CN104828838B - Preparation method for small-grain Y type molecular sieve - Google Patents
Preparation method for small-grain Y type molecular sieve Download PDFInfo
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Abstract
The invention discloses a preparation method for a small-grain Y type molecular sieve. According to the method, a NaY type molecular sieve raw material with a high silica-alumina ratio, a high degree of crystallization and good stability is employed and successively undergoes ammonium exchange, primary hydro-thermal treatment, treatment with an alkali-containing solution, secondary hydro-thermal treatment and treatment with a mixed solution of acid and an ammonium salt; and the obtained small-grain Y type molecular sieve has a high SiO2/Al2O3 mol ratio and a high proportion of secondary pores, retains the stability of a Y type molecular sieve and has a high specific surface area and a high degree of crystallization. The small-grain Y type molecular sieve prepared in the invention is applicable as a cracking component for a hydrocracking catalyst used for high and medium oil and enables the hydrocracking catalyst to have good activity, medium oil selectivity and product properties.
Description
Technical field
The present invention relates to a kind of preparation method of y type molecular sieve, particularly a kind of deep sealumination modified little crystal grain y type molecular sieve
Preparation method.
Background technology
Y type molecular sieve is cracking active component that at present can be the most universal in residual oil cracking field, and crystal grain is generally
1000nm about, its crystal grain is larger, and duct is relatively long, and diffusional resistance is big, and macromole is difficult to enter and is reacted inside duct,
After reaction, product is also more difficult diffuses out, so the selectivity of its cracking activity and purpose product receives restriction.With conventional y type
Molecular sieve is compared, and little crystal grain y type molecular sieve has bigger external surface area and more outer surface active center, is conducive to improving big point
Sub- hydrocarbon cracking capability, thus there is more superior catalytic perfomance.Meanwhile, reduce y type zeolite crystal size acceptable
Improve inner surface active sites utilization rate.In general, diffusion in molecular sieve endoporus duct for the reactant molecule is referred to as transgranular expansion
Dissipate.Molecular sieve inner surface is made all to be used for catalyzed conversion it is necessary to make micropore diffusion speed be more than endoporus catalyzed conversion
Speed.Shortening the evolving path is the best way.The effective way that micropore diffusion limits is overcome to be to reduce zeolite crystal
Size.This not only can increase the external surface area of zeolite crystal, and shorten diffusion length simultaneously.Ep0204236 is to little
Crystal grain nay molecular sieve and big crystal grain nay molecular sieve compare, and result shows, the former has higher to RFCC
Active and preferable selectivity.The technology of preparing of therefore small crystal grain molecular sieve increasingly causes the attention of people.
At present, nay molecular sieve substantially adopts the directed agents proposed in us 3639099 and us 3671191
Method.The method is to prepare mole to consist of (15-17) na first2o∶al2o3∶(14-16)sio2∶(285-357)h2The guiding of o
Agent, then it is directed to agent with the raw material such as waterglass, sodium metaaluminate, aluminum sulfate according to mol ratio (3-6) na2o∶al2o3∶(8-12)
sio2∶(120-200)h2The ratio of o is mixed with gel, then by gel in 100 DEG C about crystallization.The nay of the method synthesis
Framework of molecular sieve sio2/al2o3Generally 5.0 about, generally below 5.2, grain size is usually 500-800nm.
The method preparing fine grain y type molecular sieve proposing in cn1081425a is first by the Synthesis liquid 80 DEG C～180 of nay
Pre- crystallization l～10 hour at DEG C, add directed agents after being cooled to room temperature, then continue crystallization 5～25 at 80 DEG C～100 DEG C little
When, this processing step is more complicated and is difficult to control to, and the hydrothermal stability of prepared fine grain y type molecular sieve is poor.
Reduce the crystal grain of molecular sieve by adding organic solvent miscible with water in synthetic system, such as
Using addition disperse medium in usp3516786 and usp4372931, methanol, the side of ethanol, dimethyl sulfoxide and left-right rotary sugar
Method, the grain size of its synthetic product is 10～100nm.The sial of the molecular sieve synthesized by the method is relatively low, is only capable of synthesizing x type
Molecular sieve, and organic solvent is readily volatilized under the conditions of hydrothermal crystallizing.
Using improving synthesis technique in usp4587115 and usp4778666, such as high-speed stirred, the method for microwave heating, its
The grain size of synthetic product is about 500nm.The method building-up process is complicated, synthesizes high cost, and the silicon of gained molecular sieve
Aluminum ratio is low, and hydrothermal stability has much room for improvement.
Cn1789125a proposes a kind of high silica alumina ratio, the preparation method of the nay molecular sieve of little crystal grain, is to close conventional method
After the gel static crystallization 0～70h at 50～100 DEG C becoming, add silicon source, then continue at 90～120 DEG C crystallization 0.5～
50h.The method need after silicon reinsertion improving silica alumina ratio, step is complicated.
A kind of preparation method of high silica alumina ratio little crystal grain nay molecular sieve that cn1785807a provides, in advance at 15～60 DEG C
Lower stirring 0.5～48 hour prepared crystallization director of ageing, is then directed to agent, water, silicon source, silicon source make reactant mixture,
By reactant mixture crystallization in two steps, first step dynamic crystallization, second step static crystallization after stirring, eventually pass filter, wash
Wash, be dried, the high silica alumina ratio little crystal grain nay molecular sieve that prepared relative crystallinity is more than 80%.But hydrothermal stability is bad, hy divides
Son sieve is relatively low through crystallization reservation degree after 750 DEG C of hydrothermal treatment consists 2 hours.
