CN102139188A - Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane - Google Patents
Preparation method and application of molecular sieve/organic composite infiltration, vaporization and separation membrane Download PDFInfo
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- CN102139188A CN102139188A CN2011100007702A CN201110000770A CN102139188A CN 102139188 A CN102139188 A CN 102139188A CN 2011100007702 A CN2011100007702 A CN 2011100007702A CN 201110000770 A CN201110000770 A CN 201110000770A CN 102139188 A CN102139188 A CN 102139188A
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Abstract
The invention belongs to the technical field of separation membranes, and relates to a preparation method and application of a molecular sieve/organic composite infiltration, vaporization and separation membrane. The preparation method comprises the following steps of: firstly adopting a hydrothermal method to prepare nano-level molecular sieve; putting the synthesized nano-level molecular sieve in a solvent, and dispersing the molecular sieve into uniform molecular sieve suspending liquid through ultrasound, wherein the mass fraction of the molecular sieve in the suspending liquid is 5-15%; uniformly coating the molecular sieve suspending liquid on an organic supporting body; drying the organic supporting body at the temperature of 20-60 DEG C to form a molecular sieve membrane; and repeating the coating for 2-4 times. Surface modification is performed on the organic supporting body by adopting methods such as plasma induction, silane coating and the like to modify the surface hydrophily. The method can be used for preparing a large-area molecular sieve/organic composite membrane; a prepared membrane can be assembled into a spirally coiled component; and the preparation method is beneficial for industrial magnification, and has a higher industrial application value. A better separation effect can be achieved when the prepared molecular sieve/organic composite membrane is used for the infiltration and vaporization of an organic water solution system.
Description
Technical field
The invention belongs to the film separation field, being specifically related to a kind of is that separating layer, organic polymer micro-filtration membrane are the preparation method of the inorganic/organic polymer compounding permeation vaporizing film of supporter with the molecular screen material, this type of film can be used for aqueous organopolysiloxane as: the infiltration evaporation of alcohols, ethers, ketone, ester class, amine etc. separates.
Background technology
Infiltration evaporation is to utilize film to the dissolving (or absorption) of component in the liquid mixture, the difference of diffusion, realize a kind of membrane process that component is separated, advantage such as have the efficient height, energy consumption is low, equipment is simple, the technology enlarge-effect is little, can substitute separation modes such as traditional distillation, extraction effectively, be used for closely boiling or the removing of the separation of vapor of mixture liquid, organic solvent minor amount of water, waste water in the recovery etc. of high value organic component in a small amount of organic separation and the aqueous solution.
The principal element that influences the infiltration evaporation separating effect is physicochemical property, temperature, feed concentration, partial pressure difference of membrane material, structure and separated component etc.Wherein the selection of membrane material is crucial.Commercial at present hydrophilic osmotic vaporization film mainly contains two kinds, and a kind of is to be the homogeneous of raw material development and the polymeric membrane of modification with the hydrophily high polymer; Another kind is to be the inoranic membrane of material with the hydrophilic molecule sieve.Infiltration evaporation organic polymer composite membrane among the patent CN101703898A with polyvinylidene fluoride microporous filtering film (PVDF) do supporting layer, dimethyl silicone polymer is done separating layer, is applied to the separation of acetic acid aqueous solution.Patent CN1221649 is a basement membrane with polyacrylonitrile (PAN), polyvinyl alcohol (PVA) with the interpolation surfactant is that separating layer makes PVA/PAN organic polymer composite membrane, the adding of surfactant improves the wettability of PVA and PAN, makes separating layer and basement membrane in conjunction with firm.It is good that macromolecule member material has pliability, filming performance is good, cost is low, be easy to advantages such as manufacturing, but mechanical strength is not high, poor chemical stability, scarcely high temperature resistant, soda acid and organic solvent etc., be difficult under harsh conditions, use, and easily incrustation stops up, and easy cleaning not is so be restricted in the application in some field.
