CN101862603A - Preparation method of tubular porous fiber molecular sieve membrane - Google Patents
Preparation method of tubular porous fiber molecular sieve membrane Download PDFInfo
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- CN101862603A CN101862603A CN 201010214061 CN201010214061A CN101862603A CN 101862603 A CN101862603 A CN 101862603A CN 201010214061 CN201010214061 CN 201010214061 CN 201010214061 A CN201010214061 A CN 201010214061A CN 101862603 A CN101862603 A CN 101862603A
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- molecular sieve
- porous fiber
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- sieve membrane
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Abstract
The invention relates to a preparation method of a tubular porous fiber molecular sieve membrane, which comprises the following steps that: taking an aluminum source, a sodium source, silica or silica sol and water as the raw materials and the molar ratio of the raw materials in a reaction system is as follows: silica: aluminum source: sodium source:water=1 to 10:1 to 8:1 to 8:80 to 1000, soaking a tubular porous fiber support body in the reaction system, reacting at the temperature of 50 to 130DEG C, and crystallizing for 3 to 40h. The preparation method has the advantages that the preparation process is simple, a plurality of contacts are arranged between an inorganic material braided hose support layer and a molecular sieve membrane composite layer and the combination is tight. Through the control of the preparation conditions, the separation capability of the prepared tubular porous fiber molecular sieve membrane is significant.
Description
Technical field
The present invention relates to a kind of preparation method of fiber molecule sieve membrane, relate in particular to a kind of preparation method of tubular porous fiber molecular sieve membrane.
Background technology
Molecular sieve is a kind of crystalline microporous material, has regular pore passage structure, good heat endurance and catalytic action, and molecular screen membrane is one of the forward position of membrane separation technique research field and focus.NaA type molecular sieve is a skeleton with Si/Al, has very strong hydrophily, and the duct size is 0.3～0.5nm, between water and most of organic molecule.High aluminium content and suitable duct size characteristics make the NaA type molecular screen membrane that forms on porous supporting body to glassware for drinking water very high selection permeability be arranged, bug hole inside exists powerful electric field and polarity effect, water there is very big affinity, the A type molecular sieve film can pervaporation be deviate from the moisture in the organic matter, calendar year 2001, reported first such as Morigami NaA type molecular screen membrane low amounts of water in removing ethanol prepare large-scale application in the absolute ethyl alcohol separation process, the separation of adopting the infiltration evaporation process of NaA type molecular screen membrane to be applied to azeotropic (near azeotropic) water/organic mixture has very wide application prospect.
The synthetic method of molecular screen membrane has original position hydrothermal synthesis method, crystal seed method, plug-hole method, microwave heating method, pulsed laser deposition and electrophoretic deposition, defective elimination and film doping method etc., wherein the original position hydrothermal synthesis method be traditional also be the most frequently used molecular screen membrane synthetic method, carrier is directly put into synthesis mother liquid in some way, under hydrothermal synthesizing condition, the molecular sieve crystal film forming of promptly on carrier surface, growing, this method is comparatively simple, and do not need special device, thereby use comparatively extensive, but synthesis cycle is longer, and micro-structural is wayward.The diauxic growth method is earlier with carrier precoating crystal seed, places mother liquor original position hydro-thermal synthetic again, crystallization film forming, the method original position hydro-thermal diauxic growth method that is otherwise known as.The diauxic growth method has following advantage: removed the nucleation period, shortened generated time; Nucleation and two steps of growth are separately carried out, be easy to control the micro-structural of crystal growth and molecular screen membrane; The existence of crystal seed makes the diauxic growth method have bigger operating flexibility.Jafar etc. have synthesized NaA type molecular screen membrane on the carbon/zirconia tubular support, be that the separation of the infiltration evaporation in 1/9 the solution is 5000 in water/ethanol mass ratio in the time of 70 ℃, and permeation flux only is 0.18kgm
-2H
-1Yang Weishen etc. are at α-Al
2O
3The permeation flux of NaA type molecular screen membrane under identical infiltration evaporation test condition synthetic on the tubular support has more significantly raising than the former, is 0.8～1kgm
-2H
-1But α-Al
2O
3The sintering temperature of porous supporting body is at 1000～1300 ℃, and preparation cost is higher.In order to reduce the preparation cost of film, Kondo etc. have synthesized NaA type molecular screen membrane on cheap supporter, and permeation flux in the time of 75 ℃ in water/ethanol (mass ratio is 1/9) system and separation are respectively up to 2.08kgm
-2H
-1With 42000.But this film only shows the characteristic of exerting gloomy diffusion in gas separation process, shows still to have more non-molecular sieve pore passage in this molecular sieve rete.Although NaA type molecular screen membrane has been realized suitability for industrialized production, but still have that less, the synthetic cost of permeation flux is higher, repeatability is good inadequately and have problem such as non-molecular sieve pore passage defective.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of tubular porous fiber molecular sieve membrane, adopting the inorganic material braided tube is supporting layer, produces a kind of molecular screen membrane thereon.