The preparation method of little crystal grain nay molecular sieve disclosed in cn92105661.3, its preparation process is: first will be without leading
To agent silica-alumina gel in the input orientation agent again in 1 ~ 10 hour of 80 ~ 180 DEG C of crystallization, then continue crystallization 5 ~ 25 at 90 ~ 100 DEG C
Hour, until crystallization is complete.The nay molecular sieve that the little crystal grain nay molecular sieve that the method is obtained is obtained with conventional method compares, and has
Identical silica alumina ratio and degree of crystallinity, simply crystal grain less is 0.1 ~ 0.5 micron.Therefore, the little crystal grain nay molecule of the method gained
The silica alumina ratio of sieve is still relatively low, and generally less than 5, and also its degree of crystallinity also awaits improving further.
Cn101722023a discloses a kind of little crystal grain nay type molecular sieve and preparation method thereof.This little crystal grain nay type molecule
The sio of sieve2/al2o3Mol ratio is 4.0～6.0, and mean diameter, in 100～700nm, is using low temperature synthesis directed agents, low temperature
The method preparation that synthesized gel rubber and two sections of alternating temperature dynamic crystallizations combine, the method is the method system using optimum synthesis condition
Standby little crystal grain nay type molecular sieve, its silica alumina ratio is still relatively low, and its heat stability and hydrothermal stability await carrying further
High.
At present, in preparation process, silicon and aluminum are easy to run off existing method little crystal grain nay type molecular sieve, and silicon utilization rate is low, and
And silicon, aluminum distributing inhomogeneity, easily occur reuniting, therefore still cannot to prepare silica alumina ratio high for existing method, and heat stability and
The again good little crystal grain nay type molecular sieve of hydrothermal stability.
Little crystal grain nay molecular sieve is that do not possess acidity, needs to be modified processing, to meet the performance of Cracking catalyst
Require.Cnl382632a discloses a kind of super stabilizing method of little crystal grain y type zeolite, and the method is gas to be dried with Silicon chloride.
Body and little crystal grain nay zeolitic contact, obtain after washing, because the heat of its raw material itself and hydrothermal stability are just poor, simultaneously
This inventive method is to process molecular sieve by the way of gas phase dealumination complement silicon, and this makes the heat of product and hydrothermal stability worse,
Activity is low.Especially poor to heat stability and hydrothermal stability little crystal grain nay zeolite, the sial framing structure in molecular sieve
Less stable, easily causes the removing of framework aluminum in modifying process, simultaneously also some framework silicon also with removing,
Easily cause part skeleton and the phenomenon caved in occurs so that the crystallization reservation degree of product is relatively low, the activity of molecular sieve is not high.
Cn200910165116.x discloses a kind of little crystal grain y type molecular sieve and preparation method thereof.Handled by the method
Raw material little crystal grain nay molecular sieve is the method preparation disclosed in cn101722023a, i.e. sio2/al2o3Mol ratio be 4.0～
6.0, mean diameter, in 100～700nm, passes sequentially through successive modified i.e. ammonium exchange, at ammonium hexafluorosilicate dealumination complement silicon, hydro-thermal
The mixed aqueous solution of reason, aluminium salt and acid is processed, and obtains little crystal grain y molecular sieve.In the method, need first to raw material ammonium hexafluorosilicate
After dealumination complement silicon is processed, then carry out hydrothermal treatment consists etc. and process, so could reduce the caving in of framing structure of molecular sieve, raising divides
The crystallization reservation degree of son sieve, but after the method is due to first using ammonium hexafluorosilicate dealumination complement silicon to process, due to occurring the sial isomorphous to take
In generation, molecular sieve silica constructed of aluminium ratio is more complete, then carries out hydrothermal treatment consists, and the secondary pore of formation is few, and secondary pore proportion is low.
At present, because the hydrothermal stability of little crystal grain nay molecular sieve is poor, structural instability, through successive modified it is impossible to
Obtain structural integrity, degree of crystallinity is high and little crystal grain y type molecular sieve that have more secondary pore.
Content of the invention
For the deficiency of existing technology of preparing, the invention provides a kind of dealumination depth is big, degree of crystallinity keeps good, secondary
The preparation method of the flourishing little crystal grain y type molecular sieve in hole.The y type molecular sieve of the method preparation is especially suitable for use as High middle distillate and adds
The acidic components of hydrogen Cracking catalyst, can make catalyst have excellent middle distillates oil selectivity and lytic activity and product property.Should
Method preparation flow is simple, and preparation cost is low.
The preparation method of the little crystal grain y type molecular sieve of the present invention, comprising:
(1) preparation of little crystal grain nay type molecular sieve；
(2) the little crystal grain nay type molecular sieve of step (1) is prepared into na2Little crystal grain nh of o content≤1.5wt%4nay；
(3) with little crystal grain nh4Nay is raw material, carries out first time hydrothermal treatment consists；
(4) molecular sieve obtaining step (3) is with containing alkaline solution treatment；
(5) molecular sieve obtaining step (4) carries out second hydrothermal treatment consists；
(6) the molecular sieve acid that step (5) obtains is processed with the mixed solution of ammonium salt, through washing and being dried to obtain little crystalline substance
Grain y type molecular sieve.
