CN104803395A - Different topological structures coexistent composite molecular sieve and preparation method thereof - Google Patents
Different topological structures coexistent composite molecular sieve and preparation method thereof Download PDFInfo
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- CN104803395A CN104803395A CN201410041135.2A CN201410041135A CN104803395A CN 104803395 A CN104803395 A CN 104803395A CN 201410041135 A CN201410041135 A CN 201410041135A CN 104803395 A CN104803395 A CN 104803395A
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Abstract
The invention discloses a different topological structures coexistent composite molecular sieve. The composite molecular sieve is characterized in that an FAU topological structure and an MWW topological structure coexist, the composite molecular sieve has a core-shell structure, the core is the FAU topological structure, and the shell is the MWW topological structure. The composite molecular sieve is prepared through direct crystal transformation of a molecular sieve with the FAU topological structure.
Description
Technical field
The invention relates to a kind of composite molecular screen of different topology architectures coexist.
Background technology
MWW topological framework molecular sieve comprises MCM-22, MCM-49, MCM-36, MCM-56, ITQ-1 and ITQ-2 equimolecular sieve.Nineteen ninety, Mobil company is template Hydrothermal Synthesis MCM-22 molecular sieve (US first with hexamethylene imine, 4954325,1990), and parsed its structure first in 1994, and with this called after MWW topological framework molecular sieve, the lamellar zeolite therefore with MWW topological framework is also called MCM-22 family molecular sieves.
MWW topological framework molecular sieve 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 topological framework molecular sieve 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.FAU topological framework molecular sieve mainly comprises X-type and Y zeolite, its structural unit is made up of β cage, connected by hexagonal prism (D6R) between adjacent β cage, form supercage structure and the 3 D pore canal system of a 12-membered ring, diameter is 0.74 × 0.74nm.FAU topological framework molecular sieve has larger void volume (accounting for 50%) and three-dimensional 12-membered ring's pore canal system, makes it in catalysis, have extremely important application.
When synthesis of molecular sieve, often have multiple crystal in same reaction system and generate, the mixed crystal in Here it is Zeolite synthesis, symbiosis or eutectic phenomena.And composite molecular screen just refers to the cocrystallization formed by two or more molecular sieves, or there is the composite crystal of two or more molecular sieve structure features.The generation of molecular sieve cocrystallization is random mostly, disadvantageous to the research for the purpose of the pure molecular sieve synthesizing certain single structure, but because the advantage of two kinds of molecular sieves often taken into account by two-phase coexisting molecular sieve or cocrystallization molecular sieve, be different from again the simple and mechanical mixing of two kinds of molecular sieves, in some chemical reaction, usually show unique catalytic performance, therefore control synthesis condition targetedly and generate some cocrystallization molecular sieve and be of great importance.
The synthesis of composite molecular screen is related in following publication.
Open source literature J.Mater.Sci., reports in the crystallization process of BEA/MOR cocrystallization molecular sieve in 2008,43:5626, first generate BEA crystalline phase, just produce MOR crystalline phase subsequently, but BEA crystalline phase does not reduce with the appearance of MOR crystalline phase; Its BEA and MOR relative proportion regulating measure is comparatively difficult, and BEA and MOR silica alumina ratio is close, all belongs to high silica alumina ratio molecular sieve.
Open source literature Sci.Technol.Adv.Mater., 2009, report in the forming process of FAU/LTA composite molecular screen in 10:15001, FAU and LTA crystalline phase almost produces simultaneously, but along with the prolongation of crystallization time, the growth velocity of the two is different, thus forms the different FAU/LTA composite molecular screen of FAU with LTA ratio; And FAU and LTA silica alumina ratio is close, all belong to low silica-alumina ratio molecular sieve.
Open source literature Micropor.Mesopor.Mater., reports in the forming process of MWW/FER composite molecular screen in 2009,121:166, first crystallization initial stage MCM-49 molecular sieve is formed; Along with the prolongation of time, ZSM-35 molecular sieve starts to occur, and is be cost with the consumption of MCM-49; Ratio is controlled by crystallization time, but product silica alumina ratio is close.
