CN105709819B - Hydrocracking catalyst and its preparation method - Google Patents
Hydrocracking catalyst and its preparation method Download PDFInfo
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- CN105709819B CN105709819B CN201410711409.4A CN201410711409A CN105709819B CN 105709819 B CN105709819 B CN 105709819B CN 201410711409 A CN201410711409 A CN 201410711409A CN 105709819 B CN105709819 B CN 105709819B
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Abstract
The invention discloses a kind of hydrocracking catalyst and its preparation method.The catalyst 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, in the hydrocracking process for using it for 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
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, is particularly evaporated for high-output qulified low solidifying centre
Divide hydrocracking catalyst of 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 hydrocracking catalyst and its preparation side
Method.The catalyst uses Modified Zeolite Y with beta-molecular sieve collectively as cracking center, wherein Y type molecular sieve used is one
The Y type molecular sieve that kind big crystal grain, high silicon, effective pore sife distribution are concentrated, the hydrogenation for high-output qulified midbarrel oil product split
During change, the characteristics of active high and selectivity is good, while can and the high-quality hydrogenation tail oil of production.
Hydrocracking catalyst of the present invention, comprising hydrogenation active metals and carrier, carrier includes Modified Zeolite Y, β point
Son sieve and aluminum oxide, the property of wherein Modified Zeolite Y are 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 hydrocracking catalyst of the present invention, the pore volume of described Modified Zeolite Y is 0.35cm3/g~0.50cm3/ g,
Specific surface area is 800m2/g~980m2/g。
In hydrocracking catalyst of the present invention, the mmol/g of infrared total acid 0.1 ~ 0.5 of described Modified Zeolite Y.
In hydrocracking catalyst of the present invention, in described Modified Zeolite Y, Na2O weight content is 0.15wt%
Below.
In 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.
In described hydrocracking catalyst, described carrier, on the basis of the weight of carrier, Modified Zeolite Y
Content is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, and the content of aluminum oxide is 40% ~ 85%.
For described hydrogenation active metals typically using vib and the metal of group VIII, vib metals are preferably molybdenum
He ∕ or tungsten, group VIII metal are preferably Gu He ∕ or nickel.In catalyst of the present invention, on the basis of the weight of catalyst, VI B
Race's metal（In terms of oxide）Content be 10.0% ~ 30.0%, group VIII metal（In terms of oxide）Content for 4.0% ~
8.0%。
The specific surface area of hydrocracking catalyst of the present invention is 250~450m2/ g, pore volume are 0.30~0.50mL/g.
The preparation method of hydrocracking catalyst of the present invention, include preparation and the load hydrogenation active metal component of carrier,
The preparation process of wherein carrier is as follows：Modified Zeolite Y, beta-molecular sieve, aluminum oxide are mixed, shaping, then dries and roasts
Burn, the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, comprises the 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, 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%, and relative crystallinity is 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 of the present invention uses, because the larger crystal molecular sieve not only has larger crystalline substance
Grain so that structure cell quantity increases to 1000 ~ 2000 in each dimension, is advantageous to macromolecular and is cracked, but also with more
Good pore size distribution range, can efficiently control the cracking degree of reactant, and is advantageous to product and is diffused in duct,
So in cracking reaction, can relative increase activated centre, and can make macromolecular carry out suitable degree cracking reaction, catalyst
Good cracking activity and product selectivity can be shown.
Catalyst of the present invention, collectively as cracking center, has both given full play to it using Modified Zeolite Y and beta-molecular sieve
Respective performance characteristics, and can enough act on concerted catalysis caused by two kinds of molecular sieves, i.e., beta molecular sieve is to alkane or aromatic hydrocarbons
On long side chain have good isomerization, can effectively reduce the condensation point of product, while Y type molecular sieve has very high open to aromatic hydrocarbons
Ring selectivity, improve the product property of purpose product.The active height of hydrocracking catalyst of the present invention, can high-output qulified centre
Cut oil product（Navigate coal+diesel oil）, while high-quality hydrogenation tail oil and can be produced.
