CN110127716A - A kind of preparation method of multistage pore canal Y molecular sieve - Google Patents
A kind of preparation method of multistage pore canal Y molecular sieve Download PDFInfo
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- CN110127716A CN110127716A CN201910503217.7A CN201910503217A CN110127716A CN 110127716 A CN110127716 A CN 110127716A CN 201910503217 A CN201910503217 A CN 201910503217A CN 110127716 A CN110127716 A CN 110127716A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The invention discloses a kind of preparation methods of multistage pore canal Y molecular sieve, are related to Zeolite synthesis field；It specifically includes step: the Y type molecular sieve that silica alumina ratio is 4-6:1 is pre-processed in alkaline solution at 20-150 DEG C；Under anhydrous condition, SiCl is carried using inert gas4And/or SiHCl3Steam reacts dealumination complement silicon with pretreatment molecular sieves；0.1-3h is handled at 60-120 DEG C with ammonium ion solution again；It roasts, wash later, is dry, finally obtaining multistage pore canal Y type molecular sieve；The invention is combined using alkali process and chemical method, does not destroy molecular sieve structure, the molecular sieve obtained specific surface area with higher and crystallinity, the multistage pore canal Y molecular sieve of preparation, and silica alumina ratio can reach 20-160；The second hole duct of generation interconnects, and channel diameter can carry out modulation according to alkali process condition between 2-50 μm；Molecular sieve relative crystallinity > 70%.
Description
Technical field
The invention belongs to Zeolite synthesis technical field, specially a kind of preparation method of multistage pore canal Y molecular sieve.
Background technique
Y type molecular sieve has high specific surface area, suitable acidity and biggish orifice diameter, has it well
Adsorption and diffusion performance and acid catalytic property, and allow macromolecular disengaging duct reacted.It is answered for the first time from generation its nineteen sixty
Since for Industrial Catalysis, it has just been increasingly becoming catalytic cracking, is hydrocracked, is alkylated, the chief active group of the reactions such as isomerization
Point, and become the most molecular sieve catalyst of our times catalytic field dosage.
The Y molecular sieve silica alumina ratio of usual commercial synthesis is lower than 6:1, higher aluminium content result in excessively high sour density with compared with
Difference hydrothermal stability, therefore industrial application it is previous as need to carry out dealumination treatment to it.Can also it divide by dealumination process simultaneously
Second level duct abundant is introduced in son sieve, is conducive to the mass transfer of reactive material or product.
What industrial application was most at present is that molecule all can be improved in hydro-thermal method or hydro-thermal-chemical method dealuminzation, both methods
Sieve sial when hydrothermal stability.But hydro-thermal method is larger to the crystal structure destruction of molecular sieve；The part two that hydro-thermal method generates
Secondary aperture be it is closed, with extraneous only by microporous connectivity, be unfavorable for spreading.The molecular sieve of chemical Treatment can keep higher
Crystallinity and structural intergrity, but the second hole generated is less, is also unfavorable for spreading.
Furthermore also there is the method dealuminzation of sour processing, but since Y molecular sieve sial is relatively low, the method for acid processing is not easy
The degree for controlling dealuminzation, easily causes molecular sieve dealuminzation uneven or framework of molecular sieve collapses.Acid processing at present is mainly used in
It is on the one hand capable of washing to dissolve the non-framework aluminum removed after hydro-thermal method dealuminzation, it on the other hand can further improve molecular sieve
Framework si-al ratio.
Alkali process be it is a kind of make mesoporous effective means, alkali process can clear up the silicon on framework of molecular sieve, to generate
Second hole abundant.The method of general alkali process is suitable for high-silica zeolite, unknown to the molecular sieve desiliconization effect of low silica-alumina ratio
It is aobvious.
Chinese patent CN107758684A is obtained by using fluosilicic acid amine chemical Treatment Y type molecular sieve dealumination complement silicon first
It obtains compared with alkaline solution treatment is used after the Y molecular sieve of high silica alumina ratio again, has obtained the Y type molecular sieve of high mesoporous amount.But alkali process makes Jie
The method in hole can seriously destroy the crystal structure of molecular sieve, reduce the crystallinity and sial of gained molecular sieve after chemical Treatment
Than the especially silica alumina ratio on molecular sieve surface layer.