Above document is all in same system, directly synthesize composite molecular screen with unbodied silicon source and aluminium source, list or double template etc. raw material.The molecular sieve that this type of two kinds of different structures coexist, its structure often has identical or close structural unit, and its synthesis interval overlaps.Namely in same synthetic system, synthesize a kind of molecular sieve, if change its crystallization condition, another kind of structure molecular screen crystal can be caused to occur, under such thinking, synthesis has two kinds of structure compound molecular sieves of different ratios, adapts to different catalyzed reactions with the pore passage structure realizing its molecular sieve of modulation.In addition, the composite molecular screen of the cocrystallization two kinds of structures reported in current document, its synthesizing Si-Al is close than all.
Following publication relates to turn crystalline substance between molecular sieve.
What what the difference due to molecular sieve stability caused turned brilliant phenomenon is the phenomenon often occurred in conventional hydrothermal building-up process.Such as along with the prolongation of crystallization time or the rising of temperature, MWW topological framework molecular sieve 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 etc. turn crystalline substance to molecular sieve and have carried out large quantity research, have done deeply systematic research respectively for Template-free method without the crystalline substance that turns turned under crystalline substance, organic formwork agent and interpolation crystal seed condition under crystal seed condition.
Open source literature Micropor.Mesopor.Mater., 2006,96:72; Chem.Mater., describing FAU topological framework molecular sieve in 2008,20:4135 turns in the process of brilliant one-tenth BEA structure molecular screen, FAU topological framework is along with the increase in treatment time, its diffraction peak intensity weakens, until metamict, the crystalline phase of BEA structure molecular screen starts to occur afterwards.
Open source literature Micropor.Mesopor.Mater., 2008,113:56; Micropor.Mesopor.Mater., 2009,112:149; J.Porous.Mater., the process that FAU topological framework molecular sieve turns brilliant one-tenth RUT structure, LEV structure and MTN structure molecular screen is described in 2009,16:465 respectively.FAU topological framework turns in brilliant process to RUT, LEV, MTN structure, FAU topological framework is along with the increase in treatment time, and its diffraction peak intensity weakens, until metamict, the crystalline phase of the structure molecular screen such as RUT, LEV, MTN starts to occur afterwards, is all experience metamicts.Open source literature J.Nanosci.Nanotechnol., 2013,13:3020 describes and turns brilliant GIS structure of one-tenth (NaOH) and LTL structure (KOH), BEA structure by FAU topological framework under Template-free method condition and turn crystalline substance and become MFI structure, and it can be occurred turn a brilliant reason be summarized as original molecular sieve with turn brilliant become a molecules of interest sieve between there is identical structural unit, such as 4MR, 5MR, 6MR, D6R etc.It should be noted that: these turn of brilliant process cannot go out the molecular sieve that two kinds of different pore passage structures coexist by modulation, and centre all experiences amorphous state process.
At present, adopt and there is the composite molecular screen that MWW topological framework that FAU topological framework molecular sieve turns brilliant the FAU topological framework and high silica alumina ratio that become to have the middle low silica-alumina ratio of different ratios coexists be not reported so far.For the molecular sieve of these two kinds of structures, it is the FAU topological framework of 100%, the MWW topological framework of 100%, not yet have open source literature report to realize composite molecular screen that FAU topological framework and MWW topological framework coexist with arbitrary proportion and preparation method.
Summary of the invention
The object of this invention is to provide a kind of composite molecular screen of novel different topology architectures coexist, and the preparation method of this composite molecular screen is provided.
The composite molecular screen of different topology architectures coexist provided by the invention, it is characterized in that wherein FAU topological framework and MWW topological framework coexist, and have core-shell construction, kernel is FAU topological framework, shell is MWW topological framework.
Present invention also offers the preparation method of the composite molecular screen of above-mentioned said different topology architectures coexist, it is characterized in that the mixture colloid that FAU topological framework molecular sieve and silicon source, alkali source, template, deionized water formed crystallization reclaim the composite molecular screen product obtained under hydrothermal conditions, wherein, said template is the template that can be used in synthesizing MWW structure molecular screen.
Composite molecular screen provided by the invention and corresponding preparation method, have following feature:
(1) modulation of FAU topological framework to high silica alumina ratio MWW topological framework of middle low silica-alumina ratio is achieved, the composite molecular screen that FAU and the MWW topological framework that can form arbitrary proportion coexists.
