CN104474922A - Preparation method of polyvinylidene fluoride hollow fiber water treatment membrane - Google Patents
Preparation method of polyvinylidene fluoride hollow fiber water treatment membrane Download PDFInfo
- Publication number
- CN104474922A CN104474922A CN201410650609.3A CN201410650609A CN104474922A CN 104474922 A CN104474922 A CN 104474922A CN 201410650609 A CN201410650609 A CN 201410650609A CN 104474922 A CN104474922 A CN 104474922A
- Authority
- CN
- China
- Prior art keywords
- casting liquid
- preparation
- hollow fiber
- liquid
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a polyvinylidene fluoride hollow fiber water treatment membrane, according to the method, a support layer membrane casting liquid and a separation layer membrane casting liquid are separately prepared, the support layer membrane casting liquid and the separation layer membrane casting liquid are respectively filtered and vacuumized, the support layer membrane casting liquid and the separation layer membrane casting liquid are extruded together with a core liquid to prepare a primary hollow fiber membrane; after coagulation processing in coagulation bath, the primary hollow fiber membrane is soaked in water for 12-72h, and is treated with a pore protection agent, and then dried to obtain a hydrophilic polyvinylidene fluoride hollow fiber membrane. The support layer membrane casting liquid and the separation layer membrane casting liquid are respectively separately prepared, the support layer membrane casting liquid and the separation layer membrane casting liquid may not affect, the membrane casting liquid composition adjustment scope is broad, the preparation method is simple, solvent recovery is convenient, energy consumption is low, and the pore size range of the separation membrane prepared by the method is between 0.01 and 1 mu m, and basically covers most of the range of microfiltration and ultrafiltration.
Description
Technical field
The present invention relates to the preparation field of hollow-fibre membrane, be specifically related to a kind of preparation method of polyvinylidene fluoride hollow fiber membrane for water treatment.
Background technology
Embrane method has the advantages such as separative efficiency is high, energy-saving and environmental protection compared with traditional isolation technics, is to solve the new and high technology alleviating current energy source crisis and environmental pollution.In application of membrane separation technology, miillpore filter be industrialization the earliest, application surface is the widest, is also the maximum film kind of consumption simultaneously.Because filtering with microporous membrane technology has, using method is simple, quick, energy-efficient lamp advantage, thus receives much concern and adopts, being widely used in the fields such as food and drink, medicine, chemical industry, electronics, the energy and environmental protection now.
Desirable film should have dissymmetrical structure, the separating layer fenestra aperture of namely playing centrifugation is far smaller than the micropore size of supporting layer, the microcellular structure of supporting layer will have high porosity to reduce filtration resistance, wide-aperture finger-like pore structure to be avoided, to strengthen the mechanical strength of film entirety simultaneously.The radial section structure of hollow fiber porous film is generally unsymmetric structure, external pressing type hollow fibrous membrane, and exodermis is the finest and close, and endodermis takes second place, and intermediate layer is the most loose.For improving the hydrophily of film and water flux, various different pore former and auxiliary agent can be added to regulate microcellular structure and the distribution of film in casting solution, but more additive, finger-like pore or large empty structure can be caused to cause the intensity of hollow fiber film thread more weak.
The normal solution phase disengagement method that adopts prepares Kynoar at present, the hollow-fibre membranes such as polysulfones, that is: by filmogen, organic solvent, pore former mixes according to a certain percentage, dissolve, then by casting solution liquid through spinneret or spinneret, enter coagulating bath, exchange through the mass transfer of solvent and non-solvent and make polymer generation phase transfer and precipitating becomes hollow-fibre membrane, simultaneously by controlling formula of casting, spinning parameter and the post processing of film silk, the hollow fiber separating film in particular range aperture can be prepared, but film inner layer prepared by the method and outer field mechanism just the same, there are some defects in the mechanical strength aspect of film.