When being used for heavy oil hydrocracking by the hydrocracking catalyst of the present invention, 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 etc.）, tool
There are very high catalytic activity and intermediate oil selectivity, and the condensation point reduction amplitude of diesel oil distillate is big, intermediate oil
Product property is improved, and can be met refinery's increase operating flexibility, increase device disposal ability, further be increased production midbarrel
The needs of oil.
Brief description of the drawings
Fig. 1 is the gained LY-1 of embodiment 1 SEM electromicroscopic photographs；
Fig. 2 is the gained DY-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.
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.
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.
Carrier of hydrocracking catalyst of the present invention loads hydrogenation active metal component by conventional methods（Vib and
Group VIII metal component such as Co, Ni, Mo, W etc.）, it is prepared into hydrocracking catalyst.Using load side conventional in the prior art
Method, preferably infusion process, can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnation catalyst containing required active component
Agent carrier, carrier after dipping are then small in 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 in 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour
When, final catalyst is made.
The following examples are used to technical scheme be described in more detail, but the scope of the present invention is not limited solely to this
The scope of a little 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
| Production code member | LY-1 | LY-2 |
| Specific surface area, m2/g | 897 | 956 |
| Pore volume, cm3/g | 0.35 | 0.37 |
| External surface area, m2/g | 80 | 82 |
| Lattice constant, nm | 2.465 | 2.463 |
| Relative crystallinity, % | 118 | 128 |
| Average crystallite size, μm | 3.0 | 2.5 |
| SiO2/Al2O3Mol ratio | 5.68 | 5.32 |
| The pore volume that bore dia 1nm ~ 10nm is accounted for accounts for total pore volume, % | 78 | 87 |
| Relative crystallinity * after roasting, % | 95 | 92 |
| Relative crystallinity * after hydro-thermal process, % | 108 | 115 |
Continued 1
| Production code member | DLY-1 | DLY-2 | DLY-3 |
| Specific surface area, m2/g | 840 | 820 | 738 |
| Pore volume, cm3/g | 0.32 | 0.32 | 0.30 |
| External surface area, m2/g | 150 | 132 | 121 |
| Lattice constant, nm | 2.468 | 2.468 | 2.472 |
| Relative crystallinity, % | 96 | 146.7 | 92 |
| Average crystallite size, μm | 0.95 | 1.80 | 1.10 |
| SiO2/Al2O3Mol ratio | 4.21 | 4.35 | 5.10 |
| The pore volume that bore dia 1nm ~ 10nm is accounted for accounts for total pore volume, % | 51 | 56 | 43 |
| Relative crystallinity * after roasting, % | 69 | 81 | 44 |
| Relative crystallinity * after hydro-thermal process, % | 70 | 70 | 76 |
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
| Production code member | LYNS-1 | LYNS-2 | LYNS-3 | LYNS-4 |
| Specific surface area, m2/g | 965 | 947 | 936 | 926 |
| Pore volume, cm3/g | 0.46 | 0.47 | 0.46 | 0.48 |
| Lattice constant, nm | 2.433 | 2.428 | 2.430 | 2.426 |
| Relative crystallinity, % | 136 | 143 | 140 | 146 |
| Average crystallite size, μm | 3.0 | 3.0 | 3.0 | 3.0 |
| SiO2/Al2O3Mol ratio | 69.8 | 105.6 | 88.1 | 113.6 |
| The pore volume that bore dia 3nm ~ 7nm is accounted for is total pore volume, % | 83 | 91 | 89 | 93 |
| Non-framework aluminum accounts for total aluminium content, % | 0.2 | 0.1 | 0.2 | 0.1 |
| Infrared total acid content, mmol/g | 0.42 | 0.28 | 0.35 | 0.24 |
| Na2O, wt% | 0.10 | 0.09 | 0.10 | 0.08 |
Continued 2
| Production code member | DYNS-1 | DYNS-2 | DYNS-3 |
| Specific surface area, m2/g | 569 | 585 | 546 |
| Pore volume, cm3/g | 0.37 | 0.36 | 0.35 |
| Lattice constant, nm | 2.429 | 2.431 | 2.430 |
| Relative crystallinity, % | 79 | 81 | 59 |
| Average crystallite size, μm | 0.95 | 0.95 | 1.10 |
| SiO2/Al2O3Mol ratio | 23.5 | 16.9 | 22.4 |
| The pore volume that bore dia 3nm ~ 7nm is accounted for is total pore volume, % | 36 | 33 | 32 |
| Non-framework aluminum accounts for total aluminium content, % | 1.8 | 2.1 | 4.5 |
| Infrared total acid content, mmol/g | 0.29 | 0.38 | 0.77 |
| Na2O, wt% | 0.16 | 0.18 | 0.22 |
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.
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-1 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Embodiment 9
By 44.44 grams of LYNS-1 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-2 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.
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-3 is obtained, carrier and corresponding catalyst property are shown in Table 3.
Embodiment 11
By 55.55 grams of LYNS-2 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.
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-4 is obtained, carrier and corresponding catalyst property are shown in Table 3.
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 ~ 15
This embodiment describes by catalyst Z C-1, ZC-2, ZC-3 and ZC-4 Activity evaluation of the present invention.In fixed bed
Evaluated on hydrogenation test apparatus, appreciation condition is：React stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250：1, volume is empty during liquid
Fast 1.5h-1, using one-stage serial once by technological process, use vacuum distillate（VGO）As feedstock oil, raw material oil nature
Table 4 is listed in, evaluation result is listed in table 5.
Comparative example 11 ~ 13
This comparative example is described by comparative example catalyst DZC-1, DZC-2 and DZC-3 Activity evaluation of the present invention.Solid
Evaluated on fixed bed hydrogenation test apparatus, appreciation condition is：React stagnation pressure 15.0MPa, hydrogen to oil volume ratio 1250：1, body during liquid
Product air speed 1.5h-1, using one-stage serial once by technological process, use vacuum distillate（VGO）As feedstock oil, feedstock oil
Property is 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
| Carrier forms and property | ||||
| Numbering | ZS-1 | ZS-2 | ZS-3 | ZS-4 |
| Y type molecular sieve, wt% | 20 | 20 | 30 | 25 |
| Beta-molecular sieve, wt% | 10 | 15 | 5 | 20 |
| Aluminum oxide | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 431 | 455 | 476 | 495 |
| Pore volume, mL/g | 0.66 | 0.63 | 0.62 | 0.63 |
| Catalyst forms and property | ||||
| Numbering | ZC-1 | ZC-2 | ZC-3 | ZC-4 |
| WO3, wt% | 25.55 | 25.59 | 25.38 | 25.33 |
| NiO, wt% | 6.94 | 6.82 | 6.87 | 6.93 |
| Specific surface area, m2/g | 301 | 311 | 332 | 341 |
| Pore volume, mL/g | 0.45 | 0.42 | 0.41 | 0.44 |
Continued 3
| Carrier forms and property | |||
| Numbering | DZS-1 | DZS-2 | DZS-3 |
| Y type molecular sieve, wt% | 20 | 20 | 20 |
| Beta-molecular sieve, wt% | 15 | 15 | 15 |
| Aluminum oxide | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 401 | 433 | 298 |
| Pore volume, mL/g | 0.59 | 0.56 | 0.45 |
| Catalyst forms and property | |||
| Numbering | DZC-1 | DZC-2 | DZC-3 |
| WO3, wt% | 25.62 | 25.61 | 25.69 |
| NiO, wt% | 6.90 | 6.90 | 6.85 |
| Specific surface area, m2/g | 269 | 256 | 197 |
| Pore volume, mL/g | 0.28 | 0.26 | 0.29 |
The raw material oil nature of table 4
| Feedstock oil | Vacuum distillate（VGO） |
| Density (20 DEG C), g/cm3 | 0.9072 |
| Boiling range, DEG C | |
| IBP/10% | 305/361 |
| 30%/50% | 394/417 |
| 70%/90% | 443/481 |
| 95%/EBP | 509/533 |
| Condensation point, DEG C | 34 |
| Sulphur, wt% | 1.98 |
| Nitrogen, μ g/g | 1228 |
| Carbon, wt% | 85.28 |
| Hydrogen, wt% | 12.46 |
| BMCI values | 45.0 |
The catalyst performance comparative evaluation's result of table 5
Continued 5
It can be seen from the evaluation result of table 5 under identical process conditions, during using catalyst of the present invention, centre evaporates
Oil selectivity, yield and product quality is divided to be superior to reference catalyst.
Claims (26)
1. a kind of hydrocracking catalyst, comprising hydrogenation active metal component and carrier, carrier includes Modified Zeolite Y, β point
Son sieve and aluminum oxide, the property of wherein Modified Zeolite Y are as follows：Average grain diameter is 2.0 ~ 5.0 μm, relative crystallinity
110% ~ 150%, SiO2/Al2O3Mol ratio is 60 ~ 120, and non-framework aluminum accounts for the 0.1% ~ 1.0% of total aluminium, cell parameter is 2.425 ~
2.435nm, bore dia are that the pore volume shared by 3nm ~ 7nm hole is the 70% ~ 95% of total pore volume.
2. according to the catalyst described in claim 1, it is characterised in that：The average grain diameter of the Modified Zeolite Y is
2.0~4.5μm。
3. according to the catalyst described in claim 2, it is characterised in that：The average grain diameter of the Modified Zeolite Y is
3.0~4.5μm。
4. according to the catalyst described in claim 1, it is characterised in that：The bore dia of the Modified Zeolite Y is 3nm ~ 7nm
Hole shared by pore volume be total pore volume 75% ~ 90%.
5. according to the catalyst described in claim 1, it is characterised in that：The Modified Zeolite Y, non-framework aluminum account for total aluminium
0.1%~0.5%。
6. according to the catalyst 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。
7. according to the catalyst described in claim 1, it is characterised in that：The infrared total acid 0.1 ~ 0.5 of the Modified Zeolite Y
mmol/g。
8. according to the catalyst described in claim 1, it is characterised in that：In the Modified Zeolite Y, Na2O weight content
For below 0.15wt%.
9. according to the catalyst described in claim 1, it is characterised in that：The property of described beta-molecular sieve is as follows：Crystal grain is averagely straight
Footpath is 200 ~ 400nm, specific surface area 600m2/g~800m2/ g, pore volume are 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.
10. according to the catalyst described in claim 1, it is characterised in that：In described hydrocracking catalyst, described load
Body, on the basis of the weight of carrier, the content of Modified Zeolite Y is 10% ~ 40%, and the content of beta-molecular sieve is 5% ~ 20%, oxidation
The content of aluminium is 40% ~ 85%.
11. according to the catalyst described in claim 1 or 10, it is characterised in that：Described hydrogenation active metals use vib
With the metal of group VIII, vib metals are Mu He ∕ or tungsten, and group VIII metal is Gu He ∕ or nickel, with the weight of catalyst
On the basis of amount, vib metals are using the content that oxide is counted as 10.0% ~ 30.0%, group VIII metal containing in terms of oxide
Measure as 4.0% ~ 8.0%.
12. the preparation method of any catalyst of claim 1 ~ 11, include preparation and the load hydrogenation active metals of carrier
The preparation process of component, wherein carrier is as follows：Modified Zeolite Y, beta-molecular sieve, aluminum oxide are mixed, shaping, then dried
And roasting, the preparation method of catalyst carrier, wherein Modified Zeolite Y is made, comprises the 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：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。
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.
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| US6284218B1 (en) * | 1998-09-23 | 2001-09-04 | Indian Oil Corporation Limited | Process for preparing an hydrothermally stable, large crystallite sized, highly crystallite sized, highly crystalline synthetic faujasite zeolite |
| CN1683246A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Process for preparing NaY molecular sieve |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
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- 2014-12-01 CN CN201410711409.4A patent/CN105709819B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284218B1 (en) * | 1998-09-23 | 2001-09-04 | Indian Oil Corporation Limited | Process for preparing an hydrothermally stable, large crystallite sized, highly crystallite sized, highly crystalline synthetic faujasite zeolite |
| CN1683246A (en) * | 2004-04-14 | 2005-10-19 | 中国石油化工股份有限公司 | Process for preparing NaY molecular sieve |
| CN101380589A (en) * | 2007-09-04 | 2009-03-11 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN101723400A (en) * | 2008-10-29 | 2010-06-09 | 中国石油化工股份有限公司 | Small crystal grain Y-shaped molecular sieve and preparation method thereof |
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