(2) the FAU topological framework molecular sieve with three-dimensional open-framework directly turns the brilliant composite molecular screen forming FAU topological framework and MWW topological framework and coexist, namely the crystalline phase of FAU topological framework reduces gradually, the crystalline phase of MWW topological framework generates gradually simultaneously, occurs without intermediate phase and metamict; Be different from the composite molecular screen that tradition is directly synthesized, be also different from the disclosed turn brilliant process of document; Its XRD spectra is different from the XRD spectra by FAU topological framework and MWW topological framework molecular sieve mechanically mixing.
(3) by the brilliant controlling factor of regulating rotary, the composite molecular screen that the FAU topological framework of synthesis different ratios and MWW topological framework coexist, widens its catalytic applications scope.This type of FAU topological framework and MWW topological framework molecular sieve can take into account the Application Areas of FAU topological framework molecular sieve and MWW topological framework molecular sieve.
(4) the non-roasting sample turning brilliant one-tenth is have the MCM-49 molecular sieve of MWW topological framework instead of have the MCM-22P molecular sieve of interlayer structure, illustrates that this turn of brilliant process directly occurs.FAU topological framework molecular sieve under the conditions such as additional silicon source, template, alkali source, water in certain temperature and stirring velocity crystallization, first on former FAU topological framework crystal grain, form the MWW topological framework molecular sieve with individual layer sheet, along with the prolongation turning the brilliant time, sheet MWW topological framework increases gradually, and FAU topological framework is consumed gradually.Whole turn of brilliant process carrying out from outside to inside; Forming shell is gradually MWW topological framework, and kernel is the composite molecular screen of FAU topological framework.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the comparative sample that comparative example 1 ~ 3 obtains
Fig. 2 is the XRD spectra of the sample that embodiment 1 ~ 5 and comparative example 4 obtain.
Fig. 3 to Fig. 7 is the SEM spectrogram of the sample that embodiment 1 ~ 5 obtains.
Embodiment
The composite molecular screen of different topology architectures coexist provided by the invention, it is characterized in that wherein FAU topological framework and MWW topological framework coexist, and have core-shell construction, kernel is FAU topological framework, shell is MWW topological framework.
In said composite molecular screen, FAU topological framework and MWW topological framework coexist.The preparation course of composite molecular screen of the present invention is observed as can be seen from SEM spectrogram, said MWW topological framework generates from outside to inside on FAU topological framework, the MWW topological framework of sheet generated from outside before this, the crystal formation of FAU topological framework reduces gradually, then diffuse to the crystalline phase that the inside also generates MWW topological framework gradually, occur without intermediate phase and metamict.
In said composite molecular screen, the mass content of FAU topological framework can change between 0.01% ~ 99.99%, and accordingly, the content of MWW topological framework also changes between 0.01% ~ 99.99%.Such as, when in said composite molecular screen, when the content of FAU topological framework is 5%, then the content of corresponding MWW topological framework is 95%; When the content of FAU topological framework is 25%, then the content of corresponding MWW topological framework is 75%; When the content of FAU topological framework is 60%, then the content of corresponding MWW topological framework is 40%, and the rest may be inferred.In specific embodiment of the invention scheme, said composite molecular screen, the mass content represented with FAU topological framework can be 54%, 56%, 62%, 64%, 65%, 78%, 81%, 82%, 84%, 91%, 92%, 93%, 95% and 96% etc., with the mass content that MWW topological framework represents, can be 78%, 80%, 81%, 84%, 87%, 89%, 92%, 93%, 95%, 97% and 98% etc.
Composite molecular screen provided by the invention, FAU topological framework wherein and the method for quantitative measuring of MWW topological framework as follows:
With the sample XRD of t=0 hour for reference, choosing with MWW topological framework molecular sieve characteristic diffraction peak nonoverlapping FAU topological framework molecular sieve characteristic diffraction peak is that (2 θ angles are 6.2 ° to target, 11.9 °, 15.7 °, 18.8 ° and 31.4 °), measure its diffraction peak height and add and, with the above-mentioned diffraction peak height of reference sample add and ratio be the content of FAU topological framework molecular sieve in composite molecular screen, if content is lower than 50%, then to transfer the sample of MWW topological framework molecular sieve completely to for reference, choosing with FAU topological framework molecular sieve characteristic diffraction peak nonoverlapping MWW topological framework molecular sieve characteristic diffraction peak is that (2 θ angles are 7.05 ° to target, 8.00 °, 21.7 °, 24.9 ° and 25.9 °), measure its diffraction peak height and add and, with the above-mentioned diffraction peak height of reference sample add and ratio be the content of MWW molecular sieve in composite molecular screen.
