CN109173743B - Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof - Google Patents
Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN109173743B CN109173743B CN201811205664.6A CN201811205664A CN109173743B CN 109173743 B CN109173743 B CN 109173743B CN 201811205664 A CN201811205664 A CN 201811205664A CN 109173743 B CN109173743 B CN 109173743B
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- ultrafiltration membrane
- nano silver
- hollow nano
- pvdf
- 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.)
- Active
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and a preparation method thereof, belonging to the technical field of ultrafiltration membranes. The invention takes the attapulgite as a carrier, and the metal nano silver particles are loaded on the surface of the attapulgite through ultrasonic dispersion and the microwave action of a microwave reactor to obtain the hollow nano silver/attapulgite. The hollow nano silver/attapulgite has the advantages of unique layered structure, loose pore canal, light weight, large specific surface area and the like, and is blended with PVDF (polyvinylidene fluoride) for extrusion and tape casting to obtain a hollow nano silver/attapulgite/PVDF ultrafiltration membrane, wherein the hollow nano silver/attapulgite is used as a water channel of the ultrafiltration membrane, and has good antibacterial, self-cleaning and anti-pollution effects.
Description
Technical Field
The invention belongs to the technical field of ultrafiltration membrane preparation, and particularly relates to a hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and a preparation method thereof.
Background
The ultrafiltration technology has good removal effect on particulate matters and protozoa in water source water, effectively ensures the safety of water quality treatment and drinking water organisms, does not generate chemical reaction in the ultrafiltration process, does not need heat input, and does not need regeneration treatment on treatment media. The ultrafiltration process occupies a small area, is easy to realize scale and has high automation degree. These advantages allow the ultrafiltration technology to be applied on a large scale in water treatment membranes. However, the ultrafiltration membrane is inevitably polluted in the using process, the membrane pollution phenomenon is relatively complex and difficult to analyze theoretically, and the influence factors of the membrane pollution mainly include the following aspects:
(1) the properties of the membrane include the material, pore size, hydrophobicity, porosity, roughness, and charging properties of the membrane. To a certain extent, the type of fouling of the membrane, the extent to which membrane fouling can be achieved, and the ease with which the membrane can be cleaned.
(2) Different external operating conditions, different pollution to the membrane.
How to alleviate the pollution problem of the ultrafiltration membrane in the use process, at present, researchers mainly propose the following measures for improvement: (1) pretreating feed liquid; (2) optimizing the operating conditions; (3) membrane cleaning and selection and modification of membrane materials.
Compared with other membrane materials, PVDF has good thermal stability and mechanical properties, and becomes an excellent membrane material for preparing separation membranes in the field of sewage treatment. The nano silver particles have excellent performances of catalysis, optics, electricity, biosensing and the like, so the nano silver particles are widely applied to the fields of chemistry, biology, materials and the like. Since the properties of silver nanoparticles are closely related to their structures, common shapes of nano-silver are mainly nanorods, nanowires, and cubic, sheet-like, and triangular particles of various sizes. At present, research on nano silver/PVDF ultrafiltration membranes is relatively few, and Majun and the like propose that the dispersibility of nano silver in the PVDF ultrafiltration membrane can be mainly improved and the pollution resistance of the membrane can be improved in the PVDF ultrafiltration membrane in a patent of 'a preparation method for in-situ synthesis of nano silver modified PVDF ultrafiltration membrane', but the prepared nano silver only plays an antibacterial role in the ultrafiltration membrane.
Disclosure of Invention
The novel hollow nano silver/attapulgite is prepared, and is subjected to melt blending extrusion and tape casting with PVDF to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane. By attaching the nano silver to the attapulgite, the use of raw materials is reduced after the formed hollow structure, so that the cost is reduced, the membrane has certain strength, and certain self-cleaning and anti-pollution performances are endowed.
The hollow nano silver/attapulgite/PVDF ultrafiltration membrane provided by the invention comprises the following raw materials in parts by weight:
100 parts of PVDF
10-30 parts of PMMA
0.1-1 part of hollow nano silver/attapulgite.
The addition of PMMA can improve the mechanical property, the hydrophilic property and the like of PVDF, and then the PVDF and hollow nano silver/attapulgite are compounded to prepare the ultrafiltration membrane with good antibacterial and anti-pollution effects, and the ultrafiltration membrane has higher water flux and water flux recovery rate.
