CN105709844B

CN105709844B - Carrier of hydrocracking catalyst and its preparation method

Info

Publication number: CN105709844B
Application number: CN201410711217.3A
Authority: CN
Inventors: 王凤来; 刘昶; 杜艳泽; 关明华; 黄薇; 赵红
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2014-12-01
Filing date: 2014-12-01
Publication date: 2018-04-10
Anticipated expiration: 2034-12-01
Also published as: CN105709844A

Abstract

The invention discloses a kind of carrier of hydrocracking catalyst and its preparation method.The catalyst carrier is using Modified Zeolite Y with beta-molecular sieve collectively as cracking center, Y type molecular sieve wherein used is a kind of big crystal grain, high silicon, the Y type molecular sieve of effective pore sife distribution concentration, hydrocracking catalyst prepared therefrom is used in the hydrocracking process of high-output qulified midbarrel oil product, the characteristics of active high and selectivity is good, while high-quality hydrogenation tail oil and can be produced.

Description

Carrier of hydrocracking catalyst and its preparation method

Technical field

The present invention relates to a kind of carrier of hydrocracking catalyst and preparation method thereof, is particularly suitable for high-output qulified low solidifying Carrier of hydrocracking catalyst of intermediate oil and preparation method thereof.

Background technology

In recent years, countries in the world refined products market constantly increases always to the demand of high-quality middle cut oil product, with Developing rapidly for economy, this imbalance between supply and demand seems more prominent.Hydrocracking technology turns into weight with its exclusive advantage The best means of the oily high-quality cleaning intermediate oil of deep processing production.At present, oil type hydrocracking catalyst in countries in the world Activity be not very high, the condensation point of gained diesel oil is also higher, it is difficult to meet refinery existing apparatus is transformed or increase processing Amount further increases production the purpose of intermediate oil to reach.

The key for being hydrocracked the low solidifying intermediate oil that raises productivity and improves the quality is to develop and using suitable catalyst.Containing single Although the hydrocracking catalyst of molecular sieve component is with very high activity, its middle distillates oil selectivity is poor, containing composite molecular screen Catalyst but show to improve the synergy that active and can improves selectivity.

Can there are Y types, β types and ZSM type molecules as the molecular sieve of cracking active component in residual oil cracking field at present Sieve etc., wherein Y type molecular sieve application is the most universal.The method of industrial production Y type molecular sieve is essentially all using the U.S. at present The directing agent method that GRACE companies propose in USP 3639099 and USP 4166099, the crystal grain of obtained common Y type molecular sieve Generally 1 μm or so, the structure cell of about 400 or so in each dimension.The Y types point for the typical die size being conventionally synthesized It is 15% ~ 20% that son, which sieves the pore size distribution ratio of former powder bore dia less than 1nm, bore dia 1nm ~ 10nm pore size distribution ratio for 45% ~ 50%, bore dia is in the pore size distribution ratio more than 10nm 30% ~ 40%.For macromolecular cracking reaction, it is adapted to raw material reaction and production The preferable pore diameter range of thing diffusion is 1nm ~ 10nm, although Y type molecular sieve can also be managed by follow-up modification appropriateness modulation Think that pore diameter range is distributed, but the pore-size distribution of original molecular sieve directly determines the pore diameter range distribution of successive modified molecular sieve, and And reaming can influence the skeleton structure of molecular sieve, and then influence the activity and stability of molecular sieve.

US 4,820,402 discloses a kind of hydrocracking catalyst of high selectivity to middle distillates, is characterized in using a kind of high The molecular sieve of silica alumina ratio such as ZSM-20, Y and β, molecular sieve silica alumina ratio are at least 50:1, preferably 200:More than 1.This method will not When being used for hydrocracking catalyst with high silica alumina ratio molecular sieve, middle distillates oil selectivity most preferably ZSM-20, next to that β.The catalysis The activity and middle distillates oil selectivity of agent are up for further improving.

CN 97122139.1 describes a kind of amorphous silicon Al catalysts.The catalyst is with amorphous silica-alumina and aluminum oxide For carrier, using tungsten, nickel as hydrogenation active metal component, prepared by the method for carrying out hydro-thermal process after being molded using carrier again.Although The activity and the middle distillates oil selectivity amorphous silicon Al catalysts more conventional than its of the catalyst are significantly improved, but required reaction Temperature is higher, and catalyst activity is poor.

US 4,419,271 discloses a kind of hydrocarbon conversion catalyst.Cracking Component is modified HY molecular sieves（LZ-10）With Decentralized sial, active metal component are tungsten, nickel.The wherein content of LZ-10 molecular sieves is 10wt%~70wt%, decentralized sial Content be 30wt%~90wt%, WO₃Content be 10wt%~30wt%, NiO content is 3wt%~10wt%.The catalyst Production intermediate oil is hydrocracked available for heavy gas oil（Such as turbine fuel and diesel oil）.The catalyst middle distillates oil selectivity is low.

A kind of method being hydrocracked using beta-molecular sieve selectivity is described in CN101578353A.Beta-molecular sieve does not enter The mol ratio of water-filling heat treatment or at relatively low temperatures hydro-thermal process, silica and aluminum oxide is less than 30：1 and at least 28wt% SF₆Adsorbance, by modified obtained this beta-molecular sieve as cracking component and the catalyst prepared, midbarrel The selectivity of oil is not high.

