CN108786914A - A kind of preparation method of ZSM-11/5 composite molecular screens - Google Patents
A kind of preparation method of ZSM-11/5 composite molecular screens Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 54
- 230000008025 crystallization Effects 0.000 claims abstract description 51
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 33
- 239000002808 molecular sieve Substances 0.000 claims description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000005352 clarification Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- -1 methanol hydrocarbon Chemical class 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003643 water by type Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- BWKAYBPLDRWMCJ-UHFFFAOYSA-N 1,1-diethoxy-n,n-dimethylmethanamine Chemical compound CCOC(N(C)C)OCC BWKAYBPLDRWMCJ-UHFFFAOYSA-N 0.000 description 1
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical class CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- FZEFLWKRCHOOCK-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enal Chemical compound C=CC=O.OCC(O)CO FZEFLWKRCHOOCK-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/80—Mixtures of different zeolites
Abstract
The present invention provides a kind of composite molecular screens of ZSM-11/5 to be synthesized in the case of no template with CTAB and crystal seed.However, when CTAB is not added, pure big six squares ZSM-5 Crystallizations are in ZSM-11 crystal seeds.ZSM-11/5 composite molecular screens have larger surface area and external surface area, higher mesopore volume and acidic site compared with traditional synthetic sample.ZSM-11/5 composite molecular screens also show excellent catalytic performance in methanol hydrocarbon reaction.
Description
Technical field
The invention belongs to molecular sieve catalysts to synthesize field, more particularly to a kind of preparation of ZSM-11/5 composite molecular screens
Method.
Background technology
ZSM-11 molecular sieves are that a kind of MEL types high-silica zeolite is patented for the first time in 1973, structure be by
What Kokotailo et al. was reported in 1978.The skeleton structure of this molecular sieve and MFI topological structures are closely related, both
Belong to same five-membered ring structure.ZSM-11 is made of two square crossing ducts there are one three dimensional topology, ZSM-11 and
The aperture size of ZSM-5 is similar, and ZSM-5 has the straight channel and sinusoidal channel of intersection.
ZSM-11 has excellent catalytic performance compared to ZSM-5 in some reactions, such as the hydrogen isomery of higher alkane
Change, the dehydration of glycerine acrolein, middle oil catalytic pyrolysis, methanol is converted into low-carbon alkene, and methanol is converted into hydrocarbon, just
The isomerization of hexane and aromatization, the alkylation of benzene, ethyl alcohol are converted into low-carbon alkene and aromatic hydrocarbons.Varvarin et al. reports H-
ZSM-11 and H-ZSM-5 is converted as being shown in the catalytic process that n-butanol is converted into hydrocarbon and yield.H-
ZSM-5 is converted into hydrocarbon in the polyethylene of low-density, and ethylene is converted into propylene and butylene, and methanol is converted into alkene, first
Alcohol is converted into propylene, and ethyl alcohol is also demonstrated by excellent catalytic performance during being converted into propylene.Directly synthesis Zn-ZSM-11 exists
Methanol be converted into hydrocarbon catalytic process and low density polyethylene (LDPE) cracking in also shown compared to Zn- beta-molecular sieves it is excellent
Different performance.The ZSM-11 of Zn loads is also used for the activation of catalytic methane, and ethane switchs to aromatic hydrocarbons etc..P be modified H-ZSM-11 also by
The catalytic process of hydrocarbon is converted into for methanol.