The PVDF of the invention has the model number of 6008, Kynar740, DS201, 720, FR906, 6010NC and the like. The PVDF is a semi-crystalline polymer, is not easy to corrode by strong oxidants such as halogen, acid and alkali at room temperature, basically keeps stable performance under the irradiation of ultraviolet rays with the wavelength of 200-400 nm, has excellent aging resistance and good film forming property.
The PMMA model of the invention is CM-201, 8N, IRG-504, HI855H, HI835H or 80N, etc. The PVDF composite membrane has good transparency, stability and weather resistance, and can effectively improve the membrane forming performance of PVDF and improve the mechanical performance of the ultrafiltration membrane.
The hollow nano silver/attapulgite is prepared by a microwave method, takes the pre-prepared attapulgite as a template, and then prepares the hollow nano silver/attapulgite through ultrasonic dispersion and microwave reaction. The nano silver is attached to the attapulgite and forms a hollow structure, so that the ultra-filtration membrane has the common characteristics of the attapulgite and the nano silver, such as higher specific surface area, lower density, self-cleaning and the like, and the unique structure can be used as a water channel of the ultra-filtration membrane, so that the ultra-filtration membrane has higher water flux and water flux recovery rate.
The preparation process of the hollow nano silver/attapulgite provided by the invention mainly comprises the following two steps:
(1) firstly, ultrasonically dispersing attapulgite serving as a carrier, PVP serving as a surfactant and AgNO serving as a silver source3；
(2) And (2) putting the treated substance obtained in the step (1) into a microwave reactor to prepare the hollow nano silver/attapulgite.
Preparing hollow nano silver/attapulgite:
(1) firstly, a reaction system is prepared, and the specific experimental steps are as follows:
glycol is taken as a solvent, and a surfactant PVP and a silver source AgNO are added3Mixing the dispersion liquid with attapulgite as a carrier, performing ultrasonic dispersion, maintaining the dispersion temperature at room temperature, and the dispersion time at 2-3 h, and sealing and protecting a dispersion container in the dispersion process.
(2) Preparing hollow nano silver/attapulgite on the basis of the prepared reaction system in the step (1):
loading metal nano silver particles on the surface of the attapulgite carrier: and placing the dispersed reaction system into a microwave reactor for microwave treatment, wherein the reaction power of the reactor is 240-300W, and the microwave reaction time is 4-5 min. And after the reaction is finished, taking out the solution, cooling at normal temperature, adding 3 times of acetone for washing, separating by using a centrifuge, and controlling the rotating speed of the centrifuge to 9000r/min and the centrifuging time t to 10 min. And after separation, collecting the lower-layer solid, washing twice with deionized water, and drying to obtain the hollow nano silver/attapulgite.
The addition amount of the attapulgite is 5-10 parts by weight; AgNO3The addition amount of (A) is 30-50 parts; the addition amount of PVP is 50-100 parts.
The invention provides a preparation method of a hollow nano-silver/attapulgite/PVDF ultrafiltration membrane, which comprises the steps of weighing according to a ratio, carrying out melt blending extrusion and tape casting to obtain the hollow nano-silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20-30 um.
The beneficial effects embodied by the invention are mainly embodied in the following aspects:
(1) the invention takes the attapulgite as a carrier, is a reinforcing agent of a high polymer material, and can improve the compatibility with PVDF matrix resin after being used as an inert filler;
(2) the preparation method of the invention adopts a microwave method, takes the pre-prepared attapulgite as a template, and then prepares the hollow nano silver/attapulgite through ultrasonic dispersion and microwave reaction.
Drawings
Fig. 1 is a schematic diagram of preparation of hollow nano silver/attapulgite.
Detailed Description
Example 1
The specific preparation method of the hollow nano silver/attapulgite comprises the following steps:
first, the preparation of the dispersion. Firstly, the reactants are dispersed, and the specific experimental steps are as follows:
glycol is used as a solvent, ATP is used as a carrier, PVP is used as a surfactant, and AgNO is used as a silver source3Mixing the mixture with PVP (the mass ratio is 1: 1), and then carrying out ultrasonic dispersion at room temperature for 3h, wherein the whole reaction process is sealed and protected.