Invention further provides the preparation method of the composite molecular screen of above-mentioned different topology architectures coexist, it is characterized in that the mixture colloid that FAU topological framework molecular sieve and silicon source, alkali source, template, deionized water formed crystallization reclaim the composite molecular screen product obtained under hydrothermal conditions, wherein, said template is the template that can be used in synthesizing MWW structure molecular screen.
Preparation method of the present invention is the molecular sieve with FAU topological framework, under being aided with the raw material effects such as supplementary silicon source and template, and the composite molecular screen that the brilliant controlling factor of regulating rotary coexists to synthesize the FAU topological framework with different ratios and MWW topological framework.In said preparation method, in mixture colloid, the mol ratio of each raw material is: SiO
2/ Al
2o
3=3 ~ 200, OH
-/ SiO
2=0.001 ~ 1.00, H
2o/SiO
2=5 ~ 100, R/SiO
2=0.01 ~ 5.00.Preferably, in mixture colloid, the mol ratio of each raw material is: SiO
2/ Al
2o
3=3 ~ 80, OH
-/ SiO
2=0.01 ~ 0.50, H
2o/SiO
2=5 ~ 50, R/SiO
2=0.05 ~ 0.50; More preferably, in mixture colloid, the mol ratio of each raw material is: SiO
2/ Al
2o
3=5 ~ 40, OH
-/ SiO
2=0.05 ~ 0.30, H
2o/SiO
2=10 ~ 30, R/SiO
2=0.05 ~ 0.35, R represents template.
In said preparation method, said FAU structure molecular screen mainly comprises X-type and Y zeolite, its structural unit is made up of β cage, connected by hexagonal prism (D6R) between adjacent β cage, form supercage structure and the 3 D pore canal system of a 12-membered ring, diameter is 0.74 × 0.74nm.FAU structure molecular screen has larger pore volume (accounting for 50%) and three-dimensional 12-membered ring's pore canal system, makes it in catalysis, have extremely important application.FAU structure molecular screen can be selected from different cation type molecular sieve, can be, but not limited to be selected from NaX, NaY, NH
4x, NH
4one or more in Y, HX, HY, REX and REY.Grain-size for said FAU structure molecular screen has no particular limits, and can be selected from the molecular sieve of various grain sizes, such as the molecular sieve of little crystal grain.
Said silicon source is selected from least one in silicon sol, solid silicone, white carbon black or water glass; Alkali source is mineral alkali, is selected from least one in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide; The said template that can be used in synthesizing 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)
2at least one in (Me represents methyl), preferably, said template at least includes hexamethylene imine.In a specific embodiment of the present invention, said silicon source is solid silicone; Said alkali source is sodium hydroxide, and said template is hexamethylene imine.
In said preparation method, crystallization temperature preferable range is 100 ~ 180 DEG C, is more preferably 130 ~ 150 DEG C, and crystallization time preferable range is 5 ~ 70h, is more preferably 24 ~ 60h.
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.
Composite molecular screen of the present invention exchanges after roasting through ammonium can be converted into acidic catalytic activity constituent element, 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 content not thereby limiting the invention.
In embodiment, X-ray diffraction (XRD) the crystalline phase figure of sample measures on Siemens D5005 type x-ray diffractometer.
Comparative example 1 ~ 3
This comparative example illustrates the thing phase feature of the molecular sieve mixture that FAU topological framework molecular sieve and MWW topological framework molecular sieve obtain through mechanically mixing.
By the NaY molecular sieve of the MCM-49 molecular sieve of pure phase MWW topological framework after roasting, pure phase FAU topological framework respectively according to the mass ratio mechanically mixing of 1:3,1:1,3:1, obtain comparative sample, numbering is respectively MF-1, MF-2, MF-3, and test obtains the XRD diffractogram (Fig. 1) of comparative sample.
