CN105727762A - Sodium alginate-amphipathy carbon material/polyacrylonitrile composite film, preparation and application - Google Patents
Sodium alginate-amphipathy carbon material/polyacrylonitrile composite film, preparation and application Download PDFInfo
- Publication number
- CN105727762A CN105727762A CN201610096675.XA CN201610096675A CN105727762A CN 105727762 A CN105727762 A CN 105727762A CN 201610096675 A CN201610096675 A CN 201610096675A CN 105727762 A CN105727762 A CN 105727762A
- Authority
- CN
- China
- Prior art keywords
- sodium alginate
- film
- carbon element
- polyacrylonitrile
- amphipathy
- 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
Classifications
-
- 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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a sodium alginate-amphipathy carbon material/polyacrylonitrile composite film. The thickness of the composite film is about 320-370 nanometers. Sodium alginate and an amphipathy carbon material are physically blended, and then a polyacrylonitrile base film is rotationally coated with the mixture, so that the sodium alginate-amphipathy carbon material/polyacrylonitrile composite film is obtained. The mass percent of the amphipathy carbon material to the sodium alginate is 2-10%. The preparation process comprises the steps that needle coke is used as a raw material, a mixed acid method is adopted, NaOH and hydrochloric acid treatment is carried out, and the amphipathy carbon material is obtained; the amphipathy carbon material and the sodium alginate solution are blended to obtain a film casting solution, and the polyacrylonitrile base film is rotationally coated with the film casting solution to obtain the composite film. The preparation process of the composite film is free of pollution, environmentally friendly and easy and convenient to operate. The prepared sodium alginate-amphipathy carbon material/polyacrylonitrile composite film is applied to pervaporation ethanol dehydration, and has the separation factor and flux.
Description
Technical field
The present invention relates to sodium alginate-amphipathic material with carbon element/polyacrylonitrile (SA-ACM/PAN) composite membrane and preparation and application,
Belong to macromolecule-inorganic composite membrane technology field.
Background technology
From the point of view of numerous energy output technologies of the high-grade energy of exploitation cleaning at present, alcohol fuel is the good substitute of following oil.
But at ambient pressure, when ethanol mass fraction is 95.6%, with water generation azeotropic.Membrane separation technique go out to have concurrently separation, purification,
Concentrate and refined function, also energy-saving and environmental protection, the advantage such as efficient, simple, easily controllable.As membrane separation technique
One, pervaporation is widely used to the separation of liquid mixture.And azeotrope to separate be that pervaporation can be made the most of the advantage
Field, use Pervaporation separating alcohol and water, than traditional method energy-conservation 1/2～1/3, and have simple to operate, produce
The advantages such as product purity height and clean environment firendly.
Hybrid organic-inorganic film then can have the advantage of high-molecular organic material and inorganic material concurrently, is to prepare high-performance high stability
The effective way of osmotic evaporation film.Two-dimensional Inorganic implant has anisotropic construction features, can spontaneously in composite membrane
Being formed in parallel with the arrangement on film surface, during casting solution is coated with casting, nanoscale twins starts sedimentation the most under gravity,
Under the common effect of gravity and polymer solution resistance, lamella can form the orientation of level.Two-dimension nano materials leads to simultaneously
Often there is the highest specific surface area so that two-dimension nano materials receives much concern in the selection of film based on Organic-inorganic hybrids.
Amphipathic material with carbon element (ACM) is a kind of Two-dimensional Inorganic implant, and ACM is in aqueous solution and other major part solvent
Having excellent dispersibility, abundant oxygen-containing functional group is contained on its surface, has higher specific surface area, easily to without unit
Divide modifying surface, it is simple to regulation organic and inorganic interface configuration, be effectively improved hydridization permeability of the membrane and selectivity, permissible
Mechanical stability and the heat stability of hybridized film are greatly improved.
Summary of the invention
For above-mentioned prior art, the present invention provides a kind of sodium alginate-amphipathic material with carbon element/polyacrylonitrile
(SA-ACM/PAN) composite membrane and preparation method and application, the preparation method that the present invention provides is simple and easy to operate, prepared
Composite membrane may be used for pervaporation ethanol dehydration, there is higher separation factor and permeation flux.
A kind of sodium alginate-amphipathic material with carbon element/polyacrylonitrile compound film that the present invention proposes, the thickness of this composite membrane is about
320-370 nanometer, is obtained by being spun on polyacrylonitrile basement membrane after physical blending with amphipathic material with carbon element by sodium alginate,
Wherein, amphipathic material with carbon element is 2～10% with the mass percent of sodium alginate.
