CN107934982A - A kind of macropore silicate molecular sieve and preparation method thereof - Google Patents
A kind of macropore silicate molecular sieve and preparation method thereof Download PDFInfo
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- CN107934982A CN107934982A CN201711290773.8A CN201711290773A CN107934982A CN 107934982 A CN107934982 A CN 107934982A CN 201711290773 A CN201711290773 A CN 201711290773A CN 107934982 A CN107934982 A CN 107934982A
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- molecular sieve
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 58
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000000634 powder X-ray diffraction Methods 0.000 claims abstract description 31
- -1 BEC molecular sieve analogs Chemical class 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 229910052682 stishovite Inorganic materials 0.000 claims description 19
- 229910052905 tridymite Inorganic materials 0.000 claims description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229940119177 germanium dioxide Drugs 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 8
- 238000009415 formwork Methods 0.000 claims description 7
- 229910052795 boron group element Inorganic materials 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052800 carbon group element Inorganic materials 0.000 claims description 4
- 150000001767 cationic compounds Chemical class 0.000 claims description 4
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 238000004377 microelectronic Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003837 high-temperature calcination Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000013461 design Methods 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000012013 faujasite Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- AVPMRIWGOGRNBF-UHFFFAOYSA-N [bromo(fluoro)methyl]benzene Chemical compound FC(Br)C1=CC=CC=C1 AVPMRIWGOGRNBF-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001641 boron group compounds Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of macropore silicate molecular sieve material and preparation method thereof, this molecular sieve has X-ray powder diffraction feature as shown in table 1, has 12 × 12 × 12 three-dimensional open-framework, belongs to BEC molecular sieve analogs.Macropore silicate molecular sieve of the present invention can be obtained by hydrothermal synthesis method, better heat stability, had larger specific surface area, can be mixed hetero atom, there is potential application value in the fields such as petrochemistry, fine chemistry industry and life science.
Description
Technical field
The invention belongs to crystalline form poromerics field, and in particular to a kind of new structure macropore silicate molecular sieve material and
Its preparation method.
Background technology
Molecular screen material is one kind by TO4(T represents the oxidation state atom under normal conditions with+4 valencys or+trivalent, as Si,
P, Al, B, Ge, Ga etc.) tetrahedron is by sharing vertex a kind of inorganic microporous solid material for forming.Molecule under normal conditions
The composition of sieve can be represented with following empirical formula：p(M1/nXO2)·qYO2·rR·wH2O, wherein, M represent one or
The organic or inorganic cation of multiple+n valencys；X represents one or more triads；Y represents one or more quadrivalent elements, leads to
It is Si in the case of often；R represents one or more organic molecules.For a certain specific structure that is obtained by specific synthetic method
Molecular sieve, sample after the product or calcination processing of either fresh synthesis, its chemical composition be usually constructed with one it is specific
Constant interval.In addition, the molecular sieve of a specific structure also needs to further be distinguish between by X-ray powder diffraction, because
The difference of crystal structure causes different molecular sieve to possess different pore passage structures, can be obtained in the test of X-ray powder diffraction
Entirely different diffraction pattern.The most important characteristic of molecular sieve is that it is straight with variable duct chemical composition, adjustable duct
Footpath and duct shape.These outstanding characteristics impart molecular screen material in absorption, separation, catalysis, microelectronics and medical diagnosis
Have a wide range of applications Deng field.
According to the number of rings in duct, molecular screen material can be divided into aperture, mesoporous, macropore and super macroporous molecular sieve, corresponding difference
With 8 yuan of rings (i.e. by 8 TO4Tetrahedron is formed) window ring following, below 10 yuan of rings, below 12 yuan of rings and more than 12 yuan of rings
Number.The molecular screen material being applied successfully in industry, its duct size usually all in below 1nm, which greatly limits absorption, are divided
From the molecular size and shape of reaction substrate in, catalytic process, become one in molecular screen material practical application and keep in check.Exploitation
Stable three dimensional intersection macropore and the super macroporous molecular sieve with a diameter of 1nm to 2nm ducts with acquisition, even mesoporous point
Son sieve, is always the great challenge that inorganic chemists are faced, this kind of material will open petrochemistry, fine chemistry industry and life
The gate of new catalytic applications in the fields such as life science.