Zeolite membrane material is a kind ofly to be basic framework, to have an inorganic material in regular duct with silicon-oxy tetrahedron and aluminum-oxygen tetrahedron.Utilize the regular mechanism in molecular sieve crystal duct, can separate by molecule screening or selectivity diffusion couple organic matter.Compare with organic film, molecular sieve has good heat endurance, chemical stability, biological stability and mechanical performance.First since having synthesized ultra-thin molecular screen membrane on the porous carrier, the research of molecular screen membrane has obtained great progress from Suzuki in 1987 etc.The preparation of molecular screen membrane is to finish on inorganic supporting body (porous ceramics, porous metals and cellular glass) mostly at present.(Kondo M such as Kondo, Kita H. Permeation mechanism through zeolite NaA and T-type membranes for practical dehydration of organic solvents[J]. JOURNAL OF MEMBRANE SCIENCE. 2010. 361 (1-2), be that supporter adopts hydrothermal synthesis method to synthesize NaA(A type molecular sieve 223-231) with mullite porous porcelain tube) molecular screen membrane and type T molecular sieve film, and it is used in water/second alcohol and water/methanol permeation vaporization (PV) and steam permeates (VP) and separate.Wang(Wang X B, Zhang X F, Liu H, et al. Preparation of titanium silicalite-1 catalytic films and application as catalytic membrane reactors[J]. CHEMICAL ENGINEERING JOURNAL. 2010,156 (3), 562-570) waiting with nanoscale silicalite-I is that crystal seed is at porous α-Al
2O
3The success of last employing hydrothermal synthesis method synthesized the TS-1 film, and use it in the catalytic film reactor of phenol hydroxylation.Patent CN101318665 adopts the method for high temperature enclosed hydrothermal synthesis reaction, at porous mullite pipe, tubulose α-Al
2O
3With the tubulose stainless steel be that supporting body surface has all formed the fine and close NaY type of one deck molecular screen membrane, be applied to separating of methyl alcohol/methyl tertiary butyl ether(MTBE), ethanol/ethyl tert-butyl ether (ETBE) and benzene/cyclohexane.Patent CN101284671 adopts the method for baking that crystal seed is coated on stainless steel metal wire, potsherd or the sheet glass in advance, carrier is put into synthetic liquid crystallization again, makes L type molecular screen membrane.
This is the molecular screen membrane of supporter preparation with the inoranic membrane, and its synthesis condition is comparatively harsh, and preparation cost is higher, and is difficult to avoid the inhomogeneous of thicknesses of layers, the large-area preparation difficulty, and it is little to load volume.Inorganic/organic composite permeable vaporizing membrane combines the high and inoranic membrane mechanical strength height of the selectivity of organic film, advantage that chemical stability is good, has reduced preparation cost, has potential application prospect.
It is separating layer that the present invention adopts molecular sieve, the organic polymer micro-filtration membrane is a supporter, adopt dip coating, spraying process and rolling process with nano level molecular sieve carried on organic supporter, make have good machinery with the separating property height, be applicable to molecular sieve/organic hybrid films that the aqueous organopolysiloxane infiltration evaporation separates.Method of the present invention can prepare large-area molecular sieve/organic hybrid films, and the film of making can be made into spiral wound module, solves the low problem of tubular type organic zeolite membrane filling area.
Summary of the invention
Purpose of the present invention is in order to overcome above-mentioned deficiency of the prior art, a kind of preparation method of molecular sieve/organic hybrid films is provided, can prepare large-area molecular sieve/organic hybrid films with this method, the film of making can be made into spiral wound module, solves the low problem of tubular type organic zeolite membrane filling area.
Of the present invention is the preparation method of a kind of molecular sieve/organic composite permeable vaporizing membrane, it is characterized in that may further comprise the steps:
Be dispersed into uniform molecular sieve suspension after nano-class molecular sieve placed the ultrasonic processing of solvent, and 5 ~ 20 min that vibrate under the room temperature; Wherein said suspension quality concentration is 5 ~ 15 %; With mass fraction is the adhesive of 10 %, is (5 ~ 10) in molecular sieve suspension/binder aqueous solution mass ratio: 1 ratio, add in the molecular sieve suspension, and wherein said adhesive is polyvinyl alcohol (PVA) or silica gel; Adopt the coating embrane method evenly to be coated on organic supporter the molecular sieve suspension that has added adhesive again,, form molecular screen membrane 20 ~ 60 ℃ of oven dry down; Repeat to film 2 ~ 4 times.
Wherein said ultrasonic processing ultrasonic power is 100 ~ 250 w among the preparation method provided by the invention.
Wherein said solvent is ethanol or water among the preparation method provided by the invention.
Coat film method described in the preparation method provided by the invention is dip coating, spraying process or rolling process.
