CN104340987A - Silicon aluminum phosphate molecular sieve with -CLO structure, and preparation method thereof - Google Patents
Silicon aluminum phosphate molecular sieve with -CLO structure, and preparation method thereof Download PDFInfo
- Publication number
- CN104340987A CN104340987A CN201310334711.8A CN201310334711A CN104340987A CN 104340987 A CN104340987 A CN 104340987A CN 201310334711 A CN201310334711 A CN 201310334711A CN 104340987 A CN104340987 A CN 104340987A
- Authority
- CN
- China
- Prior art keywords
- reaction mixture
- source
- ion
- clo
- ionic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 21
- 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 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 title abstract 4
- 238000002425 crystallisation Methods 0.000 claims abstract description 38
- 230000008025 crystallization Effects 0.000 claims abstract description 38
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 239000011541 reaction mixture Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 238000002441 X-ray diffraction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- -1 phosphine ion Chemical class 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 241000736305 Marsilea quadrifolia Species 0.000 claims description 3
- 229910017090 AlO 2 Inorganic materials 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 150000008431 aliphatic amides Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 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 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000017 hydrogel Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 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
- 238000010792 warming Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 22
- 239000000203 mixture Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 11
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000003252 repetitive effect Effects 0.000 description 10
- 238000005201 scrubbing Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 10
- 238000010189 synthetic method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- RXGWEOPUMUXXTN-UHFFFAOYSA-N [Ni].P(O)(O)O Chemical compound [Ni].P(O)(O)O RXGWEOPUMUXXTN-UHFFFAOYSA-N 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000003407 synthetizing effect Effects 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a silicon aluminum phosphate molecular sieve with -CLO (a code designated by the International Zeolite Association ) structure, and a preparation method thereof. The preparation method comprises the following steps: a phosphorous source, an aluminum source, a silicon source, a fluorine source, and organic amine are added into ionic liquid, and the mixture is well mixed, such that an initial reaction mixture is obtained; the initial reaction mixture is crystallized for 0.5-120 h under a temperature of 100-300 DEG C; a crystallization product is filtered, washed and dried, such that the raw powder of the silicon aluminum phosphate molecular sieve with the -CLO structure is obtained. According to the invention, an ion thermal synthesis method is adopted. The reaction can be carried out under normal pressure or relatively low autogenous pressure. The ionic liquid can be recycled after the reaction. Synthesis cost is low, and synthesis process is environment-friendly. The silicon aluminum phosphate molecular sieve prepared by the method has a spacious framework structure and good thermal stability, and has good application prospect in the fields such as catalysis, gas absorption and separation, and the like.
Description
Technical field
The present invention relates to and a kind of there is silicoaluminophosphamolecular molecular sieves of-CLO structure and preparation method thereof.
Background technology
Molecular screen material due to the pore passage structure of its rule and adjustable duct composition, and is widely used in the fields such as catalysis, ion-exchange, separation, absorption.Aperture size is the key character of molecular screen material, and the aperture size of most molecular sieve is less than 1nm, this strongly limits the ability of its process organic macromolecule.Thus, oversized hole (aperture number of rings is greater than 12) molecular screen material is developed significant.
2004, the Morris of University of St Andrews of Britain, the people such as R.E. developed a kind of new Zeolite synthesis method, i.e. ion thermal synthesis method (Nature, 2004,430,1012-1016).Compare with solvent process for thermosynthesizing with traditional hydro-thermal, ion process for thermosynthesizing has many advantages, as: ionic liquid does not have volatility, and ion thermal synthesis can be carried out at ambient pressure, eliminates the potential safety hazard that the spontaneous high pressure of solvent in reaction process brings; In building-up process, ionic liquid not only can as solvent, also can as template; Ionic liquid recoverable after reaction, saves production cost, and reduces environmental pollution; Ion process for thermosynthesizing has very high potential in synthesis new texture and new ingredient sieve.At present, the bibliographical information of the existing many sections of hot method synthetizing ultramacropore molecular sieves of ion.The people such as Tian Zhijian have synthesized the oversized hole aluminium phosphate molecular sieve DNL-1(CN102139885A with-CLO structure by adding 1,6-hexanediamine in ionic liquid 1-ethyl-3-methy limidazolium; Angew.Chem.Int.Ed., 2010,49,5367-5370).The people such as Yu Jihong have synthesized a kind of the phosphorous acid nickel JIS-3(Angew.Chem.Int.Ed. with 18 membered ring channels, 2010,49,2328-2331 in 1-amyl group-3-Methylimidazole hexafluorophosphate).The people such as Yang Miao use the ionic liquid of boracic to synthesize the boron cobaltous phosphate (Dalton Trans., 2010,39,10571-10573) with 16 membered ring channels as solvent and boron source.
