CN109775716A - A kind of multi-stage porous Y type molecular sieve and preparation method thereof rich in L acid - Google Patents
A kind of multi-stage porous Y type molecular sieve and preparation method thereof rich in L acid Download PDFInfo
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Abstract
The present invention discloses a kind of multi-stage porous Y type molecular sieve and preparation method thereof rich in L acid, and the molar ratio of the molecular sieve silica and aluminium oxide is 5 ~ 15；Specific surface area is 600 ~ 900m2/g；Total acid acid amount is in 1.350 ~ 1.950mmol/g；Wherein L acid acid amount is in 0.550 ~ 0.850mmol/g；Total pore volume is 0.40 ~ 0.75ml/g；Its intermediary hole pore volume is 0.10 ~ 0.45ml/g.The preparation method of the Y type molecular sieve, including following content: handling USY molecular sieve using organic alkali solution first, and sodium hydroxide and white carbon black is then added, and the multi-stage porous Y type molecular sieve rich in L acid is made after crystallization, drying, roasting.The multi-stage porous Y type molecular sieve contains a large amount of L acid acidic site, enhances the isomerization reaction in reaction process, improves the catalytic performance of molecular sieve；Also there is meso-hole structure in molecular sieve simultaneously, and meso-hole structure runs through microcellular structure, and more reaction compartments and shorter diffusion length can be provided for macromolecular.
Description
Technical field
The present invention relates to a kind of multi-stage porous Y type molecular sieve and preparation method thereof rich in L acid.Specifically, be it is a kind of both
Containing more L acid acidic sites are rich in the microcellular structure again Y type molecular sieve containing meso-hole structure, reaction process may advantageously facilitate
Isomerization reaction occurs.
Background technique
All the time, the extensive concern of numerous scientific research personnel has been obtained about the modification work of molecular sieve.Molecular sieve changes
Journal of Sex Research is mainly to be modified by conventional acid, alkali and hydro-thermal process to carry out desiliconization dealuminzation, while generating a large amount of secondary
Meso-hole structure.The a large amount of secondary pores generated are conducive to the reaction and diffusion of macromolecular.Current modified method mainly first passes through
Sour processing is carried out after the hydro-thermal process of certain temperature, and dealuminzation not only has been carried out to molecular sieve, has improved hydrothermal stability, while can
To generate a large amount of secondary pore structure.But the molecular sieve secondary pore of this method preparation is concentrated mainly on surface and amount is limited,
Advanced treating molecular sieve is just needed to improve the amount of secondary pore, this will lead to the excessive dealuminzation of molecular sieve, the acid amount drop of molecular sieve
It is low to be unable to satisfy requirement.In recent years, huge progress is achieved by the research of aqueous slkali desiliconization, passes through the laggard stepping of pickling
Row alkali process can greatly increase the amount of secondary pore, while can also improve the acid amount of molecular sieve, and just right solution is original
The problem of advanced treating bring acid amount deficiency.Although but by first hydro-thermal process, then pickling dealuminzation, further alkali cleaning
Desiliconization can bring up a large amount of secondary pore structure, while acid amount can also be met the requirements.But the aperture of the secondary pore structure of preparation
Be concentrated mainly on 3 ~ 5nm, for some two rings and its more than the conversion of aromatic hydrocarbons macromolecular or helpless, therefore prepare tool
The molecular sieve of more macroporous structure is a critically important direction of scientific rersearch.
Ke Ming etc. (the molecular sieve modified progress of MCM-22 [J], contemporary chemical industry, 2015,44(11): 2629 ~ 2634) lead to
It crosses discovery molecular sieve after alkali process after MCM-22 molecular sieve is carried out alkali process and hydro-thermal process and is maintaining original micropore
While structure, there is more meso-hole structures and macroporous structure.(Y molecular sieve is modified to its structure and acidity by Cheng Shiwen etc.
