CN103127843A - Carbon nano tube and nano silicon dioxide modified polyvinylalcohol composite ultrafiltration membrane - Google Patents
Carbon nano tube and nano silicon dioxide modified polyvinylalcohol composite ultrafiltration membrane Download PDFInfo
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- CN103127843A CN103127843A CN2012104519047A CN201210451904A CN103127843A CN 103127843 A CN103127843 A CN 103127843A CN 2012104519047 A CN2012104519047 A CN 2012104519047A CN 201210451904 A CN201210451904 A CN 201210451904A CN 103127843 A CN103127843 A CN 103127843A
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- modified polyvinylalcohol
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 42
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 39
- 235000019422 polyvinyl alcohol Nutrition 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 239000002041 carbon nanotube Substances 0.000 title abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 title abstract description 5
- 238000000108 ultra-filtration Methods 0.000 title abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 4
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 9
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical class [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 230000004907 flux Effects 0.000 abstract description 12
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 4
- 239000011147 inorganic material Substances 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 2
- 239000004088 foaming agent Substances 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract 3
- 230000021523 carboxylation Effects 0.000 abstract 1
- 238000006473 carboxylation reaction Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000000614 phase inversion technique Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 23
- 239000000243 solution Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a carbon nano tube and nano silicon dioxide modified polyvinylalcohol composite ultrafiltration membrane. Poval serves as a membrane substrate, a certain amount of carbon nano tubes and nano silicon dioxide after carboxylation are added to film casting solution, wherein the carbon nano tubes and the nano silicon dioxide are dispersed by surface active agents, polyethylene glycol serves as a pore-foaming agent, and the membrane is prepared through an immersion precipitated phase inversion method. The prepared membrane keeps hydrophilicity of the poval, and therefore the membrane has good anti-pollution capacity, and meanwhile strength and toughness of inorganic materials are kept so that the defects that a poval wet membrane is low in strength and unpressurized are overcome. The composite ultrafiltration membrane is good in anti-pollution capacity, high in water flux, good in hold back characteristics, capable of being used repeatedly and long in service life.
Description
Technical field
The present invention relates to a kind of milipore filter for separating of technique, particularly a kind of CNT, nano silicon are total to the modified polyvinylalcohol composite hyperfiltration membrane.
Background technology
Ultrafiltration is as sieving, and (0.1～1.6MPa), it only allows solvent and sees through less than the solute of membrane aperture, and stops the solute greater than membrane aperture to pass through, with purification, the separation and concentrated of completing solution under certain pressure.Ultra-filtration process has following main feature: can separate under normal temperature and low pressure, thereby energy consumption be low without the variation between the phase border (1), is about 1/ 2 of evaporation or freezing～1/ 5; (2) equipment volume is little, and is simple in structure, and investment cost is low; (3) technique is simple, easy operating; (4) variation of matter does not occur in material in the concentrating and separating process, thereby is suitable for protecting the processing of flavor and heat-sensitive substance; (5) the material classification of different relative molecular masses can be separated; (6) in use come off without any impurity, guarantee that ultrafiltrate is pure.External hyperfiltration technique is used early in the field of the film heavy contamination such as dairy husbandry, Juice Industry, biotechnology, also more successful, proportion is very large; And China is due to the technical merit and the larger gap of external existence of film; Add the reasons such as small scale of enterprise, applicable cases is just in time opposite, and application mainly concentrates on film and pollutes lighter field, pollutes heavy industry at film and basically is not applied.
Because the structure of polyvinyl alcohol (PVA) is strict line style, compound with regular structure, so stable chemical nature, the mechanical strength of material is high; The hydrogen bond that exists between molecule makes it that enough heat endurances be arranged; It is highly hydrophilic that hydroxyl on strand has it, is one of material that in existing macromolecular material, hydrophily is fabulous.Because PVA has highly hydrophilic, good stain resistance and film forming, and cheap, therefore, very suitable film material as osmotic evaporation film, reverse osmosis membrane, NF membrane, dialyser, enzyme membrane, gas separation membrane, microcapsule membrane etc., existing many relevant research and development reports, but PVA is also less as the research and development of milipore filter film material.
