CN109758916A - A kind of LTA type molecular sieve and preparation method thereof - Google Patents
A kind of LTA type molecular sieve and preparation method thereof Download PDFInfo
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- CN109758916A CN109758916A CN201910220168.6A CN201910220168A CN109758916A CN 109758916 A CN109758916 A CN 109758916A CN 201910220168 A CN201910220168 A CN 201910220168A CN 109758916 A CN109758916 A CN 109758916A
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Abstract
The present invention is suitable for technical field of inorganic material, provide a kind of LTA type molecular sieve and preparation method thereof, the preparation method includes the following steps: to prepare the LTA hydrosol: according to mass ratio be (1~1.1) by silica solution and deionized water: 11 mix, 2h is stirred in 60 DEG C of heating water baths, obtains mixed liquor；According to mass ratio be (5~6) by sodium hydroxide and deionized water: 13 mix, and aluminium is added after sodium hydroxide is completely dissolved, and the mixed liquor is added after aluminium is completely dissolved, and stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；In situ synthesis synthesizes LTA type molecular sieve: the stainless (steel) wire crossed through coupling agent treatment is placed in reaction kettle, the LTA hydrosol is added, in 50~60 DEG C react 18~for 24 hours, the stainless (steel) wire is dipped to neutrality with deionized water after reaction, drying is under the conditions of 80 DEG C to get the LTA type molecular sieve.LTA type molecular sieve preparation method of the invention is simple, and finished product efficiency is high, and flux is high, and membrane separating property is good, and mechanical strength is higher.
Description
Technical field
The invention belongs to technical field of inorganic material more particularly to a kind of LTA type molecular sieve and preparation method thereof.
Background technique
The principle of seepage slope is to be evaporated by the part of film (non-porous or porous) come separation of liquid mixtures, with steam shape
The infiltration component that formula is collected can be removed by making inert media flowing or applying low pressure in penetrant side, technological accumulation and inheritance friend
Well and low energy consumption.Due to the features such as inoranic membrane (for example, LTA molecular screen membrane) synthesis process is simple, high temperature resistant, in seepage slope point
Have broad application prospects from direction.LTA molecular screen membrane has very strong hydrophily, in the mixture of separation organic matter and water
In show it is high-throughput and highly selective.
At present on the market with hydrothermal synthesis method in α-Al2O3Fine and close LTA molecular screen membrane is grown on hollow tube, in infiltration gas
Change in the alcohol-water separation (90% ethanol solution, 75 DEG C) in experiment, separation factor is greater than 10000, but flux only 8.0kg/
(m2H), meanwhile, in α-Al2O3The LTA molecular screen membrane mechanical strength grown on hollow tube is poor, seriously restricts its industrialization.
It can be seen that using LTA molecular screen membrane made from existing LTA molecular screen membrane preparation method, that there are flux is not high,
And the problem that mechanical strength is poor.
Summary of the invention
The embodiment of the present invention provides a kind of preparation method of LTA type molecular sieve, it is intended to solve to use existing LTA molecular sieve
That there are flux is not high for LTA molecular screen membrane made from membrane preparation method, and the problem that mechanical strength is poor.
The embodiments of the present invention are implemented as follows, and a kind of preparation method of LTA type molecular sieve includes the following steps:
Prepare the LTA hydrosol:
According to mass ratio be (1~1.1) by silica solution and deionized water: 11 mix, and stir in 60 DEG C of heating water baths
2h obtains mixed liquor；
According to mass ratio be (5~6) by sodium hydroxide and deionized water: 13 mix, and are completely dissolved to sodium hydroxide
After aluminium is added, the mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；
In situ synthesis synthesizes LTA type molecular sieve:
The stainless (steel) wire crossed through coupling agent treatment is placed in reaction kettle, the LTA hydrosol is added, it is anti-in 50~60 DEG C
Answer 18~for 24 hours, the stainless (steel) wire is dipped to neutrality with deionized water after reaction, drying is under the conditions of 80 DEG C to get described
LTA type molecular sieve.