Influence [J], petrochemical technology and application, 2011,29(5): result of study 401 ~ 405) shows by hydro-thermal process, hydro-thermal-
Oxalic acid treatment etc. is modified, and Y molecular sieve can form a large amount of secondary pores, this illustrates that steam treatment can play the role of reaming,
Can be further increased after oxalic acid removing non-framework aluminum mesoporous hole hold and can adjust in a big way Y molecular sieve acids type and
Acid amount, modified total acid content decline, and strong L acid amount increases after hydro-thermal process, and strong B acid can be improved in hydro-thermal-oxalic acid combination dealuminzation
Amount.Qin Zhen etc. (it the physicochemical property of the small-grain Y molecular sieve of different silica alumina ratios and its is hydrocracked performance [J], petrochemical industry chemical industry,
2013,42(10): result of study 1080 ~ 1085) show the skeleton stability of small-grain Y molecular sieve with the increase of silica alumina ratio and
Increase；Acid amount is reduced with the increase of silica alumina ratio, and there is the small-grain Y molecular sieve of different silica alumina ratios different acid sites to be distributed；
The pore structure of small-grain Y molecular sieve is not the small-grain Y molecule it is obvious that compared with industrial Y molecular sieve with the variation of silica alumina ratio
Sifter device has biggish specific surface area, this is advantageous to heavy oil conversion.The small-grain Y acidic zeolite that silica alumina ratio is 5.2 is moderate, duct
Prosperity, skeleton stability is preferable, and high as the activity of the hydrocracking catalyst of carrier using it, light oil selectivity and industrial chemicals are received
Rate is high, is the active component of preferred light oil type hydrogen cracking catalyst.Wang Yingjun etc. (super steady Y molecular sieve modified research into
Open up [J], silicate notification, 2015,34(11): 3243 ~ 3250) describe the Dealumination of super steady Y molecular sieve, load acid changes
Property, loading cation or the methods of oxide modifying and molecular sieve are composite modified, show super steady Y molecular sieve by modified tool
There are good crystallinity, higher silica alumina ratio, biggish pore size and pore volume, high specific surface area and hydrothermal stability, fit
Suitable acid amount and acid strength, so that preparing catalyst as carrier or acidic components shows preferable catalytic performance.Simultaneously
Think that the study on the modification of ultra-steady Y molecular sieve is still to continue, on the one hand the research in terms of acid centre, USY molecular sieve has
How B acid and the acid site L, prepare the catalyst in specific acid site, is the project for needing to capture to reach best catalytic activity；
On the other hand it to improve secondary with recycling for the catalyst of super steady Y molecular sieve (or modified super steady Y molecular sieve) preparation
Number reduces increased production cost production efficiency.(the modified Y molecular sieve centering fraction selective hydrogenation Cracking catalyst such as Peng Chenghua
Influence [J], petroleum journal (PETROLEUM PROCESSING), 2006(supplementary issue): result of study 171 ~ 173) shows Y modified point
The middle fraction selectivity that sub- sifter device has lower total acid content and higher L acid ratio to be conducive to improve catalyst, and keep preferable living
Property；When product (< 370 DEG C of distillates) conversion ratio is 60%, (150-370 DEG C evaporates the middle fraction of pilot scale sizing catalyst HC-670
Divide oil) selectivity is 68.3%, and the middle fraction of similar industrial catalyst selectively only 61.8%.(the hydro-thermal process such as Li Mingxiao
Influence [J] with nitric acid treatment to modified Y molecular sieve performance, petrochemical industry, 2012,43(4): result of study table 412 ~ 419)
Bright, with the raising of hydro-thermal process temperature, the dealuminzation amount of Y molecular sieve increases, and specific surface area reduces, and total acid content reduces；It is dense with nitric acid
The increase of degree, the non-framework aluminum removing in Y molecular sieve, relative crystallinity, specific surface area and silica alumina ratio increase.With modified Y
The activity and selectivity of the standby hydrocracking catalyst of system with molecular sieve for preparing is improved, wherein Y molecular sieve through 680 DEG C of hydro-thermal process and
The hydrocracking catalyst prepared after 0.6mol/L nitric acid treatment has under the premise of keeping higher n-dodecane conversion ratio
Good middle oil (C4~8Hydrocarbon) selectivity, middle oil yield is 51.07%.Wang Wenlan (the being hydrocracked property of combination Modified Zeolite Y
Energy [J], chemistry of fuel journal, 2009,37(4): result of study 454 ~ 458) shows the mistake in Y type molecular sieve oxalic acid dealuminzation