Chinese patent CN103908898 discloses a kind of doughnut membrane preparation method adopting composite construction, the method comprises the internal layer for supporter and the skin as separating layer, and the formation of ectonexine casting solution and constituent content are limited, prepared hollow-fibre membrane is because internal layer solution solvent for use is as 1-METHYLPYRROLIDONE, N, N dimethylacetylamide, N, N-dimethylformamide cause solvent and non-solvent mass transfer rate very fast, supporting layer easily forms macropore, has adverse effect to supporting layer mechanical property; And disclose a kind of by preparing different internal layers and outer preparation liquid respectively in patent CN103877868, adopt the method for coetrusion one time to produce diffusion barrier, the skin playing centrifugation in the method is phase separation (NIPS), and passive internal layer is Thermal inactive (TIPS), diffusion barrier prepared by the method has higher permeability and mechanical strength, but supporting layer adopts TIPS method, the techniques such as the temperature control in preparation process and the separation and recovery of organic solvent are comparatively complicated and cost is higher.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, provide a kind of preparation method of polyvinylidene fluoride hollow fiber membrane for water treatment, membrane for water treatment fracture strength prepared by the method is high, rejection is high and have wider bore footpath scope and technique is simple, is convenient to suitability for industrialized production.
Technical scheme of the present invention provides a kind of preparation method of doughnut membrane for water treatment, and the preparation liquid of supporting layer and separating layer is individually prepared by the method, comprises the following steps:
1) Kynoar, pore-foaming agent, organic solvent are added in material-compound tank, at 80-150 DEG C after stirring and dissolving deaeration, leave standstill to obtain outer separating layer mold liquid after filtration;
2) by Kynoar, pore-foaming agent, organic solvent adds in material-compound tank, after stirring solvent deaeration, leaves standstill to obtain internal layer supporting layer mold liquid after filtration at 50-100 DEG C;
3), after above-mentioned two kinds of casting solutions being filtered respectively, vacuumizing, extrude together with core liquid be prepared into primary hollow tunica fibrosa through measuring pump, triple channel shower nozzle;
4), after primary hollow tunica fibrosa being solidified process by coagulating bath, be soaked in water 12-72h, and through protecting hole agent process, after drying, obtaining hydrophilic Pvdf Microporous Hollow Fiber Membrane at 20-50 DEG C.
According to the method that technique scheme provides, the content of Kynoar in skin and internal layer casting solution is respectively 18-25wt% and 15-21wt%.
According to the method that technique scheme provides, step 3) in when extruding the flow rate of outer casting solution and internal layer casting solution be 1-2:1.
According to the method that technique scheme provides, step 1) described in organic solvent be selected from 1-METHYLPYRROLIDONE, N, at least one in N dimethylacetylamide, DMF, trimethyl phosphate, triethyl phosphate or tributyl phosphate, content is the 18-38% of outer casting solution.
According to the method that technique scheme provides, step 2) described in organic solvent be 1-METHYLPYRROLIDONE, N, N dimethylacetylamide, N, at least one at least one in N-dimethylformamide and trimethyl phosphate, triethyl phosphate, tributyl phosphate is carried out composite, wherein in two class organic solvents, the former addition is 50-100%, and content is the 75-84% of internal layer casting solution.
According to the method that technique scheme provides, step 2) described in organic solvent content be the 75-84% of internal layer casting solution quality.
According to the method that technique scheme provides, step 2) described in organic solvent be the mixture of solvent orange 2 A and solvent B, solvent orange 2 A is selected from 1-METHYLPYRROLIDONE, N, N dimethylacetylamide, N, at least one in N-dimethylformamide, solvent B is selected from least one in trimethyl phosphate, triethyl phosphate, tributyl phosphate, and wherein organic solvent A proportion is 50-100%.
According to the method that technique scheme provides, described pore-foaming agent is selected from polyethylene glycol, polyvinylpyrrolidone or lithium chloride, and content is the 1-6% of internal layer, outer casting solution quality.
According to the method that technique scheme provides, the core liquid of primary filament film preparation is deionized water.
According to the method that technique scheme provides, coagulating bath be deionized water or with the mixing of organic solvent, wherein coagulation bath temperature is 0-50 DEG C.