The preparation method of above-mentioned sodium alginate-amphipathic material with carbon element/polyacrylonitrile compound film, comprises the following steps:
Step one, with needle coke as raw material, use mixed acid process prepare amphipathic material with carbon element；
Step 2, weigh deionized water and sodium alginate and add in flask, be configured to the alginic acid that mass concentration is 1-2wt.%
Sodium water solution, 30-55 DEG C of constant temperature stirring 1h；
Step 3, amphipathic material with carbon element step one obtained add in the sodium alginate aqueous solution that step 2 obtains, and wherein two
Parent's property material with carbon element is 2-10% with the mass percent of sodium alginate aqueous solution, 35-55 DEG C of constant temperature stirring 2.5-4.5h, is cast
Film liquid, is spun to this casting solution on polyacrylonitrile basement membrane, drying at room temperature；
Step 4, film step 3 obtained immerse CaCl2Solution cross-links, after drying at room temperature, obtains sodium alginate-amphipathic
Material with carbon element/polyacrylonitrile compound film.
The sodium alginate present invention prepared-amphipathic material with carbon element/polyacrylonitrile compound film is used as pervaporation ethanol dehydration
Separation film, in the case of the ethanol/water of temperature 76 DEG C, 90wt.% is material liquid, its separation factor is 1066～1816,
Permeation flux is 1359～1778g/m2h。
Compared with prior art, it is an advantage of the current invention that:
The preparation process that the present invention provides is mainly with needle coke as raw material, uses mixed acid process to prepare, at NaOH with hydrochloric acid
Manage to obtain amphipathic material with carbon element (ACM).ACM is blended to obtain casting solution, polyacrylonitrile (PAN) with sodium alginate (SA) aqueous solution
Basement membrane is basement membrane, and spin-coated method prepares this sodium alginate-amphipathic material with carbon element/polyacrylonitrile compound film.Composite membrane of the present invention
Preparation process environmental protection, simple and easy to operate.ACM is a kind of Two-dimensional Inorganic implant, and ACM is at aqueous solution and other is big
Having excellent dispersibility in partial solvent, abundant oxygen-containing functional group is contained on its surface, such as carboxyl, hydroxyl and epoxy radicals etc.,
Have higher specific surface area, easily to inorganic component modifying surface, it is simple to regulation organic and inorganic interface configuration, effectively
Improve hydridization permeability of the membrane and selectivity, mechanical stability and the heat stability of hybridized film can be greatly improved.
Composite membrane obtained by preparation method of the present invention shows higher separation factor and permeation flux, compared with pure SA film
It is respectively increased 206% and 40%.
Accompanying drawing explanation
Fig. 1 is the section SEM figure of the SA homogeneous membrane that comparative example 1 prepares；
Fig. 2 is the section SEM figure of the SA-ACM-2/PAN homogeneous membrane that embodiment 1 prepares；
Fig. 3 is the section SEM figure of the SA-ACM-4/PAN homogeneous membrane that embodiment 2 prepares；
Fig. 4 is the section SEM figure of the SA-ACM-6/PAN homogeneous membrane that embodiment 3 prepares；
Fig. 5 is the section SEM figure of the SA-ACM-8/PAN homogeneous membrane that embodiment 4 prepares；
Fig. 6 is the section SEM figure of the SA-ACM-10/PAN homogeneous membrane that embodiment 5 prepares.
Detailed description of the invention
Tell about the detailed process of the present invention by the following examples, it is provided that embodiment is for the convenience understood, is in no way intended to limit
The present invention.
The sodium alginate prepared-amphipathic material with carbon element/polyacrylonitrile compound film composite membrane is designated as in implementing by the present invention
SA-ACM-X/PAN, wherein X represents ACM and accounts for the mass percent of SA.The SA blank composite membrane of ACM will be not added with,
It is designated as SA pure/PAN.
