CN104548953A - Method for preparing NaA type zeolite membrane for ethanol dehydration - Google Patents
Method for preparing NaA type zeolite membrane for ethanol dehydration Download PDFInfo
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- CN104548953A CN104548953A CN201310498693.7A CN201310498693A CN104548953A CN 104548953 A CN104548953 A CN 104548953A CN 201310498693 A CN201310498693 A CN 201310498693A CN 104548953 A CN104548953 A CN 104548953A
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- molecular sieve
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Abstract
The invention discloses a method for preparing a NaA type zeolite membrane for ethanol dehydration. NaA type molecular sieves are taken as seed crystals, an ultra-thin uniform seed crystal layer is directly introduced into the surface of a porous support tube, and high-performance NaA type zeolite membranes with different silica-alumina ratios are synthesized by hydrothermal crystallization. The preparation method is implemented by the following steps of introducing a layer of NaA type molecular sieve into the surface of the porous support tube by adopting a hot dipping method, and then introducing a second layer of NaA type molecular sieve to form a dense ultra-thin seed crystal layer by adopting a dip coating method; preparing crystallization mother liquid from silica sol, sodium hydroxide, sodium metaaluminate and de-ionized water; adding the prepared crystallization mother liquid into a stainless steel reaction kettle containing polytetrafluoroethylene, placing the porous support tube pre-planted with seed crystals, and performing hydrothermal synthesis for 4 to 10h at the reaction temperature of 60 to 80 DEG C; taking out the support tube after reaction, washing the support tube with de-ionized water, and drying the support tube at 80 DEG C.
Description
Technical field
The invention belongs to inorganic material permeability and separation technical field, relate to a kind of preparation method of zeolite molecular sieve film, particularly a kind of preparation method of the NaA type molecular sieve for ethanol dehydration.
Background technology
Under the increasingly international background of energy scarcity, environmental problem, insider starts the new forms of energy seeking to substitute traditional energy one after another, so ethanol becomes the focus that people pay close attention to.Traditional rectifying and pressure-variable adsorption power consumption comparatively large, and support zeolite membrane and enjoy favor due to the remarkable separating effect in alcohol/aqueous mixtures.
The method of industrial high-purity ethanol is mainly divided into three kinds: (1) rectification method; (2) organic polymer membrane separation process; (3) zeolite molecular sieve membrane separation process.At present, in domestic industry, the main method of high-purity ethanol is rectification method, and zeolite molecular sieve embrane method still belongs to the elementary step, and particularly NaA molecular sieve membrane separation process is domestic does not realize industrialization, is still in laboratory stage.In actual applications, rectification method is with the feature of its high energy consumption, and be difficult to be applied in large-scale industrial production high purity ethanol, namely economic feasibility is lower.And organic polymer membrane separation process, due to the limitation of film itself, namely not easy cleaning, mechanical strength is low, service life is short, limit its ethanol/water system be separated in use.Zeolite molecular sieve film utilizes porous material to do carrier, at its surperficial synthesis zeolite, forms uniform zeolite molecular sieve film.This type of film have high temperature resistant, resistance to chemical attack, mechanical strength greatly, the not easily advantage such as swelling and even aperture distribution.NaA molecular sieve membrane, as a kind of zeolite molecular sieve film, has that easy cleaning, mechanical strength are high, long service life, selection separation high, makes it in separating alcohol/aqueous systems, has a good application prospect in large-scale production high purity ethanol.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the NaA type zeolite membrane for ethanol dehydration, NaA type zeolite membrane prepared by the method is dewatered for separating of high concentration ethanol, and separation reaches infinite in chromatogram limit range.
The following technical scheme of concrete employing:
For a preparation method for the NaA type zeolite membrane of ethanol dehydration, using NaA type molecular sieve as crystal seed, directly introduce ultra-thin homogeneous crystal seed layer at porous carrier tube-surface, hydrothermal crystallizing synthesizes the high performance NaA type zeolite membrane with Different Silicon aluminum ratio.
Its preparation method carries out as follows: first adopt hot submersion method to introduce one deck NaA type molecular sieve at porous carrier tube-surface, then adopts painting to draw to carry out the coffin upon burial into second layer NaA type molecular sieve, form fine and close ultra-thin crystal seed layer; With Ludox, NaOH, sodium metaaluminate and deionized water for raw material, by mol ratio SiO
2: Al
2o
3=0.5 ~ 3, Al
2o
3: Na
2o=2 ~ 6, H
2o:Al
2o
3=100 ~ 300 preparation elite mother liquors; Joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE) by the crystallization mother liquor prepared, and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 60 ~ 80 DEG C, Hydrothermal Synthesis 4 ~ 10h; React rear taking-up, spent deionized water, and dried at 80 DEG C.
Described porous carrier pipe average pore size is 1 ~ 3 μm;
The particle size of described NaA type molecular sieve is 0.05 ~ 5 μm.
The preparation method of NaA type zeolite membrane provided by the invention, the mol ratio of described crystallization mother liquor raw material is preferred:
SiO
2:Al
2O
3=1.5 Al
2O
3:Na
2O=4 H
2O:Al
2O
3=250。
The preparation method of NaA type zeolite membrane provided by the invention, the preferred α of described porous carrier pipe-Al
2o
3pipe, porosity is 50%.
The preparation method of NaA type zeolite membrane provided by the invention, described porous carrier pipe average pore size preferably 1 ~ 2 μm.
The preparation method of NaA type zeolite membrane provided by the invention, the particle size of described NaA type molecular sieve preferably 0.1 ~ 0.5 μm.
Compared to prior art, the two-layer NaA type molecular sieve that the present invention adopts combines and forms fine and close ultra-thin crystal seed layer, is conducive to forming uniform nucleating point, and strengthens the mechanical strength of zeolite membrane, extend its service life.And NaA type zeolite membrane prepared by the present invention has excellent separating property, and when the ethanol water of separation of high-concentration ethanol content, the content through side water is 100% under chromatogram inspection condition, water to the separation of ethanol close to infinite.
Detailed description of the invention
The following examples can make the present invention of those of ordinary skill in the art's comprehend, but do not limit the present invention in any way.
Embodiment 1
Porosity is the α-Al of 50%
2o
3its two ends polytetrafluoroethylene (PTFE) plug, as carrier, seals by earthenware.Good seal support tube is placed in the baking oven of 170 DEG C and heats 2h, then hot carrier being put into fast mass concentration is slowly take out after the large seed-solution 20s of 8wt.%, take off the water in polytetrafluoroethylene (PTFE) plug releasing support tube, dry 24h at 50 DEG C, form ground floor NaA type molecular sieve.Adopt again and be coated with daraf(reciprocal of farad) introducing second layer NaA type molecular sieve, form fine and close ultra-thin crystal seed layer.
With Ludox, NaOH, sodium metaaluminate and deionized water for raw material, by mol ratio SiO
2: Al
2o
3=0.5, Al
2o
3: Na
2o=2, H
2o:Al
2o
3=100 preparation crystallization mother liquors.First join in sodium hydroxide solution by Ludox, stirred at ambient temperature 16h forms solution A; Again sodium metaaluminate is joined in solution A with vigorous stirring slowly, then add Fluorinse, stir 1h and form stable crystallization mother liquor.
Joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE) by the crystallization mother liquor prepared, and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 60 DEG C, Hydrothermal Synthesis 10h; React rear taking-up, spent deionized water, and dried at 80 DEG C.
Described porous carrier pipe average pore size is 1 ~ 3 μm;
The particle size of described NaA type molecular sieve is 0.05 ~ 5 μm.
Described in the present embodiment, porous carrier pipe average pore size is 1 ~ 2 μm.
The particle size of the present embodiment NaA type molecular sieve is 0.1 ~ 0.5 μm.
Embodiment 2
Porosity is the α-Al of 50%
2o
3its two ends polytetrafluoroethylene (PTFE) plug, as carrier, seals by earthenware.Good seal support tube is placed in the baking oven of 170 DEG C and heats 2h, then hot carrier being put into fast mass concentration is slowly take out after the large seed-solution 20s of 8wt.%, take off the water in polytetrafluoroethylene (PTFE) plug releasing support tube, dry 24h at 50 DEG C, form ground floor NaA type molecular sieve.Adopt again and be coated with daraf(reciprocal of farad) introducing second layer NaA type molecular sieve, form fine and close ultra-thin crystal seed layer.
With Ludox, NaOH, sodium metaaluminate and deionized water for raw material, by mol ratio SiO
2: Al
2o
3=3, Al
2o
3: Na
2o=6, H
2o:Al
2o
3=300 preparation crystallization mother liquors.First join in sodium hydroxide solution by Ludox, stirred at ambient temperature 16h forms solution A; Again sodium metaaluminate is joined in solution A with vigorous stirring slowly, then add Fluorinse, stir 1h and form stable crystallization mother liquor.
Joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE) by the crystallization mother liquor prepared, and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 80 DEG C, Hydrothermal Synthesis 4h; React rear taking-up, spent deionized water, and dried at 80 DEG C.
Described porous carrier pipe average pore size is 1 ~ 3 μm;
The particle size of described NaA type molecular sieve is 0.05 ~ 5 μm.
Described in the present embodiment, porous carrier pipe average pore size is 1 ~ 2 μm.
The particle size of the present embodiment NaA type molecular sieve is 0.1 ~ 0.5 μm.
Embodiment 3
Porosity is the α-Al of 50%
2o
3its two ends polytetrafluoroethylene (PTFE) plug, as carrier, seals by earthenware.Good seal support tube is placed in the baking oven of 170 DEG C and heats 2h, then hot carrier being put into fast mass concentration is slowly take out after the large seed-solution 20s of 8wt.%, take off the water in polytetrafluoroethylene (PTFE) plug releasing support tube, dry 24h at 50 DEG C, form ground floor NaA type molecular sieve.Adopt again and be coated with daraf(reciprocal of farad) introducing second layer NaA type molecular sieve, form fine and close ultra-thin crystal seed layer.
With Ludox, NaOH, sodium metaaluminate and deionized water for raw material, by mol ratio SiO
2: Al
2o
3=1.5, Al
2o
3: Na
2o=4, H
2o:Al
2o
3=250 preparation crystallization mother liquors.First join in sodium hydroxide solution by Ludox, stirred at ambient temperature 16h forms solution A; Again sodium metaaluminate is joined in solution A with vigorous stirring slowly, then add Fluorinse, stir 1h and form stable crystallization mother liquor.
Joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE) by the crystallization mother liquor prepared, and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 80 DEG C, Hydrothermal Synthesis 4h; React rear taking-up, spent deionized water, and dried at 80 DEG C.
Described porous carrier pipe average pore size is 1 ~ 3 μm;
The particle size of described NaA type molecular sieve is 0.05 ~ 5 μm.
Described in the present embodiment, porous carrier pipe average pore size is 1 ~ 2 μm.
The particle size of the present embodiment NaA type molecular sieve is 0.1 ~ 0.5 μm.
Claims (5)
1. for a preparation method for the NaA type zeolite membrane of ethanol dehydration, using NaA type molecular sieve as crystal seed, directly introduce ultra-thin homogeneous crystal seed layer at porous carrier tube-surface, hydrothermal crystallizing synthesizes the high performance NaA type zeolite membrane with Different Silicon aluminum ratio; Its preparation method carries out as follows: first adopt hot submersion method to introduce one deck NaA type molecular sieve at porous carrier tube-surface, then adopts painting to draw to carry out the coffin upon burial into second layer NaA type molecular sieve, form fine and close ultra-thin crystal seed layer; With Ludox, NaOH, sodium metaaluminate and deionized water for raw material, by mol ratio SiO
2: Al
2o
3=0.5 ~ 3, Al
2o
3: Na
2o=2 ~ 6, H
2o:Al
2o
3=100 ~ 300 preparation elite mother liquors; Joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE) by the crystallization mother liquor prepared, and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 60 ~ 80 DEG C, Hydrothermal Synthesis 4 ~ 10h; React rear taking-up, spent deionized water, and dried at 80 DEG C;
Described porous carrier pipe average pore size is 1 ~ 3 μm;
The particle size of described NaA type molecular sieve is 0.05 ~ 5 μm.