Cheng Zhong, CTAB, which is added, can make Y type molecular sieve keep very high relative crystallinity, while improve SiO2/Al2O3Than reducing structure cell
Constant.The acid amount that CTAB participates in modified Y type molecular sieve significantly reduces, raising and partially acidic position of the reason by silica alumina ratio
Amine poisoning determines.The hydrocracking catalyst that CTAB participates in Modified Zeolite Y preparation has higher activity and midbarrel
Oil yield, VGO high conversion rate 2.42%, midbarrel than the middle fraction oil type hydrocracking catalyst of current industrial application
The high income 4.20% of oil.The reason is that CTAB, which participates in modified Y type molecular sieve, to be had richer mesoporous, make big point in VGO
Son can be more close to the acidic site of catalyst, while crackate can quickly leave the active sites of catalyst and avoid two
Secondary cracking, thus make catalyst that there is higher activity and midbarrel oil yield.Patent 200610001864.0 describes one
The method of modifying of kind Y type molecular sieve, this method have obtained high silicon using the method that surfactant is added in sour dealumination process
The Y type molecular sieve (mole silica alumina ratio 9 ~ 15 of silica and aluminium oxide) of aluminium ratio simultaneously maintains higher crystallinity, modified Y type point
The secondary pore of son sieve, which has, to be greatly improved, and sour structure has also obtained further improvement.Patent 200810104303.2 describes
A kind of method of modifying of HY type molecular sieve, this method are used by the silica solution of HY type molecular sieve dipping a certain amount of 5% ~ 10%, so
Afterwards by 120 DEG C of dry and 450 DEG C of roastings, dealumination treatment is finally carried out using certain density ammonium fluoride aqueous solution, is obtained
Micro--mesoporous remodeling molecular sieve.
Patent 200810105644.1 describes a kind of method of modifying of NaY type molecular sieve, and this method will be from using sieve
Sub-exchange resin is kept apart with molecular sieve pulp, in the discontiguous situation of the two, using concentration difference realize hydrogen ion with
The exchange of sodium ion, the problem of alleviating subsequent wastewater treatment.The sodium oxide content of obtained remodeling molecular sieve can be reduced to
1wt% is hereinafter, crystallinity is maintained at 80% or more.Patent 201110331019.0 describes a kind of modification side of NaY type molecular sieve
Method, this method are added in the mixed liquor of NaY molecular sieve, buffer and water using mixed acid and are beaten uniformly, then and adjust pH
Value is 4.0 ~ 6.5, and exchange reaction under the conditions of 70 ~ 95 DEG C, finally washs, and dries.The method achieve no ammoniums to discharge, and alleviates
The problem of subsequent wastewater treatment.The sodium oxide content of obtained remodeling molecular sieve can be reduced to 0.5wt% hereinafter, crystallinity
It is maintained at 85% or more.Patent 201310114414.2 describes a kind of method of modifying of USY molecular sieve, and this method uses
0.10mol/L ~ 0.35mol/L citric acid is modified at 50 DEG C ~ 120 DEG C, and rising to set temperature in temperature is 60 DEG C ~ 90 DEG C
Afterwards, ammonium fluosilicate solution is added with the speed of 0.1ml/min ~ 3.5ml/min, after reacting 1h ~ 6h after charging, washs, does
It is dry to obtain modified USY molecular sieve.The specific surface of molecular sieve, secondary pore hole hold and middle strong acid ratio significantly improves.Patent
201310240740.8 and 201410131823.8 describe the combination method of modifying rich in mesoporous ultra-steady Y molecular sieve, this method
Using organic acid and inorganic salt solution mixed solution, under stirring conditions, temperature reaction is carried out in closed container, reaction reaches
It is washed after to setting time, filters to neutrality, be dried to obtain modified molecular screen.Modified molecular sieve secondary pore content is significant
It improves, silica alumina ratio increases, and lattice constant reduces.Patent 201410131458.0 describes a kind of method of modifying of USY molecular sieve,
This method with ammonium fluosilicate and citric acid mixed solution 50 DEG C ~ 120 DEG C at a temperature of be modified processing, finally obtain and be rich in
The high and middle strong acid modified USY molecular sieve abundant of secondary pore structure, crystallinity.Patent 201510131458.0 describes one kind and changes
Property Y molecular sieve and its method of modifying, this method use alkaline solution to handle Y type molecular sieve first, then take dealuminzation
The method for mending silicon obtains the Y type molecular sieve of high silica alumina ratio.The modified molecular screen has strong acid ratio big, especially strong B acid ratio
Big feature.
