CN107934982B - A kind of macropore silicate molecular sieve and preparation method thereof - Google Patents
A kind of macropore silicate molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of macropore silicate molecular screen material and preparation method thereof, this molecular sieve has X-ray powder diffraction feature as shown in table 1, with 12 × 12 × 12 three-dimensional open-framework, belongs to BEC molecular sieve analog.Macropore silicate molecular sieve of the present invention can be obtained by hydrothermal synthesis method, better heat stability, had biggish specific surface area, can be mixed hetero atom, there is potential application value in the fields such as petrochemistry, fine chemistry industry and life science.
Description
Technical field
The invention belongs to crystalline form poromerics fields, and in particular to a kind of new structure macropore silicate molecular screen material and
Preparation method.
Background technique
Molecular screen material is one kind by TO4(T represents oxidation state atom under normal conditions with+4 valences or+trivalent, as Si,
P, Al, B, Ge, Ga etc.) tetrahedron is by sharing a kind of inorganic microporous solid material for constituting of vertex.Molecule under normal conditions
The composition of sieve can be indicated with following empirical formula: p (M1/nXO2)·qYO2·rR·wH2O, wherein M represent one or
The organic or inorganic cation of multiple+n valences；X represents one or more triads；Y represents one or more quadrivalent elements, leads to
It is Si in normal situation；R represents one or more organic molecules.For a certain specific structure that is obtained by specific synthetic method
Molecular sieve, sample after the product or calcination processing of either fresh synthesis, chemical composition be usually constructed with one it is specific
Constant interval.In addition, the molecular sieve of a specific structure also needs further to be distinguish by X-ray powder diffraction, because
The difference of crystal structure makes different molecular sieve possess different cellular structures, can obtain in the test of X-ray powder diffraction
Entirely different diffraction pattern.The most important characteristic of molecular sieve is that it has variable duct chemical composition, adjustable duct straight
Diameter and hole road shape.These outstanding characteristics impart molecular screen material in absorption, separation, catalysis, microelectronics and medical diagnosis
Equal fields have a wide range of applications.
According to the number of rings in duct, molecular screen material can be divided into aperture, mesoporous, macropore and super macroporous molecular sieve, corresponding difference
With 8 member rings (i.e. by 8 TO4Tetrahedron is constituted) window ring following, below 10 member rings, below 12 member rings and greater than 12 member rings
Number.The molecular screen material being applied successfully in industry, duct size is usually all in 1nm hereinafter, which greatly limits absorption, divide
Molecular size and shape from reaction substrate in, catalytic process, become one in molecular screen material practical application and keep in check.Exploitation
With obtain stable three dimensional intersection macropore and with diameter be the duct 1nm to 2nm super macroporous molecular sieve, even mesoporous point
Son sieve, is always the great challenge that inorganic chemists are faced, and this kind of materials will open petrochemistry, fine chemistry industry and life
The gate of new catalytic applications in the fields such as life science.
Due to the stability of silicate material, macropore silicate molecular screen material has important application prospect.For a long time,
β zeolite is the zeolite that people largely use, and mainly has A type and Type B.For a long time, people suspect always c-type there are a possibility that
(J.M.Newsam,M.M.J.Treacy,W.T.Koetsier,C.B.de Gruyter,Proc.R.Soc.London A
1988,420,375.).2000, Conradsson etc. reported a kind of novel molecular sieve structure FOS-5 of full germanium, was considered
Be people suspect always existing β zeolite family's architecture (T.Conradsson, M.S.Dadachov, X.Zou,
Microporous Mesoporous Mat.,2000,41,183–191).Later, Corma et al. reports a kind of BEC class molecule
Sieve structure ITQ-17 (A.Corma, M.T.Navarro, F.Rey, J.Rius, S.Valencia, Angew.Chem.Int.Ed.,
2001,40,2277–2280).Hereafter it is found successively there are many BEC molecular sieve analog, wherein the ITQ-21 with catalytic performance
(A.Corma,M.J.Diaz-Cabanas,J.Martínez-Triguero,F.Rey,J.Rius,Nature,2002,418,
514-517) it getting more and more people's extensive concerning, twelve-ring macropore three dimensional intersection in ITQ-21 forms the supercage of a 1.18nm,
It is similar with faujasite, it shows compared with the more excellent catalytic performance of faujasite, but the synthesis of the molecular sieve will use very
Expensive organic formwork agent causes its application of gained to be severely limited.