The embodiment of the invention also provides a kind of LTA type molecular sieve, the LTA type molecular sieve is by above-mentioned LTA type molecule
The preparation method of sieve is prepared.
LTA type molecular sieve provided in an embodiment of the present invention will be stainless after coupling agent treatment using in situ synthesis
Steel mesh is placed in the reaction kettle of the LTA hydrosol, and under the conditions of 50~60 DEG C of temperature reaction 18~for 24 hours so that LTA is water-soluble
Glue can the equably accumulated growth on the stainless (steel) wire, form fine and close LTA type molecular screen membrane, which has in molecule
Have in the mixture of machine object and water it is high-throughput and highly selective, meanwhile, mechanical strength is preferable, and entire preparation process is simple, item
Part is mild, and finished product efficiency is high, is conducive to industrialized production.
Detailed description of the invention
Fig. 1 is the synthesis mechanism schematic diagram of LTA type molecular sieve provided by the invention；
Fig. 2 is that the surface of LTA type molecular screen membrane made from the preparation method using the embodiment of the present invention 3 is identified by SEM
Resulting SEM spectrum；
Fig. 3 is that the surface of LTA type molecular screen membrane made from the preparation method using the embodiment of the present invention 3 is identified by SEM
SEM spectrum；
Fig. 4 is the X ray diffracting spectrum of LTA type molecular screen membrane made from the preparation method using the embodiment of the present invention 3.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The term used in embodiments of the present invention is only to be not intended to be limiting merely for for the purpose of describing particular embodiments
The present invention.Packet is also intended in the "an" and "the" of the embodiment of the present invention and singular used in the attached claims
Most forms are included, unless the context clearly indicates other meaning.It is also understood that term "and/or" used herein is
Refer to and includes that one or more associated any or all of project listed may combine.
LTA type molecular sieve provided in an embodiment of the present invention will be stainless after coupling agent treatment using in situ synthesis
Steel mesh is placed in the reaction kettle of the LTA hydrosol, and under the conditions of 50~60 DEG C of temperature reaction 18~for 24 hours so that LTA is water-soluble
Glue can the equably accumulated growth on the stainless (steel) wire, form fine and close LTA type molecular screen membrane, which has in molecule
Have in the mixture of machine object and water it is high-throughput and highly selective, meanwhile, mechanical strength is preferable, and entire preparation process is simple, item
Part is mild, and finished product efficiency is high, is conducive to industrialized production.
The embodiment of the invention provides a kind of preparation methods of LTA type molecular sieve, include the following steps:
Prepare the LTA hydrosol: according to mass ratio be (1~1.1) by silica solution and deionized water: 11 mix, in 60
DEG C heating water bath stirs 2h, obtains mixed liquor；
According to mass ratio be (5~6) by sodium hydroxide and deionized water: 13 mix, and are completely dissolved to sodium hydroxide
After aluminium is added, the mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；
In situ synthesis synthesizes LTA type molecular sieve: the stainless (steel) wire crossed through coupling agent treatment being placed in reaction kettle, is added
The LTA hydrosol, in 50~60 DEG C react 18~for 24 hours, the stainless (steel) wire is dipped to neutrality with deionized water after reaction,
Drying is under the conditions of 80 DEG C to get the LTA type molecular sieve.
In conjunction with Fig. 1, handled with sodium hydroxide solution so that-OH is had on stainless (steel) wire, then again with APTES (3- ammonia third
Ethyl triethoxy silicane alkane) stainless (steel) wire is modified, so that-OEt the reaction on the-OH and stainless (steel) wire on APTES, and due to
The LTA hydrosol contains sial macromolecular, outer to be with one layer of-OH, can react with-the NH2 on APTES, so that the sial is big
On molecular linkage to stainless (steel) wire, LTA type molecular screen membrane is formed.