According to the method that technique scheme provides, described guarantor hole agent is content is 20-50wt% glycerine, and the processing time is 12-72h.
According to the method that technique scheme provides, the material of filtering the filter membrane of casting solution is selected from stainless steel or nylon, and pore size is 300-800 order.
In certain embodiments of the present invention, described heating mixing plant is flask or reactor.
In certain embodiments of the present invention, the preparation of casting solution carries out in the device such as reactor, glassware with stirring and heater.
In certain embodiments of the present invention, water used is deionized water.
The term "or" that the present invention uses represents alternative, if properly, they can be combined, and that is, term "or" comprises each listed independent alternative and their combination.Such as, " described pore-foaming agent is selected from polyethylene glycol, polyvinylpyrrolidone or lithium chloride " pore-foaming agent is selected from the one among polyethylene glycol, polyvinylpyrrolidone or lithium chloride, also can be its more than one combination.
Unless explicitly stated otherwise in contrast, otherwise all scopes that the present invention quotes comprise end value.Such as, " wherein coagulation bath temperature is 0-50 DEG C ", represents that the scope of temperature is 0 DEG C≤T≤50 DEG C.
Drying of the present invention, refers to and to make in material water or solvent gasification by means of energy, and take away the process of generated steam.The drying mode that embodiments more of the present invention adopt is bake drying.It should be pointed out that the drying means that can reach same effect also includes but not limited to oven dry, vacuum drying, freeze drying, pneumatic conveying drying, microwave drying, infrared drying and dielectric dry etc.In certain embodiments of the present invention, baking temperature is 50-120 DEG C.
Beneficial effect of the present invention is:
The invention provides that a kind of film fracture strength is high, rejection is high and there is the diffusion barrier preparation method of wider bore footpath scope, adopt solute be separated (NIPS) be prepared by coetrusion, the preparation liquid of supporting layer and separating layer is individually prepared, can not make a difference therebetween, the adjustable range of preparation liquid composition is wide in range, preparation method is simple, convenient solvent reclaiming, consume energy low, diffusion barrier pore diameter range prepared by the method, between 0.01-1 μm, covers micro-filtration and ultrafiltration major part scope substantially.
Detailed description of the invention
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred embodiment.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, the some distortion made and improvement, all belong to protection scope of the present invention.Raw material used in embodiment all can be obtained by commercial sources.
Embodiment 1
Be Kynoar, the PEG400 of 5%, the N of 77% of 18% by mass percent, N-dimethylacetylamide joins with in the reactor stirred and heat, 24h is stirred at 80 DEG C, it is made to be uniformly dissolved, stand-by as outer preparation liquid after leaving standstill 12h after carrying out filtration with 400 object filters; Be Kynoar, the PEG400 of 1%, the N of 50.4% of 15% by mass percent, N-dimethylacetylamide, 33.6% trimethyl phosphate join with in the reactor stirred and heat, 24h is stirred at 50 DEG C, it is made to be uniformly dissolved, stand-by as internal layer preparation liquid after leaving standstill 12h after carrying out filtration with 600 object filters.By measuring pump or high-order liquid bath, inner core liquid (deionized water) is continued quantitative outflow from core fluid apertures, increase nitrogen pressure and extrude from triple channel shower nozzle by preparation liquid, and make the flow velocity of outer casting solution and internal layer casting solution be 1:1.Walk after a very short segment distance (≤20cm) in atmosphere, preparation liquid is vertically fallen into by the 25 DEG C of coagulating baths according to 1:1 composition of proportions of ethanol and pure water, thereafter 24h is soaked by deionized water, with removing pore-foaming agent wherein and a small amount of unreacted monomer, test after carrying out guarantor hole 12h with 20% glycerin solution thereafter.
Obtained Hydrophilic hollow fiber membrane is carried out to the test of water flux, rejection and contact angle, method of testing is as follows:
Water flux:
Adopt external-compression type method of testing, by measuring in the unit interval volume V flowing through water
w, the film silk area A passed through and the time t of outflow, according to formula:
calculate the water flux of polyvinylidene fluoride film.