In step (1) in the inventive method, the preparation method of little crystal grain nay type molecular sieve is as follows:
A, preparation directed agents: silicon source, silicon source, alkali source and water are fed intake according to following proportioning: (6～30) na2O:al2o3: (6
～30) sio2: (100～460) h2O, after stirring, mixture is stirred at 0～20 DEG C ageing and is obtained for 0.5～24 hour
Directed agents；
B, amorphous silica-alumina predecessor is prepared using acid-base precipitation method, the weight with the butt of amorphous silica-alumina predecessor is
Benchmark, the content that silicon is counted with silicon dioxide as 40wt%～75wt%, preferably 55 wt%～70wt%；Its preparation process includes acid
In alkali and plastic, aging, the method that wherein silicon is introduced into reaction system be in aluminiferous material and plastic before and/or plastic during
Introducing portion contain silicon materials, remainder contain silicon materials be in aluminiferous material with plastic after and introduce before ageing；
C, prepare silica-alumina gel
Press (0.5～6) na2O:al2o3: (7～11) sio2: (100～460) h2Total molar ratio of o, at 0～40 DEG C
Water, silicon source, directed agents and alkali source is added in the amorphous silica-alumina predecessor of step (2) gained under conditions of quick stirring, and
Ph value is controlled to be 9.5 ~ 12.0, uniform stirring, obtain silica-alumina gel；Wherein directed agents addition accounts for the 1% of silica-alumina gel weight
～20%,
D, the reactant mixture of step c gained are through two step dynamic crystallizations, then through filtering, wash, and are dried, obtain little crystal grain
Nay type molecular sieve.
In the present invention, in step a and c, silicon source, alkali source can prepare silicon source and the alkali source of molecular sieve, the present invention using routine
In preferably silicon source adopt sodium silicate, alkali source adopts sodium hydroxide.In step a, silicon source can prepare the silicon source of molecular sieve using routine,
Sodium metaaluminate is preferably employed in the present invention.
In the present invention, preferably in aluminiferous material and after plastic and the silicon that introduces before ageing is in terms of silicon dioxide for step b
Account for silicon in amorphous silica-alumina predecessor 5wt% ~ 85wt%, preferably 30wt% ~ 70wt% in terms of silicon dioxide.
In the present invention, the preparation method of the amorphous silica-alumina predecessor of step b, using conventional acid-base precipitation method, is wherein wrapped
Include acid-base neutralization plastic, aging, wherein acid-base neutralization plastic process is usually the neutralization reaction of acid material and alkaline material
Journey.Neutralization plastic process can be in the way of using acid material or the continuous acid-base titration of alkaline material, it would however also be possible to employ acid
Material and the mode of alkaline material cocurrent neutralization.The method that wherein silicon is introduced in reaction system is as follows: in aluminiferous material and plastic
During front and/or plastic, introducing portion contains silicon materials, remainder contain silicon materials be in aluminiferous material with plastic after and
Aging front introducing.Silicon can be according to the different property containing silicon materials in aluminiferous material and before plastic and/or during plastic
Matter be neutralized again after mix with acid material or alkaline material plastic (when such as containing silicon materials using sodium metasilicate, metasilicic acid
Sodium can be mixed with alkaline material；When adopting Ludox containing silicon materials, add in acid aluminiferous material) it is also possible to by siliceous thing
Material in aluminiferous material and plastic during be individually added in reaction system or said method combination.Plastic material
Generally comprise aluminiferous material (al2(so4)3、alcl3、al(no3)3And naalo2Deng one or more of), (water containing silicon materials
One or more of glass, Ludox and organic silicon-containing compound etc., wherein organic silicon-containing compound is silanol, silicon ether and silicon
One or more of oxygen alkane, precipitant is divided into acidic precipitation agent and alkaline precipitating agent, wherein alkaline precipitating agent be sodium hydroxide,
One or more of ammonia, sodium carbonate, sodium bicarbonate, acidic precipitation agent is co2Or nitric acid, according to the difference choosing of plastic process
Select use, conventional mode of operation mainly has: (1) acid aluminium salt (al2(so4)3、alcl3、al(no3)3) and basic aluminium salt
(naalo2) or alkaline precipitating agent (naoh, nh4Oh) plastic, (2) basic aluminium salt (naalo are neutralized2) and acidic precipitation agent (co2)
Neutralization plastic.Described plastic process is typically carried out at room temperature ~ 85 DEG C, is relatively suitably for 40 ~ 80 DEG C, preferably 50 ~ 70 DEG C.Institute
The ph value of the plastic process control system stated is 7.0 ~ 10.0, preferably 7.5 ~ 9.0.When using continuous acid-base titration, control
The ph value of final plastic system is 7.0 ~ 10.0, preferably 7.5 ~ 9.0, in using cocurrent and colloid system is made in plastic time control
Ph value remains 7.0 ~ 10.0, preferably 7.5 ~ 9.0.Carry out aging after plastic, aging condition is as follows: ph is 7.0 ~ 10.0, excellent
Elect 7.0 ~ 9.5 as, ageing time 0.2 ~ 8.0 hour, relatively it is suitable at 0.5 ~ 5 hour, preferably 1 ~ 3 hour, aging temperature was room
Temperature ~ 85 DEG C, preferably 40 ~ 80 DEG C.Temperature when aging and ph are preferably identical with temperature during neutralization and ph.
In step c, 0～40 DEG C of controlling reaction temperature, preferably 10 ~ 30 DEG C, ph value 9.5～12.0, preferably ph value 10～11.
The reactant mixture of step d gained carries out crystallization and adopts two step dynamic crystallizations, and the wherein first step carries out dynamic crystallization
Condition as follows: temperature control at 50～90 DEG C, crystallization time be 0.5～18 hour；Second step carries out the condition of dynamic crystallization
As follows: at 80～140 DEG C, crystallization time is 3～10 hours to temperature control, after the completion of crystallization, then through filtering, washing, be dried, system
Obtain product.Two step dynamic crystallization conditions are preferably as follows: the first step:, at 60～80 DEG C, crystallization time is little for 1～10 for temperature control
When；Second step: at 80～120 DEG C, crystallization time is 5～10 hours to temperature control.