In one embodiment of the invention, it before the step of in situ synthesis synthesizes LTA type molecular sieve, also wraps
It includes:
Stainless (steel) wire after pretreatment is handled with coupling agent: 3- aminopropyl triethoxysilane is pressed with toluene
Be (5~10) according to mass ratio: 200 are configured to coupling agent, and stainless (steel) wire after pretreatment is put into the coupling agent, is placed in
110 DEG C of 1~2h of reaction, discard the coupling agent in baking oven, and the stainless (steel) wire is dried and is crossed not to get through coupling agent treatment
The steel mesh that becomes rusty is spare.
In another embodiment of the invention, before described the step of being handled with coupling agent stainless (steel) wire, also
Include:
Stainless (steel) wire is pre-processed: stainless (steel) wire being cut into the disk that diameter is 15~20mm, with 1mol/L's
Hydrochloric acid solution cleans the greasy dirt on the stainless (steel) wire, washes with water to neutrality, then is soaked with the sodium hydroxide solution of 0.1mol/L
It takes out, is washed with water to neutrality after bubble 15h, it is spare to get pretreated stainless (steel) wire to be placed on drying in 60 DEG C of baking ovens.
Preferably, the density of the stainless (steel) wire is 1600 mesh, the preferably stainless (steel) wire of 316L seat type.The aperture of 1600 mesh
It is 3 μm, aperture is smaller, and the aperture for the composite material that may make LTA attachment to be formed up is straight between the dynamics of alcohol hydrone
Between diameter.The big price of mesh number is high, and mesh number it is low aperture it is too big, be not easy to modify.
In a preferred embodiment of the invention, the molar ratio group of the LTA hydrosol becomes Al2O3:SiO2:Na2O:H2O=
1:5:50:1000。
In one embodiment of the invention, described by silica solution and deionized water is (1~1.1) according to mass ratio: 11
It is mixed, in the step of 60 DEG C of heating water baths stir 2h, obtain mixed liquor, comprising:
Silica solution is mixed with deionized water according to mass ratio for 1.043:11, stirs 2h in 60 DEG C of heating water baths,
Obtain mixed liquor.
In one embodiment of the invention, described by sodium hydroxide and deionized water is (5~6) according to mass ratio: 13
Mixed, aluminium be added after sodium hydroxide is completely dissolved, be added the mixed liquor after aluminium is completely dissolved, stirring at normal temperature for 24 hours,
The step of obtaining the clear LTA hydrosol, specifically includes:
Sodium hydroxide is mixed with deionized water according to mass ratio for 5.55:13, after sodium hydroxide is completely dissolved
The aluminium of 0.075 mass parts is added, the mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, obtains clear LTA water
Colloidal sol.
In one embodiment of the invention, the step of in situ synthesis synthesis LTA molecular screen membrane, specifically includes:
The stainless (steel) wire crossed through coupling agent treatment is placed in reaction kettle, the LTA hydrosol is added, is reacted in 60 DEG C
The stainless (steel) wire is dipped to neutrality with deionized water after reaction by 20h, is dried under the conditions of 80 DEG C to get the LTA type point
Son sieve.
The present invention also provides a kind of LTA type molecular sieve, the LTA type molecular sieve by above-mentioned LTA type molecular sieve system
Preparation Method is prepared.
Further, the aperture of the LTA type molecular sieve is 0.4nm.
Technical solution of the present invention and technical effect are described further below by way of specific embodiment.
