CN104548956A - Method for preparing NaA type zeolite membrane for isopropyl alcohol dehydration - Google Patents

Method for preparing NaA type zeolite membrane for isopropyl alcohol dehydration Download PDF

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Publication number
CN104548956A
CN104548956A CN201310501059.4A CN201310501059A CN104548956A CN 104548956 A CN104548956 A CN 104548956A CN 201310501059 A CN201310501059 A CN 201310501059A CN 104548956 A CN104548956 A CN 104548956A
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naa type
molecular sieve
preparation
zeolite membrane
type molecular
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CN201310501059.4A
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秦宏佳
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Dalian Shahekou District Small and Medium Sized Enterprise Service Center
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Dalian Shahekou District Small and Medium Sized Enterprise Service Center
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Priority to CN201310501059.4A priority Critical patent/CN104548956A/en
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Abstract

The invention discloses a method for preparing a NaA type zeolite membrane for isopropyl alcohol 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; performing hydrothermal synthesis for 4 to 6h; taking the support tube out of a reaction kettle after reaction, adding the crystallization mother liquid in the same proportion, performing microwave heating to 60 to 80 DEG C, and performing reaction for 1 to 3h; washing the support tube with de-ionized water after reaction, and drying the support tube at 80 DEG C.

Description

For the preparation method of the NaA type zeolite membrane of isopropanol dehydration
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 isopropyl alcohol separation.
Background technology
Along with the enhancing day by day of people's environmental protection and awareness of saving energy, the countries in the world especially flourishing and state such as the U.S., Japan, West Europe large to import demand for energy of economic technology start to carry out large-scale technological improvement to traditional highly energy-consuming, high pollution industry.Membrane separation technique has low power consuming due to it, produce pollution, is easy to realization and is continuously separated, is easy to the advantages such as amplification compared with the isolation technics in traditional industry, obtains applying more and more widely at industrial departments such as chemical industry, food, medicine, environmental protection, metallurgy.
Molecular screen membrane because of its have high hydrothermal stability, molecule rank regular pore canal and can the feature such as ion-exchange and the skeleton Si/Al of the .NaA type molecular sieve that gets more and more people's extensive concerning is 1, there is very strong hydrophily; Duct size is 0.42nm, between water and most of organic molecule.High aluminium content and suitable duct size feature make the NaA type molecular screen membrane formed on porous supporting body have very high selective penetrated property to glassware for drinking water.The separation adopting the infiltration evaporation process of NaA type molecular screen membrane to be applied to azeotropic (nearly azeotropic) water/organic mixture has very wide application prospect.Calendar year 2001, the reported first such as Morigami NaA type molecular screen membrane prepares the large-scale application in anhydrous isopropyl alcohol separation process removing a small amount of water in isopropyl alcohol.
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 isopropanol dehydration, NaA type zeolite membrane prepared by the method is for separating of high concentration isopropanol dehydration, 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 isopropanol 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 crystallization 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 ~ 6h; React rear taking-up reactor, and add the crystallization mother liquor of identical proportioning, then heating using microwave to 60 ~ 80 DEG C, reaction 1 ~ 3h; After having reacted, spend deionized water support tube, and dry 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=2 Al 2O 3:Na 2O=6 H 2O:Al 2O 3=150。
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, improves resistance to swelling, extends its service life.And NaA type zeolite membrane prepared by the present invention has excellent separating property, and when the isopropanol water solution of separation of high-concentration isopropanol content, the content through side water is 100% under chromatogram inspection condition, water to the separation of isopropyl alcohol 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.
The half of the crystallization mother liquor prepared joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE), and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 60 DEG C, Hydrothermal Synthesis 6h; Reacted rear taking-up reactor, then added remaining crystallization mother liquor, then heating using microwave is to 60C, reaction 3h; After having reacted, spend deionized water support tube, and dry 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.
The NaA type molecular sieve that embodiment provides to the separation of high concentration aqueous isopropanol close to infinite.
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.
The half of the crystallization mother liquor prepared joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE), and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 80 DEG C, Hydrothermal Synthesis 4h; Reacted rear taking-up reactor, then added remaining crystallization mother liquor, then heating using microwave is to 60C, reaction 1h; After having reacted, spend deionized water support tube, and dry 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.
The NaA type molecular sieve that embodiment provides to the separation of high concentration aqueous isopropanol close to infinite.
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.
The half of the crystallization mother liquor prepared joined in the stainless steel cauldron containing polytetrafluoroethylene (PTFE), and put into the porous carrier pipe of planting crystal seed in advance, reaction temperature is 80 DEG C, Hydrothermal Synthesis 4h; Reacted rear taking-up reactor, then added remaining crystallization mother liquor, then heating using microwave is to 60C, reaction 1h; 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.
The NaA type molecular sieve that embodiment provides to the separation of high concentration aqueous isopropanol close to infinite.

Claims (5)

1. for a preparation method for the NaA type zeolite membrane of isopropanol 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 crystallization 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 ~ 6h; React rear taking-up reactor, and add the crystallization mother liquor of identical proportioning, then heating using microwave to 60 ~ 80 DEG C, reaction 1 ~ 3h; After having reacted, spend deionized water support tube, and dry 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 isopropanol 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=2 Al 2O 3:Na 2O=6 H 2O:Al 2O 3=150。
3. the preparation method of the NaA type zeolite membrane for isopropanol dehydration according to claim 1, 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 isopropanol 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 isopropanol dehydration according to claim 1, is characterized in that: the particle size of described NaA type molecular sieve is 0.1 ~ 0.5 μm.
CN201310501059.4A 2013-10-21 2013-10-21 Method for preparing NaA type zeolite membrane for isopropyl alcohol dehydration Pending CN104548956A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109970075A (en) * 2019-03-26 2019-07-05 上海工程技术大学 A kind of method of low temperature synthesis A type molecular sieve film
CN110615446A (en) * 2019-11-12 2019-12-27 西北大学 Method for one-step synthesis of single-layer MWW molecular sieve by aid of amphiphilic organosilane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109970075A (en) * 2019-03-26 2019-07-05 上海工程技术大学 A kind of method of low temperature synthesis A type molecular sieve film
CN109970075B (en) * 2019-03-26 2023-03-31 上海工程技术大学 Method for synthesizing A-type molecular sieve membrane at low temperature
CN110615446A (en) * 2019-11-12 2019-12-27 西北大学 Method for one-step synthesis of single-layer MWW molecular sieve by aid of amphiphilic organosilane

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Application publication date: 20150429