US 5,350,501, US 5,447,623, US 5,279,726, US 5,536,687 describe one kind and contain beta molecule The catalyst of sieve and Y type molecular sieve.During for producing intermediate oil, consisting of：Y type molecular sieve（1~15w%）, beta-molecular sieve （1~15w%）, decentralized sial, aluminum oxide, metal W and Ni.Y type molecular sieve wherein used passes through for the NaY of typical die degree Ammonium exchange, hydro-thermal process, ammonium exchanges, prepared by the method for hydro-thermal process, and the crystallinity of modified molecular screen is not high, product selectivity Difference.Catalyst reaction activity and middle distillates oil selectivity be not high, it is difficult to meets manufacturer's aggrandizement apparatus disposal ability, further Increase production the needs of intermediate oil.

From the molecular sieve with cracking function from the point of view of the application during Industrial Catalysis, its performance depends primarily on following Two aspects：Selective absorption and reaction.When reactant molecule size is less than molecular sieve aperture and overcomes molecular sieve crystal surface It energy barrier, can just diffuse into molecular sieve pore passage, specific catalytic reaction occurs, at this moment be adsorbed molecule and pass through molecular sieve crystal Hole and cage diffusion serve it is conclusive.And compared with conventional die molecular sieve, larger crystal molecular sieve has more Internal surface area, be more suitable for the pore passage structure of macromolecular reaction, using the teaching of the invention it is possible to provide more two secondary fissures of the macromolecular in molecular sieve Transforming machine meeting is solved, therefore larger crystal molecular sieve can handle the heavier raw material of the bigger oil product of molecule, improve macromolecular conversion probability Etc. show more superior performance.But for larger crystal molecular sieve, particle diameter is bigger, and duct is longer, not only influences The diffusion of reactant, and multiple cracking reaction easily occurs in molecular sieve pore passage for reactant, reduces the selectivity of catalyst.

The content of the invention

In order to overcome weak point of the prior art, the invention provides a kind of carrier of hydrocracking catalyst and its system Preparation Method.The catalyst carrier uses Modified Zeolite Y with beta-molecular sieve collectively as cracking center, wherein Y types point used Son sieve is a kind of big crystal grain, the Y type molecular sieve that high silicon, effective pore sife distribution are concentrated, and hydrocracking catalyst prepared therefrom is used , the characteristics of active high and selectivity is good, while can be simultaneous in the hydrocracking process of high-output qulified midbarrel oil product Produce high-quality hydrogenation tail oil.

Carrier of hydrocracking catalyst of the present invention, comprising Modified Zeolite Y, beta-molecular sieve and aluminum oxide, wherein modified Y The property of type molecular sieve is as follows：

Average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, relative crystallization Spend 110% ~ 150%, SiO₂/Al₂O₃Mol ratio is 60 ~ 120, and cell parameter is 2.425 ~ 2.435nm, preferably 2.427 ~ 2.434nm, bore dia are that the pore volume shared by 3nm ~ 7nm hole is the 70% ~ 95% of total pore volume, preferably 75% ~ 90%.

In Modified Zeolite Y of the present invention, non-framework aluminum accounts for the 0.1% ~ 1.0% of total aluminium, preferably 0.1% ~ 0.5%.

In carrier of hydrocracking catalyst of the present invention, the pore volume of described Modified Zeolite Y is 0.35cm³/g~ 0.50cm³/ g, specific surface area 800m²/g~980m²/g。

In carrier of hydrocracking catalyst of the present invention, infrared 0.1 ~ 0.5mmol/ of total acid of described Modified Zeolite Y g。

In carrier of hydrocracking catalyst of the present invention, in described Modified Zeolite Y, Na₂O weight content is Below 0.15wt%.

In carrier of hydrocracking catalyst of the present invention, the property of described beta-molecular sieve is as follows：Average grain diameter be 200 ~ 400nm, specific surface area 600m²/g~800m²/ g, pore volume 0.35cm³/g~0.50cm³/ g, relative crystallinity 100% ~ 140%, Infrared total acid content is 0.1 ~ 0.5mmoL/g, SiO₂/Al₂O₃Mol ratio is 40 ~ 80.The beta-molecular sieve can use hydrothermal crystallization method to close Into, typically using organic amine as template, then exchanged by the ammonium of routine, the method for acid treatment and hydro-thermal process it is modified and.

Described carrier of hydrocracking catalyst, on the basis of the weight of carrier, the content of Modified Zeolite Y for 10% ~ 40%, the content of beta-molecular sieve is 5% ~ 20%, and the content of aluminum oxide is 40% ~ 85%.

Carrier of hydrocracking catalyst property of the present invention is as follows：Specific surface area is 300 ~ 500m²/ g, pore volume is 0.5 ~ 1.0mL/g。

The preparation method of carrier of hydrocracking catalyst of the present invention, including：By Modified Zeolite Y, beta-molecular sieve, oxidation Aluminium mixes, and shaping, then dries and is calcined, and the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, including such as Lower step：

（1）The preparation of big crystal grain NaY type molecular sieves；

（2）By step（1）The big crystal grain NaY type molecular sieves of gained are prepared into big crystal grain NH₄NaY；

（3）To step（2）Gained Y type molecular sieve carries out hydro-thermal process；Wherein hydrothermal conditions：Gauge pressure be 0.28 ~ 0.50MPa, temperature are 550 ~ 700 DEG C, and processing time is 0.5 ~ 5.0 hour；

（4）With（NH₄）₂SiF₆The aqueous solution and step（3）The material of gained is contacted, then filtered and dry, is made Modified Zeolite Y.