-CLO structure is a kind of super large microvoid structure with 20 rings.It has the 3 D pore canal system of two non-crossing, one individual system is via α cage and rpa cage, there is octatomic ring aperture, and another is via cubical, have the four-leaf clover shape aperture surrounded by 20 T atoms and 24 Sauerstoffatoms, the cross section in these ducts is the large cube supercages with pocket.1991, the people such as Estermann, M. were template under hydrothermal conditions with rubane, had synthesized the phosphoric acid gallium molecular sieve cloverite(Nature with-CLO structure first, 1991,352,320-323).After this, people have synthesized the-CLO type molecular sieve of several difference composition in succession, comprising: the cloverite(Solid State Ionics of Heteroatom doping, 2002,151,269-274), aluminum phosphate DNL-1(CN102139885A; Angew.Chem.Int.Ed., 2010,49,5367-5370) and SiGe hydrochlorate PKU-12(Dalton Trans., 2013,42,1360-1363).At present, the silicoaluminophosphamolecular molecular sieves with-CLO structure yet there are no open report.
Summary of the invention
The object of the present invention is to provide and a kind of there is silicoaluminophosphamolecular molecular sieves of-CLO structure and preparation method thereof.
For achieving the above object, silicoaluminophosphamolecular molecular sieves provided by the present invention, by PO
2 +, AlO
2 -and SiO
2tetrahedron forms, and its X-ray diffraction spectrogram at least should have following characteristics diffraction peak (2 θ values represent the position of diffraction peak):
2θ/°:3.39±0.2,4.82±0.2,5.91±0.2,6.84±0.2,7.63±0.2,8.39±0.2,9.70±0.2,10.30±0.2,11.39±0.2,11.91±0.2,12.40±0.2,12.87±0.2,13.76±0.2,14.20±0.2,14.62±0.2,20.75±0.2；
Determine that its structure is the-CLO structure that International Zeolite Association confirms by comparing with XRD powder diffraction data storehouse card.This molecular sieve has the 3 D pore canal system of two non-crossing, one individual system is via α cage and rpa cage, there is octatomic ring aperture, and another is via cubical, have the four-leaf clover shape aperture surrounded by 20 T atoms (Al, Si and P atom) and 24 Sauerstoffatoms, the cross section in these ducts is the large cube supercages with pocket.
The method of the above-mentioned silicoaluminophosphamolecular molecular sieves of preparation provided by the invention, its step is as follows:
(1) phosphorus source, aluminium source, silicon source, fluorine source and organic amine are joined in ionic liquid, mix at 50 ~ 150 DEG C and obtain initial reaction mixture;
(2) by the reaction mixture of step (1) gained crystallization 0.5 ~ 120 hour at 100 ~ 300 DEG C;
(3) after step (2) terminates, product is cooled to room temperature, filters, wash and drying, namely be there is-CLO structure silicoaluminophosphamolecular molecular sieves.
SiO in reaction mixture described in above-mentioned synthetic method step (1)
2: Al
2o
3: P
2o
5: F
-: organic amine: the mol ratio of ionic liquid is 0.01 ~ 10:1:0.1 ~ 20:0.1 ~ 10:0.1 ~ 10:2 ~ 1000, is preferably 0.01 ~ 2:1:0.5 ~ 12:0.5 ~ 6:0.4 ~ 4:10 ~ 200.
Above-mentioned synthetic method intermediate ion liquid is for comprising following positively charged ion: alkyl quaternary ammonium ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that alkyl replaces
+, the pyridinium ion [Rpy] that alkyl replaces
+in one or more mixing ionic liquids, R is the alkyl of C1-C16, and wherein the negatively charged ion of ionic liquid can be: Cl
-, Br
-, I
-, BF
4 -, PF
6 -, PO
4 3-, NO
3 -, SO
4 2-, CF
3sO
3 -, N (CF
3sO
2)
2 -, C (CF
3sO
2)
3 -in one or more.
In above-mentioned synthetic method, organic amine is one or more in aliphatic amide, aromatic amine, hydramine, quaternary ammonium compound.
In above-mentioned synthetic method, silicon source is one or more in silicon sol, Silica hydrogel, water glass, white carbon black, tetraethoxy; Phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate; Aluminium source is one or more in aluminum isopropylate, pseudo-boehmite, Tai-Ace S 150, aluminium hydroxide; Fluorine source is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride.