Little crystal grain nay molecular sieve described in step (1), its property is as follows: sio2/al2o3Mol ratio is 5.0 ~ 9.0,
Preferably 6.0～9.0, more preferably 7.0～8.0, average grain diameter is 200～700nm, preferably 300～500nm；Than
Surface 800～1000 m2/ g, preferably 850～950 m2/ g, pore volume 0.30/～0.45ml/g, relative crystallinity be 90%～
130%, cell parameter is 2.460～2.470nm, through relative crystallinity after 650 DEG C of in the air roastings 3 hours generally 85% with
On, preferably 90%～110%, through relative crystallinity after 700 DEG C of water vapour hydrothermal treatment consists 2 hours generally more than 85%, excellent
Elect 90%～110% as.
In step (2), with little crystal grain nay type molecular sieve as raw material, with containing h+Ammonium salt aqueous solution at 70～120 DEG C,
Exchange 0.5～3.0 hour at preferably 80～100 DEG C.Wherein said ammonium salt such as ammonium chloride, ammonium carbonate, ammonium nitrate, sulphuric acid
One or more of ammonium, ammonium acetate, ammonium oxalate, ammonium citrate etc..H is provided in aqueous solution+Acid can be hydrochloric acid, carbonic acid,
One or more of nitric acid, sulphuric acid.In aqueous solution, h+Concentration be 0.005～0.5mol/l, nh4 +Concentration be 0.5～
5.0mol/l.Concentration in exchanging serosity for the y type molecular sieve is 0.05～0.5g/ml, and repeated exchanged l～5 time filter off mother solution,
Washing, is dried and na is obtained2O content is in below 1.5wt%.
First time hydrothermal treatment consists temperature described in step (3) be 500 DEG C～700 DEG C, water vapor pressure be 0.01～
1.0mpa, process time is 1.0～10.0 hours.
The molecular sieve that step (3) obtains is mixed homogeneously by step (4) with the aqueous solution making beating of alkali, and maintains 60～120 DEG C
Temperature conditionss under stir process 1～4h, filter, washing.Alkali is selected from the mixture of naoh, koh or naoh and koh.The water of alkali
The concentration of solution is generally 0.1～3.0 mol/l, and in serosity, the concentration of molecular sieve is 0.05～1.0g/ml.
Second hydrothermal treatment consists temperature described in step (5) is 500～800 DEG C, and water vapor pressure is 0.01～1.0mpa,
Process time is 1.0～10.0 hours, and second hydrothermal treatment consists temperature is greater than or equal to that first time hydrothermal treatment consists temperature is identical.
In step (6), by the molecular sieve after hydrothermal treatment consists with acid and contain nh4 +Salt composition mixed solution contact, exchange
Na in molecular sieve+With the part non-framework aluminum in removing molecular sieve, acid therein can be hydrochloric acid, carbonic acid, nitric acid, in sulphuric acid
One or more, containing nh4 +Salt be one or more of ammonium salt containing above acid group；H in mixed solution+Concentration be
0.05～0.6mol/l, nh4 +Concentration be 0.5～3.0mol/l, exchange temperature be 70～120 DEG C, exchange serosity in molecular sieve
Concentration be 0.1～0.5g/ml, swap time be 0.5～3.0 hour, exchange step may be repeated 1～4 time.Then remove
Mother solution, washes with water, is dried.
The y type molecular sieve that the inventive method obtains has the following characteristics that sio2/ a12o3Mol ratio is 40～120, and crystal grain is put down
All a diameter of 200～700nm, preferably 300～500nm, relative crystallinity >=95%, lattice constant 2.425～2.435nm, than
Surface area is 900～1200m2/ g, pore volume is 0.5/～0.80ml/g, and the pore volume shared by the secondary pore of 1.7～10nm is total
Pore volume more than 60%.
The preparation method that the present invention provides has the advantage that the silicon of the nay type Molecular sieve raw material due to present invention process
Aluminum ratio is higher, and degree of crystallinity is high, good stability, so in follow-up modification process, the not crystal structure of saboteur's sieve, from
And do not affect the stability of final molecular sieve.The present invention passes through hydrothermal treatment consists twice, and coordinates the alkali between hydrothermal treatment consists twice
Processing procedure, that is, reached preferable dealumination depth, and preferably maintained the rock-steady structure of molecular sieve, creates a large amount of simultaneously
Secondary pore so that modified molecular screen product has good serviceability.
The particularly suitable Cracking Component as medium oil type hydrocracking catalyst of y type molecular sieve of gained of the present invention is high
The secondary pore of specific surface area and prosperity not only promotes the performance of hydrogenation activity, and is conducive to the diffusion of product, holds charcoal
Ability also greatly enhances, and secondary pore is many, then reduce the occurrence probability of excessive fragmentation and second pyrolysises, thus catalyst can be made to have
There are good activity, middle distillates oil selectivity and excellent product property.
Brief description
Fig. 1 is the sem electromicroscopic photograph of embodiment l gained ny-1；
Fig. 2 is the xrd diffraction pattern of embodiment l gained ny-1.
Specific embodiment
In order to the present invention is better described, to further illustrate the present invention with reference to embodiment and comparative example.But this
Bright scope is not limited solely to the scope of these embodiments.Analysis method of the present invention: specific surface area, pore volume adopt low temperature liquid nitrogen physics
Absorption method, relative crystallinity and cell parameter adopt x optical diffraction method, and silica alumina ratio adopts chemical method, and the crystal grain of molecular sieve is big
Measure by the way of little (scanning electron microscope) using sem.