In the preparation process of Modified Zeolite Y used in the present invention, step（1）Described big crystal grain NaY type molecular sieves Property is as follows：

Average grain diameter is 2.0 ~ 5.0 μm, preferably 2.0 ~ 4.5 μm, more preferably 3.0 ~ 4.5 μm, and bore dia is Pore volume shared by 1nm ~ 10nm hole accounts for the 70% ~ 90% of total pore volume, preferably 70% ~ 85%, is 800m than surface²/g~1000m²/ G, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m²/g~100m²/ g, relative crystallinity are 110% ~ 150%, Cell parameter 2.460nm ~ 2.465nm.

The NaY type molecular sieves of the present invention, preferable property are as follows：It is 800m than surface²/g~1000m²/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m²/g~100m²/g。

The NaY type molecular sieves of the present invention, preferable property are as follows：SiO₂/Al₂O₃Mol ratio 3.5 ~ 6.5, preferably 4.0 ~ 6.0。

In the preparation process of Modified Zeolite Y used in the present invention, step（2）The big crystal grain NH of preparation₄Sodium oxide molybdena in NaY Weight content be 2.5% ~ 5.0%.

In the preparation process of Modified Zeolite Y used in the present invention, step（3）Hydro-thermal process be with saturated steam Manage step（2）In obtained molecular sieve, treatment conditions：0.28 ~ 0.50MPa of gauge pressure, preferably 0.3 ~ 0.5MPa, temperature 550 ~ 700 DEG C, preferably 600 ~ 700 DEG C, preferably 0.5 ~ 5.0 hour processing time, 1.0 ~ 3.0 hours.

In the inventive method, step（4）It is by step（3）In obtained material with（NH₄）₂SiF₆The aqueous solution contact, mistake Journey is as follows：Step（3）In obtained molecular sieve be beaten in aqueous, solvent and solute weight ratio 8：1~15：1, temperature is 95 ~ 130 ℃；Added into slurry（NH₄）₂SiF₆The aqueous solution, 35 ~ 80 grams are added according to every 100 grams of Y molecular sieves（NH₄）₂SiF₆Amount add Enter（NH₄）₂SiF₆The aqueous solution, 3 ~ 30 grams can be added per 100gY types molecular sieve per hour（NH₄）₂SiF₆, add（NH₄）₂SiF₆Water Solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour, then filtration drying, obtains product.

In the preparation process of Modified Zeolite Y used in the present invention, step（1）The preparation method of middle NaY types molecular sieve, bag Include following steps：

I, gel is directly prepared：At a temperature of 20 DEG C ~ 40 DEG C, at a temperature of preferably 25 DEG C ~ 35 DEG C, according to Na₂O：Al₂O₃： SiO₂：H₂O=10~15：1：10~20：500 ~ 600 molar ratio, height is slowly added under conditions of stirring by waterglass It is well mixed in alkali sodium aluminate solution, afterwards, aluminum sulfate solution and low alkali aluminium acid sodium solution is sequentially added, in said temperature Under stir；Then constant temperature aging in confined conditions, obtains gel；

II, crystallization：By step（2）Hydrothermal crystallizing 12 ~ 24 is small at 80 DEG C ~ 120 DEG C and under conditions of stirring for obtained gel When, through filtering, washing, drying after crystallization, obtain big crystal grain NaY type molecular sieves.

In the preparation process of NaY types molecular sieve used in the present invention, step I feeds intake according to following mol ratio, Na₂O： Al₂O₃：SiO₂：H₂O=10~15：1：10~20：500 ~ 600, its reclaimed water can be individually added into, and can also together be added with solution.

In the preparation process of NaY types molecular sieve used in the present invention, in step I, aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali are inclined The ratio of the addition of sodium aluminate, 1 is calculated as with aluminum oxide：（0.5~0.7）：（0.6~0.8）.

In the preparation process of NaY types molecular sieve used in the present invention, step I is added without directed agents, template in reaction system The additives such as agent, surfactant are big using a hydrothermal crystallizing synthesis by selecting suitable raw material and optimization preparation process The utilization ratio of crystal NaY type molecular sieve, silicon source and silicon source is high, and technological process is simple, and cost is low.NaY types prepared by this method The granularity of molecular sieve reaches 2.0 ~ 5.0 μm, and silica alumina ratio is high, effective pore sife distribution is more concentrated, heat endurance and hydrothermally stable Property is good.

The big crystal grain Y type molecular sieve that catalyst carrier of the present invention uses, because the larger crystal molecular sieve is not only with larger Crystal grain so that structure cell quantity increases to 1000 ~ 2000 in each dimension, is advantageous to macromolecular and is cracked, but also has There is more preferably pore size distribution range, the cracking degree of reactant can be efficiently controlled, and be advantageous to product and carried out in duct Diffusion, so in cracking reaction, can relative increase activated centre, and can make macromolecular carry out suitable degree cracking reaction, Catalyst can show good cracking activity and product selectivity.

