CN101830479B - A kind of fluorine-containing T-type zeolite molecular sieve and preparation method thereof - Google Patents
A kind of fluorine-containing T-type zeolite molecular sieve and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 92
- 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 92
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 81
- 239000010457 zeolite Substances 0.000 title claims abstract description 81
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000013078 crystal Substances 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 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 3
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229910052593 corundum Inorganic materials 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 150000002221 fluorine Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000013341 scale-up Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 238000004319 19F solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052675 erionite Inorganic materials 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 241001185310 Symbiotes <prokaryote> Species 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明提供了一种制备含氟T型沸石分子筛的方法。其特征是在合成溶胶中直接加入氟盐并以纳米T型沸石分子筛晶种诱导，制备出含氟T型沸石分子筛。所形成的SiO2-K2O-Al2O3-MF-H2O体系，溶胶配比以各物质摩尔比表示为：SiO2/Al2O3＝10～50，H2O/SiO2＝18～50，K2O/SiO2＝0.2～0.5，MF/SiO2＝0.05～1.5，溶胶在50～60℃下搅拌老化20～30小时后，加入0.1～2wt％纳米分子筛晶种，在90～130℃合成温度下水热合成0.5～4天，经离心、清洗和干燥后可得到含氟T型沸石分子筛，晶体分子筛的化学组成为： M+ (x+y)[Si18-yAlyO36Fx](x+y)-，其中x＝0.001～1，y＝2～4.5，M＝Na+或K+或NH4 +。本发明避免使用昂贵的有机模板剂和繁杂的后处理过程，一步法合成含氟T型沸石分子筛，合成过程简单，成本较低，适宜工业放大生产，能有效应用于吸附分离和催化等领域。
The present invention provides a method for preparing fluorine-containing T-type zeolite molecular sieve, which is characterized in that fluorine salt is directly added into synthetic sol and induced by nano-T-type zeolite molecular sieve seed crystals to prepare fluorine-containing T-type zeolite molecular sieve. The formed SiO2- K2O - Al2O3 - MF - H2O system has a sol ratio expressed by the molar ratio of each substance as follows: SiO2 / Al2O3 =10-50, H2O/SiO2=18-50 , K2O /SiO2=0.2-0.5, MF/ SiO2 =0.05-1.5. After the sol is stirred and aged at 50-60°C for 20-30 hours, 0.1-2wt% of nano molecular sieve seeds are added, and hydrothermal synthesis is carried out at a synthesis temperature of 90-130°C for 0.5-4 days. After centrifugation, washing and drying, a fluorine-containing T-type zeolite molecular sieve can be obtained. The chemical composition of the crystal molecular sieve is: M + (x+y) [ Si18 - yAlyO36Fx ] (x+y)- , wherein x=0.001-1, y=2-4.5, M=Na + or K + or NH 4 + . The present invention avoids the use of expensive organic templates and complicated post-treatment processes, synthesizes fluorine-containing T-type zeolite molecular sieves in one step, has a simple synthesis process, low cost, is suitable for industrial scale-up production, and can be effectively applied to fields such as adsorption separation and catalysis.
Description
Technical field
The present invention relates to the preparation and the application of T type zeolite molecular sieve, particularly the technology of preparing of fluorine-contained T-shaped zeolite molecular sieve belongs to molecular screen material preparation and Application Areas.
Background technology
Molecular sieve is one type of porous aluminum silicate crystal with single-size duct, and constituting the most basic structural unit of molecular sieve is TO
4Tetrahedron (T=Al, Si).Wherein each Sauerstoffatom all is that adjacent two tetrahedral structures institute is shared, but can not shared same Sauerstoffatom between two aluminium atoms.These tetrahedrons mutually combine, and form netted structure, so that form the pore passage structure of one dimension or multidimensional molecular dimension.Molecular sieve is widely used in shape selective catalysis, IX and fractionation by adsorption.The silica alumina ratio of T type zeolite molecular sieve is 3～4, and wetting ability is inferior to NaA type molecular sieve.T type zeolite molecular sieve is the unordered symbiote by offretite that all belongs to hexagonal system (OFF) and erionite (ERI).Both structures are very similar, and all by kankrinite cage and six prismatic compositions, their spatial disposition are different for skeleton.Erionite has the duct perpendicular to 8 yuan of rings of one dimension of c axle, and it is of a size of 0.36nm * 0.51nm.Offretite has the regular pore canal of two dimension, is parallel to the axial main aperture of c road and is of a size of 0.67nm * 0.68nm; Another secondary port is perpendicular to the c direction of principal axis, and the duct is of a size of 0.36nm * 0.49nm.T type zeolite molecular sieve absorption aperture has only about 0.36nm, is pore zeolite, and molecule is had very strong shape selectivity, and it is having more application aspect the catalysis of low carbon compound and the reformation.In addition, T type zeolite molecular sieve also has good acid resistance, and the selective adsorption that can be used for acid resistance gas separates.