Due to the stability of silicate material, macropore silicate molecular sieve material has important application prospect.For a long time,
β zeolites are the zeolites that people largely use, and mainly have A types and Type B.For a long time, people suspect possibility existing for c-type always
(J.M.Newsam,M.M.J.Treacy,W.T.Koetsier,C.B.de Gruyter,Proc.R.Soc.London A
1988,420,375.).2000, Conradsson etc. reported a kind of novel molecular sieve structure FOS-5 of full germanium, is considered
Be people suspect always existing β zeolites family's architecture (T.Conradsson, M.S.Dadachov, X.Zou,
Microporous Mesoporous Mat.,2000,41,183–191).Afterwards, Corma et al. reports a kind of BEC quasi-molecules
Sieve structure ITQ-17 (A.Corma, M.T.Navarro, F.Rey, J.Rius, S.Valencia, Angew.Chem.Int.Ed.,
2001,40,2277–2280).Hereafter a variety of BEC molecular sieve analogs are found successively, wherein the ITQ-21 with catalytic performance
(A.Corma,M.J.Diaz-Cabanas,J.Martínez-Triguero,F.Rey,J.Rius,Nature,2002,418,
514-517) get more and more people's extensive concerning, twelve-ring macropore three dimensional intersection in ITQ-21, the supercage of one 1.18nm of formation,
It is similar with faujasite, show the catalytic performance more excellent compared with faujasite, but the synthesis of the molecular sieve will use very
Expensive organic formwork agent, causes its application of gained to be severely limited.
The synthesis of new structure macropore silicate molecular sieve material and structural characterization, not only should with very important reality
Also there is very important theory significance with value, and to abundant molecular sieve structure family, is that future molecular sieves Materials
Important directions, be inorganic chemists opportunities and challenges.
The content of the invention
The object of the present invention is to provide a kind of brand-new twelve-ring three dimensional intersection macropore silicate molecular sieve material：
NUD-4.The synthetic method and design feature of this molecular sieve are mainly described, has newly added a member for BEC molecular sieve analog materials family,
Application of the molecular sieve analog material in Industrial Catalysis for this provides new selection.
Technical scheme is as follows：
A kind of macropore silicate molecular sieve, it is characterised in that this molecular sieve has X-ray powder diffraction feature as shown in table 1.
Table 1
Above-mentioned macropore silicate molecular sieve, chemical composition form, is p (M after roasting1/nXO2)·qYO2·SiO2.Wherein, M generations
The inorganic cation of table proton or+n valencys；X represents triad；Y represents the quadrivalent element in addition to Si；P=0-0.2；Q=0-
2.5.The preferred protons of M or sodium, X are preferably Al, and Y is preferably germanium, preferably p=0-0.08；It is preferred that q=0-1.8.
Present invention also offers the preparation method of above-mentioned macropore silicate molecular sieve, include the following steps：
(1) in proportion by silicon source material, boron group element compound, the carbon group element compound in addition to silicon, organic formwork agent, fluorine
Source material and water are uniformly mixed under agitation, are reacted in the case of static and dynamic agitation, obtain reaction gel, and reaction is solidifying
The chemical composition of glue is：rROH:aHF:xX2O3:yYO2:SiO2:wH2O, wherein R represent the positive charge group of organic formwork agent；X
Represent one or more triads；Y represents one or more quadrivalent elements in addition to silicon；Corresponding r, a, x, y and w's takes
Value section is respectively：R=0.1-3, a=0.1-3, x=0-0.1, y=0-1, w=1-50；
(2) by reaction gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight after, by reaction gel
It is transferred in stainless steel cauldron, 120-170 DEG C under air-proof condition, preferably 150-165 DEG C, reacts 12-25 days, preferably 15-20
My god；
(3) by after the product washing after crystallization, drying, gone after roasting 2-5 hour under 400-650 DEG C of air atmosphere
The macropore silicate molecular sieve product of template agent removing.
The preparation method of above-mentioned macropore silicate molecular sieve, preferably reaction gel rROH:aHF:xX2O3:yYO2:SiO2:
wH2O, X are Al or B；Y is germanium.
It is preferred that the interval of corresponding r, a, x, y and w are respectively：R=0.5-0.8；A=0.5-0.8；X=0-0.05；
Y=0.4-0.6；W=10-30.