The synthesis of new structure macropore silicate molecular screen material and structural characterization not only there is very important reality to answer
With value, and also there is very important theory significance to abundant molecular sieve structure family, is future molecular sieve Materials
Important directions, be the opportunities and challenges of inorganic chemists.
Summary of the invention
The object of the present invention is to provide a kind of completely new twelve-ring three dimensional intersection macropore silicate molecular screen materials:
NUD-4.The synthetic method and design feature of this molecular sieve are mainly described, has newly added a member for BEC molecular sieve analog material family,
Application of the molecular sieve analog material in Industrial Catalysis thus provides new selection.
Technical scheme is as follows:
A kind of macropore silicate molecular sieve, it is characterised in that this molecular sieve has X-ray powder diffraction as shown in table 1 special
Sign.
Table 1
Above-mentioned macropore silicate molecular sieve, chemical composition form are p (M after roasting1/nXO2)·qYO2·SiO2.Its
In, M represents the inorganic cation of proton or+n valence；X represents triad；Y represents the quadrivalent element in addition to Si；P=0-0.2；q
=0-2.5.The preferred proton of M or sodium, X are preferably Al, and Y is preferably germanium, preferably p=0-0.08；It is preferred that q=0-1.8.
The present invention also provides the preparation methods of above-mentioned macropore silicate molecular sieve, include the following steps:
(1) in proportion by silicon source substance, boron group element compound, carbon group element compound, organic formwork in addition to silicon
Agent, Fluorine source substance and water are uniformly mixed under stiring, and reaction obtains reaction gel in the case where static and dynamic agitation,
The chemical composition of reaction gel are as follows: rROH:aHF:xX2O3:yYO2:SiO2:wH2O, wherein R represents the positive charge of organic formwork agent
Group；X represents one or more triads；Y represents one or more quadrivalent elements in addition to silicon；Corresponding r, a, x, y
It is respectively as follows: r=0.1-3, a=0.1-3, x=0-0.1, y=0-1, w=1-50 with the value interval of w；
(2) by reaction gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight after, will react
Gel is transferred in stainless steel cauldron, 120-170 DEG C under air-proof condition, preferably 150-165 DEG C, and reaction 12-25 days, preferably
15-20 days；
(3) it after being washed the product after crystallization, being dry, is obtained after 2-5 hour is roasted under 400-650 DEG C of air atmosphere
To the macropore silicate zeolite product for removing template agent removing.
The preparation method of above-mentioned macropore silicate molecular sieve, preferably reaction gel rROH:aHF:xX2O3:yYO2:SiO2:
wH2O, X are Al or B；Y is germanium.
It is preferred that the value interval of corresponding r, a, x, y and w are respectively as follows: r=0.5-0.8；A=0.5-0.8；X=0-0.05；
Y=0.4-0.6；W=10-30.
The preparation method of above-mentioned macropore silicate molecular sieve, preferably silicon source substance are white carbon black, waterglass, silica solution, just
Silester or butyl silicate.When boron group element compound is selected from alkali metal/alkali earth metal aluminate or alkali metal/alkaline earth gold
Belong to molecular sieve obtained when borate, contains alkali or alkaline earth metal element: p (M after roasting in chemical constitution formula1/nXO2)·
qYO2·SiO2, M is alkali or alkaline earth metal ion, and when boron group element compound is selected from aluminium alcoholates, organic acid or inorganic acid aluminium
Molecular sieve obtained when the compounds such as salt, aluminium hydroxide or the boric acid, (M containing H:p in chemical constitution formula after roasting1/nXO2)·
qYO2·SiO2, M is proton.Above-mentioned boron group compound is preferably sodium metaaluminate, aluminium isopropoxide, 16 water aluminum sulfate, aluminium hydroxide
Or boric acid.It is preferred that Fluorine source substance is hydrofluoric acid or ammonium fluoride.The preparation method of above-mentioned large pore molecular sieve, it is described in addition to silicon
Carbon group element compound is preferably germanium dioxide.