Existing research shows that reactant (product) can be effectively shortened in zeolite in transgranular secondary Jie (big) hole of introducing of zeolite
Transgranular diffusion length reduces diffusional resistance, so that solve macromolecular spreads asking for difficult and accessibility difference in zeolite micropore
Topic.Z. Xie has been synthesized as meso-hole structure directed agents using polyvinyl butyral and has been boiled with the transgranular mesoporous Beta of about 20nm
Stone, external surface area reach 114m2/g (J. Phys. Chem. C 2008, 112, 17257-17264) .Xiao etc. is then used
Non-surface-active agent polydimethyl diallyl ammonium chloride has been synthesized as difunctional template has transgranular three-dimensional perforation mesoporous
Beta zeolite monocrystalline (J. Am. Chem. Soc. 2014,136,2503 2510).CN201210425241 disclose with
The nano silica of surface silanization is that silicon source one-step synthesis in hydrothermal crystallizing system has transgranular mesoporous nanometer Beta
The method of zeolite aggregation.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of multi-stage porous Y type molecular sieve rich in L acid and its preparation side
Method.The multi-stage porous Y type molecular sieve contains a large amount of L acid acidic site, enhances the isomerization reaction in reaction process, improves point
The catalytic performance of son sieve；Also there is meso-hole structure simultaneously, and meso-hole structure runs through microcellular structure in molecular sieve, it can be with
More reaction compartments and shorter diffusion length are provided for macromolecular.
The present invention is rich in the multi-stage porous Y type molecular sieve of L acid, has the property that the molar ratio of silica and aluminium oxide is 5
~ 15, preferably 6 ~ 10；Specific surface area is 600 ~ 900m2/ g, preferably 650 ~ 850m2/g；Total acid acid amount is in 1.350 ~ 1.950mmol/
G, preferably 1.450 ~ 1.850mmol/g；Wherein L acid acid is measured in 0.550 ~ 0.850mmol/g, preferably 0.650 ~ 0.780mmol/g,
L acid acid amount in outer surface is in 0.450 ~ 0.750mmol/g, preferably 0.580 ~ 0.720mmol/g；Total pore volume is 0.40 ~ 0.75ml/
G, preferably 0.45 ~ 0.65ml/g；Its intermediary hole pore volume is 0.10 ~ 0.45ml/g, preferably 0.15 ~ 0.35ml/g.
Above-mentioned Y type molecular sieve micropore pore volume is 0.20 ~ 0.35ml/g, preferably 0.23 ~ 0.33ml/g.
The preparation method of multi-stage porous Y type molecular sieve of the present invention rich in L acid, including following content: organic base is used first
Solution handles USY molecular sieve, and sodium hydroxide and white carbon black is then added, and is made after crystallization, drying, roasting rich in L acid
Multi-stage porous Y type molecular sieve.
