CN104211079B - A kind of preparation method of high thermal stability STW type germanium silicate molecular sieve - Google Patents
A kind of preparation method of high thermal stability STW type germanium silicate molecular sieve Download PDFInfo
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- CN104211079B CN104211079B CN201410453157.XA CN201410453157A CN104211079B CN 104211079 B CN104211079 B CN 104211079B CN 201410453157 A CN201410453157 A CN 201410453157A CN 104211079 B CN104211079 B CN 104211079B
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- molecular sieve
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Abstract
The invention discloses a kind of preparation method of high thermal stability STW type germanium silicate molecular sieve, concrete steps are as follows: (1) by OSDA:N, N diethyl ethylenediamine, water, GeO
2si (OC is added after mixing
2h
5)
4, stir 15 ~ 25 minutes, add HF, the precursor mixture of obtained molecular sieve, described material molar ratio: GeO
2: Si (OC
2h
5)
4: OSDA:H
2o:HF=1:0.8:43.4:6-24:3; (2) load in autoclave by precursor mixture obtained for step (1), 150 ~ 200 DEG C of crystallization 7 ~ 9 days, are cooled to room temperature; (3) cooled product is washed, dry, namely obtain high thermal stability STW type germanium silicate molecular sieve.Preparation method of the present invention obtains the pure phase of STW type germanium silicate molecular sieve; The SiGe ratio (mol ratio) that improve STW type germanium silicate molecular sieve is increased to Si/Ge=1.25; Thermostability is increased to 800 DEG C; Synthetic method is simple.
Description
Technical field
The invention belongs to molecular sieve technical field of inorganic material, be specifically related to a kind of preparation method of high thermal stability STW type germanium silicate molecular sieve.
Background technology
Zeolite molecular sieve is the one in porous material, the general character all with uniquenesses such as the structures of high specific surface area, high porosity and spaciousness, multiple fields can be widely used in, as Industrial Catalysis, sorbent material, environmental treatment, all kinds of carrier and ion-exchanger etc.
Silicate has extremely excellent thermostability, and germanate structure is also unstable, but germanate has special germanium clustering architecture, easily forms Ge
5bunch, Ge
7bunch, Ge
8bunch, Ge
9bunch and Ge
10bunch etc., can synthesize and there is novel topology germanate open-framework compound.Because germanium has much different character with silicon, compared with connecting with the four-coordination of Siliciumatom, germanium atom follows Sauerstoffatom can also form five, hexa-coordinate two kinds of coordination modes.Based on the diversity of its structure, can predict can obtain much special novel topological structure in the synthesis of germanate.Silicate and germanate all have respective advantage, by regulating reaction conditions, silicon and germanium junction being combined, may synthesizing the advantage simultaneously possessing silicate and germanate, are different from again the novel SiGe hydrochlorate molecular sieve structure type of the two one simultaneously.
STW type molecular sieve is the chirality poromerics having helical duct, and at chemistry and pharmaceutical industry, the porosity of material and chirality are two key propertys.Chirality poromerics may be used in corresponding selection absorption, separation and catalysis.Based on the application that these are special, the molecular sieve that synthesis has the STW structure of high thermal stability is concerned always.
Two kinds of methods are had to successfully synthesize STW structure at present.According to document Tang, L.; Shi, L.; Bonneau, C.; Sun, J.; Yue, H.; Ojuva, A.; Lee, B.L.; Kritikos, M.; Bell, R.G.; Bacsik, Z.; Mink, J.; Zou, X.Nat.Mater.2008,7,381 and Alex, R; Oriol, A; Bart, K; Shown in Miguel, A, C.J.Am.Chem.Soc.2013.135.11975, a kind of synthetic method uses commercially available organic amine Diisopropylamine to synthesize SiGe hydrochlorate molecular sieve SU-32 as structure directing agent; Another kind of synthetic method uses homemade ionic liquid, and namely achirality 2-ethyl-1,3,4-trimethylimadazolium cation has synthesized the molecular sieve HPM-1 of pure silicon as structure directing agent.These two kinds of methods are all carried out under water (solvent) heat condition.