The preparation method of above-mentioned macropore silicate molecular sieve, preferably silicon source material are white carbon, waterglass, Ludox, just
Silester or butyl silicate.When boron group element compound is selected from alkali metal/alkali earth metal aluminate or alkali metal/alkaline earth gold
Obtained molecular sieve when belonging to borate, contains alkali or alkaline earth metal element in chemical constitution formula after roasting：p(M1/nXO2)·
qYO2·SiO2, M is alkali or alkaline earth metal ion, and when boron group element compound is selected from aluminium alcoholates, organic acid or inorganic acid aluminium
Salt, aluminium hydroxide or the boric acid obtained molecular sieve when compound, contain H in chemical constitution formula after roasting：p(M1/nXO2)·
qYO2·SiO2, M is proton.Above-mentioned boron group compound is preferably sodium metaaluminate, aluminium isopropoxide, 16 water aluminum sulfate, aluminium hydroxide
Or boric acid.It is preferred that Fluorine source material is hydrofluoric acid or ammonium fluoride.The preparation method of above-mentioned large pore molecular sieve, it is described in addition to silicon
Carbon group element compound is preferably germanium dioxide.
The preparation method of above-mentioned macropore silicate molecular sieve, the positive charge group Molecule formula of the organic formwork agent is Ar-
(CH2)-(im), wherein Ar represents the substituted or non-substituted phenyl or naphthyl in any position, and im represents 1- methylimidazoles or 1,2- bis-
Methylimidazole, can be any one listed in table 2.
Table 2
The above method, before reaction gel preparation, it is necessary to which all organic cation templates are passed through amberlite Ester exchange
It is stand-by after being demarcated by the hydrochloric acid solution of 0.1M for form hydroxy, its concentration.
Under normal circumstances, in the alkali formula template solution first added the quadrivalent element in addition to silicon, stirring and dissolving,
Then add silicon source to continue to stir, finally add corresponding boron group element compound, be stirring evenly and then adding into Fluorine source material, it is red
Solvent unnecessary in removing system is heated under outer lamp or in baking oven, obtains target gel.
With p (M1/nXO2)·qYO2·SiO2Exemplified by (p=0, q=0.6, Y=Ge), carried out using the method for the invention
Prepare, product is bar-like single crystal.Synchronized at -180 DEG C radiation diffraction test, itself the result shows that, NUD-4 crystallize in space
Group I4/m, the molecular formula of elemental analysis actual measurement is Ge0.55Si0.81O2.7F0.1, Its 3 D pore canal is shown in Fig. 2, and the view in wherein c directions is shown, this molecular sieve
There is the circular straight hole road of 12 yuan of rings, and in a directions and b directions due to the blocking of four-membered ring, formation is curved 12 yuan
Annular distance road.The molecular sieve is surrounded by four-membered ring and hexatomic ring, but there are two kinds of combining forms.Can be apparent from c-axis direction
See, a kind of form is double four-membered rings along c directions stacked arrangement, is then connected by hexatomic ring, similar to ITQ-21, and another
A kind of outer form is perpendicular to single four-membered ring in c directions in the form of crisscross, is connected by hexatomic ring, with ITQ-17 phases
Seemingly, both connection modes staggeredly occur, and form a kind of 12 × 12 × 12 three dimensional intersection macropore silicate moleculars of new structure
Sieve compound.
The uniqueness of the molecular screen material of different structure shows their different chemical compositions and unique x-ray powder
On diffraction pattern.For NUD-4, chemical composition form is p (M after it is roasted1/nXO2)·qYO2·SiO2(M represents proton or+n
The inorganic cation of valency；X represents triad；Y represents the quadrivalent element in addition to Si；P=0-0.2；Q=0-2.5).Its powder X-ray
Ray diffraction data is listed in table 1.Position, relative intensity and the width at powder x-ray diffraction peak and chemical composition, the crystal grain of material
Size and shape etc. is related, and the x-ray diffractogram of powder of different samples may slightly have difference.Attached drawing 1 lists NUD-4 molecular sieves
Powder x-ray diffraction schematic diagram after original powder sample and high-temperature calcination.Further according to X-ray powder diffraction data to molecular sieve
3 D pore canal carry out analysis fitting, as a result consistent with single-crystal X-ray diffraction analysis result, pore passage structure is as shown in Figure 2.It is above-mentioned
Molecular sieve can be calcined under 400-650 DEG C of air atmosphere 2 to 4 it is small when removed template method molecule, its structure remained stable, such as scheme
Shown in 1.Sample after high-temperature calcination carries out nitrogen adsorption test under 77K, the results showed that its specific surface area reaches 600m2/g。
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (Cu before and after synthesized NUD-4 sieve sample high-temperature calcination removed template methods
Target).
