CN105561810A - Method of using carbon nanofiber layer to modify ultrafiltration membrane - Google Patents
Method of using carbon nanofiber layer to modify ultrafiltration membrane Download PDFInfo
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- CN105561810A CN105561810A CN201510970961.XA CN201510970961A CN105561810A CN 105561810 A CN105561810 A CN 105561810A CN 201510970961 A CN201510970961 A CN 201510970961A CN 105561810 A CN105561810 A CN 105561810A
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- fiber
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- carbon fiber
- ultrafiltration membrane
- milipore filter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method of using a carbon nanofiber layer to modify an ultrafiltration membrane and belongs to the field of environment-friendly water treatment. The method includes: pre-treating carbon fiber to obtain granule-like carbon fiber; ultrasonically dispersing and stirring the granule-like carbon fiber after being pre-treated in a solvent sufficiently, and pre-depositing the carbon nanofiber which is uniformly dispersed on the surface of the ultrafiltration membrane. The carbon nanofiber pre-deposited on the surface of the ultrafiltration membrane is equivalent to a simple coating which preferentially adsorbs pollutants to reduce membrane pollution. The carbon nano fiber pre-deposited on the surface of the ultrafiltration membrane is rich in source, so that operation cost is lowered greatly. The carbon nanofiber pre-deposited on the surface of the ultrafiltration membrane and the ultrafiltration membrane are in physical deposition, so that the carbon nanofiber and the ultrafiltration membrane can be completely removed by using a plastic scraper to slightly scrape and using deionized water to clean after reaction is finished. The method is simple to operate, low in cost and easy in large-scale use and popularization.
Description
Technical field
The present invention relates to a kind of carbon nano-fiber layer to the method for milipore filter modification, belong to environment-protective water process field.
Background technology
Membrane technology is more and more extensive in the application of environment-protective water process field, progressively become one of basis of world's strategy of sustainable development, more and more important effect is played in the significant problems such as solution global energy resources and environment, membrane technology is considered to one of 21 century most important new technology, but fouling membrane remains the major obstacle hindering membrane technology to apply.The early stage method mainly taked to reduce fouling membrane carries out a preprocessing process to reduce fouling membrane to sewage, and main be also the most traditional preprocessing process is chemical coagulation.In addition, also have the pretreated method such as ultrasonic, backwash, electricity flocculation, electric coagulation is carried out to film.Ultrasonicly some materials of film adsorption can only to be removed, and the contaminant particle that cannot adsorb in fenestra is removed; Backwash has than ultrasonic better removal efficiency, the particle adsorbed in fenestra can be removed, and although chemical flocculation, electricity flocculation and these methods of electric coagulation can reduce fouling membrane to a certain extent, but the chemical reagent added all can cause fouling membrane, and the fouling membrane that chemical reagent causes can drop to minimum by pre-deposition process, and preliminary sedimentation lamination is easy to remove, and not only can improve organic removal efficiency, can also reduce the decay of membrane flux.
Summary of the invention
The present invention is directed to existing deficiency in milipore filter water treatment, propose a kind of carbon nano-fiber layer to the method for milipore filter modification, carbon nano-fiber for retaining and the pollutant in adsorbed water, to reduce the method for treating water of the modified ultrafiltration membrane of film surface contamination to greatest extent.
Carbon nano-fiber layer is to a method for milipore filter modification, and concrete steps are as described below: pre-treatment of carbon fiber is obtained class graininess carbon fiber; Again by the ultrasonic abundant dispersion stirring in a solvent of pretreated class graininess carbon fiber, under constant-pressure conditions, by finely dispersed carbon nano-fiber pre-deposition at ultrafiltration membrane surface.
Described solvent to be solvent be in water, ethanol or 1-METHYLPYRROLIDONE (NMP) one or more.
Described pre-treatment of carbon fiber process is: by the immersion of carbon fiber source, freeze drying, high-temperature calcination in inert atmosphere, adds solvent in fiber after firing, grinding, and then ultrasonic abundant dispersion is stirred in a solvent, obtains pretreated class graininess carbon fiber.
Preferably, described carbon fiber is one or more in the strings such as bacteria cellulose (BC), luffa.
Preferably, described carbon fiber soak time is 1 day-14 days.
Preferably, the cryodesiccated time 48h-96h of described carbon fiber.
Preferably, the temperature of described carbon-fiber high-temperature calcining is 800-1000 degree.
Preferably, the time of described carbon-fiber high-temperature calcining is 24-48h.
Preferably, the milling time of described carbon fiber is 5-30min.