Embodiment 1:
A kind of LTA type molecular sieve, is prepared by following steps:
Stainless (steel) wire is pre-processed: stainless (steel) wire being cut into the disk that diameter is 18mm, with the hydrochloric acid of 1mol/L
Solution cleans the greasy dirt on the stainless (steel) wire, washes with water to neutrality, then impregnates 15h with the sodium hydroxide solution of 0.1mol/L
After take out, wash with water to neutrality, be placed in 60 DEG C of baking ovens drying to get pretreated stainless (steel) wire, it is spare；
3- aminopropyl triethoxysilane and toluene are configured to coupling agent according to mass ratio for 5:200, it will be preprocessed
Stainless (steel) wire afterwards is put into the coupling agent, is placed in 110 DEG C of reaction 1.5h in baking oven, is discarded coupling agent, stainless (steel) wire is dried
It is dry spare to get the stainless (steel) wire crossed through coupling agent treatment；
The preparation LTA hydrosol: silica solution (LUDOX AS-40) and deionized water are mixed according to mass ratio for 1:11
It closes, stirs 2h in 60 DEG C of heating water baths, obtain mixed liquor；
Sodium hydroxide is mixed with deionized water according to mass ratio for 6:13, is added after sodium hydroxide is completely dissolved
0.075 mass parts aluminium, is added above-mentioned mixed liquor after aluminium is completely dissolved, and stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；
In situ synthesis synthesizes LTA type molecular sieve: the stainless (steel) wire crossed through coupling agent treatment being placed in reactor bottom, is added
Enter above-mentioned LTA hydrosol 25mL, in 55 DEG C of reaction 20h, the stainless (steel) wire is dipped to neutrality with deionized water after reaction, in
Drying is under the conditions of 80 DEG C to get the LTA type molecular sieve.
Embodiment 2:
Stainless (steel) wire is pre-processed: stainless (steel) wire being cut into the disk that diameter is 15mm, with the hydrochloric acid of 1mol/L
Solution cleans the greasy dirt on the stainless (steel) wire, washes with water to neutrality, then impregnates 15h with the sodium hydroxide solution of 0.1mol/L
After take out, wash with water to neutrality, be placed in 60 DEG C of baking ovens drying to get pretreated stainless (steel) wire, it is spare；
3- aminopropyl triethoxysilane and toluene are configured to coupling agent according to mass ratio for 8:200, it will be preprocessed
Stainless (steel) wire afterwards is put into the coupling agent, is placed in 110 DEG C of reaction 1h in baking oven, is discarded coupling agent, stainless (steel) wire is dried,
It is spare up to the stainless (steel) wire crossed through coupling agent treatment；
The preparation LTA hydrosol: silica solution (LUDOX AS-40) and deionized water are mixed according to mass ratio for 1.1:11
It closes, stirs 2h in 60 DEG C of heating water baths, obtain mixed liquor；
Sodium hydroxide is mixed with deionized water according to mass ratio for 5.5:13, is added after sodium hydroxide is completely dissolved
Enter 0.075 mass parts aluminium, above-mentioned mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；
In situ synthesis synthesizes LTA type molecular sieve: the stainless (steel) wire crossed through coupling agent treatment being placed in reactor bottom, is added
Enter above-mentioned LTA hydrosol 25mL, for 24 hours in 50 DEG C of reactions, stainless (steel) wire is dipped to neutrality with deionized water after reaction, in 80 DEG C
Under the conditions of drying to get the LTA type molecular sieve.
Embodiment 3:
Stainless (steel) wire is pre-processed: stainless (steel) wire being cut into the disk that diameter is 20mm, with the hydrochloric acid of 1mol/L
Solution cleans the greasy dirt on the stainless (steel) wire, washes with water to neutrality, then impregnates 15h with the sodium hydroxide solution of 0.1mol/L
After take out, wash with water to neutrality, be placed in 60 DEG C of baking ovens drying to get pretreated stainless (steel) wire, it is spare；
3- aminopropyl triethoxysilane and toluene are configured to coupling agent according to mass ratio for 7:200, it will be preprocessed
Stainless (steel) wire afterwards is put into the coupling agent, is placed in 110 DEG C of reaction 1.5h in baking oven, is discarded coupling agent, stainless (steel) wire is dried
It is dry spare to get the stainless (steel) wire crossed through coupling agent treatment；
It prepares the LTA hydrosol: according to mass ratio being that 1.043:11 is carried out by silica solution (LUDOX AS-40) and deionized water
Mixing stirs 2h in 60 DEG C of heating water baths, obtains mixed liquor；
Sodium hydroxide is mixed with deionized water according to mass ratio for 5.55:13, after sodium hydroxide is completely dissolved
0.075 mass parts aluminium is added, above-mentioned mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, it is water-soluble to obtain clear LTA
Glue；
In situ synthesis synthesizes LTA type molecular sieve: the stainless (steel) wire crossed through coupling agent treatment being placed in reactor bottom, is added
Enter the above-mentioned LTA hydrosol, for 24 hours in 60 DEG C of reactions, stainless (steel) wire is dipped to neutrality with deionized water after reaction, in 80 DEG C of conditions
Lower drying is to get the LTA type molecular sieve.