The present invention is achieved like this, it is characterized in that the preparation method is: with aluminium source, sodium source, silica gel or Ludox and water is raw material, the feed molar ratio of components of reaction system is: silica gel: the aluminium source: the sodium source: water=1～10: 1～8: 1～8: 80～1000 proportioning preparation, the tubular porous fiber supporter is dipped in the reaction system, be reflected under 50～130 ℃ of temperature conditions crystallization 3-40 hour.
The preferred SiO of described silica gel
2Or sodium metasilicate.
Described aluminium source comprises metal aluminum foil, alundum (Al, sodium aluminate or aluminum sulfate, preferred sodium aluminate.
Described sodium source is NaOH or sodium oxide molybdena.
Described silica gel: aluminium source: sodium source: the preferred molar ratio of water is 1～5: 1～3: 1～5: 100～500.
Described tubular porous fiber supporter is selected inorganic glass fiber braided tube or stainless steel braided tube for use, is preferably the inorganic glass fiber braided tube.
Advantage of the present invention is: preparation process is simple, and is many with contact point between inorganic material braided tube supporting layer and the molecular screen membrane composite bed, in conjunction with tight.By the control of preparation condition, the separating power of prepared tubular porous fiber molecular sieve membrane is remarkable.
The specific embodiment
Embodiment one
The used medicine of preparation crystallization liquid is: sodium metasilicate Na
2S
iO
39H
2O, sodium aluminate NaAlO
299.9% (weight), NaOH NaOH 96% (weight) and deionized water.
1. take by weighing 4 gram NaOH, 4.1 gram NaAlO
2, slowly add in the 100 gram deionized waters stirred for several minute one-tenth solution A under stirring respectively.Take by weighing 14.21 gram Na
2S
iO
39H
2O stirs in the adding 150 gram deionized waters stirred for several minute one-tenth solution B.Under agitation solution B is slowly added solution A at last, colloidal sol hydrolysis under alkali condition, aging.
2. the tubular porous fiber supporter is placed reactor, the mixed liquor in 1 is poured in the reactor, crystallization is 12 hours under 100 ℃ of temperature conditions.Behind the end of synthesis,, uncap, to neutral, dry with washed with de-ionized water with running water chilling reactor.For obtaining comparatively fine and close molecular sieve rete, need to repeat above-mentioned steps and carry out repeatedly synthetic.
Embodiment two
1. take by weighing 1.6 gram NaOH, 8.2 gram NaAlO
2, slowly add in the 100 gram deionized waters stirred for several minute one-tenth solution A under stirring respectively.Take by weighing 14.21 gram Na
2S
iO
39H
2O stirs in the adding 150 gram deionized waters stirred for several minute one-tenth solution B.Under agitation solution B is slowly added solution A at last, colloidal sol hydrolysis under alkali condition, aging.
2. the tubular porous fiber supporter is placed reactor, the mixed liquor in 1 is poured in the reactor, crystallization is 28 hours under 95 ℃ of temperature conditions.Behind the end of synthesis,, uncap, to neutral, dry with washed with de-ionized water with running water chilling reactor.For obtaining comparatively fine and close molecular sieve rete, need to repeat above-mentioned steps and carry out repeatedly synthetic.