The material of the organic supporter of conduct described in the preparation method provided by the invention is poly tetrafluoroethylene (PTFE), PVDF membrane (PVDF), acetyl cellulose film (CA), nitrocellulose filter (CN), poly (ether sulfone) film (PES) or polypropylene screen (PP) etc.; The aperture of described organic supporter is 0.005 ~ 5 μ m.
Wherein said nano-class molecular sieve is nano level NaA molecular sieve (A type molecular sieve), nanoscale Silicatile-I (the MFI molecular sieve of high silica alumina ratio) molecular sieve or nanoscale ZSM-5 molecular sieve.
Be suspension with hydrophilic nano level NaA molecular sieve wherein in the above-mentioned steps, when being coated on hydrophobic organic supporter, but using plasma is induced or method such as silane-coating is carried out surface modification to hydrophobic organic supporter.
The preparation method of wherein said nano level NaA molecular sieve: with the sodium metasilicate is the silicon source, and aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=(6 ~ 9): 2: 1: the synthetic liquid of (600 ~ 900) preparation molecular sieve; And in reactor 80 ℃ of following crystallization 24 h, take out cooling, suction filtration is washed till neutrally and dry with deionized water, obtain nano level NaA molecular sieve.
The preparation method of wherein said nanoscale Silicatile-I molecular sieve: with NaOH, ethyl orthosilicate (TEOS), TPAOH (TPAOH) and water, by the mole proportioning
n(NaOH):
n(TEOS):
n(TPAOH):
n(H
2O)=1:50: 18: the 1000 synthetic liquid of preparation molecular sieve, magnetic agitation at room temperature, aging 40 h, 100 ℃ of following crystallization 60 h in reactor take out cooling, suction filtration, be washed till with deionized water neutral and dry, nanoscale Silicatile-I molecular sieve;
The preparation method of wherein said nanoscale ZSM-5 molecular sieve: with NaOH, ethyl orthosilicate (TEOS), 4-propyl bromide (TPABr) and water, by the mole proportioning
n(NaOH):
n(TEOS):
n(TPABr):
n(H
2O)=and 1: 4: the synthetic liquid of 1:200 preparation molecular sieve; Pour in the crystallizing kettle, put into 175 ℃ baking oven, crystallization 36 h, the taking-up cooling, suction filtration is washed till neutral and drying with deionized water, gets nanoscale ZSM-5 molecular sieve.
The application of molecular sieve/organic hybrid films of the present invention, the infiltration evaporation that can be used for aqueous organopolysiloxane separates.
The molecular sieve that the present invention synthesized/organic composite permeable vaporizing membrane can be used to make the membrane module of spiral wound.
The application of the molecular sieve that the present invention synthesized/organic composite permeable vaporizing membrane is used for the separation of organic matter/aqueous systems, as: the infiltration evaporation of alcohols, ethers, ketone, ester class, amide-type and aldehydes etc. separates, and has good separating property.
The invention has the advantages that: preparation technology is simple, and the separating layer performance is controlled, and film surface continuity is good, is easy to large-area preparation.The film of preparation can be made into rolled membrane module, is convenient to increase the filling area of film, is beneficial to industry and amplifies, and has higher industrial application value.
The specific embodiment:
Embodiment 1
With the sodium metasilicate is the silicon source, and aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=and 6: 2: 1: the synthetic liquid of 800 preparation molecular sieves.Put it into the bottom of the stainless steel cauldron that has polytetrafluoroethylene bushing, at 80 ℃ of following crystallization 24 h, the taking-up cooling, suction filtration is washed till neutral and drying with deionized water, gets nanoscale NaA molecular sieve.Water is a solvent, and sonic oscillation is mixed with the suspension that mass fraction is 10 % with the NaA molecular sieve.With mass fraction is the PVA aqueous solution of 10 %, is the ratio of 5:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.Adopt dip coating to film 4 times on the polytetrafluoroethylene (PTFE) organic micro film of plasma modification, 60 ℃ of following dry 24 h get NaA molecular sieve/PTFE composite membrane, and membrane area is 1.6 m
2, the separating layer thickness is about 7 μ m.Film is characterized and dimethyl formamide (DMF)/water (H
2O) the infiltration evaporation performance measurement of system.The DMF mass fraction of charging is 20 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 20 ml/min, records DMF/H
2The permeation flux of O solution infiltration evaporation is 1.24 kg m
-2H
-1, separation factor is 42, the DMF mass fraction is 0.5 % in the penetrating fluid.