Embodiment 4:
Stainless (steel) wire is pre-processed: stainless (steel) wire being cut into the disk that diameter is 18mm, with the hydrochloric acid of 1mol/L
Solution cleans the greasy dirt on the stainless (steel) wire, washes with water to neutrality, then impregnates 15h with the sodium hydroxide solution of 0.1mol/L
After take out, wash with water to neutrality, be placed in 60 DEG C of baking ovens drying to get pretreated stainless (steel) wire, it is spare；
3- aminopropyl triethoxysilane and toluene are configured to coupling agent according to mass ratio for 10:200, it will be preprocessed
Stainless (steel) wire afterwards is put into the coupling agent, is placed in 110 DEG C of reaction 2h in baking oven, is discarded coupling agent, stainless (steel) wire is dried,
It is spare up to the stainless (steel) wire crossed through coupling agent treatment；
It prepares the LTA hydrosol: according to mass ratio being that 1.05:11 is carried out by silica solution (LUDOX AS-40) and deionized water
Mixing stirs 2h in 60 DEG C of heating water baths, obtains mixed liquor；
Sodium hydroxide is mixed with deionized water according to mass ratio for 5.6:13, is added after sodium hydroxide is completely dissolved
Enter 0.075 mass parts aluminium, above-mentioned mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；
In situ synthesis synthesizes LTA type molecular sieve: the stainless (steel) wire crossed through coupling agent treatment being placed in reactor bottom, is added
Enter the above-mentioned LTA hydrosol, in 60 DEG C of reaction 18h, stainless (steel) wire is dipped to neutrality with deionized water after reaction, in 80 DEG C of conditions
Lower drying is to get the LTA type molecular sieve.
Embodiment 5:
Stainless (steel) wire is pre-processed: stainless (steel) wire being cut into the disk that diameter is 18mm, with the hydrochloric acid of 1mol/L
Solution cleans the greasy dirt on the stainless (steel) wire, washes with water to neutrality, then impregnates 15h with the sodium hydroxide solution of 0.1mol/L
After take out, wash with water to neutrality, be placed in 60 DEG C of baking ovens drying to get pretreated stainless (steel) wire, it is spare；
3- aminopropyl triethoxysilane and toluene are configured to coupling agent according to mass ratio for 9:200, it will be preprocessed
Stainless (steel) wire afterwards is put into the coupling agent, is placed in 110 DEG C of reaction 2h in baking oven, is discarded coupling agent, stainless (steel) wire is dried,
It is spare up to the stainless (steel) wire crossed through coupling agent treatment；
The preparation LTA hydrosol: silica solution (LUDOX AS-40) and deionized water are mixed according to mass ratio for 1:11
It closes, stirs 2h in 60 DEG C of heating water baths, obtain mixed liquor；
Sodium hydroxide is mixed with deionized water according to mass ratio for 5.8:13, is added after sodium hydroxide is completely dissolved
Enter 0.075 mass parts aluminium, above-mentioned mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；
In situ synthesis synthesizes LTA type molecular sieve: the stainless (steel) wire crossed through coupling agent treatment being placed in reactor bottom, is added
Enter the above-mentioned LTA hydrosol, in 60 DEG C of reaction 20h, stainless (steel) wire is dipped to neutrality with deionized water after reaction, in 80 DEG C of conditions
Lower drying is to get the LTA type molecular sieve.