Preferably, described carbon fiber pre-deposition at constant pressure, constant voltage is here 0.05-0.2MPa.
Preferably, the load capacity of described carbon fiber is 3g/m
2-96g/m
2(the effective usable floor area relative to milipore filter).
Modified milipore filter, through cleaning, loaded particle can Reusability again.
Beneficial effect
1), the carbon nano-fiber of ultrafiltration membrane surface pre-deposition is equivalent to an easy rete, Preferential adsorption pollutant, minimizing fouling membrane.
2), the carbon nano-fiber source of ultrafiltration membrane surface pre-deposition enriches, and greatly reduces running cost.
3), the carbon nano-fiber of ultrafiltration membrane surface pre-deposition and milipore filter be physical deposition, after question response, it to be wiped off gently wash it can be removed completely by deionized water again with plastic wipers.
4), the inventive method is simple to operate, with low cost, and is easy to scale and uses and promote.
Accompanying drawing explanation
Be 24g/m in polyvinylidene fluoride (PVDF) ultrafiltration membrane surface pre-deposition load capacity in Fig. 1, case study on implementation one
2bacteria cellulose to the absorption flux decline figure of organic matter bovine serum albumin (BSA) solution.
Be 24g/m in polyvinylidene fluoride (PVDF) ultrafiltration membrane surface pre-deposition load capacity in Fig. 2, case study on implementation two
2bacteria cellulose to the absorption flux decline figure of organic matter sodium alginate (SA) solution.
Be 12g/m in polyvinylidene fluoride (PVDF) ultrafiltration membrane surface pre-deposition load capacity in Fig. 3, case study on implementation three
2by the bacteria cellulose of ethanol and 1-METHYLPYRROLIDONE modification to the absorption flux decline figure of organic matter bovine serum albumin (BSA) solution.
Be 12g/m in polyvinylidene fluoride (PVDF) ultrafiltration membrane surface pre-deposition load capacity in Fig. 4, case study on implementation four
2by the bacteria cellulose of ethanol and 1-METHYLPYRROLIDONE modification to the absorption flux decline figure of organic matter sodium alginate (SA) solution.
The scanning electron microscope diagram (SEM) of bacteria cellulose after Fig. 5, aeroge bacteria cellulose and calcining.
Detailed description of the invention
Below in conjunction with accompanying drawing and case study on implementation, the inventive method is described further.Should be understood that these cases are only limitted to the inventive method is described, and be not used in the restriction scope of application of the present invention.
Case study on implementation one
1), the bacteria cellulose of water-setting glue is cut into bulk (about 1*2*1.5cm
3), soak two days in deionized water, freeze drying 48h becomes airsetting gluey, and 950 degree of high-temperature calcination 24h in argon gas atmosphere, then taking load capacity is 24g/m
2bacteria cellulose after calcining drips a small amount of deionized water and soaks, grinding 15min, ultrasonic disperse 5min, magnetic agitation 10min in 50ml deionized water, under constant voltage 0.1MPa condition, by finely dispersed bacteria cellulose pre-deposition to segregation fluoride ultrafiltration membrane surface.
2), in 300 ml deionized water, add the sodium bicarbonate solution of 3 milliliters of 0.5M, then add the BSA storing solution of the 3g/L of 1 milliliter, regulate pH to be 7 ± 0.1, by this BSA solution above-mentioned steps 1 with the hydrochloric acid solution of 0.1M) in pre-deposition 24g/m
2the polyvinylidene fluoride (PVDF) ultrafiltration membrane ultrafiltration of bacteria cellulose, by electronic balance connection data receiver image data, the change of membrane flux as shown in Figure 1.The membrane flux of 75% can be kept after 300 ml water experiments, repeat above-mentioned steps twice, compared to first time, the film initial flux of second time and third time recovers to reach 90.47% and 85.49%, and last membrane flux still can remain on 70% and about 63%.This carbon nano-fiber of surface greatly reduces the pollution of albumen to film.
Case study on implementation two
1), the bacteria cellulose of water-setting glue is cut into bulk (about 1*2*1.5cm
3), soak two days in deionized water, freeze drying 48h becomes airsetting gluey, and 950 degree of high-temperature calcination 24h in argon gas atmosphere, then taking load capacity is 24g/m
2bacteria cellulose after calcining drips a small amount of deionized water and soaks, grinding 15min, ultrasonic disperse 5min, magnetic agitation 10min in 50ml deionized water, under constant voltage 0.1MPa condition, by finely dispersed bacteria cellulose pre-deposition to segregation fluoride ultrafiltration membrane surface.