The preferred raw material mixing temperature of above-mentioned synthetic method step (1) is 70 ~ 110 DEG C, the preferred crystallization temperature of step (2) is 150 ~ 250 DEG C, preferred crystallization time is 1h ~ 72h, the type of heating of crystallization process can adopt traditional heating mode, as: baking oven for heating, oil bath heating, also can adopt microwave heating.
A certain proportion of water can be contained in reaction mixture described in above-mentioned synthetic method step (1), water can be brought into by the raw material such as phosphoric acid solution or hydrofluoric acid solution, also additionally can add when adopting anhydrous raw material, water content is the 0-10wt% of reaction mixture gross weight.
The silicoaluminophosphamolecular molecular sieves of-the CLO of having structure provided by the invention has spacious skeleton structure and good thermostability, is with a wide range of applications in the field such as catalysis, atmosphere storage.Preparation method's economy that the present invention adopts is strong, easy-to-operate, environmental friendliness.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of sample in the embodiment of the present invention 1.
Fig. 2 is the XRD spectra of sample in the embodiment of the present invention 2.
Fig. 3 is the XRD spectra of sample in the embodiment of the present invention 3.
Fig. 4 is the XRD spectra of sample in the embodiment of the present invention 4.
Fig. 5 is the XRD spectra of sample in the embodiment of the present invention 5.
Fig. 6 is the XRD spectra of sample in the embodiment of the present invention 6.
Fig. 7 is the XRD spectra of sample in the embodiment of the present invention 7.
Fig. 8 is the XRD spectra of sample in the embodiment of the present invention 8.
Fig. 9 is the XRD spectra of sample in the embodiment of the present invention 9.
Figure 10 is the XRD spectra of sample in the embodiment of the present invention 10;
Figure 11 is the SEM electromicroscopic photograph of sample in the embodiment of the present invention 1.
Embodiment
Below by embodiment, the present invention will be further described, but embodiments of the present invention are not limited thereto, and can not be interpreted as limiting the scope of the invention.
Embodiment 1
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.15 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 2
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.30 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 3
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.45 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 4
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.60 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 5
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.74 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 6
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.30 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 210 DEG C of baking oven crystallization 3h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 7
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.30 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 1.0 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 8
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.30 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.84 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 9
The phosphoric acid being 85wt% by 1.61 grams of concentration joins in 100 ml beakers that 53.5 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.30 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.
XRD spectra shows that this white powder has-CLO topological framework.
Embodiment 10
The phosphoric acid being 85wt% by 0.89 gram of concentration joins in 100 ml beakers that 80.3 grams of 1-ethyl-3-methy limidazolium ionic liquids are housed, 1.43 grams of aluminum isopropylates and 0.30 gram of tetraethoxy is added under 90 DEG C and agitation condition, stir after 30 minutes, adding 0.56 gram of concentration is the hydrofluoric acid of 40wt%, continue stirring after 30 minutes, add 0.50 gram of 1,6-hexanediamine, be stirred to and evenly obtain initial reaction mixture.Said mixture being transferred to 100ml tetrafluoroethylene is in the stainless steel cauldron of lining, puts into 180 DEG C of baking oven crystallization 24h after sealing.
After crystallization terminates, reactor is taken out cool to room temperature, leach crystallization product.By product deionized water and ethanol repetitive scrubbing, dry at 90 DEG C, namely obtain white powder product.
XRD spectra shows that this white powder has-CLO topological framework.
Claims (11)
1. a silicoaluminophosphamolecular molecular sieves, by PO
2 +, AlO
2 -and SiO
2tetrahedron forms, and it is characterized in that: its X-ray diffraction spectrogram should at least have following characteristics diffraction peak:
2 θ values represent the position of diffraction peak, 2 θ/°: 3.39 ± 0.2,4.82 ± 0.2,5.91 ± 0.2,6.84 ± 0.2,7.63 ± 0.2,8.39 ± 0.2,9.70 ± 0.2,10.30 ± 0.2,11.39 ± 0.2,11.91 ± 0.2,12.40 ± 0.2,12.87 ± 0.2,13.76 ± 0.2,14.20 ± 0.2,14.62 ± 0.2,20.75 ± 0.2;
Its structure is the-CLO structure that International Zeolite Association confirms, there is the 3 D pore canal system of two non-crossing, one individual system is via α cage and rpa cage, there is octatomic ring aperture, and another is via cubical, have the four-leaf clover shape aperture surrounded by 20 T atoms (Al, Si and P) and 24 Sauerstoffatoms, the cross section in these ducts is the large cube supercages with pocket.