Embodiment 1
The present embodiment is preparing raw material little crystal grain nay type molecular sieve
The preparation of ny-1
(1) preparation of directed agents: take 8 g sodium hydrate solids to be dissolved in 80g water, add sodium metaaluminate 2.5 g (al2o3
Content is 45wt%, na2O content is 41wt%), then add 40g waterglass (sio2Content is 28wt%, na2O content is 8
Wt%), in 18 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.
(2) preparation of amorphous silica-alumina predecessor
It is 100g a1 that solid sodium aluminate is configured to 0.3l concentration2o3/ l sodium aluminate working solution (a).By strong aqua ammonia plus
Enter appropriate distilled water diluting and become about 10wt% weak ammonia (b).Take containing sio2The sodium silicate solution of 28wt%, then it is dense to be diluted to 0.5l
Spend for 140g sio2/ l sodium silicate working solution (c).Take one 5 liters of steel retort, add 0.5 liter of distilled water in tank and stir
Mix after being heated to 70 DEG C, open the valve having (a) and (b) and (c) Sulfur capacity device respectively simultaneously, control the flow of (a) and (c) with
Make the neutralization reaction time at 40 minutes, and the flow of adjustment (b) rapidly makes the ph value of system be maintained at 7～8, and control system
Temperature is at 60 DEG C about.After the completion of reacting aluminum sulfate, stop adding (b), the addition of (c) is 0.17l, the silicon-aluminum sol of generation
After stablizing 20 minutes, continuously add (c) 0.33l, add in 10 minutes, start the ageing process of system, keep ph value 8.0,
Temperature 60 C, aging 30 minutes.
(3) preparation of gel
1l h is added in the serosity obtained by step (2)2o、140g sio2/ l sodium silicate working solution 0.6l and step
(1) directed agents 100g prepared, the ph value of gel is 11.5,15 DEG C of controlling reaction temperature, and uniform stirring 30 minutes staticizes 2.5
Hour.
(4) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 5 hours at 75 DEG C, then heat up
To 110 DEG C, stirring crystallization 7 hours, then filter, washing, dry nay zeolite product ny-1, property is listed in table l.
The preparation of ny-2
(1) preparation of directed agents: take 10 g sodium hydrate solids to be dissolved in 90g water, add sodium metaaluminate 3 g (al2o3
Content is 45wt%, na2O content is 41wt%), then add 50g waterglass (sio2Content is 28wt%, na2O content is 8
Wt%), in 20 DEG C of stirring 4 hours prepared directed agents of ageing after mix homogeneously.
(2) preparation of amorphous silica-alumina predecessor
It is 80g a1 that Solid aluminum sulfate is configured to 0.5l concentration2o3/ l aluminum sulfate working solution (a).Strong aqua ammonia is added
Appropriate distilled water diluting becomes about 10wt% weak ammonia (b).Take containing sio2The sodium silicate solution of 28wt%, then it is diluted to 0.4l concentration
For 150g sio2/ l sodium silicate working solution (c).Take one 5 liters of steel retort, add 0.5 liter of distilled water in tank and stir
After being heated to 70 DEG C, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) and (c) so that in
With the response time at 40 minutes, and the flow of adjustment (b) rapidly makes the ph value of system be maintained at 7～8, and the temperature of control system
At 60 DEG C about.After the completion of reacting aluminum sulfate, stop adding (b), the addition of (c) is 0.2l, and the silicon-aluminum sol of generation is stable
After 20 minutes, continuously add (c) 0.2l, add in 10 minutes, start the ageing process of system, keep ph value 8.0, temperature 60
DEG C, aging 30 minutes.
(3) preparation of gel
1.2l h is added in the serosity obtained by step (2)2o、150g sio2/ l sodium silicate working solution 0.8l and step
Suddenly directed agents 120g that prepared by (1), the ph value of gel is 12,30 DEG C of controlling reaction temperature, and uniform stirring 30 minutes staticizes 3 little
When.
(4) crystallization
Gel obtained by step (2) is poured in stainless steel cauldron, stirs crystallization 6 hours at 80 DEG C, then heat up
To 120 DEG C, stirring crystallization 5 hours, then filter, washing, dry nay zeolite product ny-2, property is listed in table l.
Embodiment 2
First ammonium exchange is carried out to raw material little crystal grain nay type molecular sieve ny-1.Prepare and contain nh4 +And h+Concentration be respectively
10 liters of the solution (ammonium chloride and hydrochloric acid mixed solution) of 1.0mol/l and 0.02mol/l.Weigh little crystal grain nay molecular sieve 1000
Gram, it is added in above-mentioned mixed solution, speed of agitator is 300rpm, constant temperature stirring l hour, then filtering molecular at 90 DEG C
Sieve, and stay sample, analyze na2O content；Repeat aforesaid operations, na in molecular sieve2O content reach 1.5wt%, done
Sample number into spectrum after dry is nny-1.
Embodiment 3
First ammonium exchange is carried out to raw material little crystal grain nay type molecular sieve ny-2.Prepare and contain nh4 +And h+Concentration be respectively
0.8.0mol/l 10 liters of the solution (ammonium nitrate and nitric acid mixed solution) with 0.01mol/l.Weigh little crystal grain nay molecular sieve
1000 grams, it is added in above-mentioned mixed solution, speed of agitator is 300rpm, at 95 DEG C, constant temperature stirring l hour, then filters and divide
Son sieve, and stay sample, analyze na2O content；Repeat aforesaid operations, na in molecular sieve2O content reach 1.5wt%, obtain
Dried sample number into spectrum is nny-2.