Aspect type T molecular sieve prepares, people such as Wang Xingqiao (SCI, 1984,5 (1): 83) at (Na
2O+K
2O)/SiO
2Be 0.3～0.33 to have synthesized T type zeolite molecular sieve, their research shows, could obviously promote reaction when seed load increases to 3wt%.Other document has also been studied and has been added the influence of crystal seed to crystallization, and their addition is at 1～5wt%.Zhourong flies to wait people (Chinese Journal of Inorganic Chemistry, 2006,9 (22): 1719～1722) adopt colloidal sol proportioning n
SiO2: n
Al2O3: n
Na2O: n
K2O: n
H2OUnder microwave heating condition add the T type zeolite molecular sieve of template or crystal seed synthetic high-crystallinity at=1: 0.055: 0.23: 0.08: 11.7, and the result shows, the quickening crystallization rate that microwave heating can be at double reduces particle size and distribution range.(modern chemical industry, 2007,27,269～273) such as Zhang Zhi states are raw material with industrial aluminum sulphate and water glass, at SiO
2/ Al
2O
3Be to synthesize the pure T type zeolite of the high crystalline phase of percent crystallinity in 16～32 scopes.
Fluorine-containing zeolite molecular sieve has unique catalytic activity and selectivity.Yet most fluorine-containing zeolite molecular sieves obtain through last handling process at present.Patent CN1348922A has announced the preparation method of fluorine-containing mordenite, this invention be the mol ratio with silica be about 10: 1 be that about aqueous hydrogen fluoride solution of 0.1 to about 10wt% contacts so that generate fluorine-containing mordenite to about 100: 1 mordenite and hydrofluoric concentration.Patent US4444902; US4427790 and EP0295020A1 disclose under certain reaction conditions; The mixed type zeolite [molecular sieve (zeolite molecular sieve that contains types such as X, Y and ZSM-5) of preparation is soaked in hydrofluoric acid or villiaumite solution for some time; Zeolite molecular sieve after the activation treatment has higher Bronsted acidity, ion-exchange equivalent and catalytic activity, and the fluorine-containing ZSM-5 zeolite molecular sieve of particularly handling through fluorine shows higher catalytic activity in petroleum catalytic cracking.Patent CN1037097A and US604178 will contain metals ion villiaumite solution zeolite molecular sieve will be carried out aftertreatment; Find framework aluminum by the F-complexing and from zeolite, remove, thereby metallic cation inserts and replaces aluminium to obtain the heteroatomic zeolite molecular sieve of containing metal in the skeleton.Li Jixia etc. (the chemistry of fuel journal, 36 (2008): 508) discover: the ZSM-5 catalyst surface after the hydrogen fluoride trealment is etched, and crystal grain is broken, but the MFI feature structure of catalyst sample is not destroyed, and percent crystallinity does not have considerable change; The pore volume of zeolite molecular sieve and mean pore size all increase than before handling; Variation has taken place in the surface acidity of catalyzer, and strong acid reduces relatively, and weak acid increases relatively.
Many researchs show that zeolite molecular sieve makes zeolite molecular sieve phenomenons such as dealuminzation, desiliconization occur after handling through fluorine, thereby causes the zeolite molecular sieve skeleton stability to reduce.On the other hand, the fluorine sources such as hydrofluoric acid that last handling process uses have strong corrodibility and toxicity, and process is difficult to control and the harm operator is healthy.Directly in resulting solution, add fluorine source synthesis zeolite report is also arranged.Patent CN101353171A has reported the method for synthetic fluorine-containing nanometer beta zeolite molecular sieve; This method is earlier with mixing with silica gel after the acidifying of aluminium source; Make the abundant dispersing and mixing of silica gel and aluminium source with UW; Drying is ground, and mixes the back crystallization then with tetraethylammonium cation template, fluorochemical and water and is prepared from.Research shows that this zeolite molecular sieve has higher thermostability and specific surface area.US5338525 has described at SiO
2-Ga
2O
3-Al
2O
3-NaF-H
2Synthetic Ga, Al type ZSM-5 zeolite molecular sieve in the O system, however the product results of elemental analyses shows does not find the F element in the product.