Fig. 2 is the pore passage structure figure along three directions that NUD-4 single crystal structure determinations obtain.
Embodiment
Illustrate the specific steps of the present invention by the following examples, but be not limited by the example.
Used term in the present invention, unless otherwise indicated, generally there are those of ordinary skill in the art usually to manage
The implication of solution.
The present invention is described in further detail with reference to specific embodiment and with reference to data.It is to be understood that these embodiments are only
It is in order to demonstrate the invention, rather than to limit the scope of the invention in any way.
In the examples below, the various processes and method not being described in detail are conventional methods as known in the art.
Embodiment 1：By taking template 6 in table 2 as an example, the building-up process of pattern of descriptive parts agent.By 25g neighbour's fluoro benzyl bromide and
75mL tetrahydrofurans are mixed in the round-bottomed flask of a 250mL, and under reflux state, 1- methyl miaows are added dropwise dropwise into mixed liquor
The tetrahydrofuran solution (11.98g/75mL) of azoles.System is reacted two days under stirring, and the rotated evaporation of reaction mixture removes
Go solvent to obtain crude product, product 33.586g, yield 95% can be obtained through ethyl alcohol recrystallization.Product is through liquid nuclear-magnetism (D2O it is) and electric
Electrospray mass spectrometry characterizes, and confirms as target compound.
Products therefrom is dissolved in 100mL deionized waters, column friendship is carried out by 717 strong-base anion-exchange resins
Change, exchange the aqueous solution for the template 6 that can obtain hydroxyl form.Weigh this appropriate solution, with the hydrochloric acid solution of 0.1mol/L into
Rower is determined, and phenolphthalein is as indicator.The result of calibration confirms that bromide reaches 92% to exchange efficiency hydroxy.
It can refer to the template 1-5 that the above method is prepared in table 2.
Embodiment 2：According to molar ratio 1SiO2：0.5GeO2：0.6ROH：0.6HF：10H2The ratio of O prepares Zeolite synthesis
Gel, general step is as follows：Weigh it is appropriate it is exchanged after 6 solution of template, add 2.5mmol (0.262g) thereto
Germanium dioxide powder, stir about half an hour is completely dissolved the germanium dioxide of addition, is adding 5mmol (1.042g) just later
Silester, stir about is completely dissolved ethyl orthosilicate in two hours under room temperature, then adds the hydrofluoric acid solution of design flow, stirs
Mix uniformly, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight.Last gained is anti-
Gel is answered to be transferred in stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, lower 150 DEG C of air-proof condition reacts 15 days, production
Thing through washing twice, wash twice by ethanol, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample with
When calcining 2 is small under 550 DEG C of air atmospheres in Muffle furnace, template is removed, elemental analysis shows that its molecular formula is 0.68GeO2·
SiO2.Select the bar-like single crystal of suitable size, synchronized at -180 DEG C radiation test, itself the result shows that, NUD-4 crystallization in
Space group I4/m, Such as Fig. 2 institutes
Showing, its 3 D pore canal is shown in Fig. 2, and the view in wherein c directions is shown, this molecular sieve has the circular straight hole road of 12 yuan of rings,
And in a directions and b directions due to the blocking of four-membered ring, formation is curved 12 membered ring channel.The molecular sieve by four-membered ring and
Hexatomic ring surrounds, but there are two kinds of combining forms.It can see clearly that from c-axis direction, a kind of form is double four-membered rings
Along c directions stacked arrangement, then connected by hexatomic ring, it is similar to ITQ-21, and another form is perpendicular to c directions
Single four-membered ring is connected in the form of crisscross by hexatomic ring, similar to ITQ-17, both connection modes staggeredly occur,
Form a kind of 12 × 12 × 12 three dimensional intersection macropore silicate molecular sieve compounds of new structure.The X-ray powder of the molecular sieve
Last diffraction patterns are as shown in table 1.Powder x-ray diffraction schematic diagram after original powder sample and high-temperature calcination is as shown in Figure 1.According to X