The preparation method of above-mentioned macropore silicate molecular sieve, the positive charge group Molecule formula of the organic formwork agent are Ar-
(CH2)-(im), wherein Ar represents the substituted or non-substituted phenyl or naphthyl in any position, and im represents 1- methylimidazole or 1,2- bis-
Methylimidazole can be any one listed in table 2.
Table 2
The above method, before reaction gel preparation, it is necessary to which all organic cation templates are passed through ion exchange resin
It is exchanged for form hydroxy, it is stand-by after the hydrochloric acid solution calibration that concentration passes through 0.1M.
Under normal circumstances, in the alkali formula the template solution first quadrivalent element in addition to silicon being added, stirring and dissolving,
Silicon source is then added to continue to stir, finally adds corresponding boron group element compound, is stirring evenly and then adding into Fluorine source substance, it is red
Solvent extra in removing system is heated under outer lamp or in baking oven, obtains target gel.
With p (M1/nXO2)·qYO2·SiO2For (p=0, q=0.6, Y=Ge), carried out using the method for the invention
Preparation, product is bar-like single crystal.Radiation diffraction test is synchronized at -180 DEG C, the result shows that, NUD-4 is crystallized in space
Group I4/m, the molecular formula of elemental analysis actual measurement are Ge0.55Si0.81O2.7F0.1, Its 3 D pore canal is shown in Fig. 2, and wherein the view in the direction c is shown, this molecular sieve
There is the round straight hole road of 12 member rings, and in the direction a and the direction b due to the blocking of four-membered ring, formation is curved 12 yuan
Annular distance road.The molecular sieve is surrounded by four-membered ring and hexatomic ring, but there are two kinds of combining forms.It can be apparent from c-axis direction
See, a kind of form is double four-membered rings along the direction c stacked arrangement, similar to ITQ-21 then by hexatomic ring connection, and another
A kind of outer form is perpendicular to single four-membered ring in the direction c in criss-cross form, is connected by hexatomic ring, with ITQ-17 phase
Seemingly, both connection types staggeredly occur, and form a kind of new structural 12 × 12 × 12 three dimensional intersection macropore silicate molecular
Sieve compound.
The uniqueness of the molecular screen material of different structure shows their different chemical compositions and unique x-ray powder
On diffraction pattern.For NUD-4, chemical composition form is p (M after roasting1/nXO2)·qYO2·SiO2(M represents proton or+n
The inorganic cation of valence；X represents triad；Y represents the quadrivalent element in addition to Si；P=0-0.2；Q=0-2.5).Its powder X-ray
Ray diffraction data is listed in table 1.Position, relative intensity and the width at powder x-ray diffraction peak and chemical composition, the crystal grain of substance
Size and shape etc. is related, and the x-ray diffractogram of powder of different samples may slightly have difference.Attached drawing 1 lists NUD-4 molecular sieve
Powder x-ray diffraction schematic diagram after original powder sample and high-temperature calcination.Further according to X-ray powder diffraction data to molecular sieve
3 D pore canal carry out analysis fitting, as a result consistent with single-crystal X-ray diffraction analysis result, cellular structure is as shown in Figure 2.It is above-mentioned
Molecular sieve can calcine 2 to 4 hours removed template method molecules under 400-650 DEG C of air atmosphere, and structure remained stable is such as schemed
Shown in 1.Sample after high-temperature calcination carries out nitrogen adsorption test at 77K, the results showed that its specific surface area reaches 600m2/g。
Detailed description of the invention
Fig. 1 is the X-ray diffractogram (Cu before and after synthesized NUD-4 sieve sample high-temperature calcination removed template method
Target).
Fig. 2 is the cellular structure figure along three directions that NUD-4 single crystal structure determination obtains.
Specific embodiment
Illustrate specific steps of the invention by the following examples, but is not limited by the example.
Term as used in the present invention generally there are those of ordinary skill in the art usually to manage unless otherwise indicated
The meaning of solution.
The present invention is described in further detail combined with specific embodiments below and referring to data.It should be understood that these embodiments are only
It is in order to demonstrate the invention, rather than to limit the scope of the invention in any way.
In the examples below, the various processes and method being not described in detail are conventional methods as known in the art.