From existing document, directly add fluorine source report of synthesis zeolite in the colloidal sol and also be difficult to fluorine atom is introduced directly in the crystalline framework of zeolite molecular sieve.The report that does not also have at present fluorine-contained T-shaped zeolite molecular sieve.The invention provides a kind of SiO that in synthetic colloidal sol, adds villiaumite
2-K
2O-Al
2O
3-MF-H
2The O system is through the synthetic method that directly prepares fluorine-contained T-shaped zeolite molecular sieve of hydro-thermal, F/SiO in the crystalline framework
2Mol ratio is 0.0001～0.1.
Summary of the invention
The invention provides a kind of preparation method of fluorine-contained T-shaped zeolite molecular sieve, this method is simple to operation, repeatability is high, the prices of raw and semifnished materials are cheap.In colloidal sol, directly add villiaumite and with the nano T-type zeolite molecular sieve for inducing crystal seed, avoid adopting expensive organic template, hydro-thermal is synthesized the fluorine-contained T-shaped zeolite molecular sieve of preparing high-crystallinity fast under 90～130 ℃ temperature.Crystal chemistry consists of: M
+ (x+y)[Si
18-yAl
yO
36F
x]
(x+y)-, x=0.001～1 wherein, y=2～4.5, M=Na
+Or K
+Or NH
4 +
(application number is the patent of the preparation of nano T-type zeolite molecular sieve such as our application: 200710009615.0) embodiment 1 and 2 synthesis step synthesis of nano T type zeolite molecular sieve.Concrete steps are: the aluminium source is dissolved in the proper quantity of lye, waits to dissolve complete back with needed water dilution, add required template.Under condition of stirring, add the silicon source, and keep and stirred 12 hours, form uniform and stable colloidal sol, the proportioning of colloidal sol is SiO
2/ Al
2O
3=10, (Na
2O+K
2O+ (TMA)
2O)/SiO
2=0.37, H
2O/SiO
2=16, Na/K=2, (TMA)
2O/ (Na
2O+K
2O)=1.The colloidal sol for preparing is poured in the quartz glass tube that has condensing works, and inserted that to carry out hydro-thermal in the microwave heating installation synthetic, control reaction temperature is 80 ℃, through 24 hours after, finishes to react., the cleaning centrifugal of reaction feed liquid through supercentrifuge, and following dry 10 hours at 110 ℃.Sample in 550 ℃ retort furnace roasting this crystalline specific surface area was up to 500～580m with removed template method in 8 hours
2G
-1, crystallographic dimension is 80～200nm.
Fluorine-contained T-shaped zeolite molecular sieve of the present invention the preparation method as follows:
(1) selects for use white lake or sodium metaaluminate or aluminium foil or aluminium powder as the aluminium source, the aluminium source is added in the alkali lye of Pottasium Hydroxide to heating for dissolving;
(2) again silica flour or silicon sol silicon source and fluorine source are slowly dropped in the alkali lye formed SiO under stirring state
2-K
2O-Al
2O
3-MF-H
2The O system, the colloidal sol proportioning is expressed as with each material mol ratio:
SiO
2/Al
2O
3＝10～50，
H
2O/SiO
2＝18～50，
K
2O/SiO
2＝0.2～0.5，
MF/SiO
2＝0.05～1.5，
Colloidal sol adds 0.1～2wt% nano molecular sieve crystal seed after 50～60 ℃ stirring was worn out 20～30 hours down;
(3) the colloidal sol reaction kettle of packing into, hydro-thermal is synthetic 0.5～5 day under 90～130 ℃ of synthesis temperatures, after centrifugal, cleaning and drying, obtains fluorine-contained T-shaped zeolite molecular sieve.
The silicon source that the preparation fluorine-contained T-shaped zeolite molecular sieve adopts among the present invention is silicon sol or amorphous silica powder or water glass, and silicon sol is preferred.Adopting the potassium source is Pottasium Hydroxide or Repone K or both mixtures, and Pottasium Hydroxide is preferred.The aluminium source of adopting is that white lake is sodium metaaluminate or aluminium foil or aluminium powder etc., and white lake is preferred.The employing villiaumite is Sodium Fluoride (NaF) or Neutral ammonium fluoride (NH
4F) and Potassium monofluoride (KF), Neutral ammonium fluoride is preferred.
The preferred colloidal sol constitutive molar ratio that the present invention adopts is:
SiO
2/Al
2O
3＝15～30，
H
2O/SiO
2＝18～50，
K
2O/SiO
2＝0.2～0.45，
MF/SiO
2＝0.1～1。
The hydro-thermal synthesis temperature is 80～160 ℃ when synthesizing fluorine-contained T-shaped zeolite molecular sieve among the present invention, and 90～130 ℃ is preferred; Generated time is 0.25～7 day, and optimum value is 0.5～4 day.