Catalyst carrier of the present invention, collectively as cracking center, was both given full play to using Modified Zeolite Y and beta-molecular sieve Its respective performance characteristics, and can enough act on concerted catalysis caused by two kinds of molecular sieves, i.e., beta molecular sieve to alkane or Long side chain on aromatic hydrocarbons has good isomerization, can effectively reduce the condensation point of product, while Y type molecular sieve has very to aromatic hydrocarbons High selectivity of ring-opening, improve the product property of purpose product.The active height of hydrocracking catalyst prepared by carrier of the present invention, Can high-output qulified midbarrel oil product（Navigate coal+diesel oil）, while high-quality hydrogenation tail oil and can be produced.

When the hydrocracking catalyst prepared by carrier of the present invention is used for heavy oil hydrocracking, particularly in condition of high voltage （12~20MPa）Lower processing wax slop（VGO, CGO and DAO）, poor ignition quality fuel can also be added（Coker gas oil and catalytic diesel oil Deng）, there is very high catalytic activity and intermediate oil selectivity, and the condensation point reduction amplitude of diesel oil distillate is big, and centre evaporates The product property of point oil is improved, and can meet refinery's increase operating flexibility, increase device disposal ability, further in volume increase Between distillate needs.

Brief description of the drawings

Fig. 1 is the gained LY-1 of embodiment 1 SEM electromicroscopic photographs；

Fig. 2 is the gained DLY-1 of comparative example 1 SEM electromicroscopic photographs；

Fig. 3 is the gained LY-1 of embodiment 1 XRD diffraction patterns.

Embodiment

Aluminum oxide can use oxygen used in conventional hydrocracking catalyst in carrier of hydrocracking catalyst of the present invention Change aluminium, such as macroporous aluminium oxide and ∕ or small porous aluminum oxide.0.7 ~ 1.0mL/g of pore volume of macroporous aluminium oxide used, specific surface area 200~500m²/g.The pore volume of small porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m²/g。

Conventional shaping assistant such as peptization acid, extrusion aid can also be added in catalyst carrier preparation process of the present invention Deng.

In the preparation process of Modified Zeolite Y used in the present invention, step（1）Big crystal grain NaY type molecular sieves preparation In method, Na in high alkali deflection aluminium acid sodium solution₂O content is 260 ~ 320g/L, Al₂O₃Content is 30 ~ 50g/L, can use routine side Method is prepared.Na in low alkali aluminium acid sodium solution₂O content is 100 ~ 130g/L, Al₂O₃Content is 60 ~ 90g/L, can use routine side Method is prepared.Al in aluminum sulfate solution₂O₃Content be 80 ~ 100g/L.SiO in waterglass₂Content be 200 ~ 300g/L, modulus For 2.8 ~ 3.5.

In the preparation process of Modified Zeolite Y used in the present invention, step（1）Big crystal grain NaY type molecular sieves preparation Method, specifically comprise the following steps：

I, according to Na₂O：Al₂O₃：SiO₂：H₂O=10~15：1：10~20：500 ~ 600 molar ratio, at 20 DEG C ~ 40 DEG C At a temperature of, at a temperature of preferably 25 ~ 35 DEG C, waterglass is slowly added into high alkali deflection aluminium acid sodium solution under conditions of stirring It is well mixed, afterwards, aluminum sulfate solution and low alkali aluminium acid sodium solution are added, is stirred at the temperature disclosed above, generally 0.5 ~ 1.0 hours；Then mixed liquor is enclosed in synthesis reactor, static constant temperature aging, preferably ageing time are 1.0 ~ 2.0 hours；

II, by synthesis mother liquid in confined conditions, using the method for a thermostatic crystallization.A described thermostatic crystallization is Refer to crystallization under agitation.Under agitation, first by the slower speed of gel（Typically at 2 ~ 4 DEG C/minute）It is warming up to Under the conditions of 90 DEG C ~ 110 DEG C, and thermostatic crystallization 12 ~ 24 hours at this temperature.After crystallization terminates, quickly synthesis reactor is cooled down Cooling, filtered, washing and drying, obtain big crystal grain NaY type molecular sieves.

In the preparation process of Modified Zeolite Y used in the present invention, step（2）Can using ammonium concentration as 0.1mol/L ~ 1.0mol/L ammonium salt solution, one or more of the described ammonium salt in ammonium nitrate, ammonium sulfate, ammonium chloride and ammonium acetate, It is 50 ~ 100 DEG C in temperature, solvent and solute weight ratio 8：1~15：Under conditions of 1, constant temperature processing big crystal grain NaY, the time is 0.5 ~ 1.5 Hour, it is filtered, then repeat ammonium exchange under these conditions, obtained product is filtered, stand-by after drying.Wherein The weight content for seeking sodium oxide molybdena in the larger crystal molecular sieve after controlling ammonium exchange is 2.5% ~ 5.0%.

In the preparation process of Modified Zeolite Y used in the present invention, step（3）It is by step（2）In obtained product water It is heat-treated and obtains.With saturated steam processing step（2）In obtained molecular sieve, add step in pipe type water heat-treatment furnace （2）In obtained molecular sieve, treatment conditions：0.28 ~ 0.50MPa of gauge pressure, preferably 0.3 ~ 0.5MPa, 550 ~ 700 DEG C of temperature are excellent Elect 600 ~ 700 DEG C as, 0.5 ~ 5 hour processing time, preferably 1 ~ 3 hour.

Stirring described in the inventive method is using conventional stirring means, typically using mechanical agitation.