ZSM-11 Zeolite synthesis usually uses TBA+As Organic structure directing agent, dynamics research shows to lure for a long time
After leading the phase, it has been initially formed the ball member of 20-70nm, oval MEL crystal is then formed by rapid aggregation, it will be apparent that is living
Change can be shown that induction process needs more energy than propagation process.Excellent ZSM-11 crystal grain can be synthesized by low temperature crystallization, pure
Silicon ZSM-11（S-2）It is dissolved in TBAOH clear solutions and synthesizes in TEOS.However, in no TBA+When, with SiO2As silicon
Source, ZSM-11 cannot be synthesized, on the contrary, pure natural zeolite synthesizes.However, having synthesized ZSM-11 using TBAOH as template
It is proved that the actually composite molecular screen of ZS-11/5, Gonzalez et al. are found with TBA+ZSM-11 is synthesized for template, it is brilliant
Phase composition depends on Al content.Jablonski et al. reports to obtain the ZSM-11 composite materials of high-content, and synthesis should be
Under low temperature, high K/K+Na ratios carry out, and it is an orthogonal symbiosis that Tsapatsis and colleague, which report MFI-MEL symbiotic structures,
The formation of multistage porous molecular sieve, pure ZSM-11 phases is caused to be prepared by certain moduli plate agent, such as 3,5- lutidines derives
Object and hexahydropyridine derivative, diethoxy trimethyl ammonia, N, N- diethyl -3,5- lupetidine hydroxide etc..Miscellaneous original
Attached bag contains ZSM-11, such as Zr-ZSM-11 and Zn-ZSM-11, and the hetero atom that presoma is added in crystallizing colloidal sol can be closed directly
At, however, it is the ZSM-11 using TBAOH as templated synthesis, the composite molecular screen of ZSM-11/5 illustrate it is above-mentioned
Excellent properties in some reactions.
The composite molecular screen of multi-stage porous ZSM-11/5, Song et al. report evaporation induced self-assembly in order to obtain,
Preforming xerogel is generated by hexadecyl trimethoxy silane auxiliary, is changed into later by steam assisting crystallisation
Molecular sieve.Chen et al. uses a kind of diamines of linear carbochain to obtain multistage later in 448 K long period crystallization as single mode plate
Hole ZSM-5 and ZSM-11 microsphere aggregation is in the nanocrystal of containing mesopore, when carbochain is C8And C10When, product is ZSM-11.Li
The composite molecular screen of multi-stage porous ZSM-11/5 is synthesized by different crystallisation modes with a small amount of TBABr with his colleague.?
This process, a small amount of TBABr are considered directly foring the symbiosis form of ZSM-11 frames and it, and crystallisation mode includes one
The temperature change of stage and two-stage crystallize, and are mainly responsible for the mesoporous property of adjustable particle size and sample.Also may be used in this way
It handles to have obtained multistage using the mixed solution of NaOH or NaOH and CTAB to synthesize multi-stage porous Zn-ZSM-11, Xu and colleague
Hole ZSM-11 molecular sieves.Xu and colleague also use alumina treatment ZSM-11/5 composite molecular screens, have obtained mesoporous.Chen et al. is used
Trimethylammonium and tetrabutylammonium hydroxide binary templated synthesis ZSM-11 composite materials.Use TBA+As template, polyvinyl alcohol contracting
Butyraldehyde is as mesoporous generator, synthesising mesoporous ZSM-11.
Invention content
The purpose of the present invention is in no TBABr or other specific templates, provide a kind of by adding CTAB
The method for synthesizing ZSM-11/5 composite molecular screens with crystal seed revulsion.
This realization above-mentioned purpose, the technical solution adopted by the present invention are a kind of preparation sides of ZSM-11/5 composite molecular screens
Method includes the following steps：
1）The preparation of S-Z：By SiO2、NaAlO2And Na2CO3It is add to deionized water mixing, is uniformly mixing to obtain gel A（It is solidifying
A mole group of glue A becomes：1.0SiO2:0.08NaAlO2:0.3Na2CO3:10H2O）, the gel A of preparation is added and contains polytetrafluoroethyl-ne
In the autoclave of alkene liner, for 24 hours, then 443K crystallization 48h are quickly cooled to room temperature to first 363K crystallization, filtering and washing to pH=7,
353K is dried overnight is named as S-Z to get S-2,823K after roasting 6h（The molecular weight of S-Z is defaulted as 1 to count in the present invention
It calculates, it is hereinafter same such as the i.e. corresponding 2.5g of 2.5mol）；
2）By NaAlO2In deionized water half needed for being added while stirring with NaOH, S-Z is added after solution becomes clarification, it will
CTAB is dissolved in the other half deionized water and is added above-mentioned solution, after solution again become clarification after, with vigorous stirring by
It is added dropwise to Ludox 4h is stirred at room temperature and obtain gel B（Mole group of gel B becomes 8Na:100SiO2:2Al2O3:2.5S-
Z:yCTAB:2500H2O, y=0.5-3）, obtained gel B is transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K
Crystallization 12 ~ for 24 hours, then 3 ~ 48h of 443K crystallization；It is cooled to room temperature, filtering and washing to pH=7.5,363K dries 12h, 443K roastings
6h；
3）By step 2）Obtained molecular sieve is by solid-to-liquid ratio 1g:16.5mL is added to the NH of 1mol/L4NO3353K is stirred in solution
2h is mixed, it is cooling, it filters, washing to pH=7.5；This self-care exchange step is repeated 3 times, obtained sample 363K dryings
12h, 823K roast 6h.
