CN1218774C - Method for making composite membrane for separation of polymer fluid - Google Patents
Method for making composite membrane for separation of polymer fluid Download PDFInfo
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- CN1218774C CN1218774C CN 02113599 CN02113599A CN1218774C CN 1218774 C CN1218774 C CN 1218774C CN 02113599 CN02113599 CN 02113599 CN 02113599 A CN02113599 A CN 02113599A CN 1218774 C CN1218774 C CN 1218774C
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- microporous barrier
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Abstract
The present invention relates to a method for making composite polymer membranes for fluid separation, which comprises the following steps: firstly, making a polymer microporous membrane used as a supporting layer; submerging the microporous membrane in a solvent to saturate the pores of the microporous membrane by the solvent, taking the microporous membrane out of the solvent, and removing the solvent attached to the surface of the membrane; then, dissolving another polymer, corresponding crosslinking agents, additive, compounding agents, etc. in another solvent to prepare membrane making liquid for an active cortical layer; finally, polymerizing the membrane making liquid and the microporous membrane into a composite membrane. The composite membrane made by the method has the advantages of uniform thickness of the separated active cortical layer without defects, and stable separation selectivity. Meanwhile, the active cortical layer easily becomes ultrathin, and the intrinsic permeation rate is high. Because the pores of the microporous membrane are expedite, the membrane has very high permeation flux. The compaction cortical layer of the composite membrane made by the method can be a reverse permeation membrane, a permeation vaporization membrane, or a permeation extraction membrane, etc. The composite membrane made by the method is an ideal composite membrane used for fluid separation.
Description
One, technical field
The present invention relates to a kind of manufacture method of composite membrane of polymer, particularly relate to a kind of manufacture method of the composite membrane of polymer with dense non-porous isolating active cortex of aspects such as being used for counter-infiltration that fluid separates and infiltration evaporation.
Two, background technology
The dense non-porous multilayer complex films overwhelming majority who is used for aspects such as counter-infiltration that fluid separates and infiltration evaporation is made by high molecular polymer.In order to obtain high film permeation flux and to guarantee the separation selectivity of film, must make very thin and flawless film.The film that manufacturing has thin or ultra-thin isolating active cortex generally can adopt two kinds of methods.The one, the so-called L-S that makes anisotropic membrane immerses gel method, and the anisotropic membrane of making has had the ultra-thin dense top layer of centrifugation and the support substrate of porous.The geometry of anisotropic membrane on the film thickness cross section is asymmetric, but membrane material is uniform.Most typical example is exactly that Loeb and Sourirajan adopt this method to make initial " asymmetric cellulose acetate reverse osmosis membrane " [S.Loeb, S.Sourirajan, Adv.Chem.Ser., 38 (1963), 117-].Another kind method is to make the multilayer complex films that different materials is formed.Be exactly at first make with a kind of material have good chemical, many micropores support membrane of physical and mechanical property, compound dense layer surface on support membrane again with another kind of material of good stalling characteristic.The micropore supporting layer is generally symmetrical structure, and its manufacture method has solvent evaporated method, water vapour inhalation and hot gel method etc.Dense layer surface also is a symmetrical structure, its film forming and have following several with the supporting layer composite methods: 1, the cortex of independent film forming is directly overlayed the mechanical composite algorithm on the supporting layer; 2, on support layer surface, apply preparation liquid, the physics composite algorithm of film forming after the solvent evaporates; 3, carry out the chemically composited method of interfacial polymerization or in-situ polymerization or plasma polymerization or surface grafting film forming in support layer surface.