And step two, preparing the hollow nano silver/attapulgite on the basis of the prepared dispersion system in the step one.
And putting the prepared dispersion into a microwave reactor for reaction, wherein the reaction power is 240W, and the reaction time is 4 min. Preparing the hollow nano silver/attapulgite. And after the reaction is finished, taking the solution out, cooling at normal temperature, adding 3 times of acetone for washing, separating by using a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 9000r/min, and centrifuging for three times, wherein the centrifuging time is 10min each time. And washing the separated lower-layer solid twice by using deionized water, and drying to obtain the hollow nano silver/attapulgite.
The addition amount of the attapulgite is 10 parts by weight; the adding amount of silver nitrate is 50 parts; the addition amount of PVP is 50 parts.
Preparation of hollow nano-silver/attapulgite/PVDF ultrafiltration membrane
PVDF 6008100 parts
PMMA CM-20110 part
0.1 part of hollow nano silver/attapulgite
Weighing according to the formula, blending, extruding and casting to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20 um.
Example 2
The specific preparation method of the hollow nano silver/attapulgite comprises the following steps:
first, the preparation of the dispersion.
First a dispersion is prepared. The specific experimental steps are as follows: glycol is used as a solvent, ATP is used as a carrier, PVP is used as a surfactant, and AgNO is used as a silver source3Mixing with PVP, performing ultrasonic dispersion, dispersing for 4h at room temperature, and sealing and protecting in the whole dispersion process.
And step two, preparing the hollow nano silver/attapulgite on the basis of the prepared dispersion system in the step one.
And (3) putting the dispersed reactants into a microwave reactor for reaction, wherein the reaction power is 260W, and the reaction time is 5 min. Preparing the hollow nano silver/attapulgite. And after the reaction is finished, taking the solution out, cooling at normal temperature, adding 3 times of acetone for washing, separating by using a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 9000r/min, and centrifuging for three times, wherein the centrifuging time is 8min each time. And washing the separated lower-layer solid twice by using deionized water, and drying to obtain the hollow nano silver/attapulgite.
The addition amount of the hollow nano silver/attapulgite is 10 parts by weight; the adding amount of silver nitrate is 40 parts; the addition amount of PVP is 80 parts.
Preparation of hollow nano-silver/attapulgite/PVDF ultrafiltration membrane
PVDF kynar 740100 parts
PMMA 8N 20 parts
0.5 part of hollow nano silver/attapulgite
Weighing according to the formula, blending, extruding and casting to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 25 um.
Example 3
The hollow nano silver/attapulgite is specifically prepared as follows:
first, the preparation of the dispersion. The reactants were first dispersed, the specific experimental procedure was as follows:
glycol is used as a solvent, ATP is used as a carrier, PVP is used as a surfactant, and AgNO is used as a silver source3Mixing with PVP (the mass ratio is 1: 3), performing ultrasonic dispersion, dispersing for 5 hours at room temperature, and sealing and protecting in the whole dispersion process.
And step two, preparing the hollow nano silver/attapulgite on the basis of the prepared dispersion system in the step one.
And (3) placing the dispersed reactants into a microwave reactor for reaction, wherein the reaction power is 270W, and the reaction time is 6 min. Preparing the hollow nano silver/attapulgite. And after the reaction is finished, taking the solution out, cooling at normal temperature, adding 3 times of acetone for washing, separating by using a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 9000r/min, and centrifuging for three times, wherein the centrifuging time is 7min each time. And washing the separated lower-layer solid twice by using deionized water, and drying to obtain the hollow nano silver/attapulgite.
The addition amount of the attapulgite is 10 parts by weight; the adding amount of silver nitrate is 40 parts; the addition amount of PVP is 100 parts.
Preparation of hollow nano-silver/attapulgite/PVDF ultrafiltration membrane
PVDF DS 201100 parts
PMMA IRG-50430 parts
Hollow nano silver/attapulgite 1 part
Weighing according to the formula, blending, extruding and casting to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 30 um.
Example 4
The silver source AgNO in example 13The mass ratio of the PVP to the surface active agent is changed to 3: 7, silver source AgNO3The addition amount of (b) is 30 parts, the addition amount of the surfactant PVP is 70 parts, and the addition amount of the attapulgite is 10 parts. Microwave power is changed to 290W, centrifugation time is changed to 6min, other conditions are not changed, and the obtained product isEmpty nanosilver/attapulgite.