Pure PVA basement membrane is easy swelling, wet film intensity difference, not withstand voltage in water, has limited to a great extent its industrial applications, must carry out modification to it so will obtain the PVA milipore filter that intensity is good, water-swellable is low.Common method of modifying is to introduce the second component, can with the PVA molecule in hydroxyl form covalent bond or hydrogen bond, make it change into water-fast group, and then improve the water resistance of film, obtain high-intensity PVA milipore filter.In recent years, organic-inorganic nano particle composite membrane combines the characteristics of organic polymer and inorganic material, becomes the focus of membrane science research.Studies show that in a large number, add inorganic nano-particle in organic basement membrane, can increase mechanical strength and the life-span of film, suppress the formation of macroporous structure, thereby make film have excellent permeance property, can also increase the Film conductivity energy simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of CNT, nano silicon modified polyvinylalcohol composite hyperfiltration membrane altogether, this composite hyperfiltration membrane has stronger contamination resistance, high water flux and holds back preferably characteristic, but Reusability, long service life.
In order to realize above goal of the invention, the present invention by the following technical solutions: a kind of CNT, nano silicon be the modified polyvinylalcohol composite hyperfiltration membrane altogether, comprises the raw material of following weight portion proportioning: 100 parts of polyvinyl alcohol; 1～6 part of CNT; 1～4 part of nano silicon, 10～25 parts of polyethylene glycol; 30～40 parts of saturated metabisulfite solutions; 1～6 part of lauryl sodium sulfate.
Described polyvinyl alcohol average degree of polymerization is 1750 ± 50.
Described CNT is SWCN, and caliber is 0.5～1nm.
Described nano silicon particle diameter is 20～40nm.
CNT is novel One-dimensional nanoreticular carbon materials, since being found, has started the upsurge of people's researchs due to the performance of its unique structure and excellence.CNT is widely used in the fields such as hydrogen storage material, composite reinforcing agent, superconductor because having good mechanical property, electric property, toughness, the large characteristics such as specific area.The progress of nanometer technology makes the nano-porous films based on CNT be developed.
Nano silicon is one of ultra tiny New Inorganic Materials of extremely important high-tech, because of its particle diameter very little, specific area is large, adsorption power is strong, the surface can be large, and the aspects such as chemical purity is high, dispersive property good, thermal resistance, resistance have special performance, with its superior stability, reinforcement, thickening property and thixotropy, show unique characteristics in numerous subjects and field, the effect of not replacing is arranged.And because polyvinyl alcohol and nano silicon are all hydroaropic substances, polyvinyl alcohol has good wellability to the surface of nano silicon, and nano silicon has huge specific area and surface energy, has larger activity, polyvinyl alcohol can be adsorbed on nano-silica surface securely, make between polyvinyl alcohol and nano silicon and can form hydrogen bond, can improve the performance of polyvinyl alcohol milipore filter.
Advantage of the present invention: take polyvinyl alcohol as the film matrix material, add in casting solution a certain amount of with surfactant-dispersed good carbon nanotube functionalized with carboxylic acid group and nano silicon, take polyethylene glycol as pore-foaming agent, by immersion precipitation phase inversion masking.Prepared film had both kept the hydrophily of polyvinyl alcohol, thereby had stronger contamination resistance, and the intensity of the inorganic material of having withed a hook at the end and toughness have made up polyvinyl alcohol wet film intensity low, the not withstand voltage defective that gets.Composite hyperfiltration membrane has stronger contamination resistance, high water flux and holds back preferably characteristic, but Reusability, long service life.
The specific embodiment
Embodiment one:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 2 parts of CNTs; 2 parts of nano silicons, 20 parts of polyethylene glycol; 30 parts of saturated metabisulfite solutions; 1 part of lauryl sodium sulfate.
Embodiment two:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 3 parts of CNTs; 1 part of nano silicon, 10 parts of polyethylene glycol; 35 parts of saturated metabisulfite solutions; 2 parts of lauryl sodium sulfate.
Embodiment three:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 1 part of CNT; 4 parts of nano silicons, 25 parts of polyethylene glycol; 40 parts of saturated metabisulfite solutions; 3 parts of lauryl sodium sulfate.
Embodiment four:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 6 parts of CNTs; 1 part of nano silicon, 25 parts of polyethylene glycol; 30 parts of saturated metabisulfite solutions; 3 parts of lauryl sodium sulfate.