It is a kind of specific preferably the preparation method is as follows: under agitation, USY molecular sieve is added to equipped with organic alkali soluble
In the synthesis reactor of liquid, and it is closed, 50 ~ 150 DEG C are then heated to, heated at constant temperature 1 ~ 8 hour, is then cooled down, and in stirring
Under, sodium hydroxide and white carbon black is added, after mixing evenly, sealing then heats to 30 ~ 50 DEG C, and heated at constant temperature 12 ~ 48 hours,
80 ~ 120 DEG C are then heated to, heated at constant temperature 24 ~ 60 hours, is then cooled down, is filtered, dries and roast, ammonium exchange is rich in
The multi-stage porous Y type molecular sieve of L acid.
In the method for the present invention, the USY molecular sieve being added in organic alkali solution, silica/alumina molar ratio
It is 5 ~ 25, preferably 7 ~ 18；Water quality ratio in the additional amount and organic alkali solution of USY molecular sieve is 1:1 ~ 1:5, preferably 1:
1.5~1:3。
In the method for the present invention, the organic base is tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide or tetrabutyl hydrogen-oxygen
Change one or more of ammonium, the concentration of organic alkali solution is 0.05 ~ 0.35mol/L, preferably 0.10 ~ 0.30mol/L.
In the method for the present invention, it is logical that tetraethyl ammonium halide, tetrapropyl ammonium halide or tetrabutyl ammonium halide can also be directly added into
It crosses it and reacts generation tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide with sodium hydroxide.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.05 ~ 0.20:0.2
~0.5:1。
In the method for the present invention, filter to pH value less than 9；Drying condition is 6 ~ 24 hours dry under the conditions of 80 ~ 120 DEG C；
Roasting condition is to roast 2 ~ 8 hours under the conditions of 450 ~ 650 DEG C；Ammonium exchange at least carries out 2 times, and exchange temperature is 80 ~ 100 DEG C,
Ammonium salt used is ammonium chloride, ammonium sulfate or ammonium nitrate, and the concentration of ammonium salt is 0.1 ~ 2mol/L, and preferably ammonium salt is ammonium nitrate,
Preferred concentration is 0.2 ~ 1.5mol/L, and the liquid-solid ratio (ml/g) of exchange process is 5 ~ 30, preferably 10 ~ 20；Swap time is every time
0.5 ~ 2.0 hour, preferably 1 ~ 1.5 hour.
The method of the present invention is using USY molecular sieve is handled in organic alkali solution, due to having season in USY molecular sieve
The protection of Ammonium Salt Ionic, sieve particle cuts out amorphous silicon aluminium fragment in irregular shape by alkaline solution, in these nothings
The rejected region of sizing sial fragment forms a large amount of L acidic site, then under conditions of adding sodium hydroxide and white carbon black,
Carry out secondary crystallization so that formed amorphous silicon aluminium fragment recombine as Y type molecular sieve crystal grain, in the grain between
A large amount of meso-hole structure and the defective bit comprising L acid are formd, the progress of isomerization reaction can be strengthened during the reaction, had
Wide application prospect.
Detailed description of the invention
Fig. 1 is the XRD spectra of the multi-stage porous Y type molecular sieve rich in L acid prepared by embodiment 1.
Specific embodiment
Preparation process of the invention is further illustrated below with reference to embodiment, but following embodiment is not constituted to present invention side
The limitation of method.
Embodiment 1
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 8 is added to the tetraethyl hydrogen of 0.15mol/L
In the synthesis reactor of ammonium hydroxide solution, the additional amount and solution quality ratio of USY molecular sieve are 1:2, closed, then heat to 90 DEG C,
It heated at constant temperature 4 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, after mixing evenly, sealing, so
After be warming up to 35 DEG C, heated at constant temperature 18 hours, then heat to 90 DEG C, heated at constant temperature 56 hours, then cool down, filter to pH value
It is 12 hours dry under the conditions of 110 DEG C less than 9, it is roasted under the conditions of 550 DEG C 6 hours, then uses the ammonium chloride of 1.0mol/L
Solution constant temperature at 90 DEG C exchanges 2.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 15, obtains richness
The multi-stage porous Y type molecular sieve of the acid containing L.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.15:0.25:1.