Embodiment three
1. take by weighing 4.1 gram NaAlO
2, slowly add in the 100 gram deionized waters stirred for several minute one-tenth solution A under stirring respectively.Take by weighing 14.21 gram Na
2S
iO
39H
2O stirs in the adding 150 gram deionized waters stirred for several minute one-tenth solution B.Under agitation solution B is slowly added solution A at last, colloidal sol hydrolysis under alkali condition, aging.
2. the tubular porous fiber supporter is placed reactor, the mixed liquor in 1 is poured in the reactor, crystallization is 28 hours under 95 ℃ of temperature conditions.Behind the end of synthesis,, uncap, to neutral, dry with washed with de-ionized water with running water chilling reactor.For obtaining comparatively fine and close molecular sieve rete, need to repeat above-mentioned steps and carry out repeatedly synthetic.
Claims (6)
1. the preparation method of a tubular porous fiber molecular sieve membrane, it is characterized in that the preparation method is: with aluminium source, sodium source, silica gel or Ludox and water is raw material, the feed molar ratio of components of reaction system is: silica gel: the aluminium source: the sodium source: water=1～10: 1～8: 1～8: 80～1000 proportioning preparation, the tubular porous fiber supporter is dipped in the reaction system, be reflected under 50～130 ℃ of temperature conditions crystallization 3-40 hour.
2. the preparation method of a kind of tubular porous fiber molecular sieve membrane according to claim 1 is characterized in that the preferred SiO of described silica gel
2Or sodium metasilicate.
3. the preparation method of a kind of tubular porous fiber molecular sieve membrane according to claim 1, the described aluminium of its feature source comprises metal aluminum foil, alundum (Al, sodium aluminate or aluminum sulfate, preferred sodium aluminate.
4. the preparation method of a kind of tubular porous fiber molecular sieve membrane according to claim 1, the described sodium of its feature source is NaOH or sodium oxide molybdena.
5. the preparation method of a kind of tubular porous fiber molecular sieve membrane according to claim 1, the described silica gel of its feature: aluminium source: sodium source: the preferred molar ratio of water is 1～5: 1～3: 1～5: 100～500.
6. the preparation method of a kind of tubular porous fiber molecular sieve membrane according to claim 1, the described tubular porous fiber supporter of its feature is selected inorganic glass fiber braided tube or stainless steel braided tube for use, is preferably the inorganic glass fiber braided tube.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010214061 CN101862603A (en) | 2010-06-30 | 2010-06-30 | Preparation method of tubular porous fiber molecular sieve membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010214061 CN101862603A (en) | 2010-06-30 | 2010-06-30 | Preparation method of tubular porous fiber molecular sieve membrane |
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|---|---|
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Family
ID=42954642
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247767A (en) * | 2011-04-19 | 2011-11-23 | 南京工业大学 | Preparation method for preparing NaA molecular sieve membrane by induction of nano seed crystal |
| CN108371890A (en) * | 2018-04-03 | 2018-08-07 | 江苏理工学院 | A kind of preparation method of molecular sieve-hybrid films |
| CN113174002A (en) * | 2021-04-26 | 2021-07-27 | 上海化工研究院有限公司 | Ultrahigh molecular weight polyethylene catalyst, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08257301A (en) * | 1995-03-23 | 1996-10-08 | Mitsui Eng & Shipbuild Co Ltd | Production of y-type zeolite membrane and liquid mixture separation membrane |
-
2010
- 2010-06-30 CN CN 201010214061 patent/CN101862603A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08257301A (en) * | 1995-03-23 | 1996-10-08 | Mitsui Eng & Shipbuild Co Ltd | Production of y-type zeolite membrane and liquid mixture separation membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247767A (en) * | 2011-04-19 | 2011-11-23 | 南京工业大学 | Preparation method for preparing NaA molecular sieve membrane by induction of nano seed crystal |
| CN108371890A (en) * | 2018-04-03 | 2018-08-07 | 江苏理工学院 | A kind of preparation method of molecular sieve-hybrid films |
| CN113174002A (en) * | 2021-04-26 | 2021-07-27 | 上海化工研究院有限公司 | Ultrahigh molecular weight polyethylene catalyst, and preparation method and application thereof |
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Application publication date: 20101020 |