Rejection:
Use ultraviolet-visible-infrared spectrophotometer to test, under 0.1MPa, adopting external-compression type to measure, is that the bovine serum albumin of 80000 is as tested object using the molecular weight of 500ppm/L.By the rejection of the residual quantity determination polyvinylidene fluoride film of bovine serum albumin on test membrane.Rejection
wherein C
pfor bovine serum albumin concentration in water inlet, C
ffor bovine serum albumin concentration in water purification.
Contact angle:
Adopt the contact angle of contact angle tester test membrane silk and water.
Hot strength:
Use the hot strength of universal material puller system test polyvinylidene fluoride film.
The result of test is: the pure water flux under 0.1MPa is 860Lm
-2h
-1, be 87.9% to the BSA rejection of 1g/L, hot strength is 4MPa.
Embodiment 2
Be Kynoar, the lithium chloride of 6%, the N of 69% of 25% by mass percent, N-dimethylacetylamide joins with in the reactor stirred and heat, 24h is stirred at 150 DEG C, it is made to be uniformly dissolved, stand-by as outer preparation liquid after leaving standstill 12h after carrying out filtration with 500 object filters; Be Kynoar, the Macrogol 600 of 4%, the N of 56.25% of 21% by mass percent, N-dimethylacetylamide, 18.75% trimethyl phosphate join with in the reactor stirred and heat, 24h is stirred at 100 DEG C, it is made to be uniformly dissolved, stand-by as internal layer preparation liquid after leaving standstill 12h after carrying out filtration with 500 object filters.By measuring pump or high-order liquid bath, inner core liquid (deionized water) is continued quantitative outflow from core fluid apertures, increase nitrogen pressure and extrude from triple channel shower nozzle by preparation liquid, and make the flow velocity of outer casting solution and internal layer casting solution be 1:1.Walk after a very short segment distance (≤20cm) in atmosphere, preparation liquid is vertically fallen into 35 DEG C by 20% N, in N-dimethylacetamide aqueous coagulation bath, thereafter 24h is soaked by deionized water, with removing pore-foaming agent wherein and a small amount of unreacted monomer, thereafter test after carrying out guarantor hole 24h with 50% glycerin solution, test condition is with embodiment 1, and the pure water flux under 0.1MPa is 720Lm
-2h
-1, be 92% to the BSA rejection of 1g/L, hot strength is 3.8MPa.
Embodiment 3
Be the Kynoar of 20% by mass percent, the PEG400 of 2%, the trimethyl phosphate of 78% join with stir and heating reactor in, 24h is stirred at 120 DEG C, it is made to be uniformly dissolved, stand-by as outer preparation liquid after leaving standstill 12h after carrying out filtration with 600 object filters; Be Kynoar, the Macrogol 600 of 6%, the N of 38% of 18% by mass percent, N-dimethylacetylamide, 38% tricresyl phosphate propyl ester join with in the reactor stirred and heat, 24h is stirred at 70 DEG C, it is made to be uniformly dissolved, stand-by as internal layer preparation liquid after leaving standstill 12h after carrying out filtration with 500 object filters.By measuring pump or high-order liquid bath, inner core liquid (deionized water) is continued quantitative outflow from core fluid apertures, increase nitrogen pressure and extrude from triple channel shower nozzle by preparation liquid, and make the flow velocity of outer casting solution and internal layer casting solution be 2:1.Walk after a very short segment distance (≤20cm) in atmosphere, preparation liquid is vertically fallen into 30 DEG C by 10% 1-METHYLPYRROLIDONE aqueous coagulation bath, thereafter 24h is soaked by deionized water, with removing pore-foaming agent wherein and a small amount of unreacted monomer, thereafter test after carrying out guarantor hole with 40% glycerin solution, test condition is with embodiment 1, and the pure water flux under 0.1MPa is 750Lm
-2h
-1, be 92.8% to the BSA rejection of 1g/L, hot strength is 4.2MPa.