Preparation of hollow nano-silver/attapulgite/PVDF ultrafiltration membrane
PVDF 6008100 parts
PMMA CM-20110 part
0.1 part of hollow nano silver/attapulgite
Weighing according to the formula, blending, extruding and casting to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20 um.
Example 5
The silver source AgNO in example 13The mass ratio of the PVP to the surface active agent is changed to 3: 8, silver source AgNO3The addition amount of (b) is 30 parts, the addition amount of the surfactant PVP is 80 parts, and the addition amount of the attapulgite is 10 parts. The microwave power is changed to 300W, the centrifugal time is changed to 5min, and other conditions are unchanged, so that the hollow nano silver/attapulgite is obtained.
Preparation of hollow nano-silver/attapulgite/PVDF ultrafiltration membrane
PVDF 6008100 parts
PMMA CM-20110 part
0.1 part of hollow nano silver/attapulgite
Weighing according to the formula, blending, extruding and casting to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20 um.
Comparative example 1
PVDF 6008100 parts
PMMA CM-20110 part
Weighing according to the formula, blending, extruding and casting to obtain the PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20 mu m.
Comparative example 2
PVDF 6008100 parts
PMMA CM-20110 part
Attapulgite powder 0.1 part
Weighing according to the formula, blending, extruding and casting to obtain the attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20 mu m.
Comparative example 3
PVDF 6008100 parts
0.5 part of hollow nano silver/attapulgite powder
The preparation method of the hollow nano silver/attapulgite is the same as that of example 2.
Weighing according to the formula, blending, extruding and casting to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20 mu m.
Comparative example 4
Weighing according to the formula, blending, extruding and casting to obtain the nano silver/attapulgite/PVDF ultrafiltration membrane. Wherein the extrusion temperature is 200 ℃, and the thickness of the ultrafiltration membrane is 20 mu m.
And (4) relevant testing:
determination of pure Water flux: a Millipore 8200 back type ultrafilter is adopted, a certain area of wet membrane sample is fixed in an ultrafiltration membrane, and the water flux is measured. Compaction with deionized water was done at room temperature and 0.15MPa for 30min before the experiment. Then, the volume of water passing through the membrane within 1min was recorded on line at 0.1MPa, the effective membrane area was 28.4cm2. The pure water flux J of the membrane was calculated according to the formula (1)0：
J0＝V/(At)
Wherein V is the volume of the permeated water, A is the area of the effective membrane, and t is the measurement time.
Determination of water flux recovery rate: prepressing the membrane with deionized water at room temperature and 0.15MPa for 30min, and measuring pure water flux J of the membrane at 0.1MPa0. Changing the deionized water to 500mg/L BSA solution, filtering under 0.1MPaTesting the permeate flux J of the membranes after a period of timep. The BSA contaminated ultrafiltration membrane was washed with deionized water for 30 min. The pure water flux J of the ultrafiltration membrane was then retested at 0.1MPa with deionized water1Then the flux recovery of the ultrafiltration membrane is:
m＝J1/J0×100％
the results are shown in table 1:
TABLE 1
The results of the above examples and comparative examples show that: the hollow nano silver/attapulgite has the advantages of unique hollow structure, light weight, large specific surface area, good surface permeability and the like, can be used as a water channel of an ultrafiltration membrane, and has larger water flux compared with a PVDF ultrafiltration membrane without nano silver.
Claims (7)
1. A hollow nano silver/attapulgite/PVDF ultrafiltration membrane is characterized in that: the ultrafiltration membrane comprises the following raw materials in parts by weight:
100 parts of PVDF
10-30 parts of PMMA
0.1-1 part of hollow nano silver/attapulgite;
the hollow nano silver/attapulgite takes attapulgite as a carrier, and metal nano silver particles are loaded on the surface of the attapulgite to form the hollow nano silver/attapulgite, and the preparation method of the hollow nano silver/attapulgite comprises the following steps:
(1) sequentially adding a surface active agent PVP, a silver source and attapulgite into an ethylene glycol solvent, and performing ultrasonic dispersion to obtain a reaction system;
(2) and (2) putting the reaction system prepared in the step (1) into a microwave reactor for reaction, wherein the power of the microwave reactor is 240-300W, the reaction time is 4-5 min, cooling to room temperature after obtaining a reactant, washing, centrifugally separating, collecting precipitates, and drying to obtain the hollow nano silver/attapulgite.