Ray powder diffraction data carries out analysis fitting to the 3 D pore canal of molecular sieve, as a result with single-crystal X-ray diffraction analysis result one
Cause, its pore passage structure is as also shown in Figure 2.Above-mentioned molecular sieve can be calcined under 400-650 DEG C of air atmosphere 2 to 4 it is small when remove
Template molecule, its structure remained stable, as shown in Figure 1.Sample after high-temperature calcination carries out nitrogen adsorption test under 77K,
The result shows that its specific surface area reaches 600m2/g。
Embodiment 3：According to molar ratio 1SiO2：0.5GeO2：0.6ROH：0.6NH4F：10H2The ratio of O prepares molecular sieve and closes
Into gel, general step is as follows：Weigh it is appropriate it is exchanged after 5 solution of template, add 2.5mmol thereto
The germanium dioxide of (0.262g), stir about half an hour are completely dissolved the germanium dioxide of addition, add 5mmol (1.042g) later
Ethyl orthosilicate, stir about is completely dissolved ethyl orthosilicate in two hours under room temperature, then adds the ammonium fluoride of design flow, stirs
Mix uniformly, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight.Last gained is anti-
Gel is answered to be transferred in stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, lower 150 DEG C of air-proof condition reacts 15 days, production
Thing through washing twice, wash twice by ethanol, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample with
When calcining 2 is small under 600 DEG C of air atmospheres in Muffle furnace, template is removed, elemental analysis shows that its molecular formula is 0.71GeO2·
SiO2.The X-ray powder diffraction result and table 1 of the molecular sieve are basically identical.X-ray powder after original powder sample and high-temperature calcination
Diffraction schematic diagram and embodiment 2 are basically identical, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 4：According to molar ratio 1SiO2：0.8GeO2：0.5ROH：0.5HF：15H2The ratio of O prepares Zeolite synthesis
Gel, general step is as follows：Weigh it is appropriate it is exchanged after 4 solution of template, add 4mmol's (0.426g) thereto
Germanium dioxide, stir about half an hour are completely dissolved the germanium dioxide of addition, add the positive silicic acid second of 5mmol (1.042g) later
Ester, stir about is completely dissolved ethyl orthosilicate in two hours under room temperature, then adds the hydrofluoric acid solution of design flow, and stirring is equal
It is even, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight.Last gained reaction is coagulated
Glue is transferred in stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, and lower 170 DEG C of air-proof condition reacts 12 days, product warp
Twice, ethanol is washed twice for washing, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample and Muffle
When calcining 2 is small under 550 DEG C of air atmospheres in stove, template is removed, elemental analysis shows that its molecular formula is 0.78GeO2·SiO2。
The X-ray powder diffraction result and table 1 of the molecular sieve are basically identical.Powder x-ray diffraction after original powder sample and high-temperature calcination
Schematic diagram and embodiment 2 are basically identical, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 5：According to molar ratio 1SiO2：0.5GeO2：0.1ROH：0.1HF：1H2The ratio of O prepares Zeolite synthesis
Gel, general step is as follows：Weigh it is appropriate it is exchanged after 3 solution of template, add 2.5mmol (0.262g) thereto
Germanium dioxide, stir about half an hour is completely dissolved the germanium dioxide of addition, adds the hard charcoal of 5mmol (0.301g) later
Black, stir about is uniformly mixed gel in two hours under room temperature, then adds the hydrofluoric acid solution of design flow, stirs evenly, will be mixed
Close gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight.Will last gained reaction gel transfer
Into stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, lower 130 DEG C of air-proof condition reacts 25 days, and product is through washing two
Secondary, ethanol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample and in Muffle furnace 550
When calcining 2 is small under DEG C air atmosphere, template is removed, elemental analysis shows that its molecular formula is 0.6GeO2·SiO2.The molecular sieve