Detailed process prepared by catalyst carrier for hydrgenating of the present invention is as follows：By Modified Zeolite Y, beta-molecular sieve, aluminum oxide Mixing, extruded moulding, then dry and be calcined, be prepared into carrier；Drying can dry 3~6 at a temperature of 80 DEG C to 150 DEG C Hour, roasting is calcined 2.5~6.0 hours at 500 DEG C~600 DEG C.

The following examples are used for the preparation method that carrier of the present invention is described in more detail, but the scope of the present invention not only limits In the scope of these embodiments.

Analysis method of the present invention：Specific surface area, pore volume and external surface area, pore size distribution use low temperature liquid nitrogen physisorphtion Measuring, relative crystallinity and cell parameter are measured using X-ray diffraction method, and silica alumina ratio is measured using chemical analysis, point The grain size of son sieve uses SEM（SEM）Mode determine.

The preparation big crystal grain NaY molecular sieve of the embodiment of the present invention 1 and comparative example 1 prepare feed stock used in DLY-3 molecular sieves Matter is as follows：

High alkali deflection aluminium acid sodium solution：Na₂O content 291g/L, Al₂O₃Content 42g/L；

Low alkali aluminium acid sodium solution：Na₂O content 117g/L, Al₂O₃Content 77g/L；

Aluminum sulfate solution：Al₂O₃Content 90g/L；

Waterglass：SiO₂Content 250g/L, modulus 3.2.

Embodiment 1

The present embodiment is to prepare big crystal grain NaY molecular sieve using the inventive method.

LY-1 preparation

（1）The preparation of gel：Temperature is 25 DEG C, under stirring condition, is slowly added into 63mL high alkali deflection aluminium acid sodium solution Enter 165mL waterglass, after being well mixed, sequentially add 42.5mL aluminum sulfate solution and 35.6mL low alkali aluminium acid sodium solutions, Constant temperature stirs 0.5 hour, then by obtained Synthesis liquid static aging 1 hour at the temperature disclosed above, obtains gel；

（2）Crystallization：Under agitation, the gel in synthesis reactor is raised to 100 DEG C with 2.5 DEG C/minute of heating rate, perseverance Temperature stirring crystallization 16 hours, after crystallization terminates, is quickly cooled with cold water, and is opened synthesis reactor and taken out synthetic molecular sieve, warp It is filtered, washed and dried, obtains product LY-1, product property is shown in Table 1.

LY-2 preparation：

（1）The preparation of gel：Temperature is 35 DEG C, under stirring condition, is slowly added into 48mL high alkali deflection aluminium acid sodium solution Enter 156mL waterglass, after being well mixed, sequentially add 39.6mL aluminum sulfate solution and 28.5mL low alkali aluminium acid sodium solutions, Constant temperature constant speed stirs 1 hour, then by obtained Synthesis liquid static aging 2 hours at the temperature disclosed above, obtains gel；

（2）Crystallization：Under agitation, the gel in synthesis reactor is raised to 110 DEG C with 3 DEG C/minute of heating rate, constant temperature Stir crystallization 24 hours, after crystallization terminates, quickly cooled with cold water, and open synthesis reactor and take out synthetic molecular sieve, pass through Filter, wash and dry, obtain product LY-2, product property is shown in Table 1.

Comparative example 1

This comparative example is to prepare big crystal grain NaY molecular sieve raw material using art methods.

DLY-1：

Using USP 3639099, molecular sieve is prepared using directing agent method.Specifically preparation process is：The preparation of directed agents, will 26g aluminium hydroxides are dissolved in 153g sodium hydroxides and 279mL water, form A raw materials；Then 525g water glass is added into A raw materials Glass（Modulus 3.3）, after above-mentioned gel quickly stirring, aging 24 hours, stand-by at room temperature；

At 37.8 DEG C, to 2223g waterglass（Modulus 3.3）Middle addition aluminum sulfate solution containing 601g（Sulfuric acid aluminium content with Al₂O₃Count=16.9 wt%）, then 392g directed agents are added in above-mentioned solution, stirred, then add 191g aluminic acids Sodium solution（Contain 126g aluminium hydroxides and 96.5g sodium hydroxides）, above-mentioned solution is quickly stirred and then in 98.8 DEG C of hydro-thermal crystalline substances Change 10 hours and obtain NaY molecular sieve, sample number into spectrum DLY-1, product property is shown in Table 1.

DLY-2：

Molecular sieve is prepared using CN101481120A method.By 0.699g Ludox（40wt%）, 0.156g hydroxides Sodium, 0.212g sodium aluminates and 2.94mL water purification are stirred at room temperature uniformly, obtain white gels, and then 2.4g OP10,1.6g be just Butanol, 1.8mL hexamethylenes, stir, and 100 DEG C of hydrothermal crystallizings 24 hours, obtain product DLY-2, product property is shown in Table 1.

DLY-3：

The preparation of directed agents, take 153g sodium hydrate solids to be dissolved in 279mL deionized waters, after being cooled to room temperature, add Enter 22.5g sodium metaaluminates and high alkali deflection aluminium acid sodium solution is made.Then high alkali deflection aluminium acid sodium solution is added in 525g waterglass, is mixed Aging 24 hours at room temperature after closing uniformly, it is stand-by.

In 1547g waterglass stir under sequentially add 720g deionized waters, 222.5g low alkali aluminium acid sodium solutions and 242g directed agents, after being well mixed, it is fitted into stainless steel cauldron, it is then filtered, wash in 100 DEG C of static crystallization 24 hours Wash and dry, obtain product DLY-3, product property is shown in Table 1.