In the synthesis of SiGe hydrochlorate molecular sieve SU-32, the STW structural instability obtained, skeleton structure is easily caved in, and also generates another phase Beta molecular sieve (beta-molecular sieve) SU-15 in synthesis, two kinds of structures are vied each other, and cannot obtain STW pure phase.And in the synthesis of HPM-1, although obtain the STW structure of pure silicon, and have very high thermostability, in structure synthesis, the ionic liquid that uses not easily synthesizes, composite structure directed agents not only raw material costly, and generated time is longer.
Summary of the invention
The object of this invention is to provide a kind of preparation method of high thermal stability STW type germanium silicate molecular sieve, the present invention uses organic amine N, N-diethyl ethylenediamine is as structure directing agent, and synthesized the pure phase of STW type germanium silicate molecular sieve, this pure phase also has higher thermostability.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for high thermal stability STW type germanium silicate molecular sieve is template and solvent with N, N-diethyl ethylenediamine, F
-for mineralizer, synthesize STW topological framework molecular sieve under hydrothermal conditions, its step is as follows:
(1) by OSDA (Organic structure directing agent) N, N diethyl ethylenediamine, water, germanium dioxide (GeO
2) fully mix after add tetraethyl orthosilicate Si (OC
2h
5)
4, stir 15 ~ 25 (preferably 20) minute, add HF, the precursor mixture of obtained molecular sieve, proportioning raw materials (mol ratio): GeO
2: Si (OC
2h
5)
4: OSDA:H
2o:HF=1:0.8:43.4:6-24:3;
(2) loaded by precursor mixture in high pressure stainless steel cauldron, 150 ~ 200 DEG C of (preferably 170 DEG C) crystallization 7 ~ 9 days (preferably 7 days), are cooled to room temperature;
(3) product is washed, dry, obtain the preparation method of high thermal stability STW type germanium silicate molecular sieve.
The STW type germanium silicate molecular sieve prepared by aforesaid method.
The application of STW type germanium silicate molecular sieve in chemistry and pharmaceutical industry prepared by aforesaid method.
Beneficial effect of the present invention:
1. preparation method of the present invention obtains the pure phase of STW type germanium silicate molecular sieve;
2. improve the SiGe ratio (mol ratio) of STW type germanium silicate molecular sieve: be increased to Si/Ge=1.25 by Si/Ge=0.9;
3. improve the thermostability of STW type germanium silicate molecular sieve: be increased to 800 DEG C by 400 DEG C;
The molecular sieve HPM-1 of 4.STW type pure silicon, although there is very high thermostability, synthetic method is complicated, and invention increases the thermostability of STW type germanium silicate molecular, and synthetic method is simple.
Accompanying drawing explanation
Fig. 1 is the XRD figure of embodiment 1 gained sample;
Fig. 2 is the stereoscan photograph figure for embodiment 1 gained sample;
Fig. 3 is the in-situ TiC particles figure for embodiment 1 gained sample.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described.
Embodiment 1
A preparation method for high thermal stability STW type germanium silicate molecular sieve is template and solvent with N, N-diethyl ethylenediamine, F
-for mineralizer, synthesize STW topological framework molecular sieve under hydrothermal conditions, its step is as follows:
(1) in 50ml beaker, add 2.46gOSDA (Organic structure directing agent) N, N diethyl ethylenediamine and 0.12g water, add 0.1g germanium dioxide (GeO under agitation
2) fully after mixing 2h, add 0.149g tetraethyl orthosilicate Si (OC
2h
5)
4, stir 15 minutes, add 0.17gHF and stir 20min, the precursor mixture of obtained molecular sieve;
(2) moved into by precursor mixture in 25ml high pressure stainless steel cauldron, 170 DEG C of crystallization 7 days, are cooled to room temperature;
(3) product is washed, dry, namely obtain high thermal stability STW type germanium silicate molecular sieve.
As shown in Figure 1 and Figure 2, the molecular sieve of gained meets STW structure, and as shown in Figure 3, during 800 DEG C, the molecular sieve of gained, structure is still stablized.