Embodiment 1 ~ 5
The present embodiment illustrates composite molecular screen provided by the invention.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and production piece NaY(Na
2o content is 11.8w%, SiO
2/ Al
2o
3=4.95) molecular sieve adds in above-mentioned solution, after stirring, adds hexamethylene imine, continues to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.04Al
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, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Take out product after cooling, after filtration, washing, after dry and roasting, gained sample number into spectrum is respectively FM-1, FM-2, FM-3, FM-4, FM-5, tests its XRD diffractogram (Fig. 2).
As can be seen from Figure 2,2 θ=6.14 ° are FAU topological features diffraction peak, and die down with the prolongation peak intensity turning the brilliant time; 2 θ=7.15 °, 7.95 °, 10.04 °, 22.69 °, 23.65 °, 25.95 ° be MWW topological features diffraction peak, and with turning the prolongation peak intensity grow of brilliant time.The molecular sieve of result display synthesis is the composite molecular screen that the FAU topological framework of a series of different ratios (95%FAU, 84%FAU, 62%FAU, 84%MWW, 95%MWW) and MWW topological framework coexist.
As can be seen from Fig. 1 and Fig. 2, the comparative sample through mechanically mixing is compared with composite molecular screen of the present invention, and its XRD diffraction peak is comparatively sharp-pointed, this illustrates, in the sieve sample of mechanically mixing, FAU and MWW two kinds of topological frameworks are comparatively complete, textural defect is few, and respective Individual existence; And the diffraction peak of composite molecular screen of the present invention is wide in range, then illustrate, in composite molecular screen, FAU with MWW two kinds of topological frameworks are relative imperfect, and textural defect is many, for FAU and MWW two kinds of topological frameworks coexist.
Fig. 3 to 7 is the composite molecular screen sample F M-1 of embodiment 1 ~ 5, the SEM spectrogram of FM-2, FM-3, FM-4 and FM-5, as can be seen from spectrogram, extends with crystallization time, and the MWW molecular sieve of the laminate structure of FAU structure molecular screen Surface Creation gets more and more.
Comparative example 4
With embodiment 1, difference is that crystallization time is 70 hours, and gained comparative sample is numbered FM-6, tests its XRD diffractogram (Fig. 2).This comparative example illustrates under the raw material and conditions of mixture ratios of embodiment 1, and crystallization time equals or is longer than 70h, then obtaining product is pure phase MWW topological framework molecular sieve.
Embodiment 6 ~ 10
The present embodiment illustrates composite molecular screen provided by the invention.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and NH
4naY-2 molecular sieve (NaY molecular sieve in 90 DEG C through NH
4 +exchange 2h, twice) add in above-mentioned solution, after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.04Al
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, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Product is taken out after cooling, after filtration, after washing, drying and roasting, test its XRD spectra, the molecular sieve of result display synthesis is the composite molecular screen that the FAU topological framework of a series of different ratios (96%FAU, 82%FAU, 65%FAU, 81%MWW, 93%MWW) and MWW topological framework coexist.
Comparative example 5
With embodiment 6, difference is that crystallization time is 70 hours, and gained comparative sample tests its XRD diffractogram, has the feature of FM-6 comparative sample XRD diffractogram in Fig. 2.This comparative example illustrates under the raw material and conditions of mixture ratios of embodiment 6, and crystallization time equals or is longer than 70h, then obtaining product is pure phase MWW topological framework molecular sieve.
Embodiment 11 ~ 15
The present embodiment illustrates composite molecular screen provided by the invention.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and HNaY-2 molecular sieve (NaY molecular sieve in 90 DEG C through NH
4 +exchange 2 times, in 550 DEG C of roasting 4h, Na
2o content is 2.53w%) add in above-mentioned solution, after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.04Al
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, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Product is taken out after cooling, after filtration, after washing, drying and roasting, test its XRD spectra, the molecular sieve of result display synthesis is the composite molecular screen (92%FAU, 78%FAU, 54%FAU, 89%MWW, 98%MWW) that the FAU topological framework of a series of different ratios and MWW topological framework coexist.
Comparative example 6
With embodiment 11, difference is that crystallization time is 70 hours, and gained comparative sample tests its XRD diffractogram, has the feature of FM-6 comparative sample XRD diffractogram in Fig. 2.This comparative example illustrates under the raw material and conditions of mixture ratios of embodiment 11, and crystallization time equals or is longer than 70h, then obtaining product is pure phase MWW topological framework molecular sieve.
Embodiment 16 ~ 20
The present embodiment illustrates composite molecular screen provided by the invention.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, the NaY molecular sieve of solid silicone and little crystal grain is added in above-mentioned solution, after stirring, adds hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.04Al
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, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Product is taken out after cooling, after filtration, after washing, drying and roasting, test its XRD spectra, the molecular sieve of result display synthesis is the composite molecular screen (93%FAU, 81%FAU, 56%FAU, 87%MWW, 97%MWW) that the FAU topological framework of a series of different ratios and MWW topological framework coexist.
Comparative example 7
With embodiment 16, difference is that crystallization time is 70 hours, and gained comparative sample tests its XRD diffractogram, has the feature of FM-6 comparative sample XRD diffractogram in Fig. 2.This comparative example illustrates under the raw material and conditions of mixture ratios of embodiment 16, and crystallization time equals or is longer than 70h, then obtaining product is pure phase MWW topological framework molecular sieve.
Embodiment 21 ~ 25
The present embodiment illustrates composite molecular screen provided by the invention.
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=2.0) add in above-mentioned solution, after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.04Al
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, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Product is taken out after cooling, after filtration, after washing, drying and roasting, test its XRD spectra, the molecular sieve of result display synthesis is the composite molecular screen (91%FAU, 82%FAU, 64%FAU, 80%MWW, 93%MWW) that the FAU topological framework of a series of different ratios and MWW topological framework coexist.
Comparative example 8
With embodiment 21, difference is that crystallization time is 70 hours, and gained comparative sample tests its XRD diffractogram, has the feature of FM-6 comparative sample XRD diffractogram in Fig. 2.This comparative example illustrates under the raw material and conditions of mixture ratios of embodiment 21, and crystallization time equals or is longer than 70h, then obtaining product is pure phase MWW topological framework molecular sieve.
Embodiment 26 ~ 30
The present embodiment illustrates composite molecular screen provided by the invention.
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=2.0) add in above-mentioned solution, after stirring, add hexamethylene imine, continue to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.056Al
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, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Product is taken out after cooling, after filtration, after washing, drying and roasting, test its XRD spectra, the molecular sieve of result display synthesis is the composite molecular screen (93%FAU, 86%FAU, 65%FAU, 78%MWW, 92%MWW) that the FAU topological framework of a series of different ratios and MWW topological framework coexist.
Comparative example 9
With embodiment 26, difference is that crystallization time is 70 hours, and gained comparative sample tests its XRD diffractogram, has the feature of FM-6 comparative sample XRD diffractogram in Fig. 2.This comparative example illustrates under the raw material and conditions of mixture ratios of embodiment 26, and crystallization time equals or is longer than 70h, then obtaining product is pure phase MWW topological framework molecular sieve.
Embodiment 31 ~ 35
The present embodiment illustrates composite molecular screen provided by the invention.
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=2.0) add in above-mentioned solution, 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, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Product is taken out after cooling, after filtration, after washing, drying and roasting, test its XRD spectra, the molecular sieve of result display synthesis is the composite molecular screen (94%FAU, 86%FAU, 67%FAU, 78%MWW, 92%MWW) that the FAU topological framework of a series of different ratios and MWW topological framework coexist.
Comparative example 10
With embodiment 31, difference is that crystallization time is 70 hours, and gained comparative sample tests its XRD diffractogram, has the feature of FM-6 comparative sample XRD diffractogram in Fig. 2.This comparative example illustrates under the raw material and conditions of mixture ratios of embodiment 31, and crystallization time equals or is longer than 70h, then obtaining product is pure phase MWW topological framework molecular sieve.
Embodiment 36 ~ 40
The present embodiment illustrates composite molecular screen provided by the invention.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and production piece NaY(Na
2o content is 11.8w%, SiO
2/ Al
2o
3=4.95) molecular sieve adds in above-mentioned solution, after stirring, adds N, and N, N-trimethylammonium adamantyl ammonium hydroxide, continues to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.04Al
2o
3: 0.30TMADOH:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Take out product after cooling, after filtration, washing, after dry and roasting, test its XRD diffractogram.The molecular sieve of result display synthesis is the composite molecular screen (93%FAU, 86%FAU, 69%FAU, 80%MWW, 95%MWW) that the FAU topological framework of a series of different ratios and MWW topological framework coexist.
Embodiment 41 ~ 45
The present embodiment illustrates composite molecular screen provided by the invention.
Sodium hydroxide is dissolved in deionized water, is stirred to and dissolves completely, by solid silicone and production piece NaY(Na
2o content is 11.8w%, SiO
2/ Al
2o
3=4.95) molecular sieve adds in above-mentioned solution, after stirring, adds piperidines, continues to stir.Gained mixture colloid mol ratio is: 0.18NaOH:SiO
2: 0.04Al
2o
3: 0.30PI:15H
2o.Then, be transferred to by gained mixture in airtight crystallizing kettle, crystallization temperature is 145 DEG C, and dynamic crystallization, crystallization time is respectively 48h, 60h, 64h, 66h, 68h.Take out product after cooling, after filtration, washing, after dry and roasting, test its XRD diffractogram.The molecular sieve of result display synthesis is the composite molecular screen (96%FAU, 89%FAU, 75%FAU, 80%MWW, 93%MWW) that the FAU topological framework of a series of different ratios and MWW topological framework coexist.
Claims (15)
1. a composite molecular screen for different topology architectures coexist, it is characterized in that wherein FAU topological framework and MWW topological framework coexist, and have core-shell construction, kernel is FAU topological framework, shell is MWW topological framework.
2. according to the composite molecular screen of claim 1, wherein, the mass content of said FAU topological framework is 0.01% ~ 99.99%.
3. according to the composite molecular screen of claim 1, it is characterized in that, said MWW topological framework generates from outside to inside on FAU topological framework.
4. the preparation method of the composite molecular screen of a different topology architectures coexist, it is characterized in that the mixture colloid that FAU topological framework molecular sieve and silicon source, alkali source, template, deionized water formed crystallization reclaim the composite molecular screen product obtained under hydrothermal conditions, wherein, said template is the template that can be used in synthesizing MWW structure molecular screen.
5. according to the method for claim 4, wherein, in said mixture colloid, the mol ratio of each raw material is: SiO
2/ Al
2o
3=3 ~ 200, OH
-/ SiO
2=0.001 ~ 1, H
2o/SiO
2=5 ~ 100, R/SiO
2=0.01 ~ 5, R represents template.
6., according to the method for claim 5, wherein, in said mixture colloid, the mol ratio of each raw material is: SiO
2/ Al
2o
3=3 ~ 80, OH
-/ SiO
2=0.01 ~ 0.50, H
2o/SiO
2=5 ~ 50, R/SiO
2=0.05 ~ 0.50.
7., according to the method for claim 6, wherein, in said mixture colloid, the mol ratio of each raw material is: SiO
2/ Al
2o
3=5 ~ 40, OH
-/ SiO
2=0.05 ~ 0.30, H
2o/SiO
2=10 ~ 30, R/SiO
2=0.05 ~ 0.35.
8. 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 alkali source is selected from least one in lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide.
9. according to the method for claim 4, wherein, the said template that can be used in synthesizing 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.
10. according to the method for claim 4, wherein, said template is at least containing hexamethylene imine.
11. according to the method for claim 4, and wherein, said FAU topological framework molecular screening is from X-type and/or Y zeolite.
12. methods according to claim 11, wherein, said FAU topological framework molecular screening is from NaX, NaY, NH
4x, NH
4one or more in Y, HX, HY, REX and REY.
13. according to the method for claim 4, and wherein, said silicon source is solid silicone; Said alkali source is sodium hydroxide, and said template is hexamethylene imine.
14. according to the method for claim 4, and wherein, crystallization under said hydrothermal condition, temperature is 100 ~ 180 DEG C.
15. according to the method for claim 4, and wherein, crystallization under said hydrothermal condition, the time is 5 ~ 70 hours.
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| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
| CN102441425A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method for Y/MCM-41 composite molecular sieve |
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| CN101186311A (en) * | 2007-11-22 | 2008-05-28 | 复旦大学 | Y/MCM-48 composite molecular screen and preparation method thereof |
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