Embodiment 2
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 6 is added to the tetrapropyl hydrogen of 0.25mol/L
In the synthesis reactor of ammonium hydroxide solution, the additional amount and solution quality ratio of USY molecular sieve are 1:2.5, closed, then heat to 60
DEG C, it heated at constant temperature 6 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, it is after mixing evenly, close
Envelope, then heats to 40 DEG C, heated at constant temperature 18 hours, then heats to 100 DEG C, heated at constant temperature 48 hours, then cool down, and filters
It is 12 hours dry under the conditions of 90 DEG C to pH value less than 9, it is roasted under the conditions of 500 DEG C 6 hours, then using 0.5mol/L's
Ammonium nitrate solution constant temperature at 100 DEG C exchanges 2.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is
10, obtain the multi-stage porous Y type molecular sieve rich in L acid.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.08:0.3:1.
Embodiment 3
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 11 is added to the tetrabutyl of 0.20mol/L
In the synthesis reactor of Ammonia, the additional amount and solution quality ratio of USY molecular sieve are 1:4, closed, then heat to 70
DEG C, it heated at constant temperature 4 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, it is after mixing evenly, close
Envelope, then heats to 35 DEG C, heated at constant temperature 18 hours, then heats to 100 DEG C, heated at constant temperature 36 hours, then cool down, and filters
It is 20 hours dry under the conditions of 90 DEG C to pH value less than 9, it is roasted under the conditions of 580 DEG C 3 hours, then using 1.5mol/L's
Ammonium sulfate constant temperature at 90 DEG C exchanges 1.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 20,
Obtain the multi-stage porous Y type molecular sieve rich in L acid.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.15:0.45:1.
Embodiment 4
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 8 is added to the tetraethyl hydrogen of 0.15mol/L
In the synthesis reactor of ammonium hydroxide solution, the additional amount and solution quality ratio of USY molecular sieve are 1:3, closed, then heat to 60 DEG C,
It heated at constant temperature 6 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, after mixing evenly, sealing, so
After be warming up to 35 DEG C, heated at constant temperature 24 hours, then heat to 110 DEG C, heated at constant temperature 36 hours, then cool down, filter to pH
Value is 8 hours dry under the conditions of 100 DEG C less than 9, roasts 3 hours under the conditions of 600 DEG C, then uses the ammonium chloride of 2mol/L
Solution constant temperature at 90 DEG C exchanges 1.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 18, obtains richness
The multi-stage porous Y type molecular sieve of the acid containing L.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.18:0.35:1.
Embodiment 5
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 7 is added to the tetraethyl hydrogen of 0.30mol/L
In the synthesis reactor of ammonium hydroxide solution, the additional amount and solution quality ratio of USY molecular sieve are 1:2, closed, then heat to 60 DEG C,
It heated at constant temperature 2 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, after mixing evenly, sealing, so
After be warming up to 40 DEG C, heated at constant temperature 20 hours, then heat to 90 DEG C, heated at constant temperature 48 hours, then cool down, filter to pH value
It is 12 hours dry under the conditions of 90 DEG C less than 9, it is roasted under the conditions of 550 DEG C 4 hours, it is then molten using the ammonium chloride of 2mol/L
Liquid constant temperature at 100 DEG C exchanges 1.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 20, obtains richness
The multi-stage porous Y type molecular sieve of the acid containing L.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.06:0.25:1.
Embodiment 6
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 18 is added to the tetrabutyl of 0.30mol/L
In the synthesis reactor of Ammonia, the additional amount and solution quality ratio of USY molecular sieve are 1:2.5, closed, then heat to 90
DEG C, it heated at constant temperature 2 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, it is after mixing evenly, close
Envelope, then heats to 35 DEG C, heated at constant temperature 24 hours, then heats to 100 DEG C, heated at constant temperature 48 hours, then cool down, and filters
It is 12 hours dry under the conditions of 90 DEG C to pH value less than 9, it is roasted under the conditions of 500 DEG C 6 hours, then using 1.5mol/L's
Ammonium chloride solution constant temperature at 100 DEG C exchanges 1.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is
15, obtain the multi-stage porous Y type molecular sieve rich in L acid.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.06:0.24:1.