2. a preparation method for silicoaluminophosphamolecular molecular sieves described in claim 1, its step is as follows:
(1) phosphorus source, aluminium source, silicon source, fluorine source and organic amine are joined in ionic liquid to mix obtain initial reaction mixture;
(2) by the reaction mixture of step (1) gained crystallization 0.5 ~ 120 hour at 100 ~ 300 DEG C;
(3) after step (2) terminates, product is cooled to room temperature, filters, wash and drying, namely be there is the silicoaluminophosphamolecular molecular sieves of-CLO structure.
3. method according to claim 2, is characterized in that: ionic liquid is for comprising following positively charged ion: alkyl quaternary ammonium ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion [Rim] that alkyl replaces
+, the pyridinium ion [Rpy] that alkyl replaces
+in one or more mixing ionic liquids, R is the alkyl of C1-C16.
4. method according to claim 2, is characterized in that: SiO in the reaction mixture described in step (1)
2: Al
2o
3: P
2o
5: F
-: organic amine: the mol ratio of ionic liquid is 0.01 ~ 10:1:0.1 ~ 20:0.1 ~ 10:0.1 ~ 10:2 ~ 1000.
5. the method according to claim 2 or 4, is characterized in that: SiO in the reaction mixture described in step (1)
2: Al
2o
3: P
2o
5: F
-: organic amine: the mol ratio of ionic liquid is 0.01 ~ 2:1:0.5 ~ 12:0.5 ~ 6:0.4 ~ 4:10 ~ 200.
6. method according to claim 2, is characterized in that: silicon source is one or more in silicon sol, Silica hydrogel, water glass, white carbon black, tetraethoxy; Phosphorus source is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate; Aluminium source is one or more in aluminum isopropylate, pseudo-boehmite, Tai-Ace S 150, aluminium hydroxide; Fluorine source is one or more in hydrofluoric acid, Neutral ammonium fluoride, Sodium Fluoride.
7. method according to claim 2, is characterized in that: organic amine is one or more in aliphatic amide, aromatic amine, hydramine, quaternary ammonium compound.
8. method according to claim 2, is characterized in that: crystallization condition is at 150 ~ 250 DEG C, and under normal pressure or autogenous pressure, crystallization time is 1h ~ 72h.
9. method according to claim 2, is characterized in that: step (1) intermediate ion liquid is warming up to 50 ~ 150 DEG C before raw material adds, and namely raw material mixing temperature is 50 ~ 150 DEG C.
10. the method according to claim 2 or 9, is characterized in that: the raw material mixing temperature in step (1) is 70 ~ 110 DEG C.
11. methods according to claim 2, is characterized in that: can contain a certain proportion of water in the reaction mixture described in step (1), water can be brought into by raw material, also can additionally add, and water content is the 0-10wt% of reaction mixture gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310334711.8A CN104340987A (en) | 2013-08-02 | 2013-08-02 | Silicon aluminum phosphate molecular sieve with -CLO structure, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310334711.8A CN104340987A (en) | 2013-08-02 | 2013-08-02 | Silicon aluminum phosphate molecular sieve with -CLO structure, and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104340987A true CN104340987A (en) | 2015-02-11 |
Family
ID=52497528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310334711.8A Pending CN104340987A (en) | 2013-08-02 | 2013-08-02 | Silicon aluminum phosphate molecular sieve with -CLO structure, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104340987A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107601521A (en) * | 2017-11-14 | 2018-01-19 | 兰州理工大学 | A kind of method of synthesis CLO type aluminium phosphate molecular sieves |
| CN110184120A (en) * | 2019-05-20 | 2019-08-30 | 李科成 | A kind of preparation method of edible oil depickling processing particle |
| CN111333083A (en) * | 2020-04-27 | 2020-06-26 | 北京化工大学 | Organic hybrid-CLO structure aluminum phosphate molecular sieve and preparation method thereof |
| CN111498866A (en) * | 2020-04-27 | 2020-08-07 | 北京化工大学 | Organic hybrid-C L O structure silicoaluminophosphate molecular sieve and preparation method thereof |
| CN112939005A (en) * | 2021-03-30 | 2021-06-11 | 北京化工大学 | Synthesis method of-CLO structure ultra-large pore aluminum phosphate and heteroatom aluminum phosphate molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850606A (en) * | 2006-06-07 | 2006-10-25 | 中国科学院大连化学物理研究所 | Method for preparing AlPO4 or SAPO molecular sieve |
