in that：Step（2）Middle reaction temperature be 30~90 DEG C, cocurrent at It is 0.2 ~ 4.0 hour that pH value control, which is 6.0 ~ 11.0 gelation times, when glue.

14. according to the method for claim 13, 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.

15. 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, and ageing time is 0.5 ~ 6.0 hour.

16. according to the method for claim 15, 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.

17. 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。

18. the method described in claim 17, 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.

19. 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.

20. 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.