The beneficial effect comprise that：Present invention firstly discloses in no TBABr or other specific template feelings
Under condition, the composite molecular screen of ZSM-11/5 can be synthesized with crystal seed revulsion by addition CTAB.In addition, ZSM-11/5 compound molecules
Sieve has larger specific surface area and external surface area, higher mesopore volume and acidic site, ZSM compared with traditional synthetic sample
- 11/5 composite molecular screen also shows excellent catalytic performance in methanol hydrocarbon reaction.
Description of the drawings
Fig. 1 is to be added and CTAB, different crystallization temperatures, the XRD diagram of different crystallization time samples are not added；.
Fig. 2 is the XRD diagram that different CTAB amounts synthesis ZSM-11/5 composite molecular screens are added.
Specific implementation mode
The present invention is further explained in the light of specific embodiments, and but the scope of the present invention is not limited thereto.For
Research ZSM-11/5 composite molecular screen formation mechenisms, crystallization process stop in the different stages, and sample is named as S-363-mh-
443- lh（M and l respectively represents the crystallization time of 363 and 443K）.
Embodiment 1
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is added in 25ml deionized waters and mixes, stir evenly,
363K crystallization 12h in the autoclave containing polytetrafluoroethyllining lining are added in the gel of preparation, are quickly cooled to room temperature, filtering and washing
To PH=7,353K is drying over night, and 823K roasts 6h up to sample S-363-12h.
Embodiment 2
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is add to deionized water mixing, is stirred evenly, will be made
Standby gel is added 363K crystallization in the autoclave containing polytetrafluoroethyllining lining and for 24 hours, is quickly cooled to room temperature, filtering and washing to PH
=7,353K are drying over night, and 823K roasts 6h up to sample S-363-24h.
Embodiment 3
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is added in 25ml deionized waters and mixes, stir evenly,
363K crystallization in the autoclave containing polytetrafluoroethyllining lining is added in the gel of preparation, and for 24 hours, 443K crystallization 3h are quickly cooled to room
Temperature, filtering and washing to PH=7,353K is drying over night, and 823K roasts 6h up to sample S-363-24h-443-3h.
Embodiment 4
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is added in 25ml deionized waters and mixes, stir evenly,
363K crystallization in the autoclave containing polytetrafluoroethyllining lining is added in the gel of preparation, and for 24 hours, 443K crystallization 6h are quickly cooled to room
Temperature, filtering and washing to PH=7,353K is drying over night, and 823K roasts 6h up to sample S-363-24h-443-6h.
Embodiment 5
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is added in 25ml deionized waters and mixes, stir evenly,
363K crystallization in the autoclave containing polytetrafluoroethyllining lining is added in the gel of preparation, and for 24 hours, 443K crystallization 9h are quickly cooled to room
Temperature, filtering and washing to PH=7,353K is drying over night, and 823K roasts 6h up to sample S-363-24h-443-9h.
Embodiment 6
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is added in 25ml deionized waters and mixes, stir evenly,
363K crystallization in the autoclave containing polytetrafluoroethyllining lining is added in the gel of preparation, and for 24 hours, 443K crystallization 12h are quickly cooled to
Room temperature, filtering and washing to PH=7,353K is drying over night, and 823K roasts 6h up to sample S-363-24h-443-12h.
Embodiment 7
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is added in 25ml deionized waters and mixes, stir evenly,
363K crystallization in the autoclave containing polytetrafluoroethyllining lining is added in the gel of preparation, and for 24 hours, 443K crystallization for 24 hours, is quickly cooled to
Room temperature, filtering and washing to PH=7,353K is drying over night, and 823K roasts 6h up to sample S-363-24h-443-24h.