2), in 300 ml deionized water, add the sodium bicarbonate solution 3 milliliters of 0.5M, then add the SA storing solution of 1 milliliter of 3g/L, regulate pH to be 7 ± 0.1, by this SA solution above-mentioned steps 1 with the hydrochloric acid solution of 0.1M) in pre-deposition 24g/m
2the polyvinylidene fluoride (PVDF) ultrafiltration membrane ultrafiltration of bacteria cellulose, by electronic balance connection data receiver image data, the change of membrane flux as shown in Figure 2.Repeat above-mentioned steps three times, compared to first time, the film initial flux of second time and third time recovers to reach 93.27% and 88.55%.
Case study on implementation three
1), the bacteria cellulose of water-setting glue is cut into bulk (about 1*2*1.5cm
3), soak two days in deionized water, freeze drying 48h becomes airsetting gluey, and 950 degree of high-temperature calcination 24h in argon gas atmosphere, then taking load capacity is 12g/m
2bacteria cellulose after calcining drips a small amount of ethanol wet, grinding 15min, ultrasonic disperse 5min, then magnetic agitation 24h in 35ml ethanol and 15mlN-methyl pyrrolidone mixed liquor, under constant voltage 0.1MPa condition, by surperficial to segregation fluoride ultrafiltration membrane for the finely dispersed bacteria cellulose pre-deposition by ethanol and 1-METHYLPYRROLIDONE modification.
2), in 300 ml deionized water, add the sodium bicarbonate solution 3 milliliters of 0.5M, then add the BSA storing solution of 1 milliliter of 3g/L, regulate pH to be 7 ± 0.1, by this BSA solution above-mentioned steps 1 with the hydrochloric acid solution of 0.1M) in pre-deposition 12g/m
2the polyvinylidene fluoride (PVDF) ultrafiltration membrane ultrafiltration of bacteria cellulose, by electronic balance connection data receiver image data, the change of membrane flux as shown in Figure 3.After 300 ml water filtration experiments, membrane flux still can remain on about 60%.
Case study on implementation four
1), the bacteria cellulose of water-setting glue is cut into bulk (about 1*2*1.5cm
3), soak two days in deionized water, freeze drying 48h becomes airsetting gluey, and 950 degree of high-temperature calcination 24h in argon gas atmosphere, then taking load capacity is 12g/m
2bacteria cellulose after calcining drips a small amount of ethanol wet, grinding 15min, ultrasonic disperse 5min, then magnetic agitation 24h in 35ml ethanol and 15mlN-methyl pyrrolidone mixed liquor, under constant voltage 0.1MPa condition, by surperficial to segregation fluoride ultrafiltration membrane for the finely dispersed bacteria cellulose pre-deposition by ethanol and 1-METHYLPYRROLIDONE modification.
2), in 300 ml deionized water, add the sodium bicarbonate solution 3 milliliters of 0.5M, then add the SA storing solution of 1 milliliter of 3g/L, regulate pH to be 7 ± 0.1, by this SA solution above-mentioned steps 1 with the hydrochloric acid solution of 0.1M) in pre-deposition 12g/m
2the polyvinylidene fluoride (PVDF) ultrafiltration membrane ultrafiltration of bacteria cellulose, by electronic balance connection data receiver image data, the change of membrane flux as shown in Figure 4.After 300 ml water filtration experiments, membrane flux still can remain on about 60%.
Claims (6)
1. carbon nano-fiber layer is to a method for milipore filter modification, it is characterized in that: concrete steps are as described below: pre-treatment of carbon fiber is obtained class graininess carbon fiber; Again by the ultrasonic abundant dispersion stirring in a solvent of pretreated class graininess carbon fiber, under constant-pressure conditions, by finely dispersed carbon nano-fiber pre-deposition at ultrafiltration membrane surface, obtain modified milipore filter.
2. a kind of carbon nano-fiber layer as claimed in claim 1 is to the method for milipore filter modification, it is characterized in that: described pre-treatment of carbon fiber process is: by the immersion of carbon fiber source, freeze drying, high-temperature calcination in inert atmosphere, solvent is added in fiber after firing, grinding, then ultrasonic abundant dispersion is stirred in a solvent, obtains pretreated class graininess carbon fiber.
3. a kind of carbon nano-fiber layer as claimed in claim 1 or 2 is to the method for milipore filter modification, it is characterized in that: described solvent to be solvent be in water, ethanol or 1-METHYLPYRROLIDONE (NMP) one or more.