The morphology characterization of LTA type molecular screen membrane:
SEM identification in surface is carried out to LTA type molecular sieve made from embodiment 3, it is as illustrated in fig. 1 and 2 to obtain photo.By Fig. 1
With 2 as can be seen that the matrix surface of LTA type molecular sieve made from the embodiment of the present invention 3 generates the continuous LTA molecule of one layer of densification
Sieve film.
The composition of LTA type molecular sieve is identified:
X-ray diffraction identification is carried out to LTA type zeolite matrix made from the embodiment of the present invention 3, is tied as shown in Figure 3
Fruit.As seen from Figure 3, LTA type molecular sieve made from embodiment 3 is pure phase, is generated without stray crystal body.
The surface SEM qualification result and X-ray diffraction of the LTA type molecular screen membrane as made from Examples 1 to 2,4~5
Spectrogram is very close with embodiment 3, to save space, Examples 1 to 2 not shown herein, 4~5 SEM qualification result and X
X ray diffraction spectrogram.
Comparative example 1: comparative example 1 and the embodiment of the present invention 3 use essentially identical preparation method to prepare LTA type molecular sieve,
It the difference is that only, comparative example 1 in situ growth method synthesis LTA type molecular sieve the step of in the base material that uses for oxygen
Change aluminium ceramics.
Comparative example 2: comparative example 2 and the embodiment of the present invention 3 use essentially identical preparation method to prepare LTA type molecular sieve,
The step of it the difference is that only, prepare the LTA hydrosol are as follows: the preparation LTA hydrosol: by silica solution (LUDOX AS-40) with
Deionized water is that 0.5215:11 is mixed according to mass ratio, stirs 2h in 60 DEG C of heating water baths, obtains mixed liquor；
Sodium hydroxide is mixed with deionized water according to mass ratio for 2.775:13, after sodium hydroxide is completely dissolved
0.0375 mass parts aluminium is added, above-mentioned mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, it is water-soluble to obtain clear LTA
Glue.
Comparative example 3: comparative example 3 and the embodiment of the present invention 3 use essentially identical preparation method to prepare LTA type molecular sieve,
The step of it the difference is that only, prepare the LTA hydrosol are as follows: the preparation LTA hydrosol: by silica solution (LUDOX AS-40) with
Deionized water is that 2.086:11 is mixed according to mass ratio, stirs 2h in 60 DEG C of heating water baths, obtains mixed liquor；
Sodium hydroxide is mixed with deionized water according to mass ratio for 11.1:13, after sodium hydroxide is completely dissolved
0.15 mass parts aluminium is added, above-mentioned mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, it is water-soluble to obtain clear LTA
Glue.
Comparative example 4: comparative example 4 and the embodiment of the present invention 3 use essentially identical preparation method to prepare LTA type molecular sieve,
It the difference is that only, 3- aminopropyl triethoxysilane and toluene are configured to coupling agent according to mass ratio for 3.5:200.
Comparative example 5~6: comparative example 5~6 and the embodiment of the present invention 3 are using essentially identical preparation method preparation LTA type point
Son sieve, the difference is that only, in situ in the step of growth method synthesis LTA type molecular sieve, when controlling the reaction of reaction kettle
Between be respectively 12h and 48h.
Comparative example 7~8: comparative example 7~8 and the embodiment of the present invention 3 are using essentially identical preparation method preparation LTA type point
Son sieve, the difference is that only, in situ in the step of growth method synthesis LTA type molecular sieve, control the reaction temperature of reaction kettle
Degree is respectively 40 DEG C and 70 DEG C.
Below using SEM qualification test above-mentioned to LTA type made from the embodiment of the present invention 1~5 and comparative example 1~8
Molecular sieve thicknesses of layers, coating growth situation are tested, and are analyzed the flux of each group LTA type molecular sieve, as a result such as
Shown in the following table 1.
Wherein, the analysis method of flux is measurement each group LTA type analysis sieve membrane at alcohol water (90% ethanol solution, 75 DEG C) point
From the flux in experiment.
Table 1
From the test result of upper table 1, it can be concluded that, LTA type molecular screen membrane made from the embodiment of the present invention 1~5 is uniform
Densification is generated without stray crystal, and the mixed liquor for analyzing second alcohol and water has excellent separation selectivity energy.