Embodiment 2

Ammonium exchange is carried out to raw material big crystal grain NaY molecular sieve LY-1 first.Compound concentration is that 0.5mol/L ammonium nitrate is water-soluble 10 liters of liquid.2000 grams of small crystal grain NaY molecular sieve is weighed, is dissolved in 10 liters of aqueous ammonium nitrate solutions prepared, speed of agitator is 300rpm, constant temperature stirs 1 hour at 90 DEG C, and then filtering molecular sieves, and stays sample, analyzes Na₂O content；Repeat above-mentioned behaviour Make, until Na in molecular sieve₂O content reaches 2.5~5.0wt%, and it is LYN-1 to obtain dried sample number into spectrum.

Embodiment 3

Change the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into LY-2, repeat the process of embodiment 2, obtained sample Product, numbering LYN-2.

Embodiment 4

Weigh 200g LYN-1 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 590 DEG C, in gauge pressure Handle 2.0 hours under 0.30MPa, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 100 DEG C, speed of agitator 300rpm.Within the time of 2 hours, 386mL ammonium hexafluorosilicates are added at the uniform velocity into molecular sieve slurry The aqueous solution, 38.6 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-1, property are listed in table 2

Embodiment 5

Weigh 200g LYN-1 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 650 DEG C, in gauge pressure 0.4MPa Lower processing 1.0 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 120 DEG C, is stirred Mix rotating speed is 300rpm.Within the time of 2 hours, 676mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, altogether 67.6 grams of ammonium hexafluorosilicates are added, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-2, property It is listed in table 2.

Embodiment 6

Weigh 200g LYN-2 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 600 DEG C, in gauge pressure Handle 3.0 hours under 0.45MPa, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, be rapidly heated stirring, and temperature is 110 DEG C, speed of agitator 300rpm.Within the time of 2 hours, 435mL ammonium hexafluorosilicates are added at the uniform velocity into molecular sieve slurry The aqueous solution, 43.5 grams of ammonium hexafluorosilicates are added altogether, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-3, property are listed in table 2.

Embodiment 7

Weigh 200g LYN-2 molecular sieves to be put into pipe type water heat-treatment furnace, temperature programming is to 680 DEG C, in gauge pressure 0.3MPa Lower processing 1.5 hours, after hydro-thermal process, molecular sieve is dissolved in 1 liter of water purification, and be rapidly heated stirring, and temperature is 100 DEG C, is stirred Mix rotating speed is 300rpm.Within the time of 2 hours, 723mL hexafluorosilicic acid aqueous ammoniums are added at the uniform velocity into molecular sieve slurry, altogether 72.3 grams of ammonium hexafluorosilicates are added, then constant temperature constant speed stirs 2 hours, filters, and dries, obtains production code member LYNS-4, property It is listed in table 2.

Comparative example 2 ~ 4

Change the big crystal grain NaY molecular sieve LY-1 in embodiment 2 into DLY-1, DLY-2 and DLY-3 respectively, repeat embodiment 2 process, obtained sample, numbering DLYN-1, DLYN-2 and DLYN-3.

Comparative example 5 ~ 7

Change the LYN-1 in embodiment 5 into DLYN-1, DLYN-2 and DLYN-3 respectively, repeat the process of embodiment 5, system The sample obtained, numbering DYNS-1, DYNS-2, DYNS-3, property are listed in table 2.

The property of the NaY type molecular sieves of table 1

Continued 1

Note：In table 1, * roasting conditions are as follows：It is calcined 3 hours in 600 DEG C of air；

* the condition of hydro-thermal process is as follows：650 DEG C of steam treatments 1 hour.

The property of the Y type molecular sieve of table 2

Continued 2

Embodiment 8

By 44.44 grams of LYNS-1 molecular sieves（Butt 90wt%）, 22.22 grams of beta-molecular sieves（Crystal grain=250nm, SiO₂/Al₂O₃= 50, pore volume 0.45ml/g, specific surface area 750m²/ g, infrared total acid 0.29mmoL/g butts 90wt%）, 142.7 grams of macropore oxidations Aluminium（Pore volume 1.0ml/g, specific surface area 400m²/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-1.

Embodiment 9

By 44.44 grams of LYNS-2 molecular sieves（Butt 90wt%）, 33.3 grams of beta-molecular sieves（Crystal grain=250nm, SiO₂/Al₂O₃= 50, pore volume 0.45ml/g, specific surface area 750m²/ g, infrared total acid 0.29mmoL/g butts 90wt%）, 128.6 grams of macropore oxidations Aluminium（Pore volume 1.0ml/g, specific surface area 400m²/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-2.

The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming Hour, catalyst Z C-2 is obtained, carrier and corresponding catalyst property are shown in Table 3.

Embodiment 10

By 66.66 grams of LYNS-3 molecular sieves（Butt 90wt%）, 11.11 grams of beta-molecular sieves（Crystal grain=250nm, SiO₂/Al₂O₃= 50, pore volume 0.45ml/g, specific surface area 750m²/ g, infrared total acid 0.29mmoL/g butts 90wt%）, 142.7 grams of macropore oxidations Aluminium（Pore volume 1.0ml/g, specific surface area 400m²/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-3.