Embodiment 4
Be the Kynoar of 23% by mass percent, the Macrogol 600 of 5%, the tricresyl phosphate propyl ester of 72% join with stir and heating reactor in, 24h is stirred at 150 DEG C, it is made to be uniformly dissolved, stand-by as outer preparation liquid after leaving standstill 12h after carrying out filtration with 400 object filters; Be Kynoar, the polyethylene glycol-800 of 4%, the N of 41% of 20% by mass percent, N-dimethylacetylamide, 35% trimethyl phosphate join with in the reactor stirred and heat, 24h is stirred at 80 DEG C, it is made to be uniformly dissolved, stand-by as internal layer preparation liquid after leaving standstill 12h after carrying out filtration with 500 object filters.By measuring pump or high-order liquid bath, inner core liquid (deionized water) is continued quantitative outflow from core fluid apertures, increase nitrogen pressure and extrude from triple channel shower nozzle by preparation liquid, and make the flow velocity of outer casting solution and internal layer casting solution be 1:1.Walk after a very short segment distance (≤20cm) in atmosphere, preparation liquid is vertically fallen into 25 DEG C by 10% isopropanol water solution coagulating bath, thereafter 72h is soaked by deionized water, with removing pore-foaming agent wherein and a small amount of unreacted monomer, thereafter after carrying out guarantor hole with 40% glycerin solution, 72h tests, test condition is with embodiment 1, and the pure water flux under 0.1MPa is 960Lm
-2h
-1, be 90.8% to the BSA rejection of 1g/L, hot strength is 4MPa.
Claims (10)
1. a preparation method for polyvinylidene fluoride hollow fiber membrane for water treatment, is characterized in that, is individually prepared by the preparation liquid of supporting layer and separating layer, comprises the following steps:
1) Kynoar, pore-foaming agent, organic solvent are added in material-compound tank, at 80-150 DEG C after stirring and dissolving deaeration, leave standstill to obtain outer separating layer mold liquid after filtration;
2) by Kynoar, pore-foaming agent, organic solvent adds in material-compound tank, after stirring solvent deaeration, leaves standstill to obtain internal layer supporting layer mold liquid after filtration at 50-100 DEG C;
3), after above-mentioned two kinds of casting solutions being filtered respectively, vacuumizing, extrude together with core liquid be prepared into primary hollow tunica fibrosa through measuring pump, triple channel shower nozzle;
4), after primary hollow tunica fibrosa being solidified process by coagulating bath, be soaked in water 12-72h, and through protecting hole agent process, after drying, obtaining hydrophilic Pvdf Microporous Hollow Fiber Membrane at 20-50 DEG C.
2. method according to claim 1, is characterized in that, the content of Kynoar in skin and internal layer casting solution is respectively 18-25wt% and 15-21wt%.
3. method according to claim 1, is characterized in that, step 3) in when extruding the flow rate of outer casting solution and internal layer casting solution be 1-2:1.
4. method according to claim 1, it is characterized in that, step 1) described in organic solvent be selected from 1-METHYLPYRROLIDONE, N, N dimethylacetylamide, N, at least one in N-dimethylformamide, trimethyl phosphate, triethyl phosphate or tributyl phosphate, content is the 18-38% of outer casting solution.
5. method according to claim 1, is characterized in that, step 2) described in organic solvent content be the 75-84% of internal layer casting solution quality.
6. method according to claim 5, it is characterized in that, described organic solvent is the mixture of solvent orange 2 A and solvent B, solvent orange 2 A is selected from 1-METHYLPYRROLIDONE, N, N dimethylacetylamide, N, at least one in N-dimethylformamide, solvent B is selected from least one in trimethyl phosphate, triethyl phosphate, tributyl phosphate, and wherein organic solvent A proportion is 50-100%.
7. method according to claim 1, is characterized in that, described pore-foaming agent is selected from polyethylene glycol, polyvinylpyrrolidone, lithium chloride, and content is the 1-6% of internal layer, outer casting solution quality.
8. method according to claim 1, is characterized in that, the core liquid of primary filament film preparation is deionized water.