From the comparison result of the embodiment of the present invention 3 and comparative example 1 as can be seen that use base material for 1600 purposes not
Rust steel mesh is improved more than 2 times compared to using the membrane flux of aluminium oxide ceramics, LTA type molecular sieve obtained.The test result table
Bright, the stainless (steel) wire for 1600 mesh that the present invention uses, aperture is 3 μm, and aperture is smaller, may make what LTA attachment was formed up
The aperture of composite material significantly improves its separation selectivity to alcohol water between the kinetic diameter of alcohol hydrone
Energy.
It can be seen that from the comparison result of the embodiment of the present invention 3 and comparative example 2,3 and increase or subtract the addition for burning silica solution
Amount, has large effect for the performance of the LTA type molecular sieve of synthesis.Specifically, being reduced when by the additive amount of silica solution
To the additive amount of embodiment 3 half when, the single crystal size of LTA type molecule of synthesis can be made to become larger, and the crystal of film layer point
Cloth compactness is poor, while reducing its membrane flux；When the additive amount of silica solution is increased to its 2 times, then it can make synthesis
The single crystal size of LTA type molecule becomes smaller, and the film layer compactness formed is poor, while also reducing its membrane flux.Therefore, silica solution
Concentration will have a direct impact on the pattern of LTA type molecular sieve, film layer compactness with membrane flux size.
It can be seen that from the comparison result of the embodiment of the present invention 3 and comparative example 4 by the 3- aminopropyl three in coupling agent
After Ethoxysilane additive amount is reduced to the half of 3 usage amount of embodiment, the film layer compactness of LTA type molecular sieve obtained is poor,
And flux depression does not still influence the form of monocrystalline substantially.
From the embodiment of the present invention 3 in the comparison result of comparative example 5~6 as can be seen that when control when reacting of reaction kettle
Between be 12h when, LTA type molecular sieve obtained will appear the unbodied situation of portion of monocrystalline, and the compactness of film layer is poor, membrane flux
Become smaller.When the reaction time for controlling reaction kettle is 48h, the single crystal size of LTA molecular sieve obtained becomes smaller, and film layer compactness
Poor, membrane flux becomes smaller.As it can be seen that the pattern of the reaction time of reaction kettle and LTA type molecular sieve, film layer compactness and membrane flux are close
Cut phase is closed.
From the embodiment of the present invention 3 in the comparison result of comparative example 7~8 as can be seen that when control reaction kettle react temperature
When degree is 40 DEG C or 70 DEG C, LTA molecular sieve obtained will appear that portion of monocrystalline is amorphous, and film layer compactness is poor, and membrane flux
It is smaller.Can be with, the pattern of the reaction temperature of reaction kettle and LTA type molecular sieve, film layer compactness and membrane flux are closely related.
LTA type molecular sieve provided in an embodiment of the present invention will be stainless after coupling agent treatment using in situ synthesis
Steel mesh is placed in the reaction kettle of the LTA hydrosol, and under the conditions of 50~60 DEG C of temperature reaction 18~for 24 hours so that LTA is water-soluble
Glue can the equably accumulated growth on the stainless (steel) wire, form fine and close LTA type molecular screen membrane, which has in molecule
Have in the mixture of machine object and water it is high-throughput and highly selective, meanwhile, mechanical strength is preferable, and entire preparation process is simple, item
Part is mild, and finished product efficiency is high, is conducive to industrialized production.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of LTA type molecular sieve, which comprises the steps of:
Prepare the LTA hydrosol:
According to mass ratio be (1~1.1) by silica solution and deionized water: 11 mix, and stir 2h in 60 DEG C of heating water baths, obtain
To mixed liquor；
According to mass ratio be (5~6) by sodium hydroxide and deionized water: 13 mix, after sodium hydroxide is completely dissolved plus
Enter aluminium, the mixed liquor is added after aluminium is completely dissolved, stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol；
In situ synthesis synthesizes LTA type molecular sieve:
The stainless (steel) wire crossed through coupling agent treatment is placed in reaction kettle, the LTA hydrosol is added, reacts 18 in 50~60 DEG C
~for 24 hours, the stainless (steel) wire is dipped to neutrality with deionized water after reaction, drying is under the conditions of 80 DEG C to get the LTA type
Molecular sieve.