Embodiment 11

By 55.55 grams of LYNS-4 molecular sieves（Butt 90wt%）, 44.44 grams of beta-molecular sieves（Crystal grain=250nm, SiO₂/Al₂O₃= 50, pore volume 0.45ml/g, specific surface area 750m²/ g, infrared total acid 0.29mmoL/g butts 90wt%）, 142.7 grams of macropore oxidations Aluminium（Pore volume 1.0ml/g, specific surface area 400m²/ g, butt 70wt%）, 133.3 grams of adhesives（Butt 30wt%, nitric acid and aperture The mol ratio of aluminum oxide is 0.4）Mixed grind in roller is put into, adds water, is rolled into paste, extrusion, extrusion bar dries 4 at 110 DEG C Hour, then it is calcined 4 hours at 550 DEG C, obtains carrier ZS-4.

Comparative example 8 ~ 10

As described in Example 9, change LYNS-2 into DYNS-1, DYNS-2, DYNS-3 respectively, be made carrier DZS-1, DZS-2, DZS-3 and catalyst DZC-1, DZC-2 and DZC-3, carrier and catalyst composition are shown in Table 3.

Embodiment 12

This embodiment describes prepare catalyst Z C-2 Activity evaluations by carrier of the present invention.Tested in fixed bed hydrogenation Evaluated on device, appreciation condition is：React stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250：1, volume space velocity 1.5h during liquid^-1, Using one-stage serial once by technological process, vacuum distillate is used（VGO）As feedstock oil, raw material oil nature is listed in table 4, Evaluation result is listed in table 5.

Comparative example 11 ~ 13

This comparative example describes catalyst DZC-1, DZC-2 and DZC-3 activity prepared by comparative example carrier of the present invention Evaluation result.Evaluated on fixed bed hydrogenation experimental rig, appreciation condition is：React stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250：1, volume space velocity 1.5h during liquid^-1, using one-stage serial once by technological process, use vacuum distillate（VGO）As Feedstock oil, raw material oil nature are listed in table 4, and evaluation result is listed in table 5.

The physico-chemical property of the catalyst carrier of table 3 and catalyst

The raw material oil nature of table 4

The catalyst performance comparative evaluation's result of table 5

It can be seen from the evaluation result of table 5 under identical process conditions, using catalysis prepared by carrier of the present invention Agent, intermediate oil selectivity, yield and product quality are superior to reference catalyst.

Claims

A kind of 1. carrier of hydrocracking catalyst, comprising Modified Zeolite Y, beta-molecular sieve and aluminum oxide, wherein modified Y types point The property of son sieve is as follows：Average grain diameter is 2.0 ~ 5.0 μm, relative crystallinity 110% ~ 150%, SiO₂/Al₂O₃Mol ratio is 60 ~ 120, cell parameter is 2.425 ~ 2.435nm, bore dia be that pore volume shared by 3nm ~ 7nm hole is total pore volume 70% ~ 95%。
2. according to the catalyst carrier described in claim 1, it is characterised in that：The crystal grain of the Modified Zeolite Y is averagely straight Footpath is 2.0 ~ 4.5 μm.
3. according to the catalyst carrier described in claim 2, it is characterised in that：The crystal grain of the Modified Zeolite Y is averagely straight Footpath is 3.0 ~ 4.5 μm.
4. according to the catalyst carrier described in claim 1, it is characterised in that：The bore dia of the Modified Zeolite Y is 3nm Pore volume shared by ~ 7nm hole is the 75% ~ 90% of total pore volume.
5. according to the catalyst carrier described in claim 1, it is characterised in that：The Modified Zeolite Y, non-framework aluminum account for always The 0.1% ~ 1.0% of aluminium.
6. according to the catalyst carrier described in claim 5, it is characterised in that：The Modified Zeolite Y, non-framework aluminum account for always The 0.1% ~ 0.5% of aluminium.
7. according to the catalyst carrier described in claim 1, it is characterised in that：The pore volume of the Modified Zeolite Y is 0.35cm³/g~0.50cm³/ g, specific surface area 800m²/g~980m²/g。
8. according to the catalyst carrier described in claim 1, it is characterised in that：The infrared total acid 0.1 of the Modified Zeolite Y ~0.5mmol/g。
9. according to the catalyst carrier described in claim 1, it is characterised in that：In the Modified Zeolite Y, Na₂O weight Content is below 0.15wt%.
10. according to the catalyst carrier described in claim 1, it is characterised in that：The property of described beta-molecular sieve is as follows：Crystal grain Average diameter is 200 ~ 400nm, specific surface area 600m²/g~800m²/ g, pore volume 0.35cm³/g~0.50cm³/ g, relative knot Brilliant degree 100% ~ 140%, infrared total acid content are 0.1 ~ 0.5mmoL/g, SiO₂/Al₂O₃Mol ratio is 40 ~ 80.
11. according to the catalyst carrier described in claim 1, it is characterised in that：Described carrier, using the weight of carrier as base Standard, the content of Modified Zeolite Y is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, and the content of aluminum oxide is 40% ~ 85%.
12. the preparation method of any catalyst carrier of claim 1 ~ 11, including：By Modified Zeolite Y, beta-molecular sieve, Aluminum oxide mixes, and shaping, then dries and is calcined, and the preparation method of catalyst carrier, wherein Modified Zeolite Y, bag is made Include following steps：

（1）The preparation of big crystal grain NaY type molecular sieves；

（2）By step（1）The big crystal grain NaY type molecular sieves of gained are prepared into big crystal grain NH₄NaY；