When making the dense non-porous multilayer complex films, the main target that people pursue is: (1) fine and close isolating active cortex has the permeation flux of very thin or ultra-thin thickness to guarantee that it is high; (2) dense layer surface does not have or does not almost have the separation selectivity of defective to guarantee that it is good; (3) the micropore supporting layer has uniform pore size distribution and high porosity can be ignored fully to guarantee its resistance to infiltration; (4) dense layer surface combines well with supporting layer, makes the swelling behavior of film be unlikely to film is produced destructive effects.In order to reach above target, people have studied various film-forming methods.As United States Patent (USP) 4857080[R.W.Baker etc., MTR Filmtec Corp., in August, 1989] three layers of composite membrane of a kind of silicon rubber-palldium alloy-polymer micro supporting layer are disclosed, silastic-layer thickness is used for separation and purification hydrogen under higher temperature less than 5 microns.The isolating active cortex of this composite membrane is a Metal Palladium, and hydrogen is had very high separation selectivity, but when ultra-thinization remarkable defective is arranged inevitably.So the ultra-thin silicon rubber of compound again one deck on the active cortex of Metal Palladium is specifically designed to the obstruction defective, but has reduced the intrinsic permeability of film again.United States Patent (USP) 4243701[R.L.Riley etc. and for example, VOP company, 1981 1 day] invented a kind of silicon rubber-two-layer composite gas separation of micropore supporting layer, be used for the separation of hydrogen-carbon dioxide.This invention is immersed in ready-made micropore support membrane in the very low dimethyl silicone polymer of concentration (PDMS) preparation liquid, makes its crosslinking curing after the taking-up, forms the active cortex of dimethyl silicone polymer.For the dimethyl silicone polymer preparation liquid is not penetrated in the hole of supporting layer, therefore join the dimethyl silicone polymer molecular weight of prepolymer of preparation liquid and want and accurately to be controlled.And determine in the practical operation that molecular weight of prepolymer is inconvenient, nor can guarantee that preparation liquid does not penetrate in the micropore of supporting layer fully.In addition, Chinese patent (application number 98114022.X) discloses " a kind of preparation of composite gas diffusion barrier and application thereof ", this invention can be used for the separation of organic steam, its manufacture method is at first to make the micropore supporting layer of polyacrylonitrile (PAN), on the micropore supporting layer, apply dimethyl silicone polymer (PDMS) casting solution then, form the active cortex of dimethyl silicone polymer (PDMS) through being heating and curing.Its shortcoming of this method is to be difficult to guarantee that dimethyl silicone polymer (PDMS) casting solution does not penetrate in the hole of micropore supporting layer.Though above prior art all has its characteristics, also there is defective separately.
Three, summary of the invention
The present invention is just at existing defective in the above prior art, a kind of a kind of manufacture method that is used for the composite membrane of polymer of aspects such as counter-infiltration that fluid separates and infiltration evaporation is proposed, the dense non-porous composite membrane made from this method can either form uniform ultra-thin isolating active cortex, again with high permeation flux and stable high score from selectivity.The composite membrane that the present invention makes can be used for counter-infiltration, infiltration evaporation and infiltration extraction etc.
Technical scheme of the present invention is realized by following measure.The method of making composite membrane for separation of polymer fluid the steps include: at first to make a kind of polymer microporous film as supporting layer; This supporting layer microporous barrier is immersed in a kind of solvent, makes the hole of microporous barrier saturated by this solvent institute; From this solvent, take out microporous barrier then, and carefully remove the solvent on microporous barrier surface, even volatilize substantially attached to the solvent on microporous barrier surface; Another kind of polymer and corresponding crosslink agent, additive and compounding ingredient etc. are dissolved in the another kind of solvent, make the polymer film making solution of active cortex; Should be coated in micropore by the satisfied supporting layer polymer microporous film of solvent surface by activity cortex film making solution again; Heat-treat then, make polymer film making solution crosslinking curing form ultra-thin active cortex; After active cortex film-forming and stabilisation, the film of moulding is placed under high temperature and the vacuum handle at last, the solvent in the supporting layer micropore is evaporated, finally obtain the composite membrane of polymer of doing.
The used polymeric material of supporting layer microporous barrier of the present invention can be selected polysulfones (PS) for use, can also select polyacrylonitrile (PAN) or other polymeric material for use.Used polymeric material can be selected polyvinyl alcohol for use in the polymer film making solution of active cortex, can also select dimethyl silicone polymer (PDMS) for use, can also be other polymeric material.The saturated solvent of supporting layer microporous barrier can be glycerine, water or other solvent, can be water, benzene or other solvent as the solvent that dissolves another kind of polymer and corresponding crosslink agent, additive and compounding ingredient.
The manufacture method of composite membrane for separation of polymer fluid of the present invention has following characteristics: its hole of supporting layer microporous barrier of the present invention is saturated by solvent glycerin institute; because the protective effect of solvent glycerin; the film making solution of active cortex can not enter in the micropore of supporting layer; solvent for use glycerine and supporting layer microporous barrier have good compatibility in addition, and it and another aqueous solvent are not dissolved each other.Solvent glycerin can not the lytic activity cortex polymer and additive, compounding ingredient etc., and the polymer of another aqueous solvent and active cortex and additive, compounding ingredient etc. can form good film making solution.Therefore, the film after compound can form uniform ultra-thin isolating active cortex, and promptly active cortex is easy to ultra-thinization.The composite membrane of polymer that the present invention makes had both had high intrinsic permeability, have stable separation selectivity again simultaneously, and the pore channel of supporting layer microporous barrier was unimpeded fully, so make composite membrane have very high permeation flux.