2. The hollow nanosilver/attapulgite/PVDF ultrafiltration membrane of claim 1, wherein: the PVDF model is 6008, Kynar740, DS201, 720, FR906 or 6010 NC; the PMMA model is CM-201, 8N, IRG-504, HI855H, HI835H or 80N.
3. The hollow nanosilver/attapulgite/PVDF ultrafiltration membrane of claim 1, wherein: the silver source in the step (1) is AgNO3。
4. The hollow nanosilver/attapulgite/PVDF ultrafiltration membrane of claim 1, wherein: according to the mass parts, the addition amount of the attapulgite is 5-10 parts; the addition amount of silver nitrate is 30-50 parts; the addition amount of PVP is 50-100 parts.
5. The hollow nanosilver/attapulgite/PVDF ultrafiltration membrane of claim 1, wherein: the ultrasonic dispersion time is 2-3 hours, and the temperature during dispersion is kept at room temperature; the rotational speed of centrifugal separation is 9000r/min, and the centrifugal separation time is 10 min.
6. The preparation method of the hollow nano silver/attapulgite/PVDF ultrafiltration membrane as claimed in claim 1, wherein the preparation method comprises the following steps: the preparation method comprises the following steps:
weighing the raw materials according to the formula, then carrying out melt blending extrusion and tape casting to obtain the hollow nano silver/attapulgite/PVDF ultrafiltration membrane.
7. The method for preparing the hollow nanosilver/attapulgite/PVDF ultrafiltration membrane according to claim 6, wherein the method comprises the following steps: the extrusion temperature is 200 ℃, and the thickness of the obtained ultrafiltration membrane is 20-30 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811205664.6A CN109173743B (en) | 2018-10-17 | 2018-10-17 | Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811205664.6A CN109173743B (en) | 2018-10-17 | 2018-10-17 | Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109173743A CN109173743A (en) | 2019-01-11 |
| CN109173743B true CN109173743B (en) | 2021-04-30 |
Family
ID=64945048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811205664.6A Active CN109173743B (en) | 2018-10-17 | 2018-10-17 | Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109173743B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114307691A (en) * | 2021-12-28 | 2022-04-12 | 上海普利特复合材料股份有限公司 | Hollow nano-silver/graphene/PE ultrafiltration membrane and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127841A (en) * | 2011-11-28 | 2013-06-05 | 中化蓝天集团有限公司 | Polyvinylidene fluoride hydrophilic modified membrane and preparation method thereof |
| CN103191651A (en) * | 2012-01-04 | 2013-07-10 | 林金建 | Preparation method of hydrophilic polyvinylidene fluoride blended hollow fiber microporous membrane |
| CN103721580A (en) * | 2012-10-15 | 2014-04-16 | 廖书辉 | High-performance polyvinylidene fluoride mesoporous fiber film |
| WO2014095749A1 (en) * | 2012-12-17 | 2014-06-26 | Basf Se | Filtration systems and membranes with enhanced flux and method for their preparation |
| CN104667763A (en) * | 2013-11-28 | 2015-06-03 | 上海一鸣过滤技术有限公司 | Supported hydrophilic polyvinylidene fluoride microporous membrane and preparation method thereof |
| CN104971631A (en) * | 2015-07-24 | 2015-10-14 | 中南大学 | Preparation method of high-flux PVDF (polyvinylidene fluoride) porous membrane |
| CN105126635A (en) * | 2015-08-07 | 2015-12-09 | 东莞理工学院 | Novel hydrophilic composite tube type microfiltration membrane and preparation method thereof |
| CN106621850A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Antibacterial composite nanofiltration membrane, and preparation method and application thereof |
| CN106621851A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Antibacterial reverse osmosis composite membrane and preparation method and application thereof |
-
2018
- 2018-10-17 CN CN201811205664.6A patent/CN109173743B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127841A (en) * | 2011-11-28 | 2013-06-05 | 中化蓝天集团有限公司 | Polyvinylidene fluoride hydrophilic modified membrane and preparation method thereof |
| CN103191651A (en) * | 2012-01-04 | 2013-07-10 | 林金建 | Preparation method of hydrophilic polyvinylidene fluoride blended hollow fiber microporous membrane |
| CN103721580A (en) * | 2012-10-15 | 2014-04-16 | 廖书辉 | High-performance polyvinylidene fluoride mesoporous fiber film |