（3）To step（2）Gained Y type molecular sieve carries out hydro-thermal process；Wherein hydrothermal conditions：Gauge pressure be 0.28 ~ 0.50MPa, temperature are 550 ~ 700 DEG C, and processing time is 0.5 ~ 5.0 hour；

（4）With（NH₄）₂SiF₆The aqueous solution and step（3）The material of gained is contacted, then filtered and dry, and Y types are made Molecular sieve.
13. in accordance with the method for claim 12, it is characterised in that：Step（1）The property of described big crystal grain NaY type molecular sieves Matter is as follows：

Average grain diameter is 2.0 ~ 5.0 μm, and bore dia is that the pore volume shared by 1nm ~ 10nm hole accounts for the 70% ~ 90% of total pore volume, Relative crystallinity is 110% ~ 150%, cell parameter 2.460nm ~ 2.465nm.
14. in accordance with the method for claim 13, it is characterised in that：Step（1）The crystalline substance of described big crystal grain NaY type molecular sieves Grain average diameter is 2.0 ~ 4.5 μm.
15. in accordance with the method for claim 14, it is characterised in that：Step（1）The crystalline substance of described big crystal grain NaY type molecular sieves Grain average diameter is 3.0 ~ 4.5 μm.
16. in accordance with the method for claim 13, it is characterised in that：Step（1）The hole of described big crystal grain NaY type molecular sieves Pore volume shared by a diameter of 1nm ~ 10nm hole accounts for the 70% ~ 85% of total pore volume.
17. in accordance with the method for claim 12, it is characterised in that：Step（1）The property of the NaY types molecular sieve is as follows： SiO₂/Al₂O₃Mol ratio 3.5 ~ 6.5.
18. in accordance with the method for claim 17, it is characterised in that：Step（1）The property of the NaY types molecular sieve is as follows： SiO₂/Al₂O₃Mol ratio is 4.0 ~ 6.0.
19. according to the method described in claim 12,13 or 17, it is characterised in that：Step（1）The property of the NaY types molecular sieve Matter is as follows：Specific surface area is 800m²/g~1000m²/ g, total pore volume are 0.30mL/g ~ 0.40mL/g, external surface area 60m²/g ~100m²/g。
20. in accordance with the method for claim 12, it is characterised in that：Step（2）The big crystal grain NH of preparation₄Sodium oxide molybdena in NaY Weight content is 2.5% ~ 5.0%.
21. in accordance with the method for claim 12, it is characterised in that：Step（3）Hydrothermal conditions it is as follows：Gauge pressure is 0.30 ~ 0.50MPa, temperature are 600 ~ 700 DEG C, and processing time is 1.0 ~ 3.0 hours.
22. in accordance with the method for claim 12, it is characterised in that：Step（4）It is by step（3）In obtained material with （NH₄）₂SiF₆The aqueous solution contact, solvent and solute weight ratio 8：1~15：1, temperature is 95 ~ 130 DEG C, is added by every 100 grams of Y molecular sieves Enter 35 ~ 80 grams（NH₄）₂SiF₆Amount add（NH₄）₂SiF₆The aqueous solution, add 3 ~ 30 grams per 100gY types molecular sieve per hour （NH₄）₂SiF₆, add（NH₄）₂SiF₆The aqueous solution using disposed slurry in temperature as at 80 ~ 120 DEG C, stir 0.5 ~ 5.0 hour.
23. in accordance with the method for claim 12, it is characterised in that：Step（1）The preparation side of middle big crystal grain NaY type molecular sieves Method, comprise the following steps：

I, at a temperature of 20 DEG C ~ 40 DEG C, according to Na₂O：Al₂O₃：SiO₂：H₂O=10~15：1：10~20：500 ~ 600 feed intake mole Than waterglass is slowly added into high alkali deflection aluminium acid sodium solution under conditions of stirring and is well mixed, afterwards, sequentially adds sulphur Sour aluminum solutions and low alkali aluminium acid sodium solution, stir at the temperature disclosed above；Then constant temperature aging in confined conditions, is obtained Gel；

II, hydrothermal crystallizing 12 ~ 24 hours by the gel that step I is obtained at 80 DEG C ~ 120 DEG C and under conditions of stirring, are passed through after crystallization Filtering, washing, dry, obtain big crystal grain NaY type molecular sieves.
24. in accordance with the method for claim 23, it is characterised in that：In step I, aluminum sulfate, high alkali deflection aluminium acid sodium and low alkali The ratio of the addition of sodium metaaluminate, 1 is calculated as with aluminum oxide：（0.5~0.7）：（0.6~0.8）.
25. in accordance with the method for claim 23, it is characterised in that：In step I, in described high alkali deflection aluminium acid sodium solution Na₂O content is 260 ~ 320g/L, Al₂O₃Content is 30 ~ 50g/L；Na in described low alkali aluminium acid sodium solution₂O content is 100 ~ 130g/L, Al₂O₃Content is 60 ~ 90g/L, Al in described aluminum sulfate solution₂O₃Content be 80 ~ 100g/L；Described water SiO in glass₂Content be 200 ~ 300g/L, modulus is 2.8 ~ 3.5.
26. in accordance with the method for claim 23, it is characterised in that：In step II, under agitation, by temperature with 2 ~ 4 DEG C/minute it is warming up to crystallization temperature i.e. 80 DEG C ~ 120 DEG C.