2. the preparation method of the NaA type zeolite membrane for ethanol dehydration according to claim 1, is characterized in that: the mol ratio of described crystallization mother liquor raw material is:
SiO
2:Al
2O
3=1.5 Al
2O
3:Na
2O=4 H
2O:Al
2O
3=250。
3. the N for ethanol dehydration according to claim 1
xthe preparation method of type A zeolite film, is characterized in that: described porous carrier pipe is α-Al
2o
3pipe, porosity is 50%.
4. the preparation method of the NaA type zeolite membrane for ethanol dehydration according to claim 1, is characterized in that: described porous carrier pipe average pore size is 1 ~ 2 μm.
5. the preparation method of the NaA type zeolite membrane for ethanol dehydration according to claim 1, is characterized in that: the particle size of described NaA type molecular sieve is 0.1 ~ 0.5 μm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478020A (en) * | 2015-12-21 | 2016-04-13 | 北京工业大学 | MOFs/NaA molecular sieve composite membrane for acetic acid dehydration and preparation method for MOFs/NaA molecular sieve composite membrane |
| CN107185487A (en) * | 2017-05-23 | 2017-09-22 | 盛朗（广州）能源科技有限公司 | A kind of A type molecular sieve dehumidifying carrier and preparation method thereof |
| CN107433140A (en) * | 2017-09-24 | 2017-12-05 | 韩小学 | A kind of preparation method of high flux molecular screen membrane |
| CN108905259A (en) * | 2018-07-18 | 2018-11-30 | 芜湖青悠静谧环保科技有限公司 | A kind of novel process unit for preparing alcohol fuel |
| CN109092080A (en) * | 2018-10-10 | 2018-12-28 | 邱海兵 | A kind of inorganic reverse osmosis membrane materials of water process |
| CN110719808A (en) * | 2017-06-07 | 2020-01-21 | 日本碍子株式会社 | Dewatering method and dewatering device |
| CN110745841A (en) * | 2019-12-02 | 2020-02-04 | 山东蓝景膜技术工程有限公司 | Method for green synthesis of NaA type zeolite molecular sieve membrane |
-
2013
- 2013-10-21 CN CN201310498693.7A patent/CN104548953A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478020A (en) * | 2015-12-21 | 2016-04-13 | 北京工业大学 | MOFs/NaA molecular sieve composite membrane for acetic acid dehydration and preparation method for MOFs/NaA molecular sieve composite membrane |
| CN107185487A (en) * | 2017-05-23 | 2017-09-22 | 盛朗（广州）能源科技有限公司 | A kind of A type molecular sieve dehumidifying carrier and preparation method thereof |
| CN110719808A (en) * | 2017-06-07 | 2020-01-21 | 日本碍子株式会社 | Dewatering method and dewatering device |
| CN110719808B (en) * | 2017-06-07 | 2021-12-28 | 日本碍子株式会社 | Dewatering method and dewatering device |
| CN107433140A (en) * | 2017-09-24 | 2017-12-05 | 韩小学 | A kind of preparation method of high flux molecular screen membrane |
| CN108905259A (en) * | 2018-07-18 | 2018-11-30 | 芜湖青悠静谧环保科技有限公司 | A kind of novel process unit for preparing alcohol fuel |
| CN109092080A (en) * | 2018-10-10 | 2018-12-28 | 邱海兵 | A kind of inorganic reverse osmosis membrane materials of water process |
| CN110745841A (en) * | 2019-12-02 | 2020-02-04 | 山东蓝景膜技术工程有限公司 | Method for green synthesis of NaA type zeolite molecular sieve membrane |
| CN110745841B (en) * | 2019-12-02 | 2022-01-18 | 山东蓝景膜技术工程有限公司 | Method for green synthesis of NaA type zeolite molecular sieve membrane |
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