Embodiment 1: by taking template 6 in table 2 as an example, the synthesis process of pattern of descriptive parts agent.By 25g neighbour's fluoro benzyl bromide and
75mL tetrahydrofuran is mixed in the round-bottomed flask of a 250mL, and under reflux state, 1- methyl miaow is added dropwise dropwise into mixed liquor
The tetrahydrofuran solution (11.98g/75mL) of azoles.System is reacted two days under stirring, and reaction mixture is removed through rotary evaporation
It goes solvent that can obtain crude product, product 33.586g, yield 95% can be obtained through ethyl alcohol recrystallization.Product is through liquid nuclear-magnetism (D2O) and electric
Electrospray mass spectrometry characterization, is confirmed as target compound.
Products therefrom is dissolved in 100mL deionized water, carries out column friendship by 717 strong-base anion-exchange resins
It changes, exchange can obtain the aqueous solution of the template 6 of hydroxyl form.Weigh this appropriate solution, with the hydrochloric acid solution of 0.1mol/L into
Rower is fixed, and phenolphthalein is as indicator.The result of calibration confirms that bromide reaches 92% to exchange efficiency hydroxy.
It can refer to the template 1-5 that the above method is prepared in table 2.
Embodiment 2: according to molar ratio 1SiO2: 0.5GeO2: 0.6ROH:0.6HF:10H2The ratio of O prepares Zeolite synthesis
Gel, it is general that steps are as follows: weigh it is appropriate it is exchanged after 6 solution of template, 2.5mmol (0.262g) is added thereto
Germanium dioxide powder, stir about half an hour make be added germanium dioxide be completely dissolved, later be added 5mmol (1.042g) just
Silester is completely dissolved ethyl orthosilicate in stir about two hours under room temperature, and the hydrofluoric acid solution of design flow is then added, stirs
Mix uniformly, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight.Last gained is anti-
Gel is answered to be transferred to 15mL in the stainless steel cauldron of polytetrafluoroethyllining lining, lower 150 DEG C of air-proof condition are reacted 15 days, are produced
Object is washed twice, and ethyl alcohol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample with
It is calcined 2 hours under 550 DEG C of air atmospheres in Muffle furnace, removes template, elemental analysis shows that its molecular formula is 0.68GeO2·
SiO2.The bar-like single crystal for selecting suitable size, synchronized at -180 DEG C radiation test, the result shows that, NUD-4 crystallization in
Space group I4/m, Such as Fig. 2 institute
Showing, 3 D pore canal is shown in Fig. 2, and wherein the view in the direction c is shown, this molecular sieve has the round straight hole road of 12 member rings,
And in the direction a and the direction b due to the blocking of four-membered ring, formation is curved 12 membered ring channel.The molecular sieve by four-membered ring and
Hexatomic ring surrounds, but there are two kinds of combining forms.It can see clearly that from c-axis direction, a kind of form is double four-membered rings
Along the direction c stacked arrangement, then connected by hexatomic ring, it is similar to ITQ-21, and another form is perpendicular to the direction c
Single four-membered ring is connected in criss-cross form by hexatomic ring, similar to ITQ-17, both connection types staggeredly occur,
Form a kind of new structural 12 × 12 × 12 three dimensional intersection macropore silicate preparation method for molecular sieve compositions.The X-ray powder of the molecular sieve
Last diffraction patterns are as shown in table 1.Powder x-ray diffraction schematic diagram after original powder sample and high-temperature calcination is as shown in Figure 1.According to X
Ray powder diffraction data carries out analysis fitting to the 3 D pore canal of molecular sieve, as a result with single-crystal X-ray diffraction analysis result one
It causes, cellular structure is as also shown in Figure 2.Above-mentioned molecular sieve can be calcined 2 to 4 hours under 400-650 DEG C of air atmosphere and be removed
Template molecule, structure remained stable, as shown in Figure 1.Sample after high-temperature calcination carries out nitrogen adsorption test at 77K,
The result shows that its specific surface area reaches 600m2/g。
Embodiment 3: according to molar ratio 1SiO2: 0.5GeO2: 0.6ROH:0.6NH4F:10H2The ratio of O prepares molecular sieve and closes
At gel, it is general that steps are as follows: weigh it is appropriate it is exchanged after 5 solution of template, 2.5mmol is added thereto
The germanium dioxide of (0.262g), stir about half an hour are completely dissolved the germanium dioxide being added, and 5mmol (1.042g) is added later
Ethyl orthosilicate, be completely dissolved ethyl orthosilicate within stir about two hours under room temperature, the ammonium fluoride of design flow be then added, stirs