Four, description of drawings
Fig. 1 is the section structure schematic diagram of supporting layer microporous barrier of the present invention.This is a kind of modelling of membrane pore structure, and the practical structures under SEM is more complex, illustrates that with this model membrane pore structure is rational.
Fig. 2 is that the hole of supporting layer microporous barrier of the present invention is by the saturated schematic diagram of solvent glycerin.
Fig. 3 is the film forming procedure schematic diagram of the active cortex of the present invention on supporting layer.Promptly be that the cortex preparation liquid that will comprise solvent, active cortex polymer, crosslinking agent, additive etc. is coated in the process schematic diagram that carries out in-situ polymerization formation cortex on the support layer surface.Evaporate gradually at solvent, in the process of active cortex film-forming, the intrapore solvent of supporting layer micropore should be kept non-volatile substantially.
Fig. 4 be composite membrane of polymer moulding of the present invention and make solvent evaporation in the supporting layer microporous barrier after the section structure schematic diagram.
In the accompanying drawing, 1 is the supporting layer polymer microporous film, and 2 is micropore, and 3 is supporting layer microporous barrier saturated solvent, and 4 for making the dissolution solvent of film making solution, and 5 is active cortex film making solution, and 6 is active cortex.
Five, the specific embodiment
Be described further below in conjunction with the composite membrane for separation of polymer fluid of drawings and Examples manufacturing of the present invention.
At first, the manufacture method of supporting layer microporous barrier 1 of the present invention adopts solvent evaporation method, and supporting layer microporous barrier 1 thickness of making is between 50～1000 microns, and optimum thickness is between 100～500 microns, its micropore 2 sizes are between 0.05～1 micron, and optimum size is between 0.1～1 micron.Selected two kinds of solvents 3 and 4 should have following characteristics: solvent 3 has compatibility preferably with the supporting layer microporous barrier, and solvent 3 does not dissolve each other with dissolution solvent 4 in the film making solution.The vacuum of solvent 3 volatilization is higher than the 90k handkerchief, volatilization temperature between 30～200 ℃, polymer and additive, compounding ingredient etc. that solvent 3 can not the lytic activity cortex; And polymer and additive, the compounding ingredient etc. of solvent 4 and active cortex can form good preparation liquid; Solvent 4 is than solvent 3 easier volatilizations.
Supporting layer microporous barrier hole can be decided according to used microporous membrane material by the saturated method of solvent 3, if solvent 3 has good compatibility with microporous membrane material, then can use infusion process, promptly directly microporous barrier is immersed in the solvent, and hole is full of by solvent.If solvent 3 is good inadequately with the microporous membrane material compatibility, then can adopt the forcing method of machinery or physics, as pressure or vacuum method solvent is pressed into hole.
Because the active cortex film making solution 5 of the present invention is weak solutions of used polymer, in the mass ratio of polymer to solvent, its concentration is between 0.1～10%, and optium concentration is between 1～5%.Active cortex crosslinking curing method can be used situ aggregation method.
In order to make active cortex 6 film forming good, the micropore of guaranteeing supporting layer microporous barrier 1 by solvent under the saturated prerequisite, should be as far as possible that the solvent cleaning on the compound interface is clean.Active cortex with the interface of supporting layer on film-forming be the volatilization process of a solvent 4, it is non-volatile solvent 3 to be remained in the hole in this process, to guarantee the uniformity and the zero defect of active cortex 6 thickness.After active cortex 6 film-formings and stabilisation, place vacuum to be higher than 90k handkerchief, temperature between 30～200 ℃ film, the solvent 3 in the supporting layer micropore is evaporated, form the composite membrane for separation of polymer fluid of doing at last.The optimum temperature of solvent for use 3 volatilizations of the present invention is between 60～100 ℃.
The made composite membrane of polymer of the present invention can be a tubular type or flat, and corresponding membrane module can be doughnut, plate basket or convoluted.The dense layer surface of composite membrane can be reverse osmosis membrane, infiltrating and vaporizing membrane or infiltration spe membrane etc.