Embodiment 7
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 5.5 is added to the tetraethyl of 0.15mol/L
In the synthesis reactor of Ammonia, the additional amount and solution quality ratio of USY molecular sieve are 1:3, closed, then heat to 140
DEG C, it heated at constant temperature 2 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, it is after mixing evenly, close
Envelope, then heats to 35 DEG C, heated at constant temperature 24 hours, then heats to 100 DEG C, heated at constant temperature 48 hours, then cool down, and filters
It is 8 hours dry under the conditions of 90 DEG C to pH value less than 9, it is roasted under the conditions of 550 DEG C 4 hours, then uses the chlorine of 1.0mol/L
Change ammonium salt solution constant temperature at 90 DEG C to exchange 2.0 hours, exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 8, is obtained
To the multi-stage porous Y type molecular sieve for being rich in L acid.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.18:0.30:1.
Embodiment 8
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 6 is added to the tetraethyl hydrogen of 0.25mol/L
In the synthesis reactor of ammonium hydroxide solution, the additional amount and solution quality ratio of USY molecular sieve are 1:2, closed, then heat to 80 DEG C,
It heated at constant temperature 4 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, after mixing evenly, sealing, so
After be warming up to 40 DEG C, heated at constant temperature 24 hours, then heat to 100 DEG C, heated at constant temperature 36 hours, then cool down, filter to pH
Value is 24 hours dry under the conditions of 90 DEG C less than 9, roasts 3 hours under the conditions of 600 DEG C, then uses the nitric acid of 0.8mol/L
Ammonium salt solution constant temperature at 100 DEG C exchanges 2.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 12, obtains
To the multi-stage porous Y type molecular sieve for being rich in L acid.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.11:0.40:1.
Embodiment 9
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 9 is added to the tetraethyl hydrogen of 0.25mol/L
In the synthesis reactor of ammonium hydroxide solution, the additional amount and solution quality ratio of USY molecular sieve are 1:3, closed, then heat to 70 DEG C,
It heated at constant temperature 2 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, after mixing evenly, sealing, so
After be warming up to 40 DEG C, heated at constant temperature 24 hours, then heat to 100 DEG C, heated at constant temperature 48 hours, then cool down, filter to pH
Value is 12 hours dry under the conditions of 110 DEG C less than 9, roasts 3 hours under the conditions of 550 DEG C, then uses the chlorination of 1.0mol/L
Ammonium salt solution constant temperature at 85 DEG C exchanges 1.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 11, obtains
Multi-stage porous Y type molecular sieve rich in L acid.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.12:0.44:1.
Embodiment 10
Under agitation, the USY molecular sieve that silica/alumina molar ratio is 9 is added to the tetraethyl hydrogen of 0.20mol/L
In the synthesis reactor of ammonium hydroxide solution, the additional amount and solution quality ratio of USY molecular sieve are 1:2.5, closed, then heat to 70
DEG C, it heated at constant temperature 2 hours, then cools down, and under stirring, sodium hydroxide and white carbon black is added, it is after mixing evenly, close
Envelope, then heats to 40 DEG C, heated at constant temperature 24 hours, then heats to 100 DEG C, heated at constant temperature 48 hours, then cool down, and filters
It is 12 hours dry under the conditions of 110 DEG C to pH value less than 9, it is roasted under the conditions of 550 DEG C 3 hours, then using 1.0mol/L's
Ammonium chloride solution constant temperature at 85 DEG C exchanges 1.0 hours, and exchange process is repeated 2 times, and the liquid-solid ratio (ml/g) of exchange process is 11,
Obtain the multi-stage porous Y type molecular sieve rich in L acid.Specific nature is as shown in table 1.
In the method for the present invention, the mass ratio of the sodium hydroxide of addition, white carbon black and USY molecular sieve are as follows: 0.14:0.41:1.