Embodiment 8
3.36g SiO2, the NaAlO of 0.36g2, the Na of 4.80g2CO3It is added in 25ml deionized waters and mixes, stir evenly,
The gel of preparation is added in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then 443K crystallization 48h, fast quickly cooling
But to room temperature, filtering and washing to PH=7,353K is drying over night, and 823K roasts 6h up to S-Z.
Embodiment 9
By NaAlO2In deionized water half needed for being added while stirring with NaOH, S-Z is added after solution becomes clarification, it will
CTAB is dissolved in the other half deionized water and is added above-mentioned solution, after solution again become clarification after, with vigorous stirring by
It is added dropwise to Ludox 4h is stirred at room temperature and obtain gel B（Mole group of gel B becomes 8Na:100SiO2:2Al2O3:2.5S-
Z:2CTAB:2500H2O）, it is transferred in the autoclave containing polytetrafluoroethyllining lining, 363K crystallization 12h；It is cooled to room temperature, filters
Washing dries 12h to PH=7.5,363K, and 823K roasts 6h.To make molecular sieve be converted into H-type, by sample in 1M NH4NO3Solution
Middle 353K stirs 2h（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters, washing to PH=7.5, this, which is taken care of oneself, exchanges step
Suddenly it is repeated 3 times, obtained sample 363K dries 12h, and 823K roasts 6h.Up to sample S-CTAB-363-12h.
Embodiment 10
By NaAlO2In deionized water half needed for being added while stirring with NaOH, S-Z is added after solution becomes clarification, it will
CTAB is dissolved in the other half deionized water and is added above-mentioned solution, after solution again become clarification after, with vigorous stirring by
It is added dropwise to Ludox 4h is stirred at room temperature and obtain gel B（Mole group of gel B becomes 8Na:100SiO2:2Al2O3:2.5S-
Z:2CTAB:2500H2O）, it is transferred in the autoclave containing polytetrafluoroethyllining lining, 363K crystallization is for 24 hours；It is cooled to room temperature, filters
Washing dries 12h to PH=7.5,363K, and 823K roasts 6h.To make molecular sieve be converted into H-type, by sample in 1M NH4NO3Solution
Middle 353K stirs 2h（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters, washing to PH=7.5, this, which is taken care of oneself, exchanges step
Suddenly it is repeated 3 times, obtained sample 363K dries 12h, and 823K roasts 6h.Up to sample S-CTAB-363-24h.
Embodiment 11
By NaAlO2In deionized water half needed for being added while stirring with NaOH, S-Z is added after solution becomes clarification, it will
CTAB is dissolved in the other half deionized water and is added above-mentioned solution, after solution again become clarification after, with vigorous stirring by
It is added dropwise to Ludox 4h is stirred at room temperature and obtain gel B（Mole group of gel B becomes 8Na:100SiO2:2Al2O3:2.5S-
Z:2CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then 443K crystallization 3h；
It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.To make molecular sieve be converted into H-type, by sample
In 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters, washing to PH=7.5,
This self-care exchange step is repeated 3 times, and obtained sample 363K dries 12h, and 823K roasts 6h.Up to sample S-
CTAB-363-24h-443-3h。
Embodiment 12
By NaAlO2In deionized water half needed for being added while stirring with NaOH, S-Z is added after solution becomes clarification, it will
CTAB is dissolved in the other half deionized water and is added above-mentioned solution, after solution again become clarification after, with vigorous stirring by
It is added dropwise to Ludox 4h is stirred at room temperature and obtain gel B（Mole group of gel B becomes 8Na:100SiO2:2Al2O3:2.5S-
Z:2CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then 443K crystallization 6h；
It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.To make molecular sieve be converted into H-type, by sample
In 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters, washing to PH=7.5,
This self-care exchange step is repeated 3 times, and obtained sample 363K dries 12h, and 823K roasts 6h.Up to sample S-
CTAB-363-24h-443-6h。
Embodiment 13
By NaAlO2In deionized water half needed for being added while stirring with NaOH, S-Z is added after solution becomes clarification, it will
CTAB is dissolved in the other half deionized water and is added above-mentioned solution, after solution again become clarification after, with vigorous stirring by
It is added dropwise to Ludox 4h is stirred at room temperature and obtain gel B（Mole group of gel B becomes 8Na:100SiO2:2Al2O3:2.5S-
Z:2CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then 443K crystallization
12h；It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.It, will to make molecular sieve be converted into H-type