Embodiment five:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 4 parts of CNTs; 2 parts of nano silicons, 22 parts of polyethylene glycol; 34 parts of saturated metabisulfite solutions; 4 parts of lauryl sodium sulfate.
Embodiment six:
Prepare raw material by following weight proportion: 100 parts of polyvinyl alcohol; 4 parts of CNTs; 2 parts of nano silicons, 20 parts of polyethylene glycol; 28 parts of saturated metabisulfite solutions; 4 parts of lauryl sodium sulfate.
The polyvinyl alcohol average degree of polymerization is 1750 ± 50.CNT is SWCN, and caliber is 0.5～1nm.The nano silicon particle diameter is 20～40nm.
CNT is mixed with concentrated hydrochloric acid, be heated to 50 ℃ and stir 5h, then add ultrasonic processing 5h in chloroazotic acid,, dry in baking oven to neutral with distilled water flushing, add lauryl sodium sulfate to be uniformly dispersed; Polyvinyl alcohol is dissolved in 90 ℃ of hot water, is made into concentration and is 15% the aqueous solution, stir 5h, add polyethylene glycol and scattered CNT, continue to stir 2h in 90 ℃ of water-baths, add nano silicon to stir 5h; Mixed liquor is incubated 24h in 60 ℃ of water-baths, be poured on and use the glass bar knifing on glass plate, immerse after air evaporation 30s in the saturated metabisulfite solution under room temperature, take out the CNT of the present invention, the nano silicon that get final product with the distilled water washing after 24h and be total to the modified polyvinylalcohol composite hyperfiltration membrane.
The performance test of composite hyperfiltration membrane:
(1) Mechanics Performance Testing: adopt electronic tensile machine to measure hot strength and the tension fracture elongation rate of composite hyperfiltration membrane, probe temperature is room temperature, and rate of extension is 2 mm/min.
(2) water flux experiment: at room temperature, film is placed in cup type ultrafilter, precompressed 1 h under 0.1MPa pressure collects the volume that sees through liquid in certain hour, the pure water flux of test compound film.
(3) film antifouling property test: be the stain resistance of investigating composite membrane, take distilled water and BSA solution as feed liquid, it tested.The pure water flux of composite membrane is J
0, composite membrane is surveyed its water flux after BSA pollutes be J
1, repeatedly rinses several times with distilled water after composite membrane pollutes, then to survey its water flux be J
2The computing formula of the resistance enhancement coefficient m of film and flux recovery rate Ф: m=(J
0-J
1)/J
1* 100%; Ф=J
2/ J
0* 100%.
(4) rejection test: at room temperature, the BSA standard liquid of a series of concentration of preparation is measured through ultraviolet-uisible spectrophotometer, obtains corresponding absorbance A, drawing standard curve A-CBSA.And then certain density BSA solution is filtered a period of time under certain pressure, after stability of flow, collect a certain amount of filtrate, measure respectively the A of material liquid and filtrate with ultraviolet-uisible spectrophotometer, can calculate corresponding concentration according to the calibration curve equation, then calculate the rejection R=(C of milipore filter
f-C
p)/C
f* 100%; C wherein
fThe concentration of material liquid, C
pSee through the concentration of liquid.
Test result sees Table 1
The performance test results of table 1 composite hyperfiltration membrane
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Hot strength/MPa | 8.75 | 9.56 | 10.32 | 8.79 | 9.78 | 10.12 |
| Elongation at break/% | 2.12 | 1.98 | 2.35 | 2.45 | 2.03 | 2.33 |
| Water flux/(Lm -2·h -1） | 129.6 | 132.6 | 142.3 | 126.4 | 134.2 | 121.8 |
| Resistance enhancement coefficient m | 0.32 | 0.29 | 0.33 | 0.28 | 0.30 | 0.31 |
| Flux recovery rate Ф | 88.32 | 80.56 | 85.73 | 86.12 | 89.34 | 87.67 |
| Rejection R | 0.81 | 0.79 | 0.77 | 0.85 | 0.86 | 0.84 |
Test result shows that composite hyperfiltration membrane has stronger contamination resistance, high water flux and holds back preferably characteristic.But and the composite hyperfiltration membrane Reusability, long service life.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (4)
1. a CNT, nano silicon are total to the modified polyvinylalcohol composite hyperfiltration membrane, it is characterized in that comprising the raw material of following weight portion proportioning: 100 parts of polyvinyl alcohol; 1～6 part of CNT; 1～4 part of nano silicon, 10～25 parts of polyethylene glycol; 30～40 parts of saturated metabisulfite solutions; 1～6 part of lauryl sodium sulfate.