Embodiment 4
Take 100 grams of nny-1 to be placed in heat-treatment furnace, control the heating rate of 500 DEG C/h, temperature is risen to 600 DEG C, with
When maintain system water vapor pressure be 0.15mpa, process 2 hours, cooling, take out sample.By the molecular sieve obtaining and 500ml
Concentration is 1 mol/l naoh solution making beating mix homogeneously, and maintains stir process 2h under 80 DEG C of temperature conditionss, filters, washes
To solution close to neutral；Wet cake is placed in heat-treatment furnace, temperature is risen to 640 DEG C, control water vapor pressure is 0.2mpa,
Constant temperature 3 hours, cooling, take out sample；Finally with containing nh4 +And h+Concentration be respectively 2.0mol/l ammonium chloride and 0.2mol/l
The solution mixed solution 600ml of hydrochloric acid is contacted with sample and stirs, and processes 2 hours at 90 DEG C, filters, and washing is dried, is produced
Product a.The physico-chemical property of product a is shown in Table 2.
Embodiment 5
Take 100 grams of nny-1 type molecular sieves to be placed in heat-treatment furnace, control 400 DEG C/h of heating rate, by temperature liter
To 650 DEG C, maintain the steam partial pressure 0.08mpa of system simultaneously, process 2 hours, cooling, take out sample；By the molecule obtaining
Sieve is that the making beating of 0.5mol/l koh solution is mixed homogeneously with 600ml concentration, and maintains stir process 2h under 90 DEG C of temperature conditionss,
Filter, be washed to solution close to neutral；Wet cake is placed in heat-treatment furnace, temperature is risen to 700 DEG C, and control water in stove to steam
Steam pressure is 0.1mpa, constant temperature 2 hours, and sample is taken out in cooling；Final sample is with containing nh4 +And h+Concentration be respectively 1.0mol/
L ammonium nitrate is contacted with sample and stirs with the mixed solution 600ml of 0.15mol/l nitric acid, processes 3 hours, mistake at 100 DEG C
Filter, washing, it is dried, obtain product b.The physico-chemical property of product b is shown in Table 2.
Embodiment 6
Take 100 grams of nny-2 type molecular sieves to be placed in heat-treatment furnace, control 450 DEG C/h of heating rate, by temperature liter
To 650 DEG C, maintain the steam partial pressure 0.15mpa of system simultaneously, process 2 hours, cooling, take out sample；By the molecule obtaining
Sieve contains h with 500ml+Koh the and naoh mixed solution making beating mix homogeneously of concentration 0.8mol/l, and maintain 100 DEG C of temperature strip
Stir process 2h under part, filters, is washed to solution close to neutral；Wet cake is placed in heat-treatment furnace, temperature is risen to 650
DEG C, and control water vapor pressure in stove to be 0.15mpa, and constant temperature 2 hours, cooling, take out sample；Final sample is with containing nh4 +And h+
Concentration be respectively 1.5mol/l with 0.3mol/l solution (ammonium nitrate and nitric acid mixed solution) 600ml contact with sample and stir
Mix, process 3 hours at 95 DEG C, filter, washing, it is dried, obtain product c.The physico-chemical property of product c is shown in Table 2.
Comparative example 1
1st, little crystal grain nay is prepared with reference to cn101722023a
In this comparative example, feedstock property used is as follows: low alkali sodium metaaluminate: na2O content 120g/l, al2o3Content
40g/l；Waterglass: sio2Content 250g/l；Aluminum sulfate: al2o3Content 90g/l.
(1) preparation of directed agents: the preparation of directed agents is with ny-1 in embodiment 1.
(2) preparation of gel: temperature is 8 DEG C, under stirring condition, sequentially adds 59.4ml sulfur in the waterglass of 208ml
Sour aluminum, the low sodium metaaluminate of 62.7ml and 42.2ml directed agents, then constant temperature constant speed stirring 1.5 hours, then by the conjunction obtaining
Become liquid static aging 8 hours at the temperature disclosed above, obtain gel.
(3) crystallization: under agitation, in 20 minutes, the gel in synthesis reactor is raised to 50 DEG C, constant temperature stirs crystallization 7
Hour；After low temperature crystallized end, in 20 minutes, the temperature in synthesis reactor is brought up to 120 DEG C, then constant temperature stirs 6 hours.
Through filtering, washing and be dried, obtain product little crystal grain cny-l, product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve cny-1, treatment conditions, with embodiment 2, obtain dried
Sample number into spectrum is cnny-1.
3rd, cnny-1 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product ca.The thing of ca
Change property and be shown in Table 2.
Comparative example 2
1st, little crystal grain nay is prepared with reference to cn1785807a
The preparation of directed agents: the preparation of directed agents is with ny-1 in embodiment 1.
14.21g water is positioned in beaker, controls temperature of liquid in beaker to be 60 DEG C, be simultaneously introduced under quick stirring
The a1 of 12.79g50wt%2(so4)3) solution and 31.91g waterglass.After stirring, add above-mentioned directed agents 1.90g, gel
Ph value be 12.5, after stirring, be loaded in stainless steel cauldron, in 60 DEG C of stirring crystallization 6 hours, then heat to
100 DEG C of static crystallizations 60 hours, then filter, washing, dry cny-2 zeolite product, product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve cny-1, treatment conditions, with embodiment 2, obtain dried
Sample number into spectrum is cnny-2.
3rd, cnny-2 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product cb.The thing of cb
Change property and be shown in Table 2.
Comparative example 3
1st, little crystal grain nay is prepared with reference to cn92105661.3
Feedstock property used by nay in this comparative example is as follows: low alkali sodium metaaluminate: na2O content 120g/l, al2o3Content
40g/l；Waterglass: sio2Content 250g/l；Aluminum sulfate: al2o3Content 90g/l.
(1) preparation of directed agents: the preparation of directed agents is with ny-1 in embodiment 1.