Recent domestic environmental protection pressure increasingly increases, and since VOCs has high bio-toxicity, induces haze and photochemistry
The risk of smog etc., so that VOCs emission problem is increasingly becoming the emphasis of environment protection field.Ultra-steady Y molecular sieve has weaker polarity
With biggish orifice diameter, polarity macromolecular is allowed to pass in and out, therefore becomes potential VOCs adsorbent.In order to promote Y molecule
The adsorption capacity of sieve, it is desirable that it has high silica alumina ratio, to be conducive to the absorption of organic molecule；It is required that it has comparatively perfect
Crystal structure, i.e., higher crystallinity；It is required that second hole that it has suitable number, being connected to from each other, especially molecular sieve
Surface layer second hole, to be conducive to the diffusion of bigger molecule organic gas.This also becomes this Ling Yu Qi problem to be solved.
Summary of the invention
The present invention overcomes the shortcomings of the prior art, provides a kind of preparation method of multistage pore canal Y molecular sieve.
The present invention is achieved through the following technical solutions.
A kind of preparation method of multistage pore canal Y molecular sieve, comprising the following steps:
1) Y type molecular sieve is pre-processed into 0.1-5h at 20-150 DEG C in alkaline solution；Molecule must be pre-processed after washing is dry
Sieve；The mass ratio of the alkaline solution and Y type molecular sieve is 1-40:1.The silica alumina ratio of the Y type molecular sieve is 4-6:1.
2) under the conditions of anhydrous, SiCl is carried using inert gas4And/or SiHCl3Steam is anti-with pretreatment molecular sieves
Answer dealumination complement silicon；Reaction time 0.1-6h, 250-800 DEG C of reaction temperature, reaction pressure absolute pressure 0.1-0.6Mpa.
3) by treated, molecular sieve is taken out, and handles 0.1-3h at 60-120 DEG C with ammonium ion solution.
4) treated that molecular sieve roasted to step 3, washs, dries, and finally obtains multistage pore canal Y type molecular sieve.
Preferably, the Y type molecular sieve is NaY or KY molecular sieve.
Preferably, the silica alumina ratio of the Y type molecular sieve is 4.8-6:1.
Preferably, the alkaline solution is inorganic alkali solution or organic alkali solution.
Preferably, the alkaline solution is NaOH, KOH, Na2CO3, ammonium hydroxide, diethylamine, one of sodium ethoxide or appoint
Meaning combination；The alkaline solution concentration is 0.1-4mol/L.
When the silica alumina ratio of the Y type molecular sieve is 4-4.8:1, Y type molecular sieve is first subjected to hydrothermal dealumination in the step 1
It after processing, is pre-processed in alkaline solution, 400-800 DEG C of the temperature of the hydro-thermal process, hydro-thermal time 0.1-5h, hydro-thermal pressure
Power absolute pressure 0.1-0.3Mpa, water are pure water vapour.
Preferably, the step 3 is to take out treated molecular sieve, be put into ammonium ion solution or ammonium ion solution and
0.1-3h, the ammonium ion solution or ammonium ion solution and acid solution are handled in the mixed liquor of acid solution at 60-120 DEG C
Mixed liquor acid solution and the mass ratio of treated molecular sieve be 1-40:1.
Preferably, the acid solution is one of hydrochloric acid, sulfuric acid, nitric acid, citric acid, oxalic acid, formic acid or any group
It closes；The acid solution concentration is 0.1-3mol/L.
Preferably, the ammonium ion solution is ammonium chloride or ammonium sulfate.
Prepared multistage pore canal Y type molecular sieve crystallinity > 70%, mesopore volume 0.1-0.4cm3/ g, molecular sieve sial
Compare 5-160:1.
The present invention first pass through alkali process manufacture be suitable for it is mesoporous, it is rear prepare high silicon Y with the combined method of chemical method dealumination complement silicon and divide
Son sieve.More general alkali process mode more exacting terms processing is first passed through compared with the molecular sieve of low silica-alumina ratio, obtains second level hole number
It is suitable for and is connected to, the controllable molecular sieve of second level pore size, so that the framework silicon of molecular sieve can be greatly improved in subsequent chemical method
Aluminium ratio, to obtain, sour density is low or nonpolar excellent product.The outstanding feature of the invention is the alkali process and postorder of preamble
Chemical method will not substantially destroy molecular sieve structure, the molecular sieve obtained specific surface area with higher and crystallinity.
Multistage pore canal Y molecular sieve prepared by the present invention, silica alumina ratio can reach 20-160；The second hole duct of generation is mutual
Connection, channel diameter can carry out modulation according to alkali process condition between 2-50 μm；Molecular sieve relative crystallinity > 70%.
The present invention is generated compared with the existing technology to be had the beneficial effect that.
Present invention utilizes low silica-alumina ratio molecular sieves to be not easy this feature of desiliconization in alkali process, uses than conventional high silicon
Molecular sieve alkali process more exacting terms, and by the severe of control alkali process condition, molecule is not being destroyed seriously
Under the premise of sieving crystal structure, it is adjustable to obtain secondary pore aperture, interconnects between secondary pore, and having is suitable for second hole
The multi-stage pore canal molecular sieve of amount.The method that dealumination complement silicon is used after alkali process, to crystal structure of molecular sieve extent of the destruction very
The molecular sieve of high silica alumina ratio is obtained under the premise of small.Two methods combine, and have complementary advantages, have been prepared needed for target
Multistage pore canal Y molecular sieve, silica alumina ratio can reach 20-160；The second hole duct of generation interconnects, and channel diameter can basis
Alkali process condition carries out modulation between 2-50 μm；Molecular sieve relative crystallinity > 70%.
Specific embodiment
In order to which technical problems, technical solutions and advantages to be solved are more clearly understood, in conjunction with reality
Example is applied, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain this
Invention, is not intended to limit the present invention.Below with reference to the embodiment technical solution that the present invention will be described in detail, but protection scope not by
This limitation.
Embodiment 1
It weighs 50gNaY molecular sieve (silica alumina ratio 5.6), is added in the NaOH solution of 250g 1mol/L, be placed in 90 DEG C of water-baths fast
Speed 1 h of stirring, takes out sample, is washed with deionized to PH < 8.
The sample of the processed drying of 10g is taken to be placed in quartz tube reactor, in the N of 40ml/min2It purges under speed with 3
DEG C/heating rate of min rises to 600 DEG C, keep 120min.Temperature is set as 450 DEG C later, when temperature is down to 450 DEG C
Switch N2For by SiCl4The N of saturation2(i.e. N2 slow transits through SiCl in the form being bubbled4Solution), wherein N2Flow velocity 40ml/min,
Maintain 120min.Gas is switched to pure N again later2, it is down to room temperature naturally after purging 120min, sample is taken out.It takes
Sample out is washed with deionized, and repeats above-mentioned SiCl again after dry4Dealumination complement silicon step.
50g hydrochloric acid and ammonium chloride mixed solution are prepared, wherein concentration of hydrochloric acid 0.5mol/L, ammonium chloride concentration 1mol/L.It will
The mixed solution is added in the sample of above-mentioned taking-up, handles 60min in 80 DEG C of water-baths.Sample washing drying is placed on Muffle furnace
In, 650 DEG C are warming up to the rate of 2 DEG C/min, maintains 300min.
The sample of roasting is added in the ammonium chloride solution of 50ml 1mol/L, handles 60min in 80 DEG C of water-baths, then
By sample washing it is dry after sample is roasted with above-mentioned calcination procedure again, H-type Y molecular sieve needed for final target, characterization result
As shown in table 1.
Embodiment 2
By step process molecular sieve described in embodiment 1, difference is concentration of lye being reduced to 0.75mol/L by 1mol/L.Most
The results are shown in Table 1 for gained sample characterization eventually.
Embodiment 3
By step process molecular sieve described in embodiment 2, difference is that the alkali process time is promoted to 2h by 1h.Final gained sample table
The results are shown in Table 1 for sign.
Embodiment 4
It weighs 50gNaY molecular sieve (silica alumina ratio 4.6), sample is added in the ammonium chloride solution of 250ml 0.5mol/L, in 70 DEG C
40min is handled in water-bath, and sample is washed into drying later；
Dry sample is placed in quartz tube reactor, 500 DEG C is warming up to the rate of 3 DEG C/min, the water of 2g/min is led to
Enter reactor, water is switched to the N of 80ml/min by hydro-thermal process 40min later2, Temperature fall after 2h is purged, sample is taken out；
Sample is added in the NaOH solution of 250g 1mol/L, is placed in 90 DEG C of water-baths and quickly stirs 1 h, taken out sample, spend
Ion water washing is to PH < 8.
The sample of the processed drying of 10g is taken to be placed in quartz tube reactor, in the N of 40ml/min2It purges under speed with 3
DEG C/heating rate of min rises to 600 DEG C, keep 120min.Temperature is set as 450 DEG C later, when temperature is down to 450 DEG C
Switch N2For by SiCl4The N of saturation2(i.e. N2SiCl is slow transitted through in the form of bubbling4Solution), wherein N2Flow velocity 40ml/min,
Maintain 120min.Gas is switched to pure N again later2, it is down to room temperature naturally after purging 120min, sample is taken out.It takes
Sample out is washed with deionized, and repeats above-mentioned SiCl again after dry4Dealumination complement silicon step.
50g hydrochloric acid and ammonium chloride mixed solution are prepared, wherein concentration of hydrochloric acid 0.5mol/L, ammonium chloride concentration 1mol/L.It will
The mixed solution is added in the sample of above-mentioned taking-up, handles 60min in 80 DEG C of water-baths.Sample washing drying is placed on Muffle furnace
In, 650 DEG C are warming up to the rate of 2 DEG C/min, maintains 300min.Final sample characterization result is as shown in table 1.
Embodiment 5
By step process molecular sieve described in embodiment 4, difference is that the temperature of hydro-thermal process is changed to 650 DEG C by 500 DEG C.Finally
The results are shown in Table 1 for sample characterization.
Embodiment 6
By step process molecular sieve described in embodiment 4, difference is that silicon chloride steam treated temperature is increased to 500 DEG C by 450 DEG C,
The processing time becomes 90min.Final sample characterization result is as shown in table 1.
Comparative example 1
By step process molecular sieve described in embodiment 1, difference is that molecular sieve without alkali process, is directly handled through SiCl4 de-
Aluminium mends silicon, and final sample characterization result is as shown in table 1.
Comparative example 2
By step process molecular sieve described in embodiment 1, difference is that molecular sieve after dealumination complement silicon, is handled without acid, only uses
Ammonium chloride solution swaps, and final sample characterization result is as shown in table 1.
Comparative example 3
By step process molecular sieve described in embodiment 3, difference is sample not hydrothermal treatment, final sample characterization result such as table
Shown in 1.
The physical and chemical performance of 1 embodiment and comparative example sample of table characterizes.
As shown in table 1, first through alkali process, after carry out SiCl again4The sample ratio of method desiliconization is without the direct SiCl of alkali process4
The second hole pore volume that the sample of method desiliconization generates increased significantly；When Y molecular sieve sial is relatively low, alkali process can not be effective
Ground introduces second hole, need to take the lead in carrying out a degree of hydro-thermal process；First alkali process, after be conducive to the method for chemical method desiliconization
Protect the integrality of crystal structure of molecular sieve, the Crystalline Quality of the especially initial relatively high molecular sieve of sial, final institute
The crystallinity for obtaining product is maintained at higher level.
The above content is combine specific preferred embodiment to the further description done of the present invention, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from the present invention, several simple deduction or replace can also be made, all shall be regarded as belonging to the present invention by being submitted
Claims determine scope of patent protection.
Claims (10)
1. a kind of preparation method of multistage pore canal Y molecular sieve, which comprises the following steps:
1) Y type molecular sieve is pre-processed into 0.1-5h at 20-150 DEG C in alkaline solution；Molecule must be pre-processed after washing is dry
Sieve；The mass ratio of the alkaline solution and Y type molecular sieve is 1-40:1；The silica alumina ratio of the Y type molecular sieve is 4-6:1；
2) under the conditions of anhydrous, SiCl is carried using inert gas4And/or SiHCl3Steam reacts de- with pretreatment molecular sieves
Aluminium mends silicon；Reaction time 0.1-6h, 250-800 DEG C of reaction temperature, reaction pressure absolute pressure 0.1-0.6Mpa；
3) by treated, molecular sieve is taken out, and handles 0.1-3h at 60-120 DEG C with ammonium ion solution；
4) treated that molecular sieve roasted to step 3, washs, dries, and finally obtains multistage pore canal Y type molecular sieve.
2. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1, which is characterized in that the Y type point
Son sieve is NaY or KY molecular sieve.
3. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1, which is characterized in that the Y type molecule
The silica alumina ratio of sieve is 4.8-6:1.
4. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1, which is characterized in that the alkalinity
Solution is inorganic alkali solution or organic alkali solution.
5. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1 or 4, which is characterized in that the alkali
Property solution be NaOH, KOH, Na2CO3, ammonium hydroxide, diethylamine, one of sodium ethoxide or any combination；The alkaline solution is dense
Degree is 0.1-4mol/L.
6. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1, which is characterized in that the Y type molecule
When the silica alumina ratio of sieve is 4-4.8:1, after Y type molecular sieve is first carried out hydrothermal dealumination processing in the step 1, then at alkaline solution
Middle pretreatment, 400-800 DEG C of the temperature of the hydro-thermal process, hydro-thermal time 0.1-5h, Hydro-thermal pressure absolute pressure 0.1-0.3Mpa, water
For pure water vapour.
7. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1, which is characterized in that the step 3 is
Treated molecular sieve is taken out, be put into ammonium ion solution or the mixed liquor of ammonium ion solution and acid solution in 60-120
The mixed liquor of 0.1-3h, the ammonium ion solution or ammonium ion solution and acid solution and treated molecular sieve are handled at DEG C
Mass ratio is 1-40:1.
8. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 7, which is characterized in that the acidity is molten
Liquid is one of hydrochloric acid, sulfuric acid, nitric acid, citric acid, oxalic acid, formic acid or any combination；The acid solution concentration is
0.1-3mol/L。
9. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1 or claim 7, which is characterized in that the ammonium from
Sub- solution is ammonium chloride solution or ammonium sulfate.
10. a kind of preparation method of multistage pore canal Y molecular sieve according to claim 1, which is characterized in that prepared is more
Grade duct Y type molecular sieve crystallinity > 70%, mesopore volume 0.1-0.4cm3/ g, molecular sieve silica alumina ratio 5-160:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112758952A (en) * | 2020-12-31 | 2021-05-07 | 中海油天津化工研究设计院有限公司 | High-silica-alumina-ratio Y molecular sieve with hierarchical pore structure and preparation method thereof |
| CN112827505A (en) * | 2020-12-31 | 2021-05-25 | 南京大学 | Integral catalyst for catalyzing ozone to degrade VOCs (volatile organic compounds), and preparation and application thereof |
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|---|---|---|---|---|
| CN104843737A (en) * | 2015-03-31 | 2015-08-19 | 中国石油天然气集团公司 | Y molecular sieve and preparation method therefor |
| CN104843736A (en) * | 2015-03-31 | 2015-08-19 | 中国石油天然气集团公司 | Y molecular sieve high in silica alumina ratio and abundant in secondary holes and preparation method therefor |
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- 2019-06-11 CN CN201910503217.7A patent/CN110127716B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843737A (en) * | 2015-03-31 | 2015-08-19 | 中国石油天然气集团公司 | Y molecular sieve and preparation method therefor |
| CN104843736A (en) * | 2015-03-31 | 2015-08-19 | 中国石油天然气集团公司 | Y molecular sieve high in silica alumina ratio and abundant in secondary holes and preparation method therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112758952A (en) * | 2020-12-31 | 2021-05-07 | 中海油天津化工研究设计院有限公司 | High-silica-alumina-ratio Y molecular sieve with hierarchical pore structure and preparation method thereof |
| CN112827505A (en) * | 2020-12-31 | 2021-05-25 | 南京大学 | Integral catalyst for catalyzing ozone to degrade VOCs (volatile organic compounds), and preparation and application thereof |
| CN112827505B (en) * | 2020-12-31 | 2022-04-22 | 南京大学 | Integral catalyst for catalyzing ozone to degrade VOCs (volatile organic compounds), and preparation and application thereof |
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