2. CNT according to claim 1, nano silicon are total to the modified polyvinylalcohol composite hyperfiltration membrane, and it is characterized in that: described polyvinyl alcohol average degree of polymerization is 1750 ± 50.
3. CNT according to claim 1, nano silicon are total to the modified polyvinylalcohol composite hyperfiltration membrane, and it is characterized in that: described CNT is SWCN, and caliber is 0.5～1nm.
4. CNT according to claim 1, nano silicon are total to the modified polyvinylalcohol composite hyperfiltration membrane, and it is characterized in that: described nano silicon particle diameter is 20～40nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210451904.7A CN103127843B (en) | 2012-11-13 | 2012-11-13 | CNT, nano silicon modified polyvinylalcohol composite hyperfiltration membrane altogether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210451904.7A CN103127843B (en) | 2012-11-13 | 2012-11-13 | CNT, nano silicon modified polyvinylalcohol composite hyperfiltration membrane altogether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103127843A true CN103127843A (en) | 2013-06-05 |
| CN103127843B CN103127843B (en) | 2016-05-04 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105561810A (en) * | 2015-12-22 | 2016-05-11 | 北京理工大学 | Method of using carbon nanofiber layer to modify ultrafiltration membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1669128A1 (en) * | 2003-08-06 | 2006-06-14 | Zhejiang Omex Environmental Engineering Ltd. | The preparation method of exo-pressure type poly(vinylidene fluoride) hollow fiber membrane spinned utilizing a immersion-coagulation method and the product thereof |
| CN101791522A (en) * | 2010-04-07 | 2010-08-04 | 浙江大学 | Hybridized composite reverse osmosis membrane containing carbon nano tubes and preparation method thereof |
-
2012
- 2012-11-13 CN CN201210451904.7A patent/CN103127843B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1669128A1 (en) * | 2003-08-06 | 2006-06-14 | Zhejiang Omex Environmental Engineering Ltd. | The preparation method of exo-pressure type poly(vinylidene fluoride) hollow fiber membrane spinned utilizing a immersion-coagulation method and the product thereof |
| CN101791522A (en) * | 2010-04-07 | 2010-08-04 | 浙江大学 | Hybridized composite reverse osmosis membrane containing carbon nano tubes and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WEN-JIA CHEN等: ""Modelling dispersion behavior of low-dimensional carbon nanofillers in liquids"", 《CARBON》, vol. 50, 10 May 2012 (2012-05-10), pages 3092 - 3116 * |
| 于海容等: ""聚乙烯醇/碳纳米管复合超滤膜的制备及应用研究"", 《工程塑料应用》, vol. 39, no. 9, 31 December 2011 (2011-12-31), pages 59 - 63 * |
| 姜云鹏等: ""纳米SiO2-聚乙烯醇复合超滤膜的制备及应用"", 《工业水处理》, vol. 22, no. 5, 31 May 2002 (2002-05-31), pages 12 - 14 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105561810A (en) * | 2015-12-22 | 2016-05-11 | 北京理工大学 | Method of using carbon nanofiber layer to modify ultrafiltration membrane |
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Effective date of registration: 20200507 Address after: 314000 Building 1, 3, 4 and 5, No. 296, Huaye Road, Fengming street, Tongxiang City, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Zhiyuan Environmental Technology Co.,Ltd. Address before: 314000 zone 2, Tongfu economic Park, Fengming street, Tongxiang, Jiaxing City, Zhejiang Province Patentee before: Tongxiang Zhiyuan Environmental Protection Technology Co.,Ltd. |
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| CP03 | Change of name, title or address |
Address after: 314500 Building 1, 3, 4 and 5, No. 296 Huaye Road, Fengming street, Tongxiang City, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Zhiyuan Environmental Technology Co.,Ltd. Address before: 314000 Building 1, 3, 4 and 5, No. 296 Huaye Road, Fengming street, Tongxiang City, Jiaxing City, Zhejiang Province Patentee before: Zhejiang Zhiyuan Environmental Technology Co.,Ltd. |