(2) preparation of gel: sequentially add the low sodium metaaluminate of 60ml aluminum sulfate, 60ml in the waterglass of 220ml,
Then constant temperature constant speed stirs 0.5 hour, prepared silica-alumina gel.
(3) crystallization: under agitation, in 30 minutes, the gel in synthesis reactor is raised to 140 DEG C, constant temperature stirs crystallization
2 hours；Add 35ml directed agents, mixing and stirring, then continue crystallization 15 hours at 100 DEG C, through filtering, washing and do
Dry, obtain product cny-3, product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve cny-3, treatment conditions, with embodiment 2, obtain dried
Sample number into spectrum is cnny-3.
3rd, cnny-3 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product cc.The thing of cc
Change property and be shown in Table 2.
Comparative example 4
1st, little crystal grain nay preparation
(1) preparation of directed agents: the preparation of directed agents is with ny-1 in embodiment 1.
(2) preparation of amorphous silica-alumina predecessor.
It is 100g a1 that solid sodium aluminate is configured to 0.3l concentration2o3/ l sodium aluminate working solution (a).By strong aqua ammonia plus
Enter appropriate distilled water diluting and become about 10wt% weak ammonia (b).Take containing sio2The sodium silicate solution of 28wt%, then it is dense to be diluted to 0.5l
Spend for 140g sio2/ l sodium silicate working solution (c).Take one 5 liters of steel retort, add 0.5 liter of distilled water in tank and stir
Mix after being heated to 70 DEG C, open the valve having (a) and (b) and (c) container respectively simultaneously, control the flow of (a) so that neutralization is anti-
At 40 minutes between seasonable, and the flow of adjustment (b) rapidly makes the ph value of system be maintained at 7～8, and the temperature of control system is 60
DEG C about.After the completion of reacting aluminum sulfate, stop adding (b), the silicon-aluminum sol of generation stablizes 40 minutes.
(3) preparation of gel is with embodiment 1.
(4) crystallization, with embodiment 1, obtains product cny-4, and product property is shown in Table 1.
2nd, ammonium exchange is carried out to raw material little crystal grain nay molecular sieve cny-4, treatment conditions, with embodiment 2, obtain dried
Sample number into spectrum is cnny-4.
3rd, cnny-4 is carried out with subsequent treatment, processing mode and condition, with embodiment 4, obtain Reference Product cd.The thing of cd
Change property and be shown in Table 2.
The property of table 1 little crystal grain nay type molecular sieve
In table 1, * roasting condition: 650 DEG C of in the air roastings 3 hours；The condition of * hydrothermal treatment consists: 700 DEG C of steam treatment
2 hours.
The property of table 2 finished product little crystal grain y type molecular sieve
Claims (18)
1. a kind of preparation method of little crystal grain y type molecular sieve, comprising:
(1) preparation of little crystal grain nay type molecular sieve；
(2) the little crystal grain nay type molecular sieve of step (1) is prepared into na2Little crystal grain nh of o content≤1.5wt%4nay；
(3) with little crystal grain nh4Nay is raw material, carries out first time hydrothermal treatment consists；
(4) molecular sieve obtaining step (3) is with containing alkaline solution treatment；
(5) molecular sieve obtaining step (4) carries out second hydrothermal treatment consists；
(6) the molecular sieve acid that step (5) obtains is processed with the mixed solution of ammonium salt, through washing and being dried, obtain little crystal grain y
Type molecular sieve；
The preparation method of little crystal grain nay type molecular sieve wherein in step (1), comprising:
A, preparation directed agents: silicon source, silicon source, alkali source and water are fed intake according to following proportioning: (6～30) na2O:al2o3: (6～
30)sio2: (100～460) h2O, after stirring, mixture is stirred at 0～20 DEG C ageing 0.5～24 hour and is obtained and lead
To agent；
B, amorphous silica-alumina predecessor is prepared using acid-base precipitation method, with the weight of the butt of amorphous silica-alumina predecessor as base
Standard, the content that silicon is counted with silicon dioxide as 40wt%～75wt%；Its preparation process includes acid-base neutralization plastic, aging, wherein silicon
Be introduced into reaction system method be in aluminiferous material and plastic before and/or plastic during introducing portion contain silicon materials, remaining
Part contain silicon materials be in aluminiferous material with plastic after and introduce before ageing；
C, prepare silica-alumina gel: by (0.5～6) na2O:al2o3: (7～11) sio2: (100～460) h2O always feeds intake mole
Than, 0～40 DEG C quick stir under conditions of to the amorphous silica-alumina predecessor of step b gained in add water, silicon source, directed agents
And alkali source, and control ph value for 9.5 ~ 12.0, and uniform stirring, obtain silica-alumina gel；Wherein directed agents addition accounts for silica-alumina gel
The 1%～20% of weight,
D, the reactant mixture of step c gained are through two step dynamic crystallizations, then through filtering, wash, and are dried, obtain little crystal grain nay type
Molecular sieve.
2. in accordance with the method for claim 1 it is characterised in that in step b, amorphous silica-alumina predecessor, with amorphous silica-alumina
On the basis of the weight of the butt of predecessor, the content that silicon is counted with silicon dioxide is for 55 wt%～70wt%.
3. in accordance with the method for claim 1 it is characterised in that in step b, in the preparation process of amorphous silica-alumina predecessor,
In aluminiferous material and after plastic and the silicon that the is introduced into before ageing silicon that accounted in amorphous silica-alumina predecessor in terms of silicon dioxide with
5wt% ~ the 85wt% of silicon dioxide meter.
4. in accordance with the method for claim 1 it is characterised in that in step b, the preparation process of amorphous silica-alumina predecessor
In, the silicon being introduced in aluminiferous material and after plastic and before ageing accounts for the silicon in amorphous silica-alumina predecessor in terms of silicon dioxide
30wt% ~ 70wt% in terms of silicon dioxide.