Sample is in 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters, washing to PH=
7.5, this self-care exchange step is repeated 3 times, and obtained sample 363K dries 12h, and 823K roasts 6h.Up to sample S-
CTAB-363-24h-443-12h。
Embodiment 14
By NaAlO2In deionized water half needed for being added while stirring with NaOH, S-Z is added after solution becomes clarification, it will
CTAB is dissolved in the other half deionized water and is added above-mentioned solution, after solution again become clarification after, with vigorous stirring by
It is added dropwise to Ludox 4h is stirred at room temperature and obtain gel B（Mole group of gel B becomes 8Na:100SiO2:2Al2O3:2.5S-
Z:2CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then 443K crystallization
24h；It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.It, will to make molecular sieve be converted into H-type
Sample is in 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters, washing to PH=
7.5, this self-care exchange step is repeated 3 times, and obtained sample 363K dries 12h, and 823K roasts 6h.Up to sample S-
CTAB-363-24h-443-24h。
Embodiment 15
By NaAlO2In deionized water half needed for being added while stirring with NaOH, 2.5 moles of S- are added after solution becomes clarification
0.5 mole of CTAB is dissolved in the other half deionized water and is added above-mentioned solution by Z, after solution becomes clarification again, in play
Ludox is added dropwise under strong stirring 4h is stirred at room temperature and obtains gel B（Mole group of gel B becomes 8Na:100SiO2:
2Al2O3:2.5S-Z:0.5CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours,
443K crystallization 48h again；It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.To make molecular sieve turn
H-type is turned to, by sample in 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it takes out
Filter is washed to PH=7.5, this self-care exchange step is repeated 3 times, and obtained sample 363K dries 12h, 823K roastings
6h.Up to sample S-2.5Z-0.5C.
Embodiment 16
By NaAlO2In deionized water half needed for being added while stirring with NaOH, 2.5 moles of S- are added after solution becomes clarification
1 mole of CTAB is dissolved in the other half deionized water and is added above-mentioned solution by Z, after solution becomes clarification again, violent
Ludox is added dropwise under stirring 4h is stirred at room temperature and obtains gel B（Mole group of gel B becomes 8Na:100SiO2:
2Al2O3:2.5S-Z:1CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then
443K crystallization 48h；It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.To make molecular sieve convert
For H-type, by sample in 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters,
To PH=7.5, this self-care exchange step is repeated 3 times for washing, and obtained sample 363K dries 12h, and 823K roasts 6h.
Up to sample S-2.5Z-1C.
Embodiment 17
By NaAlO2In deionized water half needed for being added while stirring with NaOH, 2.5 moles of S- are added after solution becomes clarification
2 moles of CTAB are dissolved in the other half deionized water and are added above-mentioned solution by Z, after solution becomes clarification again, violent
Ludox is added dropwise under stirring 4h is stirred at room temperature and obtains gel B（Mole group of gel B becomes 8Na:100SiO2:
2Al2O3:2.5S-Z:2CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then
443K crystallization 48h；It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.To make molecular sieve convert
For H-type, by sample in 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters,
To PH=7.5, this self-care exchange step is repeated 3 times for washing, and obtained sample 363K dries 12h, and 823K roasts 6h.
Up to sample S-2.5Z-2C.
Embodiment 18
By NaAlO2In deionized water half needed for being added while stirring with NaOH, 2.5 moles of S- are added after solution becomes clarification
3 moles of CTAB are dissolved in the other half deionized water and are added above-mentioned solution by Z, after solution becomes clarification again, violent
Ludox is added dropwise under stirring 4h is stirred at room temperature and obtains gel B（Mole group of gel B becomes 8Na:100SiO2:
2Al2O3:2.5S-Z:3CTAB:2500H2O）, be transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then
443K crystallization 48h；It is cooled to room temperature, filtering and washing to PH=7.5,363K dries 12h, and 823K roasts 6h.To make molecular sieve convert
For H-type, by sample in 1M NH4NO3353K stirs 2h in solution（1g molecular sieves correspond to 16.5ml NH4NO3）, it is cooling, it filters,
To PH=7.5, this self-care exchange step is repeated 3 times for washing, and obtained sample 363K dries 12h, and 823K roasts 6h.
Up to sample S-2.5Z-3C.
Fig. 1 is to be added and CTAB is not added, and different crystallization temperatures, the XRD diagram of different crystallization time samples, abscissa is angle
Degree, ordinate is crystallinity.The chart is bright, CTAB be not added, but in the presence of S-Z, pure ZSM-5 is formed at low temperature, MEL
Crystal seed causes the perfect of MFI molecular sieves to be formed.Due to low temperature and lacking CTAB, pure ZSM-5 is formed, when CTAB is added,
ZSM-5 cannot be formed under the same terms, the results showed that, CTAB prevents the formation of ZSM-5 first, and ZSM-11 crystal seeds is made to have an opportunity
It is the composite material of ZSM-11/5 to promote gel conversion.
Fig. 2 is the XRD diagram that different CTAB amounts synthesis ZSM-11/5 composite molecular screens are added, and abscissa is angle, ordinate
For crystallinity.For 24 hours for 363K, second of crystallization is 443K 48h for all samples crystallization for the first time.The XRD diagram of S-Z is shown
The characteristic peak of ZSM-11 in the case of no TBAOH, but is added the synthesis of S-Z samples, also shows the characteristic peak of ZSM-11,
Show that, in no crystal seed, CTAB makes ZSM-11 be formed, is 23.14 ° in 2 θ, 23.98 °, 24.47 ° can be observed ZSM-5
Faint peak shows that molecular sieve is the composite molecular screen of ZSM-11/5.The diffraction peak intensity of S-2.5Z-0.5C samples is weaker than other
Sample shows that this sample may include some amorphous materials, and as the amount that CTAB is added increases, the crystallinity of sample increases
By force, and the diffraction maximum of the composite molecular screen of ZSM-11/5 broadens, from intuitive, this is because compared with conventional hydrothermal method,
Sample crystal grain smaller prepared by the method.
Claims (5)
1. a kind of preparation method of ZSM-11/5 composite molecular screens, it is characterised in that include the following steps：
1）The preparation of S-Z：By SiO2、NaAlO2And Na2CO3It is add to deionized water mixing, is uniformly mixing to obtain gel A, it will
The gel A of preparation is added in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization for 24 hours, then 443K crystallization 48h, fast quickly cooling
But to room temperature, filtering and washing to pH=7,353K is dried overnight is named as S-Z to get S-2,823K after roasting 6h；
2）By NaAlO2It is added in deionized water while stirring with NaOH, S-Z is added after solution becomes clarification, CTAB is dissolved in
It in deionized water and is added above-mentioned solution, after solution becomes clarification again, Ludox is added dropwise with vigorous stirring in room
The lower stirring 4h of temperature obtains gel B, obtained gel B is transferred in the autoclave containing polytetrafluoroethyllining lining, first 363K crystallization
12 ~ for 24 hours, then 3 ~ 48h of 443K crystallization；It is cooled to room temperature, filtering and washing to pH=7.5,363K dries 12h, and 443K roasts 6h；
3）By step 2）Obtained molecular sieve uses NH4NO3Solution carries out ion exchange 3 times, obtained sample 363K dryings
12h, 823K roast 6h.
2. the preparation method of ZSM-11/5 composite molecular screens as described in claim 1, it is characterised in that step 3）Carry out ion friendship
Change the specific steps are：Molecular sieve is added to the NH of 1mol/L4NO3353K stirs 2h in solution, cooling, filters, washing to pH
=7.5。
3. the preparation method of ZSM-11/5 composite molecular screens as described in claim 1, it is characterised in that step 1）Middle gel A compositions
For：1.0SiO2:0.08NaAlO2:0.3Na2CO3:10H2O。
4. the preparation method of ZSM-11/5 composite molecular screens as described in claim 1, it is characterised in that step 2）Middle gel B compositions
For 8Na:100SiO2:2Al2O3:2.5S-Z:yCTAB:2500H2O, y=0.5-3.
5. the ZSM-11/5 composite molecular screens prepared using claim 1-4 either method.
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