9. method according to claim 1, is characterized in that, coagulating bath be deionized water or with the mixing of organic solvent, wherein coagulation bath temperature is 0-50 DEG C.
10. method according to claim 1, is characterized in that, described guarantor hole agent is content is 20-50wt% glycerine, and the processing time is 12-72h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410650609.3A CN104474922A (en) | 2014-11-14 | 2014-11-14 | Preparation method of polyvinylidene fluoride hollow fiber water treatment membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410650609.3A CN104474922A (en) | 2014-11-14 | 2014-11-14 | Preparation method of polyvinylidene fluoride hollow fiber water treatment membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104474922A true CN104474922A (en) | 2015-04-01 |
Family
ID=52749607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410650609.3A Pending CN104474922A (en) | 2014-11-14 | 2014-11-14 | Preparation method of polyvinylidene fluoride hollow fiber water treatment membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104474922A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105169974A (en) * | 2015-09-29 | 2015-12-23 | 清华大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN106731878A (en) * | 2016-12-09 | 2017-05-31 | 唐山学院 | The preparation method of gradient aperture structure Pvdf Microporous Hollow Fiber Membrane |
| CN107008163A (en) * | 2016-01-28 | 2017-08-04 | 东莞东阳光科研发有限公司 | A kind of woven tube strengthens the preparation method of Pvdf Microporous Hollow Fiber Membrane |
| CN109225121A (en) * | 2018-08-27 | 2019-01-18 | 石河子大学 | The preparation method and brine of compound adsorbent propose lithium method |
| CN109231365A (en) * | 2018-08-31 | 2019-01-18 | 浙江工业大学 | A kind of application of PIMs superthin layer composite hollow fiber membrane in separation alcohol water |
| CN110721595A (en) * | 2019-09-10 | 2020-01-24 | 梧州中科鼎新工业技术研究院(有限合伙) | Hollow fiber membrane and preparation method thereof |
| CN110732246A (en) * | 2019-09-10 | 2020-01-31 | 梧州中科鼎新工业技术研究院(有限合伙) | acid-resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN113244790A (en) * | 2021-04-27 | 2021-08-13 | 陕西禹慧智通环保科技有限公司 | Self-reinforced hollow fiber ultrafiltration membrane and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008173573A (en) * | 2007-01-19 | 2008-07-31 | Toray Ind Inc | Composite hollow fiber membrane |
| CN101954148A (en) * | 2010-09-15 | 2011-01-26 | 四川大学 | Method for accelerating dosage calculation in radiotherapy based on GPU (Graphics Processing Unit) |
| EP1935480B1 (en) * | 2005-10-13 | 2013-03-27 | Asahi Kasei Chemicals Corporation | Process for producing a porous multilayered hollow-fiber membrane |
| CN103877868A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Separation membrane preparation method and high-flux and high-strength separation membrane |
| CN103908898A (en) * | 2013-01-07 | 2014-07-09 | 吕晓龙 | Composite hollow fiber film and making method thereof |
-
2014
- 2014-11-14 CN CN201410650609.3A patent/CN104474922A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1935480B1 (en) * | 2005-10-13 | 2013-03-27 | Asahi Kasei Chemicals Corporation | Process for producing a porous multilayered hollow-fiber membrane |
| JP2008173573A (en) * | 2007-01-19 | 2008-07-31 | Toray Ind Inc | Composite hollow fiber membrane |
| CN101954148A (en) * | 2010-09-15 | 2011-01-26 | 四川大学 | Method for accelerating dosage calculation in radiotherapy based on GPU (Graphics Processing Unit) |
| CN103877868A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Separation membrane preparation method and high-flux and high-strength separation membrane |
| CN103908898A (en) * | 2013-01-07 | 2014-07-09 | 吕晓龙 | Composite hollow fiber film and making method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105169974A (en) * | 2015-09-29 | 2015-12-23 | 清华大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN107008163A (en) * | 2016-01-28 | 2017-08-04 | 东莞东阳光科研发有限公司 | A kind of woven tube strengthens the preparation method of Pvdf Microporous Hollow Fiber Membrane |