2. the preparation method of LTA type molecular sieve as described in claim 1, which is characterized in that synthesized in the in situ synthesis
Before the step of LTA type molecular sieve, further includes:
Stainless (steel) wire after pretreatment is handled with coupling agent:
According to mass ratio be (5~10) by 3- aminopropyl triethoxysilane and toluene: 200 are configured to coupling agent, will be located in advance
Stainless (steel) wire after reason is put into the coupling agent, is placed in 110 DEG C of 1~2h of reaction in baking oven, is discarded the coupling agent, will be described
Stainless (steel) wire drying is spare to get the stainless (steel) wire crossed through coupling agent treatment.
3. the preparation method of LTA type molecular sieve as claimed in claim 2, which is characterized in that it is described with coupling agent to stainless
Before the step of steel mesh is handled, further includes:
Stainless (steel) wire is pre-processed: stainless (steel) wire being cut into the disk that diameter is 15~20mm, with the hydrochloric acid of 1mol/L
Solution cleans the greasy dirt on the stainless (steel) wire, washes with water to neutrality, then impregnates 15h with the sodium hydroxide solution of 0.1mol/L
After take out, wash with water to neutrality, be placed in 60 DEG C of baking ovens drying to get pretreated stainless (steel) wire, it is spare.
4. the preparation method of LTA type molecular sieve as described in claim 1, which is characterized in that the density of the stainless (steel) wire is
1600 mesh.
5. the preparation method of LTA type molecular sieve as described in claim 1, which is characterized in that the molar ratio of the LTA hydrosol
Group becomes Al2O3:SiO2:Na2O:H2O=1:5:50:1000.
6. the preparation method of LTA type molecular sieve as described in claim 1, which is characterized in that described by silica solution and deionization
Water is (1~1.1) according to mass ratio: 11 are mixed, in the step of 60 DEG C of heating water baths stir 2h, obtain mixed liquor, comprising:
Silica solution is mixed with deionized water according to mass ratio for 1.043:11,2h is stirred in 60 DEG C of heating water baths, obtains
Mixed liquor.
7. the preparation method of LTA type molecular sieve as described in claim 1 or 6, which is characterized in that it is described by sodium hydroxide with go
Ionized water is (5~6) according to mass ratio: 13 are mixed, and aluminium are added after sodium hydroxide is completely dissolved, after aluminium is completely dissolved
It is added the mixed liquor, stirring at normal temperature for 24 hours, the step of obtaining the clear LTA hydrosol, specifically includes:
Sodium hydroxide is mixed with deionized water according to mass ratio for 5.55:13, is added after sodium hydroxide is completely dissolved
The aluminium of 0.075 mass parts, is added the mixed liquor after aluminium is completely dissolved, and stirring at normal temperature for 24 hours, obtains the clear LTA hydrosol.
8. the preparation method of LTA type molecular sieve as described in claim 1, which is characterized in that the in situ synthesis synthesizes LTA
The step of molecular screen membrane, specifically includes:
The stainless (steel) wire crossed through coupling agent treatment is placed in reaction kettle, the LTA hydrosol is added, in 60 DEG C of reaction 20h, instead
The stainless (steel) wire is dipped to neutrality by Ying Houyong deionized water, and drying is under the conditions of 80 DEG C to get the LTA type molecular sieve.
9. a kind of LTA type molecular sieve, which is characterized in that the LTA type molecular sieve is as described in claim 1~8 any one
The preparation method of LTA type molecular sieve be prepared.
10. LTA type molecular sieve as claimed in claim 9, which is characterized in that the aperture of the LTA type molecular sieve is 0.4nm.
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