Embodiment one
Employing solvent evaporation method making a slice diameter is 200 millimeters a circular supporting layer microporous barrier, and used polymeric material is polysulfones (PS), and its pore size is 0.6 micron, porosity 60%, 150 microns of microporous barrier thickness.Make its hole saturated with solvent glycerin by this sheet micro-pore-film filtration, again the glycerine on film surface is carefully removed by glycerine.Polyvinyl alcohol (PVA) and corresponding crosslink agent, additive and compounding ingredient etc. are dissolved in the aqueous solvent, make the film making solution of the active cortex of polyvinyl alcohol, the concentration of polyvinyl alcohol is 5% (W/W).The polyvinyl alcohol film making solution is coated in micropore by on the satisfied polysulfones support membrane of glycerine, place then under 60 ℃ the temperature to make polyvinyl alcohol solidify to form active cortex, reseal membrane places to handle under the vacuum of 100 ℃ temperature and 10k handkerchief and promptly obtained the composite membrane done in 2 hours.The SEM photo of this composite membrane shows that its skin thickness is about 4 microns.Sodium-chloride water solution with 0.2% carries out the counter-infiltration evaluation experimental, and its permeation flux surpasses 5kg/m
2H, salt rejection rate surpasses 96%.
Embodiment two
Employing solvent evaporation method making a slice diameter is 200 millimeters a circular support layer microporous barrier, and material therefor is polyacrylonitrile (PAN), and its pore size of microporous barrier is 0.22 micron, and porosity is greater than 60%, and microporous barrier thickness is 150 microns.Make its hole saturated with solvent glycerin by this sheet micro-pore-film filtration, the glycerine on film surface is carefully removed by glycerine.Polyvinyl alcohol (PVA) and corresponding crosslink agent, additive and compounding ingredient etc. are dissolved in the aqueous solvent, and the concentration of polyvinyl alcohol is 2% (W/W), makes the film making solution of the active cortex of polyvinyl alcohol.This film making solution is coated in micropore by on the satisfied polyethylene nitrile support membrane of glycerine, being positioned under 60 ℃ the temperature makes polyvinyl alcohol solidify to form active cortex, again film is placed under the vacuum of 100 ℃ temperature and 10k handkerchief and handled 2 hours, promptly obtain the composite membrane of doing.The SEM photo of this composite membrane shows that its skin thickness is about 1.5 microns.Be 95% ethanol-water solution carries out water under 70 ℃ temperature pervaporation evaluation experimental with concentration of alcohol, its permeation flux surpasses 0.6kg/m
2H, selectivity factor (separation factor) surpasses 900.
Embodiment three
Make polysulfones (PS) microporous hollow fiber film, 500 microns of fibre pipe external diameters, 250 microns of internal diameters, 0.1 micron in aperture with the L-S phase inversion.Fibre pipe is immersed in the aqueous solvent, make its hole saturated by water institute.Dimethyl silicone polymer (PDMS) and corresponding crosslink agent, catalyst and additive etc. are dissolved in the solvent benzol, and dimethyl silicone polymer (PDMS) concentration is 10% (W/W).Seal the fibre pipe two ends, will immerse 1～2 millimeter of dimethyl silicone polymer preparation liquid then, take out benzene volatilize naturally, place then under 100 ℃ temperature and the 10k handkerchief vacuum and handle 3 hours dried hollow fiber composite membranes of formation.The SEM photo of composite membrane shows that its dimethyl silicone polymer (PDMS) composite bed thickness is 2 microns.When being used for air separation, O
2/ N
2Separation factor is 2.4, permeability 4.53 * 10
-8Mlcm/cm
2ScmHg.
Claims (11)
1, is used for a kind of manufacture method of the composite membrane of polymer of fluid separation, it is characterized in that this step of manufacturing is: at first make a kind of polymer microporous film (1) as supporting layer; This supporting layer microporous barrier (1) is immersed in a kind of solvent (3), makes the hole of microporous barrier saturated by solvent (3) institute; From solvent (3), take out microporous barrier then, and remove the solvent on microporous barrier surface, even attached to the solvent evaporates on film surface; Another kind of polymer and corresponding crosslink agent, additive and compounding ingredient are dissolved in the another kind of solvent (4), make the film making solution (5) of active cortex (6); Should be coated in micropore (2) by solvent (3) institute satisfied supporting layer polymer microporous film (1) surface by activity cortex film making solution (5) again; Heat-treat then, make polymer film making solution crosslinking curing be compounded to form ultra-thin active cortex (6); After active cortex (6) film-forming and stabilisation, the film with moulding places under high temperature and the vacuum at last, and the solvent (3) in the micropore (2) of supporting layer microporous barrier (1) is evaporated, the final composite membrane of polymer of doing that forms.