The present invention with nano T-type zeolite molecular sieve crystal seed for inducing, its addition 0.2～1wt%, the crystalline size size is 50～200 nanometers.
Synthetic fluorine-contained T-shaped zeolite molecular sieve crystal of the present invention passes through
19F solid state nmr technology for detection goes out F and SiF
x 4-xForm exist, promptly F gets in the crystalline framework fully, combines x XRD X sign, plasma emission spectrum and the analysis of F electrode characterization result, the chemical constitution of synthetic fluorine-contained T-shaped zeolite molecular sieve is: M
+ (x+y)[Si
18-yAl
yO
36F
x]
(x+y)-, x=0.001～1 wherein, y=2～4.5, M=Na
+Or K
+Or NH
4 +
Synthetic fluorine-contained T-shaped zeolite molecular sieve crystal of the present invention has than bigger size pattern of the composite crystals in the floride-free system under the same terms and the crystalline framework Si/Al ratio of Geng Gao.Synthetic fluorine-contained T-shaped zeolite molecular sieve crystallographic dimension is 2～5 μ m under the optimal conditions, and the Si/Al ratio is 4.14.And synthetic T type zeolite molecular sieve crystal size is 2～5 μ m under the floride-free condition, and the Si/Al ratio is 3.4.Higher silica alumina ratio helps the stability of type T molecular sieve under acidic conditions.
The method of the synthetic fluorine-contained T-shaped zeolite molecular sieve that provides among the present invention; Its preparation process is simple and easy to repetition; The adding villiaumite as inducing, reduces the loaded down with trivial details subsequent processes of the fluorine-containing molecular sieve of hydrogen fluoride aftertreatment other kind of preparation with crystal seed in synthetic colloidal sol, reduces waste discharge.Can be applicable to the aspect such as catalysis and reformation of low carbon compound, at organism/water and gas separation field good application prospects is arranged as crystal seed synthetic mould material with it.
Description of drawings
Fig. 1 is the x x ray diffration pattern x of synthetic fluorine-contained T-shaped zeolite molecular sieve.
Fig. 2 is the sem photograph of synthetic fluorine-contained T-shaped zeolite molecular sieve.
Fig. 3 is the not sem photograph of fluorine-contained T-shaped zeolite molecular sieve of synthetic.
Embodiment
In order to further describe the present invention, provided several practical implementation cases below, but patent right is not limited to these examples.
Embodiment 1: the preparation of fluorine-contained T-shaped zeolite molecular sieve
Select for use white lake as the aluminium source, silicon sol is the silicon source, and Neutral ammonium fluoride is the fluorine source; Under agitation, the aluminium source is added in the alkali lye of Pottasium Hydroxide to heating for dissolving; Silicon source and fluorine source are slowly added in the alkali lye, silicon sol adds rate-controlling at 0.5～2ml/min, formed SiO again
2-K
2O-Al
2O
3-MF-H
2The O system, the colloidal sol proportioning is expressed as with each material mol ratio: SiO
2/ Al
2O
3=20, H
2O/SiO
2=20, K
2O/SiO
2=0.35, MF/SiO
2=0.1, colloidal sol adds 0.5wt% nano molecular sieve crystal seed after 60 ℃ stirring was worn out 24 hours down; The colloidal sol reaction kettle of packing into, hydro-thermal is synthetic 3 days under 100 ℃ of synthesis temperatures, after centrifugal, cleaning and drying, obtains fluorine-contained T-shaped zeolite molecular sieve.
The synthetic molecular sieve characterizes through the x XRD X, shows like Fig. 1, and the molecular sieve of preparation locates to occur T type zeolite molecular sieve characteristic diffraction peak diffraction angle 2 θ=7.7 °, 11.6 °, 20.5 ° and 23.53 °, and crystal is pure T type zeolite molecular sieve crystal.Adopt
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, promptly F gets in the crystalline framework fully, combines x XRD X sign, plasma emission spectrum and the analysis of F electrode characterization result, the elementary composition of synthetic fluorine-contained T-shaped zeolite molecular sieve is: K
3.6[Si
14.5Al
3.5O
36F
0.1]
3.6-Fig. 2 and be the sem photograph of synthetic T type zeolite molecular sieve analyzes from figure and can know that the T type zeolite molecular sieve of formation is bar-shaped, and crystallographic dimension is 2～5 μ m.