X-ray powder diffraction result and table 1 it is basically identical.Powder x-ray diffraction schematic diagram after original powder sample and high-temperature calcination with
Embodiment 2 is basically identical, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 6：According to molar ratio 1SiO2：1GeO2：3ROH：3HF：50H2The ratio of O prepares the solidifying of Zeolite synthesis
Glue, general step are as follows：Weigh it is appropriate it is exchanged after 2 solution of template, add the dioxy of 5mmol (0.523g) thereto
Change germanium, stir about half an hour is completely dissolved the germanium dioxide of addition, adds the ethyl orthosilicate of 5mmol (1.042g) later,
Stir about is completely dissolved ethyl orthosilicate in two hours under room temperature, then adds the hydrofluoric acid solution of design flow, stirs evenly, will
Mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight.Last gained reaction gel is turned
Move in stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, lower 170 DEG C of air-proof condition reacts 12 days, and product is through washing
Twice, ethanol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take in appropriate amount of sample and Muffle furnace
When calcining 2 is small under 550 DEG C of air atmospheres, template is removed, elemental analysis shows that its molecular formula is 0.68GeO2·SiO2.This point
The X-ray powder diffraction result and table 1 of son sieve are basically identical.Powder x-ray diffraction signal after original powder sample and high-temperature calcination
Figure is basically identical with embodiment 2, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 7：According to molar ratio 1SiO2：1GeO2：2ROH：2HF：30H2The ratio of O prepares the solidifying of Zeolite synthesis
Glue, general step are as follows：Weigh it is appropriate it is exchanged after 1 solution of template, add the dioxy of 5mmol (0.523g) thereto
Change germanium, stir about half an hour is completely dissolved the germanium dioxide of addition, adds the ethyl orthosilicate of 5mmol (1.042g) later,
Stir about is completely dissolved ethyl orthosilicate in two hours under room temperature, then adds the hydrofluoric acid solution of design flow, stirs evenly, will
Mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight.Last gained reaction gel is turned
Move in stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, lower 120 DEG C of air-proof condition reacts 30 days, and product is through washing
Twice, ethanol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take in appropriate amount of sample and Muffle furnace
When calcining 2 is small under 500 DEG C of air atmospheres, template is removed, elemental analysis shows that its molecular formula is 0.68GeO2·SiO2.This point
The X-ray powder diffraction result and table 1 of son sieve are basically identical.Powder x-ray diffraction signal after original powder sample and high-temperature calcination
Figure is basically identical with embodiment 2, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 8：According to molar ratio 1SiO2：0.1Al2O3：1ROH：1.6HF：3H2The ratio of O prepares Zeolite synthesis
Gel, general step are as follows：Weigh it is appropriate it is exchanged after 6 solution of template, add the inclined aluminium of 1.0mmol thereto first
Sour sodium (0.082g) and a small amount of crystal seed (0.0010g, 2 product of embodiment), stir ten minutes or so, add 5mmol later
The ethyl orthosilicate of (1.042g), stir about is completely dissolved ethyl orthosilicate in two hours under room temperature, then adds design flow
Hydrofluoric acid solution, stirs evenly, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory
Weight.Last gained reaction gel is transferred in stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, under air-proof condition
150 DEG C are reacted 15 days, and product through washing twice, wash twice by ethanol, and drying is stand-by.X-ray powder diffraction Discriminating materials its be
NUD-4.When taking appropriate amount of sample and calcining 2 is small under 550 DEG C of air atmospheres in Muffle furnace, template is removed, elemental analysis shows it
Molecular formula is 0.02 (NaAlO2)·0.01GeO2·SiO2.The X-ray powder diffraction result and table 1 of the molecular sieve are basically identical.
Powder x-ray diffraction schematic diagram and embodiment 2 after original powder sample and high-temperature calcination is basically identical, three-dimensional open-framework figure and figure
2 is consistent.
