CN101830479A - Fluorine-contained T-shaped zeolite molecular sieve and preparation method thereof - Google Patents
Fluorine-contained T-shaped zeolite molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention provides a method for preparing a fluorine-contained T-shaped zeolite molecular sieve and a preparation method thereof. The preparation method is characterized by comprising the following steps of: directly adding villiaumite in synthetic sol, and then inducing by using a nano T-shaped zeolite molecular sieve seed crystal to prepare the fluorine-contained T-shaped zeolite molecular sieve. In a formed SiO2-K2O-Al2O3-MF-H2O system, the sol proportions are expressed as follows by the molar ratio of each substance: 10-50% of SiO2-Al2O3, 18-50% of H2O/SiO2, 0.2-0.5% of K2O/SiO2 and 0.05-1.5% of MF/SiO2. The method concretely comprises the following steps of: adding 0.1-2 wt% of nano molecular sieve seed crystal after stirring and aging the sol for 20-30 hours at 50-60 DEG C, thermally synthesizing for 0.5-4 days in water at the synthetic temperature of 90-130 DEG C, and then centrifuging, cleaning and drying to obtain the fluorine-contained T-shaped zeolite molecular sieve; and the chemical formula of the crystal molecular sieve is M+(x+y)[Si18-yAlyO36Fx](x+y)<->, wherein x is equal to 0.001-1, y is equal to 2-4.5, and M is Na<+>or K<+>or NH<4+>. The invention synthesizes the fluorine-contained T-shaped zeolite molecular sieve in one step without using expensive organic template agents and a complicated postprocessing process, has the advantages of simple synthesizing process, lower cost and suitability for industrial amplified production, and can be effectively applied to the fields of adsorption separation, catalysis and the like.
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 the porous aluminum silicate crystal that a class has the single-size duct, and constituting the most basic structural unit of molecular sieve is TO
4Tetrahedron (T=Al, Si).Wherein each Sauerstoffatom is all shared by two adjacent tetrahedral structures, 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, ion-exchange 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 skeleton is all formed their spatial disposition differences by cancrinite cage and six prisms.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, they studies show that, 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 degree of crystallinity in 16～32 scopes.
Fluorine-containing zeolite molecular sieve has unique catalytic activity and selectivity.Yet most fluorine-containing zeolite molecular sieves obtain by 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 particularly the fluorine-containing ZSM-5 zeolite molecular sieve of handling through fluorine shows higher catalytic activity in petroleum catalytic cracking.Patent CN1037097A and US604178 will contain metal 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 that the MFI feature structure of catalyst sample does not have is destroyed, and degree of 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 studies show that, zeolite molecular sieve make zeolite molecular sieve phenomenons such as dealuminzation, desiliconization occur after handling through fluorine, thereby cause 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 harm operator health.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 will to mix with silica gel after the acidifying of aluminium source earlier, make the abundant dispersing and mixing of silica gel and aluminium source with ultrasonic wave, dry, grind, mix the back crystallization then with tetraethylammonium cation template, fluorochemical and water and be prepared from.Studies show 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 by 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.Add the silicon source under condition of stirring, 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 ℃, finishes reaction after 24 hours., 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 aluminium hydroxide or sodium metaaluminate or aluminium foil or aluminium powder as the aluminium source, the aluminium source is added in the alkali lye of potassium 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 reactor of packing into, hydro-thermal is synthetic 0.5～5 day under 90～130 ℃ of synthesis temperatures, obtains fluorine-contained T-shaped zeolite molecular sieve after centrifugal, cleaning and drying.
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 potassium hydroxide or Repone K or both mixtures, and potassium hydroxide is preferred.The aluminium source of adopting is that aluminium hydroxide is sodium metaaluminate or aluminium foil or aluminium powder etc., and aluminium hydroxide 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 enters in the crystalline framework fully, analyzes in conjunction with x ray diffraction sign, plasma emission spectrum and 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 that the hydrogen fluoride aftertreatment prepares the fluorine-containing molecular sieve of other kind with crystal seed in synthetic colloidal sol, reduces waste discharge.Can be applicable to aspects such as the catalysis of low carbon compound and reformation, 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 concrete case study on implementation 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 aluminium hydroxide 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 potassium 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 reactor of packing into, hydro-thermal is synthetic 3 days under 100 ℃ of synthesis temperatures, obtains fluorine-contained T-shaped zeolite molecular sieve after centrifugal, cleaning and drying.
The synthetic molecular sieve characterizes through the x ray diffraction, shows as 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 enters in the crystalline framework fully, analyzes in conjunction with x ray diffraction sign, plasma emission spectrum and 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 the T type zeolite molecular sieve that forms as can be known and is bar-shaped from figure, 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 ℃, and the silica alumina ratio Si/Al=3.2 of crystalline framework, crystal morphology are carefully bar-shaped as shown in Figure 3, and crystallographic dimension is about 1 μ m.