Embodiment 2
With the sodium metasilicate is the silicon source, and aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=and 7.5: 2: 1: the synthetic liquid of 800 preparation molecular sieves.Put it into the bottom of the stainless steel cauldron that has polytetrafluoroethylene bushing, at 80 ℃ of following crystallization 24 h, the taking-up cooling, suction filtration is washed till neutral and drying with deionized water, gets nanoscale NaA molecular sieve.Use water as solvent, sonic oscillation is mixed with the suspension that mass fraction is 10 % with the NaA molecular sieve.With mass fraction is the PVA aqueous solution of 10 %, is the ratio of 10:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.Adopt dip coating to film 3 times on the PVDF of plasma modification organic micro film, dry 24 h under the room temperature get NaA molecular sieve/PVDF composite membrane, and membrane area is 1.1m
2, the separating layer thickness is about 6 μ m.It is characterized and n-butanol/H
2The infiltration evaporation performance measurement of O system.The n-butanol mass fraction of charging is 30 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 30 ml/min, records n-butanol/H
2The permeation flux of O solution infiltration evaporation is 1.07kgm
-2H
-1, separation factor is 33, the n-butanol mass fraction of discharging is 0.5 %.
Embodiment 3
By the mole proportioning
n(NaOH):
n(TEOS):
n(TPAOH):
n(H
2O)=and 0.5:25: 9: the 500 synthetic liquid of preparation molecular sieve, magnetic agitation at room temperature, aging 40 h, put it into the bottom of the stainless steel cauldron that has polytetrafluoroethylene bushing, at 100 ℃ of following crystallization 60 h, take out cooling, suction filtration, be washed till neutral and drying with deionized water, get nanoscale Silicatile-I molecular sieve.Make solvent with ethanol, sonic oscillation is mixed with the suspension that mass fraction is 10 % with the Silicatile-I molecular sieve.With mass fraction is the PVA aqueous solution of 10 %, is the ratio of 8:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.Adopt dip coating to film on the PP organic micro film 3 times, dry 24 h under the room temperature get Silicatile-I molecular sieve/PP composite membrane, and membrane area is 0.4 m
2, the separating layer thickness is about 6 μ m.It is characterized and acetone/H
2The infiltration evaporation performance measurement of O system.The acetone mass fraction of charging is 30 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 35 ml/min, records acetone/H
2The permeation flux of O solution infiltration evaporation is 0.89kg m
-2H
-1, separation factor is 26, the acetone mass fraction of discharging is 0.3 %.
Embodiment 4
By the mole proportioning
n(NaOH):
n(TEOS):
n(TPABr):
n(H
2O)=and 1: 4: the synthetic liquid of 1:200 preparation molecular sieve.Pour in the band teflon-lined stainless steel crystallizing kettle, put into 175 ℃ baking oven, crystallization 36 h, the taking-up cooling, suction filtration is washed till neutrality and dry with deionized water, gets nanoscale ZSM-5 molecular sieve.Use water as solvent, sonic oscillation is mixed with the suspension that mass fraction is 10 % with the ZSM-5 molecular sieve.With mass fraction is the PVA aqueous solution of 10 %, is the ratio of 5:1 in molecular sieve suspension/PVA aqueous solution mass ratio, joins in the molecular sieve suspension.Adopt dip coating to film on the PP organic micro film 3 times, dry 24 h under the room temperature get ZSM-5 molecular sieve/PP composite membrane, and membrane area is 0.4 m
2, the separating layer thickness is about 7 μ m.It is characterized and isopropyl alcohol/H
2The infiltration evaporation performance measurement of O system.The isopropyl alcohol mass fraction of charging is 25 %, and the penetration operation temperature is 70 ℃, and osmotic lateral pressure is 20 kPa, and feed rate is under the condition of 30 ml/min, records isopropyl alcohol/H
2The permeation flux of O solution infiltration evaporation is 1.00kg m
-2H
-1, separation factor is 19, the isopropyl alcohol mass fraction of discharging is 0.4 %.