| CN102139885A (en) * | 2010-01-29 | 2011-08-03 | 中国科学院大连化学物理研究所 | -CLO structural aluminum phosphate molecular sieve and preparation method thereof |
| CN102139888A (en) * | 2010-01-29 | 2011-08-03 | 中国科学院大连化学物理研究所 | Synthesis method of silicoaluminophosphate molecular sieve with AFO structure |
-
2013
- 2013-08-02 CN CN201310334711.8A patent/CN104340987A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850606A (en) * | 2006-06-07 | 2006-10-25 | 中国科学院大连化学物理研究所 | Method for preparing AlPO4 or SAPO molecular sieve |
| CN102139885A (en) * | 2010-01-29 | 2011-08-03 | 中国科学院大连化学物理研究所 | -CLO structural aluminum phosphate molecular sieve and preparation method thereof |
| CN102139888A (en) * | 2010-01-29 | 2011-08-03 | 中国科学院大连化学物理研究所 | Synthesis method of silicoaluminophosphate molecular sieve with AFO structure |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107601521A (en) * | 2017-11-14 | 2018-01-19 | 兰州理工大学 | A kind of method of synthesis CLO type aluminium phosphate molecular sieves |
| CN110184120A (en) * | 2019-05-20 | 2019-08-30 | 李科成 | A kind of preparation method of edible oil depickling processing particle |
| CN111333083A (en) * | 2020-04-27 | 2020-06-26 | 北京化工大学 | Organic hybrid-CLO structure aluminum phosphate molecular sieve and preparation method thereof |
| CN111498866A (en) * | 2020-04-27 | 2020-08-07 | 北京化工大学 | Organic hybrid-C L O structure silicoaluminophosphate molecular sieve and preparation method thereof |
| CN112939005A (en) * | 2021-03-30 | 2021-06-11 | 北京化工大学 | Synthesis method of-CLO structure ultra-large pore aluminum phosphate and heteroatom aluminum phosphate molecular sieve |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102139885B (en) | -CLO structural aluminum phosphate molecular sieve and preparation method thereof | |
| CN104340987A (en) | Silicon aluminum phosphate molecular sieve with -CLO structure, and preparation method thereof | |
| CN104340992A (en) | Metallic aluminum phosphate (MeAPO) molecular sieve with -CLO structure, and preparation method thereof | |
| CN107892309B (en) | A kind of preparation method of super big hole silicate molecular sieve | |
| CN102491304B (en) | Method for preparing lithium iron phosphate in ionic eutectic mixture | |
| CN102807229B (en) | Method for synthesizing SAPO-31 (silicoaluminophosphate-31) molecular sieves at ordinary pressure | |
| CN104370296A (en) | Super-macroporous silicate molecular sieve NUD-1 and preparation method thereof | |
| CN102786063A (en) | Method for synthesizing silicoaluminophosphate molecular sieve SAPO-11 at normal pressure | |
| CN102476806A (en) | Method of synthesizing super large micropore aluminium phosphate molecular sieve in eutectic mixture | |
| CN104445244B (en) | Aluminophosphate molecular sieve AlPO4-34 and fluoride-free preparation method thereof | |
| CN105800634A (en) | Nanometer total-silicon beta molecular sieve and preparation method thereof | |
| CN102936018A (en) | Preparation method for high stability mesoporous molecular sieve under ionothermal system | |
| CN105753013B (en) | The preparation of one kind-CLO structure nano aluminium phosphate molecular sieves and molecular sieve | |
| CN102092737B (en) | Synthetic method of AlPO4-34 aluminum phosphate molecular sieve | |
| CN102910611A (en) | Method for preparing ferrous phosphate-based lithium salt | |
| CN106731838B (en) | A kind of lithium isotope efficiently separates method | |
| CN103121697B (en) | Pure silicon ANA-type zeolite molecular sieve and preparation method thereof | |
| CN102139889B (en) | Synthesis method of silicoaluminophosphate molecular sieve with AFO structure | |
| CN103708495A (en) | Preparation method of nanorod particle ordered-assembly ZSM-5 zeolite molecular sieve | |
| CN103570767A (en) | Method for synthesizing micropore ZNI-type zeolite imidazole skeleton species by ionothermal process | |
| CN105776241A (en) | Synthesis method of aluminum phosphate molecular sieve with-CLO structure | |
| CN106809860A (en) | A kind of ion process for thermosynthesizing of ATS types Metal-aluminophosphate Molecular Siever | |
| CN107254067B (en) | It is a kind of based on lamella silicate modified APP and preparation method thereof and fire-retardant high polymer | |
| CN108584977A (en) | The method of one step green syt cobalt doped SBA-15 meso-porous molecular sieve materials | |
| CN102476797B (en) | Preparation method for expansible graphite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150211 |