4. a kind of carbon nano-fiber layer as claimed in claim 1 or 2 is to the method for milipore filter modification, it is characterized in that: described carbon fiber is one or more in the strings such as bacteria cellulose (BC), luffa.
5. a kind of carbon nano-fiber layer as claimed in claim 1 is to the method for milipore filter modification, it is characterized in that: described carbon fiber soak time is 1 day-14 days; The cryodesiccated time 48h-96h of described carbon fiber; The temperature of described carbon-fiber high-temperature calcining is 800-1000 degree; The time of described carbon-fiber high-temperature calcining is 24-48h; The milling time of described carbon fiber is 5-30min; Described carbon fiber pre-deposition at constant pressure, constant voltage is here 0.05-0.2MPa; The load capacity of described carbon fiber is 3g/m
2-96g/m
2.
6. a kind of carbon nano-fiber layer as claimed in claim 1 is to the method for milipore filter modification, it is characterized in that: described modified milipore filter, and through cleaning, loaded particle can Reusability again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510970961.XA CN105561810A (en) | 2015-12-22 | 2015-12-22 | Method of using carbon nanofiber layer to modify ultrafiltration membrane |
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|---|---|---|---|
| CN201510970961.XA CN105561810A (en) | 2015-12-22 | 2015-12-22 | Method of using carbon nanofiber layer to modify ultrafiltration membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185411A (en) * | 2017-05-19 | 2017-09-22 | 北京理工大学 | It is a kind of in method of the metal cation crosslinking-oxidization graphene nanometer sheet to ultrafiltration membrane modifying |
| CN107486025A (en) * | 2017-09-18 | 2017-12-19 | 河海大学 | A kind of preparation method of compound poly (ether-sulfone) ultrafiltration membrane of modified activated carbon fiber and its gained milipore filter and application |
| CN110482649A (en) * | 2019-07-24 | 2019-11-22 | 北京工业大学 | Method of the group technology regeneration for the nano composite membrane of micropollutants removal in water |
| CN112619420A (en) * | 2019-09-24 | 2021-04-09 | 天津天元新材料科技有限公司 | Loofah sponge modified composite reverse osmosis membrane and preparation method thereof |
Citations (3)
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| CN103127843A (en) * | 2012-11-13 | 2013-06-05 | 高润宝 | Carbon nano tube and nano silicon dioxide modified polyvinylalcohol composite ultrafiltration membrane |
| CN104230056A (en) * | 2014-09-21 | 2014-12-24 | 北京工业大学 | Method for relieving pollution to ultrafiltration membrane under joint action of pre-oxidation and membrane modification |
| CN104532407A (en) * | 2014-12-24 | 2015-04-22 | 暨南大学 | Carbon nanofibers based on carbonized bacterial cellulose as well as composition and application of carbon nanofibers |
-
2015
- 2015-12-22 CN CN201510970961.XA patent/CN105561810A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127843A (en) * | 2012-11-13 | 2013-06-05 | 高润宝 | Carbon nano tube and nano silicon dioxide modified polyvinylalcohol composite ultrafiltration membrane |
| CN104230056A (en) * | 2014-09-21 | 2014-12-24 | 北京工业大学 | Method for relieving pollution to ultrafiltration membrane under joint action of pre-oxidation and membrane modification |
| CN104532407A (en) * | 2014-12-24 | 2015-04-22 | 暨南大学 | Carbon nanofibers based on carbonized bacterial cellulose as well as composition and application of carbon nanofibers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185411A (en) * | 2017-05-19 | 2017-09-22 | 北京理工大学 | It is a kind of in method of the metal cation crosslinking-oxidization graphene nanometer sheet to ultrafiltration membrane modifying |
| CN107486025A (en) * | 2017-09-18 | 2017-12-19 | 河海大学 | A kind of preparation method of compound poly (ether-sulfone) ultrafiltration membrane of modified activated carbon fiber and its gained milipore filter and application |
| CN107486025B (en) * | 2017-09-18 | 2020-02-18 | 河海大学 | Preparation method of modified activated carbon fiber composite polyether sulfone ultrafiltration membrane, ultrafiltration membrane obtained by preparation method and application of ultrafiltration membrane |
| CN110482649A (en) * | 2019-07-24 | 2019-11-22 | 北京工业大学 | Method of the group technology regeneration for the nano composite membrane of micropollutants removal in water |
| CN112619420A (en) * | 2019-09-24 | 2021-04-09 | 天津天元新材料科技有限公司 | Loofah sponge modified composite reverse osmosis membrane and preparation method thereof |
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