Under the immovable situation of other condition, as only in colloidal sol, not adding the fluorine source.Reaction only needs 1 day under 100 ℃, the silica alumina ratio Si/Al=3.2 of crystalline framework, and crystal morphology is as shown in Figure 3, is carefully bar-shaped, and crystallographic dimension is about 1 μ m.
Embodiment 2: the preparation of fluorine-contained T-shaped zeolite molecular sieve
Building-up process such as embodiment 1 are said, and different is, and synthesis temperature brings up to 160 ℃ of generated times foreshortens to 1 day, and reaction product is cleaned to the pH value neutral through spinning, 110 ℃ of oven dry 12 hours down.The synthetic molecular sieve is characterized by pure T type zeolite molecular sieve crystal through the x XRD X, uses
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, show that F gets in the crystalline framework fully.
Embodiment 3: the preparation of fluorine-contained T-shaped zeolite molecular sieve
Building-up process such as embodiment 1 are said, and different is that Neutral ammonium fluoride is become Sodium Fluoride.Reaction product is cleaned to the pH value neutral through spinning, dried 12 hours down at 110 ℃.The synthetic molecular sieve is characterized by pure T type zeolite molecular sieve crystal through the x XRD X, uses
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, show that F gets in the crystalline framework fully.Ultimate analysis shows that the F/Si mol ratio in the crystal drops to 0.12%.
Embodiment 4: the preparation of fluorine-contained T-shaped zeolite molecular sieve
Building-up process such as embodiment 1 are said, and that different is NH during the colloidal sol mole is formed
4F/SiO
2=0.5, generated time increased to 5 days.The synthetic molecular sieve is characterized by pure T type zeolite molecular sieve crystal through the x XRD X, uses
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, show that F gets in the crystalline framework fully.Analyze in conjunction with x XRD X sign, plasma emission spectrum and F electrode characterization result, the elementary composition of synthetic fluorine-contained T-shaped zeolite molecular sieve is: K
2.4[Si
16Al
2O
36F
0.4]
2.4-
Embodiment 5: the preparation of fluorine-contained T-shaped zeolite molecular sieve
Building-up process such as embodiment 1 are said, and that different is H during the colloidal sol mole is formed
2O/SiO
2=30, generated time increased to 4 days.The synthetic molecular sieve is characterized by pure T type zeolite molecular sieve crystal through the x XRD X, and crystalline structure and composition are close with embodiment 1.
Claims (5)
1. fluorine-contained T-shaped zeolite molecular sieve, its chemical constitution is: M
+ (x+y)[Si
18-yAl
yO
36F
x]
(x+y)-, x=0.001～1 wherein, y=2～4.5, M=Na
+Or K
+Or NH
4 +
2. preparation method of fluorine-contained T-shaped zeolite molecular sieve according to claim 1; It is characterized in that in synthetic colloidal sol, directly adding villiaumite, induce down through the nanometer crystal seed and prepare fluorine-contained T-shaped zeolite molecular sieve, its concrete steps are: (1) selects for use white lake or sodium metaaluminate or aluminium foil or aluminium powder as the aluminium source; Silicon sol or silica flour are the silicon source; Sodium Fluoride or Potassium monofluoride or Neutral ammonium fluoride are the fluorine source, the aluminium source are added in the alkali lye of Pottasium Hydroxide to heating for dissolving; (2) silicon source and fluorine source slowly are added in (1) formed SiO
2-K
2O-Al
2O
3-MF-H
2The O system, the colloidal sol proportioning is expressed as with each material mol ratio: SiO
2/ Al
2O
3=10～50, H
2O/SiO
2=18～50, K
2O/SiO
2=0.2～0.5, MF/SiO
2=0.05～1.5, colloidal sol 50～60 ℃ down stir aging 20～30 hours after, with nano T-type zeolite molecular sieve crystal seed for inducing, its addition 0.2～1wt%, the crystalline size size is 50～200 nanometers; (3) the colloidal sol reaction kettle of packing into, hydro-thermal is synthetic 0.5～5 day under 90～130 ℃ of synthesis temperatures, after centrifugal, cleaning and drying, obtains fluorine-contained T-shaped zeolite molecular sieve.
3. the preparation method of fluorine-contained T-shaped zeolite molecular sieve according to claim 2 is characterized in that in the synthetic sol system by material mol ratio H
2O/SiO
2=18～30.
4. the preparation method of fluorine-contained T-shaped zeolite molecular sieve according to claim 2 is characterized in that in the synthetic sol system by material mol ratio SiO
2/ Al
2O
3=15～30.
5. the preparation method of fluorine-contained T-shaped zeolite molecular sieve according to claim 2 is characterized in that in the synthetic sol system by material mol ratio K
2O/SiO
2=0.2～0.45.
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