Embodiment 2: the preparation of fluorine-contained T-shaped zeolite molecular sieve
Building-up process is as described in the embodiment 1, 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 centrifugation, 110 ℃ of oven dry 12 hours down.The synthetic molecular sieve is characterized by pure T type zeolite molecular sieve crystal through the x ray diffraction, uses
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, show that F enters in the crystalline framework fully.
Embodiment 3: the preparation of fluorine-contained T-shaped zeolite molecular sieve
Building-up process is as described in the embodiment 1, and different is that Neutral ammonium fluoride is become Sodium Fluoride.Reaction product is cleaned to the pH value neutral through centrifugation, dried 12 hours down at 110 ℃.The synthetic molecular sieve is characterized by pure T type zeolite molecular sieve crystal through the x ray diffraction, uses
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, show that F enters 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 is as described in the embodiment 1, 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 ray diffraction, uses
19F solid state nmr characterized by techniques F and SiF
x 4-xForm exist, show that F enters in the crystalline framework fully.Analyze in conjunction with x ray diffraction 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 is as described in the embodiment 1, 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 ray diffraction, and crystalline structure and composition are close with embodiment 1.
Claims (7)
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. the preparation method of a fluorine-contained T-shaped zeolite molecular sieve, it is characterized in that in synthetic colloidal sol, directly adding villiaumite, induce down through the nanometer crystal seed and to prepare fluorine-contained T-shaped zeolite molecular sieve, its concrete steps are: (1) selects for use aluminium hydroxide 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 potassium 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 adds 0.1～2wt% nano molecular sieve crystal seed after 50～60 ℃ stirring was worn out 20～30 hours down; (3) the colloidal sol reactor of packing into, hydro-thermal is synthetic 0.5～5 day under 90～130 ℃ of synthesis temperatures, obtains fluorine-contained T-shaped zeolite molecular sieve after centrifugal, cleaning and drying.
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.
6. the preparation method of fluorine-contained T-shaped zeolite molecular sieve according to claim 2 is characterized in that directly adding villiaumite and prepares fluorine-containing molecular sieve in synthetic colloidal sol, and villiaumite is Neutral ammonium fluoride or Sodium Fluoride or Potassium monofluoride, and its addition is for pressing material mol ratio MF/SiO
2=0.1～1.
7. the preparation method of fluorine-contained T-shaped zeolite molecular sieve according to claim 2 is characterized in that with nano T-type zeolite molecular sieve crystal seed for inducing, its addition 0.2～1wt%, and the crystalline size size is 50～200 nanometers.
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Cited By (3)
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|---|---|---|---|---|
| CN103933871A (en) * | 2014-04-15 | 2014-07-23 | 南京工业大学 | Preparation method of high-stability all-silicon MFI type molecular sieve membrane |
| CN104891518A (en) * | 2015-05-08 | 2015-09-09 | 大连理工大学 | Method for preparing novel zeolite molecular sieve for adsorption purpose |
| CN113264539A (en) * | 2017-05-04 | 2021-08-17 | 安徽工程大学 | Method for directly synthesizing zeolite molecular sieve by using natural mineral clay |
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|---|---|---|---|---|
| CN101164883A (en) * | 2007-09-27 | 2008-04-23 | 江西师范大学 | Preparation method for nano T-type molecular sieve |
| CN101259384A (en) * | 2008-05-05 | 2008-09-10 | 江西师范大学 | T type molecular sieve membrane containing rich erionite, preparation and application in gas separation |
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2010
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| CN101164883A (en) * | 2007-09-27 | 2008-04-23 | 江西师范大学 | Preparation method for nano T-type molecular sieve |
| CN101259384A (en) * | 2008-05-05 | 2008-09-10 | 江西师范大学 | T type molecular sieve membrane containing rich erionite, preparation and application in gas separation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103933871A (en) * | 2014-04-15 | 2014-07-23 | 南京工业大学 | Preparation method of high-stability all-silicon MFI type molecular sieve membrane |
| CN103933871B (en) * | 2014-04-15 | 2016-02-10 | 南京工业大学 | Preparation method of high-stability all-silicon MFI type molecular sieve membrane |
| CN104891518A (en) * | 2015-05-08 | 2015-09-09 | 大连理工大学 | Method for preparing novel zeolite molecular sieve for adsorption purpose |
| CN113264539A (en) * | 2017-05-04 | 2021-08-17 | 安徽工程大学 | Method for directly synthesizing zeolite molecular sieve by using natural mineral clay |
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