Claims (10)
1. the preparation method of molecular sieve/organic composite permeable vaporizing membrane is characterized in that may further comprise the steps: after being placed the ultrasonic processing of solvent, nano-class molecular sieve is dispersed into uniform molecular sieve suspension, and 5 ~ 20 min that vibrate under the room temperature; Wherein said suspension quality concentration is 5 ~ 15 %; With mass fraction is the adhesive of 10 %, is (5 ~ 10) in molecular sieve suspension/binder aqueous solution mass ratio: 1 ratio, add in the molecular sieve suspension, and wherein said adhesive is polyvinyl alcohol (PVA) or silica gel; Adopt the coating embrane method evenly to be coated on organic supporter the molecular sieve suspension that has added adhesive again,, form molecular screen membrane 20 ~ 60 ℃ of oven dry down; Repeat to film 2 ~ 4 times.
2. according to the preparation method of the described molecular sieve of claim 1/organic composite permeable vaporizing membrane, it is characterized in that wherein said ultrasonic processing ultrasonic power is 100 ~ 250 w among the preparation method provided by the invention; Wherein said solvent is ethanol or water, and wherein said coat film method is dip coating, spraying process or rolling process.
3. according to the preparation method of the described molecular sieve of claim 1/organic composite permeable vaporizing membrane, it is characterized in that wherein said material as organic supporter is poly tetrafluoroethylene (PTFE), PVDF membrane (PVDF), acetyl cellulose film (CA), nitrocellulose filter (CN), poly (ether sulfone) film (PES) or polypropylene screen (PP); The aperture of described organic supporter is 0.005 ~ 5 μ m.
4. according to the preparation method of the described molecular sieve of claim 1/organic composite permeable vaporizing membrane, it is characterized in that being suspension wherein with hydrophilic nano level NaA molecular sieve, when being coated on hydrophobic organic supporter, using plasma is induced or the silane-coating method is carried out surface modification to hydrophobic organic supporter.
5. according to the preparation method of the described molecular sieve of claim 1/organic composite permeable vaporizing membrane, it is characterized in that wherein said nano-class molecular sieve is nano level NaA molecular sieve, nanoscale Silicatile-I molecular sieve or nanoscale ZSM-5 molecular sieve.
6. according to the preparation method of the described molecular sieve of claim 5/organic composite permeable vaporizing membrane, it is characterized in that the preparation method of wherein said nano level NaA molecular sieve: be the silicon source with the sodium metasilicate, aluminum sulfate is the aluminium source, in molar ratio
n(Na
2O):
n(SiO
2):
n(Al
2O
3):
n(H
2O)=(6 ~ 9): 2: 1: the synthetic liquid of (600 ~ 900) preparation molecular sieve; And in reactor 80 ℃ of following crystallization 24 h, take out cooling, suction filtration is washed till neutrally and dry with deionized water, obtain nano level NaA molecular sieve.
7. according to the preparation method of the described molecular sieve of claim 5/organic composite permeable vaporizing membrane, the preparation method who it is characterized in that wherein said nanoscale Silicatile-I molecular sieve: with NaOH, ethyl orthosilicate (TEOS), TPAOH (TPAOH) and water, by the mole proportioning
n(NaOH):
n(TEOS):
n(TPAOH):
n(H
2O)=1:50: 18: the 1000 synthetic liquid of preparation molecular sieve, magnetic agitation at room temperature, aging 40 h, 100 ℃ of following crystallization 60 h in reactor take out cooling, suction filtration, be washed till with deionized water neutral and dry, nanoscale Silicatile-I molecular sieve.
8. according to the preparation method of the described molecular sieve of claim 5/organic composite permeable vaporizing membrane, the preparation method who it is characterized in that wherein said nanoscale ZSM-5 molecular sieve: with NaOH, ethyl orthosilicate (TEOS), 4-propyl bromide (TPABr) and water, by the mole proportioning
n(NaOH):
n(TEOS):
n(TPABr):
n(H
2O)=and 1: 4: the synthetic liquid of 1:200 preparation molecular sieve; Pour in the crystallizing kettle, put into 175 ℃ baking oven, crystallization 36 h, the taking-up cooling, suction filtration is washed till neutral and drying with deionized water, gets nanoscale ZSM-5 molecular sieve.
9. the application of molecular sieve/organic composite permeable vaporizing membrane can be used for the infiltration evaporation separation of aqueous organopolysiloxane or the separation of organic matter/aqueous systems.
10. the application of molecular sieve/organic composite permeable vaporizing membrane can be used to make the membrane module of spiral wound.
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