| WO2014095749A1 (en) * | 2012-12-17 | 2014-06-26 | Basf Se | Filtration systems and membranes with enhanced flux and method for their preparation |
| CN104667763A (en) * | 2013-11-28 | 2015-06-03 | 上海一鸣过滤技术有限公司 | Supported hydrophilic polyvinylidene fluoride microporous membrane and preparation method thereof |
| CN104971631A (en) * | 2015-07-24 | 2015-10-14 | 中南大学 | Preparation method of high-flux PVDF (polyvinylidene fluoride) porous membrane |
| CN105126635A (en) * | 2015-08-07 | 2015-12-09 | 东莞理工学院 | Novel hydrophilic composite tube type microfiltration membrane and preparation method thereof |
| CN106621850A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Antibacterial composite nanofiltration membrane, and preparation method and application thereof |
| CN106621851A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Antibacterial reverse osmosis composite membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109173743A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Metal-organic framework membranes for wastewater treatment and water regeneration | |
| Skorski et al. | The chemical, mechanical, and physical properties of 3D printed materials composed of TiO2-ABS nanocomposites | |
| CN108744990B (en) | Silver nanoparticle modified titanium dioxide nanofiber membrane material and preparation method and application thereof | |
| Nawaz et al. | Photodegradation of textile pollutants by nanocomposite membranes of polyvinylidene fluoride integrated with polyaniline–titanium dioxide nanotubes | |
| WO2005073302A1 (en) | Porous film and method for preparation thereof | |
| KR102217853B1 (en) | Water treatment membrane comprising metal-organic framework and cellulose nanofiber composite and the preparation method thereof | |
| CN102689018A (en) | Production method of nanometer silver wire material | |
| JP7078038B2 (en) | Fibrous carbon nanostructure dispersion liquid and its manufacturing method, and fibrous carbon nanostructure | |
| CN109173743B (en) | Hollow nano-silver/attapulgite/PVDF ultrafiltration membrane and preparation method thereof | |
| JP5918580B2 (en) | Method for purifying fine particles, and method for producing transition metal compound-supported titanium oxide fine particles including the method for purifying fine particles | |
| CN109603573A (en) | The preparation method of zeolite imidazole ester skeleton polyamine nanoparticle composite membrane | |
| CN109879349A (en) | A kind of preparation method of slightly acidic water processing special molding filter core | |
| Makhetha et al. | Stable zeolitic imidazolate framework-8 supported onto graphene oxide hybrid ultrafiltration membranes with improved fouling resistance and water flux | |
| JP2010046621A (en) | Separation refining method of inorganic nanoparticle | |
| CN110917894B (en) | Preparation method of polyvinylidene fluoride hollow fiber porous membrane | |
| Azhar et al. | Self-Cleaning antifouling performance based on the surface area of flower-like TiO 2 as additive for PSf mixed matrix membrane | |
| CN107694356B (en) | beta-CD/HNTs (beta-CD/HNTs) blended polyvinylidene fluoride film and preparation method thereof | |
| CN110871068A (en) | TiO 22Synthesis method of porous frame/Pd nanoparticle composite catalyst, composite catalyst and application thereof | |
| Sun et al. | Enhancing the permeation and antifouling performance of PVDF hybrid membranes by incorporating Co–Fe hydroxide nanoparticles in reverse microemulsion | |
| CN114307691A (en) | Hollow nano-silver/graphene/PE ultrafiltration membrane and preparation method thereof | |
| KR101458442B1 (en) | Filtration membrane using nanoparticle grafted by hydrophilic polymer and method thereof | |
| Moghadassi et al. | Cuprous oxide (Cu2O) nanoparticles in nanofiltration membrane with enhanced separation performance and anti-fouling properties | |
| Abbasa et al. | Fabrication of polysulfone/carbon nanospheres ultrafiltration membranes for removing some dyes from aqueous solutions | |
| JP2017001029A (en) | Multilayer separation film | |
| CN107626215A (en) | A kind of antifouling composite hyperfiltration membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |