CN104803397A - MCM-49 molecular sieve with low silica-alumina ratio, and preparation method thereof - Google Patents
MCM-49 molecular sieve with low silica-alumina ratio, and preparation method thereof Download PDFInfo
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- CN104803397A CN104803397A CN201410041275.XA CN201410041275A CN104803397A CN 104803397 A CN104803397 A CN 104803397A CN 201410041275 A CN201410041275 A CN 201410041275A CN 104803397 A CN104803397 A CN 104803397A
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Abstract
The invention discloses an MCM-49 molecular sieve with a low silica-alumina ratio. A molar ratio of SiO2 to Al2O3 of the MCM-49 molecular sieve with a low silica-alumina ratio is not greater than 15. The molecular sieve is obtained through direct crystal transformation of an FAU structure molecular sieve with a middle and low silica-alumina ratio. The lower limit of the silica-alumina ratio for synthesizing the MCM-49 molecular sieve is broken through, and the range of the silica-alumina ratio for synthesizing the MCM-49 molecular sieve is widened.
Description
Technical field
The invention relates to a kind of MCM-49 molecular sieve and preparation method thereof, is about a kind of MCM-49 molecular sieve of low silica-alumina ratio and to turn the preparation method that crystal type is feature furtherly.
Background technology
MWW structure molecular screen comprises MCM-22, MCM-49, MCM-36, MCM-56, ITQ-1 and ITQ-2 equimolecular sieve.Nineteen ninety, Mobil company first with hexamethylene imine (HMI) for template Hydrothermal Synthesis MCM-22 molecular sieve (US, 4954325,1990), and parsed its structure first in 1994, and with this called after MWW structure molecular screen, the lamellar zeolite therefore with MWW topological framework is also called MCM-22 family molecular sieves.
MWW structure molecular screen has the non-cross independent duct of two covers: layer internal orifice dimension is the sinusoidal duct of oval 10MR two dimension of 0.40 × 0.59nm; Interlayer is the 12MR supercage of 0.71 × 0.71 × 1.82nm, and communicates with the external world with the 10MR opening of 0.40 × 0.54nm; Also distribute on its surface some 12MR holes in addition, and be the half of supercage, the degree of depth is about 0.91nm (Science, 1994,264:1910).MWW structure molecular screen is because the pore passage structure of its uniqueness and physico-chemical property are at alkylation (US, 5600048,1997), aromizing (catalysis journal, 2002,23:24), words (J.Catal., 1997,167:438) and isomerization (J.Catal. are split in catalysis, 1996,158:561) etc. reaction in have broad application prospects.
The difference of MCM-49 molecular sieve and MCM-22 molecular sieve is: in 2 θ=6.5, there is diffraction peak at ° (interplanar crystal spacing d=1.35nm) place to MCM-22P, and MCM-49 salt free ligands peak herein, spectrum peak is sharp-pointed, clear in structure; MCM-49 diffraction peak within the scope of 2 θ=20-29 ° is sharp-pointed, high-visible; After roasting, the XRD spectra of MCM-22 with MCM-49 molecular sieve is consistent.Lawton etc. think the structure cell c-axis parameter of MCM-49 0.2nm (Stud.Surf.Sci.Catal., 1994,84:331) longer than MCM-22, and guess that the framework aluminum distribution that these may be different from both is relevant.The content of MCM-22 interlayer template is higher than MCM-49, and in MCM-49, the content of framework aluminum, higher than MCM-22, all shows the catalytic activity higher than MCM-22 in inoic acid catalyzed reaction.
The template range expansion of synthesis MWW structure molecular screen is by CN101489677A (2007): cyclopentamine, hexahydroaniline, cycloheptylamine, hexamethylene imine, heptamethylene imines, homopiperazine and their binding substances.CN102452665A (2012) reports with non-equivalence tetraalkylammonium cation for template, and the additive such as mixture, crystal seed adding alkali metal chloride and oxyhydroxide successfully synthesizes MWW structure molecular screen, and exists mesoporous in this product.
Introduce in J.Phys.Chem.1996,100:3788 in synthetic system, synthesizing Si-Al is than between 20 ~ 30, and the low MCM-49 molecular sieve that is beneficial to of silica alumina ratio generates, and silica alumina ratio height is then beneficial to MCM-22 molecular sieve and generates; In addition, under dynamic crystallization condition, hexamethylene imine/Na
+mol ratio is less than 2.0, tends to generate MCM-49 molecular sieve, is greater than 2.0 and tends to MCM-22 molecular sieve.
Introduce the synthesis of MCM-22 family molecular sieves in US8021643B2 (2011) and US2011/0038789A1 (2011), it provides the SiO that feeds intake of the MCM-49 molecular sieve of synthesis
2/ Al
2o
3>10, but, its product of MCM-49 molecular sieve SiO in embodiment
2/ Al
2o
3>17, and without SiO
2/ Al
2o
3<15 embodiment.
Patent and document have carried out a lot of research and report for the scope of template used dose of MWW structure molecular screen, but hexamethylene imine is still the template that synthesis MWW structure molecular screen is commonly used the most, and structure-directing effect is irreplaceable.
What the difference due to molecular sieve stability caused turns crystalline substance is the phenomenon often occurred in conventional hydrothermal building-up process.Such as along with crystallization time extends or temperature raises, MWW structure molecular screen can turn the FER structure molecular screen that crystalline substance becomes more stable on thermodynamics.Along with the prolongation of crystallization time, it is GIS structure molecular screen that LTA structure molecular sieve can turn brilliant.
Over nearly 10 years, Sano turns crystalline substance to molecular sieve and has carried out large quantity research, furthers investigate respectively for Template-free method without the turning brilliant and adding crystal seed under crystalline substance, organic formwork agent condition that turn under crystal seed condition on the impact turning crystalline substance.
Micropor.Mesopor.Mater., 2006,96:72; Chem.Mater., describing FAU structure molecular screen in 2008,20:4135 turns in the process of brilliant one-tenth BEA structure molecular screen, FAU structure is along with the increase in treatment time, its diffraction peak intensity is weakening, until metamict, the crystalline phase of BEA structure molecular screen starts to occur afterwards.
Micropor.Mesopor.Mater., the process that FAU structure molecular screen turns brilliant one-tenth RUT structure molecular screen is described in 2008,113:56; Micropor.Mesopor.Mater., the process that FAU structure molecular screen turns brilliant one-tenth LEV structure molecular screen is described in 2009,112:149; J.Porous.Mater., the process that FAU structure molecular screen turns brilliant one-tenth MTN structure molecular screen is described in 2009,16:465.FAU structure turns in brilliant process to RUT, LEV, MTN structure, and are all the increases along with the treatment time of FAU structure, its diffraction peak intensity is weakening, until metamict, the crystalline phase of other structure molecular screens starts to occur afterwards, and centre all will experience metamict.
At present, SiO
2/ Al
2o
3the MCM-49 molecular sieve of≤15 has no report, in adopting simultaneously low silica-alumina ratio have FAU structure molecular screen turn brilliant become the MCM-49 molecular sieve of low silica-alumina ratio be not reported so far.
Summary of the invention
The object of this invention is to provide a kind of that be different from prior art, that there is low silica-alumina ratio feature MCM-49 molecular sieve and preparation method thereof.
The MCM-49 molecular sieve of low silica-alumina ratio provided by the invention, is characterized in that SiO
2with Al
2o
3mol ratio be less than or equal to 15.
Present invention also offers the preparation method of the MCM-49 molecular sieve of above-mentioned low silica-alumina ratio, it is characterized in that the mixture colloid that FAU structure molecular screen and silicon source, alkali source, template, deionized water formed crystallization reclaim product under hydrothermal conditions, the silicon oxide of said FAU structure molecular screen and the molar ratio of aluminum oxide are 2 ~ 5, SiO in said mixture colloid
2/ Al
2o
3=5 ~ 15, OH
-/ SiO
2=0.001 ~ 1, H
2o/SiO
2=5 ~ 100, R/SiO
2=0.01 ~ 5, wherein, R representative can be used in the template of synthesizing MWW structure molecular screen.
MCM-49 molecular sieve provided by the invention, has the low silica-alumina ratio feature being different from prior art, breaks through the silica alumina ratio lower limit of synthesis.This molecular sieve directly turns crystalline substance by the FAU structure molecular screen of middle low silica-alumina ratio to obtain.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the sample of preparation in embodiment 1.
Fig. 2 is the SEM spectrogram of the NaX molecular sieve used in embodiment 1.
Fig. 3 is the SEM spectrogram of the sample of preparation in embodiment 1.
Embodiment
The MCM-49 molecular sieve of low silica-alumina ratio provided by the invention, is characterized in that SiO
2with Al
2o
3mol ratio be less than or equal to 15, further preferred SiO
2with Al
2o
3mol ratio be 5 ~ 15, preferred SiO
2with Al
2o
3mol ratio be 6 ~ 14, in specific embodiment of the present invention, the SiO of said MCM-49 molecular sieve
2with Al
2o
3mol ratio can be 6 ~ 9.
Present invention also offers the preparation method of the MCM-49 molecular sieve of above-mentioned low silica-alumina ratio, it is characterized in that the mixture colloid that FAU structure molecular screen and silicon source, alkali source, template, deionized water formed crystallization reclaim product under hydrothermal conditions, the silicon oxide of said FAU structure molecular screen and the molar ratio of aluminum oxide are 2 ~ 5, SiO in said mixture colloid
2/ Al
2o
3=5 ~ 15, OH
-/ SiO
2=0.001 ~ 1, H
2o/SiO
2=5 ~ 100, R/SiO
2=0.01 ~ 5, wherein, R representative can be used in the template of synthesizing MWW structure molecular screen.
In method of the present invention, preferably, in said mixture colloid, SiO
2/ Al
2o
3=5 ~ 15, OH-/SiO
2=0.01 ~ 0.5, H
2o/SiO
2=5 ~ 50, R/SiO
2=0.05 ~ 0.5; Preferred, in said mixture colloid, SiO
2/ Al
2o
3=8 ~ 15, OH-/SiO
2=0.05 ~ 0.3, H
2o/SiO
2=10 ~ 30, R/SiO
2=0.05 ~ 0.35.
In method of the present invention, said silicon source is selected from least one in silicon sol, solid silicone, white carbon black or water glass, and alkali source is selected from least one in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide.The said template for the synthesis of MWW structure molecular screen can be selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, 1,4-phenodiazine suberane, suberane amine, hexamethylene alkanamine, cyclopentamine, aniline, piperidines, piperazine, N, N, N-trimethylammonium adamantyl ammonium hydroxide, Me
3n
+(CH
2)
5n
+me
3(Me
2cH)
2hN
+(CH
2)
5nH
+(Me
2cH)
2at least one in (Me represents methyl), wherein, preferred template at least includes hexamethylene imine.
Said FAU structure molecular screen is selected from X-type and/or Y zeolite.Different cation type molecular sieve can be selected from.Such as be selected from NaX, NaY, NH
4x, NH
4one or more in Y, HX, HY, REX and REY, preferred FAU structure molecular screen is NaX or HX.
In a concrete embodiment of the present invention, said silicon source is preferably solid silicone, and alkali source is preferably sodium hydroxide, and said template is preferably hexamethylene imine.
In method of the present invention, crystallization under said hydrothermal condition, its temperature can be 100 ~ 180 DEG C, be preferably 130 ~ 150 DEG C.Under different raw materials and proportioning, crystallization time also has difference, and the crystallization time being usually low to moderate 5 hours just can occur MWW crystalline structure.Preferably, turn the brilliant result for MWW structure completely to obtain FAU structure, crystallization time is normally more than 70 hours.
The process of said recovery product is familiar with by those skilled in the art, normally cools after crystallization terminates, is taken out by anti-product, filter, dry, obtains molecular screen primary powder; Roasting is with the process of removed template method.
Method of the present invention, in the process being turned brilliant one-tenth MWW structure by FAU structure, the crystalline phase of FAU structure fades away, and the crystalline phase of MWW structure generates gradually, occurs without intermediate phase and metamict, illustrates that FAU structure directly turns brilliant one-tenth MWW structure.
Method of the present invention, in employing, the FAU structure molecular screen of low silica-alumina ratio prepares to turn crystal type the MCM-49 molecular sieve that silica alumina ratio is less than or equal to the low silica-alumina ratio of 15, but what " turn brilliant " that the present invention defines and prior art were mentioned need experience " amorphous " stage to turn crystal technique different, obvious differences.In the inventive method, first said turn of brilliant process form the MWW structure molecular screen with individual layer sheet on former FAU structure crystal grain, and along with the prolongation turning the brilliant time, sheet MWW structure increases gradually, and FAU structure is consumed gradually.Macro manifestations is MWW structure molecular screen is generate from outside to inside on former FAU structure crystal grain.
In method of the present invention, the unfired sample turning brilliant one-tenth is have the MCM-49 molecular sieve of three-dimensional structure instead of have the MCM-22P molecular sieve of interlayer structure, illustrate that this turn of brilliant process directly occurs, namely, under the effect such as additional silicon source and template, the MCM-49 molecular sieve with three-dimensional MWW structure is directly changed into by the FAU structure with three-dimensional structure.
Molecular sieve of the present invention, the grain-size of its grain-size and former FAU structure molecular screen is close, illustrates that preparation-obtained MWW structure molecular screen generates at former FAU structure molecular screen.
Acidic catalytic activity constituent element can be converted into after molecular sieve through ammonium exchange roasting prepared by the inventive method, can be used for different hydrocarbons conversion reaction: the reactions such as alkylation, aromizing, cracking, isomerization.
Below by embodiment, the invention will be further described, but scope not thereby limiting the invention.
In embodiment and comparative example, X-ray diffraction (XRD) the crystalline phase figure of sample measures on Siemens D5005 type x-ray diffractometer.Be that the ratio of diffracted intensity (peak height) sum at diffractive features peak between 22.5 ° ~ 25.0 ° is to represent the degree of crystallinity of sample relative to authentic specimen, i.e. relative crystallinity at 2 θ with sample and authentic specimen.With comparative example 1 sample for authentic specimen, its degree of crystallinity counts 100%.Sample silica alumina ratio (refers to SiO
2with Al
2o
3mol ratio, rear same) Xray fluorescence spectrometer mensuration.
Comparative example 1
This comparative example illustrates the process preparing MCM-49 molecular sieve according to the method for US5326575.
By sodium metaaluminate (traditional Chinese medicines group, analytical pure) and sodium hydroxide (Beijing Reagent Company, analytical pure) be dissolved in deionized water, be stirred to and dissolve completely, solid silicone (Haiyang Chemical Plant, Qingdao, butt 97%) is added above-mentioned solution, then adds hexamethylene imine, after stirring, gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.033Al
2o
3: 0.30HMI:15H
2o.Then be transferred in airtight crystallizing kettle by gained mixture, crystallization temperature is 145 DEG C, and dynamic crystallization 72h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains comparative sample.
The XRD diffractogram of test comparison sample, 25 to 35 °, θ angles.Product is MCM-49 molecular sieve.
The grain-size of this comparative sample is by sem test, and its grain-size of result is about 3.0 ~ 4.0 μm, and silica alumina ratio is 27.6.
Embodiment 1
The present embodiment illustrates molecular sieve provided by the invention and synthetic method thereof.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and production piece NaX (SiO
2/ Al
2o
3=2.54, grain-size is 300 ~ 500nm about, and SEM figure is shown in Fig. 2, Na
2o content is 16.8w%) molecular sieve adds in above-mentioned solution, and after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.067Al
2o
3: 0.30HMI:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization 66h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains sample number into spectrum M-1.
Test its XRD diffractogram (Fig. 1).Product is MCM-49 molecular sieve, and relative crystallinity is 106%, and silica alumina ratio is 13.2.
The grain-size of this sample is shown in Fig. 3 by sem test, and its grain-size of result is about 500 ~ 700nm, is assembled forming by some crystal grain.As can be seen from Fig. 2 and Fig. 3, it is on NaX, turn crystalline substance form that molecular sieve turns brilliant process, but owing to mending silicon effect, volume can increase, but original pattern can keep, and only becomes from bulk the crystal be made up of sheet.
Embodiment 2
The present embodiment illustrates molecular sieve provided by the invention and synthetic method thereof.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and NaX (SiO
2/ Al
2o
3=2.54, grain-size is 300 ~ 500nm about, Na
2o content is 16.8w%) molecular sieve adds in above-mentioned solution, and after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.15NaOH:SiO
2: 0.10Al
2o
3: 0.20HMI:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization 54h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains sample number into spectrum M-2.
Test its XRD diffractogram, have the feature of Fig. 1, product is MCM-49 molecular sieve, and relative crystallinity is 101%.Grain-size is about 500 ~ 700nm, and silica alumina ratio is 8.6.
Embodiment 3
The present embodiment illustrates molecular sieve provided by the invention and synthetic method thereof.
Be dissolved in by sodium hydroxide in deionized water, be stirred to and dissolve completely, by solid silicone and HX molecular sieve, (90 DEG C of conditions, twice ammonium exchanges roasting and obtains, and grain-size is 300 ~ 500nm about, SiO
2/ Al
2o
3=2.54, Na
2o content is 0w%) add in above-mentioned solution, after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.15NaOH:SiO
2: 0.10Al
2o
3: 0.20HMI:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization 54h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains sample number into spectrum M-3.
Test its XRD diffractogram, have the feature of Fig. 1, product is MCM-49 molecular sieve, and relative crystallinity is 100%.Grain-size is about 500 ~ 700nm, and silica alumina ratio is 8.9.
Embodiment 4
The present embodiment illustrates molecular sieve provided by the invention and synthetic method thereof.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and NaX molecular sieve (SiO
2/ Al
2o
3=2.54, grain-size is 300 ~ 500nm about, Na
2o content is 16.8w%) molecular sieve adds in above-mentioned solution, and after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.10NaOH:SiO
2: 0.1Al
2o
3: 0.20HMI:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature 145 DEG C, dynamic crystallization 88h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains sample number into spectrum M-4.
Test its XRD diffractogram, have the feature of Fig. 1, product is MCM-49 molecular sieve, and relative crystallinity is 100%.Grain-size is about 500 ~ 700nm, and silica alumina ratio is 8.5.
Embodiment 5
The present embodiment illustrates molecular sieve provided by the invention and synthetic method thereof.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and NaX molecular sieve (SiO
2/ Al
2o
3=2.54, grain-size is 300 ~ 500nm about, Na
2o content is 16.8w%) add in above-mentioned solution, after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.10NaOH:SiO
2: 0.125Al
2o
3: 0.20HMI:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization 72h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains sample number into spectrum M-5.
Test its XRD diffractogram, have the feature of Fig. 1, product is MCM-49 molecular sieve, and relative crystallinity is 100%.Grain-size is about 500 ~ 700nm, and silica alumina ratio is 6.3.
Embodiment 6
The present embodiment illustrates molecular sieve provided by the invention and synthetic method thereof.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and NaX molecular sieve (SiO
2/ Al
2o
3=2.54, grain-size is 300 ~ 500nm about, Na
2o content is 16.8w%) add in above-mentioned solution, after stirring, add N, N, N-trimethylammonium adamantyl ammonium hydroxide, continues to stir.Gained mixture colloid mol ratio is: 0.10NaOH:SiO
2: 0.125Al
2o
3: 0.20TMADOH:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization 72h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains sample number into spectrum M-6.
Test its XRD diffractogram, have the feature of Fig. 1, product is MCM-49 molecular sieve, and relative crystallinity is 105%.Grain-size is about 500 ~ 700nm, and silica alumina ratio is 6.2.
Embodiment 7
The present embodiment illustrates molecular sieve provided by the invention and synthetic method thereof.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and NaX molecular sieve (SiO
2/ Al
2o
3=2.54, grain-size is 300 ~ 500nm about, Na
2o content is 16.8w%) add in above-mentioned solution, after stirring, add piperidines, continue to stir.Gained mixture colloid mol ratio is: 0.10NaOH:SiO
2: 0.125Al
2o
3: 0.20PI:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization 72h, takes out product after cooling, after filtration, washing, after dry and roasting, obtains sample number into spectrum M-5.
Test its XRD diffractogram, have the feature of Fig. 1, product is MCM-49 molecular sieve, and relative crystallinity is 95%.Grain-size is about 500 ~ 700nm, and silica alumina ratio is 5.9.
Claims (15)
1. a MCM-49 molecular sieve for low silica-alumina ratio, is characterized in that SiO
2with Al
2o
3mol ratio be less than or equal to 15.
2. according to the MCM-49 molecular sieve of claim 1, wherein, said SiO
2with Al
2o
3mol ratio be 5 ~ 15.
3. according to the MCM-49 molecular sieve of claim 1, wherein, said SiO
2with Al
2o
3mol ratio be 6 ~ 14.
4. the preparation method of a MCM-49 molecular sieve, it is characterized in that the mixture colloid that FAU structure molecular screen and silicon source, alkali source, template, deionized water formed crystallization reclaim product under hydrothermal conditions, the silicon oxide of said FAU structure molecular screen and the molar ratio of aluminum oxide are 2 ~ 5, SiO in said mixture colloid
2/ Al
2o
3=5 ~ 15, OH
-/ SiO
2=0.001 ~ 1, H
2o/SiO
2=5 ~ 100, R/SiO
2=0.01 ~ 5, wherein, R representative can be used in the template of synthesizing MWW structure molecular screen.
5. according to the method for claim 4, wherein, in said mixture colloid, SiO
2/ Al
2o
3=5 ~ 15, OH
-/ SiO
2=0.01 ~ 0.5, H
2o/SiO
2=5 ~ 50, R/SiO
2=0.05 ~ 0.5.
6. according to the method for claim 4, wherein, in said mixture colloid, SiO
2/ Al
2o
3=8 ~ 15, OH
-/ SiO
2=0.05 ~ 0.3, H
2o/SiO
2=10 ~ 30, R/SiO
2=0.05 ~ 0.35.
7. according to the method for claim 4, wherein, said silicon source is selected from least one in silicon sol, solid silicone, white carbon black or water glass, and said alkali source is selected from least one in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide.
8. according to the method for claim 4, wherein, said FAU structure molecular screen is X-type and/or Y zeolite.
9. according to the method for claim 4, wherein, said FAU structure molecular screen is selected from different cation type molecular sieve.
10. method according to claim 9, wherein, said FAU structure molecular screen is selected from NaX, NaY, NH
4x, NH
4one or more in Y, HX, HY, REX and REY.
11. according to the method for claim 4, wherein, the template of said synthesis MWW structure molecular screen is selected from pentamethylene imines, hexamethylene imine, heptamethylene imines, 1,4-phenodiazine suberane, suberane amine, hexamethylene alkanamine, cyclopentamine, aniline, piperidines, piperazine, N, N, N-trimethylammonium adamantyl ammonium hydroxide, Me
3n
+(CH
2)
5n
+me
3(Me
2cH)
2hN
+(CH
2)
5nH
+(Me
2cH)
2in at least one, wherein Me represents methyl.
12. according to the method for claim 4, and wherein, said template at least includes hexamethylene imine.
13. according to the method for claim 4, and wherein, silicon source is solid silicone, and alkali source is sodium hydroxide, and the template of synthesis MWW structure is hexamethylene imine.
14. according to the method for claim 4, and wherein, said hydrothermal condition is temperature 100 ~ 180 DEG C.
15. according to the method for claim 14, and wherein, said hydrothermal condition is temperature 130 ~ 150 DEG C.
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CN108217673A (en) * | 2016-12-22 | 2018-06-29 | 中国石油天然气股份有限公司 | Low silica-alumina ratio MCM-49 molecular sieves and preparation method thereof |
CN113457471A (en) * | 2021-08-05 | 2021-10-01 | 安徽工程大学 | Molecular sieve membrane and preparation method and application thereof |
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