5. in accordance with the method for claim 1 it is characterised in that in step a and c, silicon source, alkali source are respectively sodium silicate and hydrogen
Sodium oxide；In step a, silicon source is selected from sodium metaaluminate.
6. in accordance with the method for claim 1 it is characterised in that in step b, aluminiferous material is al2(so4)3、alcl3、al
(no3)3And naalo2One or more of, containing silicon materials be waterglass, one of Ludox and organic silicon-containing compound or
Several, wherein organic silicon-containing compound is one or more of silanol, silicon ether and siloxanes, precipitant be acidic precipitation agent or
Alkaline precipitating agent, wherein alkaline precipitating agent are one or more of sodium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, acid heavy
Shallow lake agent carbon dioxide or nitric acid.
7. in accordance with the method for claim 1 it is characterised in that step b adopt acid-base precipitation method in, acid-base neutralization plastic
Process is the neutralization reaction process of acid material and alkaline material, and neutralization plastic process is continuous using acid material or alkaline material
The mode of acid-base titration, or by the way of acid material and the neutralization of alkaline material cocurrent.
8. in accordance with the method for claim 7 it is characterised in that in step b, containing silicon materials in aluminiferous material and before plastic
And/or during plastic introduce, be according to the different properties containing silicon materials with acidity material or alkaline material mix after enter again
Go and neutralize plastic, or silicon materials will be contained and and be individually added in reaction system during plastic in aluminiferous material, or on
State the combination of method.
9. in accordance with the method for claim 1 it is characterised in that in step b, described plastic process is entered at room temperature ~ 85 DEG C
OK, the ph value of control system is 7.0 ~ 10.0；Carry out aging after plastic, aging condition is as follows: aging ph is 7.0 ~ 10.0, aging
0.2 ~ 8.0 hour time, aging temperature is room temperature ~ 85 DEG C.
10. in accordance with the method for claim 1 it is characterised in that in step c, 10 ~ 30 DEG C of controlling reaction temperature, ph value 10～
11.
11. in accordance with the method for claim 1 it is characterised in that step d adopts two step dynamic crystallizations, and the wherein first step is carried out
The condition of dynamic crystallization is as follows: at 50～90 DEG C, crystallization time is 0.5～18 hour to temperature control；It is brilliant that second step enters Mobile state
The condition changed is as follows: at 80～140 DEG C, crystallization time is 3～10 hours to temperature control.
12. in accordance with the method for claim 1 it is characterised in that step d adopts two step dynamic crystallizations, and the wherein first step is carried out
The condition of dynamic crystallization is as follows: at 60～80 DEG C, crystallization time is 1～10 hour to temperature control；Second step carries out dynamic crystallization
Condition as follows: temperature control at 80～120 DEG C, crystallization time be 5～10 hours.
13. in accordance with the method for claim 1 it is characterised in that in step (2), with little crystal grain nay type molecular sieve as raw material,
With containing h+The aqueous solution of ammonium salt exchange 0.5～3.0 hour at 70～120 DEG C；Containing h+The aqueous solution of ammonium salt in, h+Dense
Spend for 0.005～0.5mol/l, nh4 +Concentration be 0.5～5.0mol/l, molecular sieve exchange serosity in concentration be 0.05～
0.50 g/ml, repeated exchanged l～5 time.
14. in accordance with the method for claim 13 it is characterised in that in step (2), described ammonium salt is ammonium chloride, carbonic acid
One or more of ammonium, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium oxalate, ammonium citrate, provide h in aqueous solution+Acid be salt
One or more of acid, carbonic acid, nitric acid, sulphuric acid.
15. in accordance with the method for claim 1 it is characterised in that the first time hydrothermal treatment consists temperature described in step (3) is 500
DEG C～700 DEG C, water vapor pressure is 0.01～1.0mpa, and process time is 1.0～10.0 hours.
16. in accordance with the method for claim 1 it is characterised in that the water of step (4) molecular sieve that obtains step (3) and alkali
Solution making beating mix homogeneously, and maintain stir process 1～4h under 60～120 DEG C of temperature conditionss, filter, wash；Described alkali
Selected from the mixture of naoh, koh or naoh and koh, the concentration of the aqueous solution of alkali is 0.1～3.0 mol/l, molecular sieve in serosity
Concentration be 0.05～1.0g/ml.
17. in accordance with the method for claim 1 it is characterised in that second hydrothermal treatment consists temperature described in step (5) is 500
～800 DEG C, water vapor pressure is 0.01～1.0mpa, and process time is 1.0～10.0 hours, and second hydrothermal treatment consists temperature is high
In or be equal to first time hydrothermal treatment consists temperature.
18. in accordance with the method for claim 1 it is characterised in that in step (6), processed with the mixed solution of acid and ammonium salt,
Acid therein is one or more of hydrochloric acid, carbonic acid, nitric acid, sulphuric acid, ammonium salt be one of ammonium salt containing above acid group or
Multiple；H in mixed solution+Concentration be 0.05～0.6mol/l, nh4 +Concentration be 0.5～3.0mol/l, exchange temperature be 70
～120 DEG C, the concentration exchanging molecular sieve in serosity is 0.1～0.5g/ml, and swap time is 0.5～3.0 hour, exchange step
May be repeated 1～4 time.
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| DE3927034A1 (en) * | 1989-08-16 | 1991-02-28 | Degussa | PROCESS FOR THE PREPARATION OF ZEOLITE Y |
| CN1170634C (en) * | 2001-05-30 | 2004-10-13 | 中国石油化工股份有限公司 | Prepn of high-silicon Y-Zeolite |
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