Embodiment 9：According to molar ratio 1SiO2：0.5GeO2：0.05Al2O3：1ROH：1.3HF：5H2The ratio of O prepares molecule
The gel of synthesis is sieved, general step is as follows：Weigh it is appropriate it is exchanged after 3 solution of template, add thereto first
The aluminium isopropoxide (0.102g) of 0.5mmol, is stirred ten minutes or so, then adds the dioxy of 2.5mmol (0.262g) thereto
Change germanium, stir about half an hour is completely dissolved the germanium dioxide of addition, adds the ethyl orthosilicate of 5mmol (1.042g) later,
Stir about is completely dissolved ethyl orthosilicate in two hours under room temperature, then adds the hydrofluoric acid solution of design flow, stirs evenly, will
Mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theoretical value.Last gained reaction gel is turned
Move in stainless steel cauldrons of the 15mL with polytetrafluoroethyllining lining, lower 160 DEG C of air-proof condition reacts 20 days, and product is through washing
Twice, ethanol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Appropriate amount of sample is taken in Muffle furnace
When calcining 2 is small under 550 DEG C of air atmospheres, template is removed, elemental analysis shows that its molecular formula is 0.08 (HAlO2)·
0.4GeO2·SiO2.The X-ray powder diffraction result and table 1 of the molecular sieve are basically identical.After original powder sample and high-temperature calcination
Powder x-ray diffraction schematic diagram and embodiment 2 are basically identical, and three-dimensional open-framework figure is consistent with Fig. 2.
Claims (10)
- A kind of 1. macropore silicate molecular sieve, it is characterised in that this molecular sieve has X-ray powder diffraction feature as shown in table 1,Table 1
- 2. macropore silicate molecular sieve according to claim 1, it is characterised in that the molecular sieve composition form, roasting It is p (M after burning1/nXO2)·qYO2·SiO2, wherein, M represents the inorganic cation of proton or+n valencys；X represents triad；Y generations Quadrivalent element of the table in addition to Si；P=0-0.2；Q=0-2.5.
- 3. macropore silicate molecular sieve according to claim 2, it is characterised in that the M represents proton or sodium ion；X generations Table aluminium or boron element；Y represents Germanium.
- 4. macropore silicate molecular sieve according to claim 2, it is characterised in that the p=0-0.08.
- 5. macropore silicate molecular sieve according to claim 2, it is characterised in that the q=0-1.8.
- 6. according to the preparation method of claim 1-5 any one of them macropore silicate molecular sieves, it is characterised in that including such as Lower step：(1) in proportion by silicon source material, boron group element compound, the carbon group element compound in addition to silicon, organic formwork agent, fluorine Source material and water are uniformly mixed under agitation, obtain reaction gel, and the chemical composition of reaction gel is：rROH:aHF:xX2O3: yYO2:SiO2:wH2O, wherein R represent the positive charge group of organic formwork agent；X represents one or more triads；Y represents one A or multiple quadrivalent elements in addition to silicon；The interval of corresponding r, a, x, y and w is respectively：R=0.1-3, a=0.2- 3, x=0-0.1, y=0-1, w=1-50；(2) by reaction gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove unnecessary solvent to theory weight after, by reaction gel It is transferred in stainless steel cauldron, is reacted 12-20 days for 120-170 DEG C under air-proof condition；(3) by after the product washing after crystallization, drying, gone after roasting 2-5 hour under 400-650 DEG C of air atmosphere The macropore silicate molecular sieve product of template agent removing.
- 7. the preparation method of macropore silicate molecular sieve according to claim 6, it is characterised in that reaction gel rROH: aHF:xX2O3:yYO2:SiO2:wH2O, X are Al or B；Y is germanium.
- 8. the preparation method of macropore silicate molecular sieve according to claim 6, it is characterised in that reaction gel rROH: aHF:xX2O3:yYO2:SiO2:wH2O, the interval of corresponding r, a, x, y and w are respectively：R=0.5-1；A=0.5-0.8；x =0-0.05；Y=0.4-0.6；W=10-30.
- 9. the preparation method of macropore silicate molecular sieve according to claim 6, it is characterised in that the silicon source material is White carbon, waterglass, Ludox, ethyl orthosilicate or butyl silicate；The boron group element compound is sodium metaaluminate, isopropyl Aluminium alcoholates, 16 water aluminum sulfate, aluminium hydroxide or boric acid；The Fluorine source material is hydrofluoric acid or ammonium fluoride, the organic formwork agent Positive charge group Molecule formula be Ar- (CH2)-(im), wherein Ar represents the phenyl of any position substitution, and im represents 1- methylimidazoles Or 1,2- methylimidazole, the carbon group element compound in addition to silicon are germanium dioxide.
- 10. according to claim 1-5 any one of them macropore silicate molecular sieves in absorption, separation, catalysis, microelectronics or doctor Treat the application in diagnostic field.
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