| CN106731878A (en) * | 2016-12-09 | 2017-05-31 | 唐山学院 | The preparation method of gradient aperture structure Pvdf Microporous Hollow Fiber Membrane |
| CN109225121A (en) * | 2018-08-27 | 2019-01-18 | 石河子大学 | The preparation method and brine of compound adsorbent propose lithium method |
| CN109231365A (en) * | 2018-08-31 | 2019-01-18 | 浙江工业大学 | A kind of application of PIMs superthin layer composite hollow fiber membrane in separation alcohol water |
| CN109231365B (en) * | 2018-08-31 | 2021-07-27 | 浙江工业大学 | Application of PIMs (platelet-enhanced membranes) ultrathin layer composite hollow fiber membrane in separation of alcohol water |
| CN110721595A (en) * | 2019-09-10 | 2020-01-24 | 梧州中科鼎新工业技术研究院(有限合伙) | Hollow fiber membrane and preparation method thereof |
| CN110732246A (en) * | 2019-09-10 | 2020-01-31 | 梧州中科鼎新工业技术研究院(有限合伙) | acid-resistant hollow fiber nanofiltration membrane and preparation method thereof |
| CN113244790A (en) * | 2021-04-27 | 2021-08-13 | 陕西禹慧智通环保科技有限公司 | Self-reinforced hollow fiber ultrafiltration membrane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104474922A (en) | Preparation method of polyvinylidene fluoride hollow fiber water treatment membrane | |
| Jin et al. | Hydrophobic modification of poly (phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation | |
| Zhang et al. | The unidirectional regulatory role of coagulation bath temperature on cross-section radius of the PVDF hollow-fiber membrane | |
| CN103877868B (en) | A kind of preparation method separating film and high flux high intensity separation film | |
| CN103071404B (en) | Composite reverse osmosis membrane and preparation method thereof | |
| CN101293185A (en) | Method for producing polyvinylidene fluoride porous membrane | |
| CN107570020B (en) | Polyarylene sulfide sulfone composite separation membrane and preparation method thereof | |
| CN102649028A (en) | Hydrophobic separation membrane and preparation method | |
| CN103055724B (en) | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method | |
| CN109304098B (en) | Preparation method of polymer-ceramic composite inner membrane | |
| CN106621866A (en) | Polyether sulfone hollow fiber ultrafiltration membrane and processing device and preparation method thereof | |
| CN104383818A (en) | Composite microporous diaphragm, preparation method and application thereof | |
| CN102160969A (en) | Method for preparing fluorocarbon polymer microporous film with interpenetrating network bicontinuous pore structure | |
| CN109621751B (en) | Amphiphilic solvent-resistant aliphatic polyamide ultrafiltration membrane and preparation method and application thereof | |
| WO2017043233A1 (en) | Film-forming stock solution for use in non-solvent-induced phase separation methods, and method for producing porous hollow fiber membrane using same | |
| CN102631844B (en) | Preparation method of hydrophobe polysulfone microporous membrane | |
| CN106621848A (en) | Aliphatic polyamide hollow fiber membrane and preparation method and application thereof | |
| CN108499361A (en) | A kind of preparation method of the adjustable nano-porous polymer film in aperture | |
| CN104209024A (en) | Polyarylenesulfidesulfone/sulfonated polymer composite separation membrane and preparation method thereof | |
| CN110327794B (en) | Preparation method of nanofiltration membrane | |
| CN105435655B (en) | A kind of solvent resistant separation membrane material and preparation method thereof | |
| CN112808019B (en) | Method for preparing polyaryletherketone tubular membrane by using green solvent thermal-induced phase method | |
| CN111013400A (en) | Method for preparing polyvinylidene fluoride tubular membrane by low-temperature thermal induced phase method | |
| CN104043344A (en) | Polyvinylidene fluoride hollow fiber microporous membrane and preparation method | |
| JP4100215B2 (en) | Manufacturing method of water vapor permeable membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150401 |
|
| RJ01 | Rejection of invention patent application after publication |