Mix uniformly, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight.Last gained is anti-
Gel is answered to be transferred to 15mL in the stainless steel cauldron of polytetrafluoroethyllining lining, lower 150 DEG C of air-proof condition are reacted 15 days, are produced
Object is washed twice, and ethyl alcohol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample with
It is calcined 2 hours under 600 DEG C of air atmospheres in Muffle furnace, removes template, elemental analysis shows that its molecular formula is 0.71GeO2·
SiO2.The X-ray powder diffraction result and table 1 of the molecular sieve are almost the same.X-ray powder after original powder sample and high-temperature calcination
Diffraction schematic diagram and embodiment 2 are almost the same, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 4: according to molar ratio 1SiO2: 0.8GeO2: 0.5ROH:0.5HF:15H2The ratio of O prepares Zeolite synthesis
Gel, it is general that steps are as follows: weigh it is appropriate it is exchanged after 4 solution of template, be added thereto 4mmol (0.426g)
Germanium dioxide, stir about half an hour are completely dissolved the germanium dioxide being added, and the positive silicic acid second of 5mmol (1.042g) is added later
Ester is completely dissolved ethyl orthosilicate in stir about two hours under room temperature, and the hydrofluoric acid solution of design flow is then added, and stirring is equal
It is even, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight.Last gained reaction is coagulated
Glue is transferred to 15mL in the stainless steel cauldron of polytetrafluoroethyllining lining, and lower 170 DEG C of air-proof condition are reacted 12 days, product warp
Twice, ethyl alcohol is washed twice for washing, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample and Muffle
It is calcined 2 hours under 550 DEG C of air atmospheres in furnace, removes template, elemental analysis shows that its molecular formula is 0.78GeO2·SiO2。
The X-ray powder diffraction result and table 1 of the molecular sieve are almost the same.Powder x-ray diffraction after original powder sample and high-temperature calcination
Schematic diagram and embodiment 2 are almost the same, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 5: according to molar ratio 1SiO2: 0.5GeO2: 0.1ROH:0.1HF:1H2The ratio of O prepares Zeolite synthesis
Gel, it is general that steps are as follows: weigh it is appropriate it is exchanged after 3 solution of template, 2.5mmol (0.262g) is added thereto
Germanium dioxide, stir about half an hour make be added germanium dioxide be completely dissolved, later be added 5mmol (0.301g) hard charcoal
It is black, it is uniformly mixed gel, the hydrofluoric acid solution of design flow is then added, stirs evenly, will mix
Close gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight.It will last gained reaction gel transfer
To 15mL in the stainless steel cauldron of polytetrafluoroethyllining lining, lower 130 DEG C of air-proof condition are reacted 25 days, and product is through washing two
Secondary, ethyl alcohol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.It takes 550 in appropriate amount of sample and Muffle furnace
It is calcined 2 hours under DEG C air atmosphere, removes template, elemental analysis shows that its molecular formula is 0.6GeO2·SiO2.The molecular sieve
X-ray powder diffraction result and table 1 it is almost the same.Powder x-ray diffraction schematic diagram after original powder sample and high-temperature calcination with
Embodiment 2 is almost the same, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 6: according to molar ratio 1SiO2: 1GeO2: 3ROH:3HF:50H2The ratio of O prepares the solidifying of Zeolite synthesis
Glue, general steps are as follows: weigh it is appropriate it is exchanged after 2 solution of template, the dioxy of 5mmol (0.523g) is added thereto
Change germanium, stir about half an hour is completely dissolved the germanium dioxide being added, the ethyl orthosilicate of 5mmol (1.042g) is added later,
It is completely dissolved ethyl orthosilicate within stir about two hours under room temperature, the hydrofluoric acid solution of design flow is then added, stirs evenly, it will
Mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight.Last gained reaction gel is turned
15mL is moved to in the stainless steel cauldron of polytetrafluoroethyllining lining, lower 170 DEG C of air-proof condition are reacted 12 days, and product is through washing
Twice, ethyl alcohol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.It takes in appropriate amount of sample and Muffle furnace
It is calcined 2 hours under 550 DEG C of air atmospheres, removes template, elemental analysis shows that its molecular formula is 0.68GeO2·SiO2.This point
The X-ray powder diffraction result and table 1 of son sieve are almost the same.Powder x-ray diffraction signal after original powder sample and high-temperature calcination
Figure is almost the same with embodiment 2, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 7: according to molar ratio 1SiO2: 1GeO2: 2ROH:2HF:30H2The ratio of O prepares the solidifying of Zeolite synthesis
Glue, general steps are as follows: weigh it is appropriate it is exchanged after 1 solution of template, the dioxy of 5mmol (0.523g) is added thereto
Change germanium, stir about half an hour is completely dissolved the germanium dioxide being added, the ethyl orthosilicate of 5mmol (1.042g) is added later,
It is completely dissolved ethyl orthosilicate within stir about two hours under room temperature, the hydrofluoric acid solution of design flow is then added, stirs evenly, it will
Mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight.Last gained reaction gel is turned
15mL is moved to in the stainless steel cauldron of polytetrafluoroethyllining lining, lower 120 DEG C of air-proof condition are reacted 30 days, and product is through washing
Twice, ethyl alcohol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.It takes in appropriate amount of sample and Muffle furnace
It is calcined 2 hours under 500 DEG C of air atmospheres, removes template, elemental analysis shows that its molecular formula is 0.68GeO2·SiO2.This point
The X-ray powder diffraction result and table 1 of son sieve are almost the same.Powder x-ray diffraction signal after original powder sample and high-temperature calcination
Figure is almost the same with embodiment 2, and three-dimensional open-framework figure is consistent with Fig. 2.
Embodiment 8: according to molar ratio 1SiO2: 0.1Al2O3: 1ROH:1.6HF:3H2The ratio of O prepares Zeolite synthesis
Gel, general steps are as follows: weigh it is appropriate it is exchanged after 6 solution of template, the inclined aluminium of 1.0mmol is added thereto first
Sour sodium (0.082g) and a small amount of crystal seed (0.0010g, 2 product of embodiment) stir ten minutes or so, 5mmol are added later
The ethyl orthosilicate of (1.042g) is completely dissolved ethyl orthosilicate in stir about two hours under room temperature, and design flow is then added
Hydrofluoric acid solution stirs evenly, by mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory
Weight.Last gained reaction gel is transferred to 15mL to have in the stainless steel cauldron of polytetrafluoroethyllining lining, under air-proof condition
150 DEG C are reacted 15 days, and product is washed twice, and ethyl alcohol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be
NUD-4.It takes in appropriate amount of sample and Muffle furnace and is calcined 2 hours under 550 DEG C of air atmospheres, remove template, elemental analysis shows it
Molecular formula is 0.02 (NaAlO2)·0.01GeO2·SiO2.The X-ray powder diffraction result and table 1 of the molecular sieve are almost the same.
Powder x-ray diffraction schematic diagram and embodiment 2 after original powder sample and high-temperature calcination is almost the same, three-dimensional open-framework figure and figure
2 is consistent.
Embodiment 9: according to molar ratio 1SiO2: 0.5GeO2: 0.05Al2O3: 1ROH:1.3HF:5H2The ratio of O prepares molecule
Sieve the gel of synthesis, general steps are as follows: weigh it is appropriate it is exchanged after 3 solution of template, be added thereto first
The aluminium isopropoxide (0.102g) of 0.5mmol stirs ten minutes or so, the dioxy of 2.5mmol (0.262g) is then added thereto
Change germanium, stir about half an hour is completely dissolved the germanium dioxide being added, the ethyl orthosilicate of 5mmol (1.042g) is added later,
It is completely dissolved ethyl orthosilicate within stir about two hours under room temperature, the hydrofluoric acid solution of design flow is then added, stirs evenly, it will
Mixed gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theoretical value.Last gained reaction gel is turned
15mL is moved to in the stainless steel cauldron of polytetrafluoroethyllining lining, lower 160 DEG C of air-proof condition are reacted 20 days, and product is through washing
Twice, ethyl alcohol is washed twice, and drying is stand-by.X-ray powder diffraction Discriminating materials its be NUD-4.Take appropriate amount of sample in Muffle furnace
It is calcined 2 hours under 550 DEG C of air atmospheres, removes template, elemental analysis shows that its molecular formula is 0.08 (HAlO2)·
0.4GeO2·SiO2.The X-ray powder diffraction result and table 1 of the molecular sieve are almost the same.After original powder sample and high-temperature calcination
Powder x-ray diffraction schematic diagram and embodiment 2 are almost the same, and three-dimensional open-framework figure is consistent with Fig. 2.
Claims (9)
1. a kind of macropore silicate molecular sieve, it is characterised in that this molecular sieve has X-ray powder diffraction feature as shown in table 1,
Round straight hole road with 12 member rings, in curved 12 membered ring channel that the direction a and the direction b are formed, the molecular sieve by
Four-membered ring and hexatomic ring surround, and there are two kinds of combining forms: a kind of form is double four-membered rings along the direction c stacked arrangement, is then led to
Cross hexatomic ring connection；Another form is perpendicular to single four-membered ring in the direction c in criss-cross form, is connected by hexatomic ring
It connecing, both connection types staggeredly occur, 12 × 12 × 12 three dimensional intersection macropore silicate preparation method for molecular sieve compositions are formed,
Table 1
2. macropore silicate molecular sieve according to claim 1, it is characterised in that the molecular sieve composition form, roasting
It is p (M after burning1/nXO2)·qYO2·SiO2, wherein M represents the inorganic cation of proton or+n valence；X represents triad；Y generation
Quadrivalent element of the table in addition to Si；P=0-0.2；Q=0-2.5.
3. macropore silicate molecular sieve according to claim 2, it is characterised in that the M represents proton or sodium ion；X generation
Table aluminium or boron element；Y represents Germanium.
4. macropore silicate molecular sieve according to claim 2, it is characterised in that the p=0-0.08.
5. macropore silicate molecular sieve according to claim 2, it is characterised in that the q=0-1.8.
6. the preparation method of macropore silicate molecular sieve according to claim 1-5, it is characterised in that including such as
Lower step:
(1) in proportion by silicon source substance, boron group element compound, carbon group element compound, organic formwork agent, fluorine in addition to silicon
Source substance and water are uniformly mixed under stiring, obtain reaction gel, the chemical composition of reaction gel are as follows:
rROH:aHF:xX2O3:yYO2:SiO2:wH2O, wherein R represents the positive charge group of organic formwork agent；X represents one or more
A triad；Y represents one or more quadrivalent elements in addition to silicon；The value interval of corresponding r, a, x, y and w are distinguished
Are as follows: r=0.5-1；A=0.5-0.8；X=0-0.05；Y=0.4-0.6；W=10-30；
(2) by reaction gel be placed under infrared lamp or 80 DEG C of baking ovens in, remove extra solvent to theory weight after, by reaction gel
It is transferred in stainless steel cauldron, 120-170 DEG C reaction 12-20 days under air-proof condition；
(3) it after being washed the product after crystallization, being dry, is gone after roasting 2-5 hour under 400-650 DEG C of air atmosphere
The macropore silicate zeolite product of template agent removing.
7. the preparation method of macropore silicate molecular sieve according to claim 6, it is characterised in that reaction gel rROH:
aHF:xX2O3:yYO2:SiO2:wH2O, X are Al or B；Y is germanium.
8. the preparation method of macropore silicate molecular sieve according to claim 6, it is characterised in that the silicon source substance is
White carbon black, waterglass, silica solution, ethyl orthosilicate or butyl silicate；The boron group element compound is sodium metaaluminate, isopropyl
Aluminium alcoholates, 16 water aluminum sulfate, aluminium hydroxide or boric acid；The Fluorine source substance is hydrofluoric acid or ammonium fluoride, the organic formwork agent
Positive charge group Molecule formula be Ar- (CH2)-(im), wherein Ar represents the phenyl that any position replaces, and im represents 1- methylimidazole
Or 1,2- methylimidazole, the carbon group element compound in addition to silicon is germanium dioxide.
9. macropore silicate molecular sieve described in one of -5 items is in absorption, separation, catalysis, microelectronics or doctor according to claim 1
Treat the application in diagnostic field.
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