2, according to the manufacture method of the described composite membrane of polymer of claim 1, the polymer that it is characterized in that being used to making supporting layer microporous barrier (1) is polysulfones (PS), polyacrylonitrile (PAN).
3,, it is characterized in that used polymer is polyvinyl alcohol (PVA), dimethyl silicone polymer (PDMS) in the polymer film making solution (5) of said active cortex (6) according to the manufacture method of the described composite membrane of polymer of claim 1.
4, according to the manufacture method of the described composite membrane of polymer of claim 1, it is characterized in that being glycerine, aqueous solvent as the solvent (3) of submergence saturated polymer microporous barrier (1), is water, benzene solvent as the solvent (4) that dissolves another kind of polymer and corresponding crosslink agent, additive and compounding ingredient.
5,, it is characterized in that solvent (3) and solvent (4) can not dissolve each other, and solvent (4) is than the easier volatilization of solvent (3) according to the manufacture method of the described composite membrane of polymer of claim 4.
6, according to the manufacture method of the described composite membrane of polymer of claim 1, the thickness that it is characterized in that supporting layer microporous barrier (1) is between 50～1000 microns, and its micropore (2) size is between 0.05～1 micron.
7, according to the manufacture method of the described composite membrane of polymer of claim 6, the thickness that it is characterized in that supporting layer microporous barrier (1) is between 100～500 microns, and its micropore (2) size is between 0.1～1 micron.
8, according to the manufacture method of the described composite membrane of polymer of claim 1, it is characterized in that described active cortex film making solution (5) is the weak solution of used polymer, in its mass ratio to solvent, concentration is between 0.1～10%.
9,, it is characterized in that concentration is between 1～5% according to the manufacture method of the described composite membrane of polymer of claim 8.
10, according to the manufacture method of the described composite membrane of polymer of claim 4, it is characterized in that the vacuum of its volatilization of solvent (3) of the saturated microporous barrier of submergence is higher than 90kPa, the temperature of volatilization is between 30～200 ℃.
11, according to the manufacture method of the described composite membrane of polymer of claim 10, microporous barrier submergence solvent, the temperature of solvent (3) volatilization that it is characterized in that the saturated microporous barrier of submergence just can make the interior solvent evaporates of micropore (2) clean between 60～100 ℃.
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| CN 02113599 CN1218774C (en) | 2002-04-12 | 2002-04-12 | Method for making composite membrane for separation of polymer fluid |
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| CN 02113599 CN1218774C (en) | 2002-04-12 | 2002-04-12 | Method for making composite membrane for separation of polymer fluid |
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| CN1218774C true CN1218774C (en) | 2005-09-14 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100395008C (en) * | 2006-03-31 | 2008-06-18 | 华南理工大学 | A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same |
| CN102228803B (en) * | 2011-04-19 | 2013-08-07 | 蒋兰英 | Method for preparing hollow fiber composite membrane |
| CN103657437A (en) * | 2012-09-18 | 2014-03-26 | 中南大学 | Preparation method of hollow-fiber asymmetric composite membrane |
| CN103599708B (en) * | 2013-11-30 | 2016-06-08 | 大连欧科膜技术工程有限公司 | A kind of composite membrane and preparation method thereof |
| CN105435655B (en) * | 2014-08-22 | 2018-07-20 | 上海颐润科技有限公司 | A kind of solvent resistant separation membrane material and preparation method thereof |
| CN106731887A (en) * | 2017-01-06 | 2017-05-31 | 宁波大学 | A kind of VOCs extracts perforated membrane |
| CN108654399A (en) * | 2018-05-16 | 2018-10-16 | 南京帝膜净水材料开发有限公司 | A kind of preparation method of high-flux composite reverse osmosis membrane |
| CN109701468A (en) * | 2019-01-24 | 2019-05-03 | 四川大学 | The percdation of composite function nano material-synthesis building method |
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