The physico-chemical property of multi-stage porous Y type molecular sieve of the table 1 rich in L acid
Claims (10)
1. being rich in the multi-stage porous Y type molecular sieve of L acid, it is characterised in that: have the property that the molar ratio of silica and aluminium oxide
It is 5 ~ 15；Specific surface area is 600 ~ 900m2/g；Total acid acid amount is in 1.350 ~ 1.950mmol/g；Wherein L acid acid amount 0.550 ~
0.850mmol/g, outer surface L acid acid amount are in 0.450 ~ 0.750mmol/g；Total pore volume is 0.40 ~ 0.75ml/g；Its intermediary hole
Pore volume is 0.10 ~ 0.45ml/g.
2. molecular sieve according to claim 1, it is characterised in that: the molar ratio of silica and aluminium oxide is 6 ~ 10；Compare table
Area is 650 ~ 850m2/g；Total acid acid amount is in 1.450 ~ 1.850mmol/g；Wherein L acid acid is measured in 0.650 ~ 0.780mmol/g,
L acid acid amount in outer surface is in 0.580 ~ 0.720mmol/g；Total pore volume is 0.45 ~ 0.65ml/g；Its intermediary hole pore volume is 0.15
~0.35ml/g。
3. molecular sieve according to claim 1, it is characterised in that: Y type molecular sieve micropore pore volume is 0.20 ~ 0.35ml/
g。
4. the preparation method of any molecular sieve of claims 1 to 3, it is characterised in that: including following content: using organic base first
Solution handles USY molecular sieve, and sodium hydroxide and white carbon black is then added, and is made after crystallization, drying, roasting rich in L acid
Multi-stage porous Y type molecular sieve.
5. according to the method described in claim 4, it is characterized by: under agitation, USY molecular sieve is added to
In the synthesis reactor of machine aqueous slkali, and it is closed, 50 ~ 150 DEG C are then heated to, heated at constant temperature 1 ~ 8 hour, is then cooled down, and stirring
It mixes under state, sodium hydroxide and white carbon black is added, after mixing evenly, sealing then heats to 30 ~ 50 DEG C, heated at constant temperature 12 ~ 48
Hour, 80 ~ 120 DEG C are then heated to, heated at constant temperature 24 ~ 60 hours, is then cooled down, is filtered, dries and roast, ammonium exchange obtains
To the multi-stage porous Y type molecular sieve for being rich in L acid.
6. according to the method described in claim 5, it is characterized by: the USY molecular sieve being added in organic alkali solution,
Silica/alumina molar ratio is 5 ~ 25；Water quality ratio in the additional amount and organic alkali solution of USY molecular sieve is 1:1 ~ 1:5.
7. according to the method described in claim 5, it is characterized by: the organic base is tetraethyl ammonium hydroxide, tetrapropyl
One or more of ammonium hydroxide or tetrabutylammonium hydroxide, the concentration of organic alkali solution are 0.05 ~ 0.35mol/L.
8. according to the method described in claim 7, it is characterized by: tetraethyl ammonium halide, tetrapropyl ammonium halide or four fourths are added
Base ammonium halide, which is reacted by it with sodium hydroxide, generates tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide
Ammonium.
9. according to the method described in claim 5, it is characterized by: the matter of the sodium hydroxide being added, white carbon black and USY molecular sieve
Measure ratio are as follows: 0.05 ~ 0.20:0.2 ~ 0.5:1.
10. according to the method described in claim 5, it is characterized by: filtering to pH value less than 9；Drying condition is 80 ~ 120
It is 6 ~ 24 hours dry under the conditions of DEG C；Roasting condition is to roast 2 ~ 8 hours under the conditions of 450 ~ 650 DEG C；Ammonium exchange at least carries out 2
Secondary, exchange temperature is 80 ~ 100 DEG C, and ammonium salt used be ammonium chloride, ammonium sulfate or ammonium nitrate, the concentration of ammonium salt for 0.1 ~
2mol/L。
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