Embodiment 2
A preparation method for high thermal stability STW type germanium silicate molecular sieve is template and solvent with N, N-diethyl ethylenediamine, F
-for mineralizer, synthesize STW topological framework molecular sieve under hydrothermal conditions, its step is as follows:
(1) in 50ml beaker, add 7.38gOSDA (Organic structure directing agent) N, N diethyl ethylenediamine and 0.18 water, add 0.15g germanium dioxide (GeO under agitation
2) fully after mixing 2h, add 0.223g tetraethyl orthosilicate Si (OC
2h
5)
4, stir 20 minutes, add 0.246gHF and stir 20min, the precursor mixture of obtained molecular sieve;
(2) moved into by precursor mixture in 25ml high pressure stainless steel cauldron, 150 DEG C of crystallization 9 days, are cooled to room temperature;
(3) product is washed, dry, namely obtain high thermal stability STW type germanium silicate molecular sieve.
Embodiment 3
A preparation method for high thermal stability STW type germanium silicate molecular sieve is template and solvent with N, N-diethyl ethylenediamine, F
-for mineralizer, synthesize STW topological framework molecular sieve under hydrothermal conditions, its step is as follows:
(1) in 50ml beaker, add 2.46gOSDA (Organic structure directing agent) N, N diethyl ethylenediamine and 0.4g water, add 0.1g germanium dioxide (GeO under agitation
2) fully after mixing 2h, add 0.149g tetraethyl orthosilicate Si (OC
2h
5)
4, stir 15 minutes, add 0.17gHF and stir 20min, the precursor mixture of obtained molecular sieve;
(2) moved into by precursor mixture in 25ml high pressure stainless steel cauldron, 200 DEG C of crystallization 7 days, are cooled to room temperature;
(3) product is washed, dry, obtain high thermal stability STW type germanium silicate molecular sieve.
Embodiment 4
A preparation method for high thermal stability STW type germanium silicate molecular sieve is template and solvent with N, N-diethyl ethylenediamine, F
-for mineralizer, synthesize STW topological framework molecular sieve under hydrothermal conditions, its step is as follows:
(1) in 50ml beaker, add 2.46gOSDA (Organic structure directing agent) N, N diethyl ethylenediamine and 0.12g water, add 0.1g germanium dioxide (GeO under agitation
2) fully after mixing 2h, add 0.149g tetraethyl orthosilicate Si (OC
2h
5)
4, stir 15 minutes, add 0.17gHF and stir 20min, the precursor mixture of obtained molecular sieve;
(2) moved into by precursor mixture in 25ml high pressure stainless steel cauldron, 160 DEG C of crystallization 8 days, are cooled to room temperature;
(3) product is washed, dry, obtain high thermal stability STW type germanium silicate molecular sieve.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (6)
1. a preparation method for high thermal stability STW type germanium silicate molecular sieve, is characterized in that, is template and solvent with N, N-diethyl ethylenediamine, F
-for mineralizer, synthesize STW topological framework molecular sieve under hydrothermal conditions, concrete steps are as follows:
(1) by Organic structure directing agent: N, N diethyl ethylenediamine, water, GeO
2si (OC is added after mixing
2h
5)
4, stir 15 ~ 20 minutes, add HF, the precursor mixture of obtained molecular sieve, described material molar ratio: GeO
2: Si (OC
2h
5)
4: Organic structure directing agent: H
2o:HF=1:0.8:43.4:6-24:3;
(2) load in autoclave by precursor mixture obtained for step (1), 150 ~ 200 DEG C of crystallization 7 ~ 9 days, are cooled to room temperature;
(3) cooled product is washed, dry, namely obtain high thermal stability STW type germanium silicate molecular sieve.
2. preparation method as claimed in claim 1, is characterized in that, stirs 20 minutes in described step (1).
3. preparation method as claimed in claim 1, is characterized in that, described step (2) 170 DEG C of crystallization 7 days.
4. STW type germanium silicate molecular sieve prepared by the preparation method as described in as arbitrary in claim 1-3.
5. STW type germanium silicate molecular sieve as claimed in claim 4, is characterized in that, mol ratio Si/Ge=1.25.
6. the application of the STW type germanium silicate molecular sieve as described in claim 4 or 5 in chemistry and pharmaceutical industry.
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