The present invention tests device therefor and technological process: the separating property of film uses the processing of new technology development center, the huge northeast part of China
Pervaporation experimental provision test, including feed liquid circulating system, film room and vacuum cooling system.During operation, raw material
Liquid is sent into film room by gear pump through spinner flowmeter, and film upstream side liquid flows through film surface Posterior circle feed back flow container, a part of liquid
Body enters downstream through film with gas phase, collects through vacuum cooling system.Film room is the core component of whole device, by
The P-28 type plate film assembly transformation of CM-Celfa AG company of Switzerland forms.The concrete operation step of pervaporation experiment is:
(1) film is loaded film room, add certain density ethanol/water solution to material liquid tank, open electric heating cover and gear pump, enter
Row heating and feed liquid circulate, and regulation heating power and gear pump rotating speed make feed temperature and stability of flow in setting value；(2)
Material liquid sample analysis, after device reaches stable state, accesses collecting pipe, opens vacuum pump and makes downstream pressure side be down to a 0.1kPa left side
The right side, immerses liquid nitrogen cold trap by collecting pipe, terminates the permeate in the collecting pipe that post analysis is changed, every film at least sampling and testing
Three times, results averaged；(3) closing electric heating cover, feed liquid circulation and vacuum cooled after having tested, opening film room will
Film takes out, and experiment terminates.
Comparative example 1: prepare pure SA film.
Being added by SA in deionized water, 30 DEG C of constant temperature stirring 1h make it fully dissolve, and being configured to mass concentration is 1wt.%'s
SA solution.Obtain uniform casting solution, be spun on PAN basement membrane, drying at room temperature.Preparation CaCl2Solution, subsequently will
The composite membrane of preparation immerses CaCl2Solution cross-links.Obtain thickness after drying at room temperature 48h and be about the SA blank of 320 nanometers
Composite membrane, is designated as SA pure/PAN.Its section SEM schemes as shown in Figure 1.
This film is carried out pervaporation ethanol dehydration test in the situation that ethanol/water is material liquid of temperature 76 DEG C, 90wt.%,
Its separation factor and permeation flux are shown in Table 1.
Embodiment 1: preparation SA-ACM-2/PAN composite membrane, comprises the following steps:
The preparation of ACM: with needle coke as raw material, uses mixed acid process to prepare ACM.NC is pulverized, with concentrated sulphuric acid, dense
Nitric acid mixes, and after reaction terminates, adds distilled water, filters, and washing to filtrate is neutrality, collects solid matter, with NaOH
Solution mixes, stirring, filters, and collects filtrate.Adding hydrochloric acid in filtrate, collect precipitation, distilled water wash is to without Cl-,
Dry to obtain ACM.This mixed acid process is prepared ACM and is belonged to general knowledge known in this field.
Composite membrane preparation and film forming: added by SA in deionized water, 35 DEG C of constant temperature stirring 1h make it fully dissolve, preparation
The SA solution becoming concentration to be 1.2wt.%.Adding a certain amount of ACM in SA solution, its consumption is the 2wt.% of SA,
Continue stirring 2.5h at 35 DEG C, obtain uniform casting solution, be spun on PAN basement membrane, drying at room temperature.Preparation
CaCl2Solution, immerses CaCl by the composite membrane of preparation subsequently2Solution cross-links.Obtain thickness after drying at room temperature and be about 330
The SA-ACM-2/PAN hybridization compounding film of nanometer.Its section SEM schemes as shown in Figure 2.
This film is carried out pervaporation ethanol dehydration test in the situation that ethanol/water is material liquid of temperature 76 DEG C, 90wt.%,
Its separation factor and permeation flux are shown in Table 1.
Embodiment 2: preparation SA-ACM-4/PAN composite membrane, comprises the following steps:
The preparation of ACM: same as in Example 1；
Composite membrane preparation and film forming: added by SA in deionized water, 40 DEG C of constant temperature stirring 1h make it fully dissolve, preparation
The SA solution becoming concentration to be 1.4wt.%.Adding a certain amount of ACM in SA solution, its consumption is the 4wt.% of SA,
Continue stirring 3h at 40 DEG C, obtain uniform casting solution, be spun on PAN basement membrane, drying at room temperature.Preparation CaCl2
Solution, immerses CaCl by the composite membrane of preparation subsequently2Solution cross-links.Obtain thickness after drying at room temperature and be about 340 nanometers
SA-ACM-4/PAN hybridization compounding film.Its section SEM schemes as shown in Figure 3.
This film is carried out pervaporation ethanol dehydration test in the situation that ethanol/water is material liquid of temperature 76 DEG C, 90wt.%,
Its separation factor and permeation flux are shown in Table 1.
Embodiment 3: preparation SA-ACM-6/PAN composite membrane, comprises the following steps:
The preparation of ACM: same as in Example 1；
Composite membrane preparation and film forming: added by SA in deionized water, 45 DEG C of constant temperature stirring 1h make it fully dissolve, preparation
The SA solution becoming concentration to be 1.6wt.%.Adding a certain amount of ACM in SA solution, its consumption is the 6wt.% of SA,
Continue stirring 3.5h at 45 DEG C, obtain uniform casting solution, be spun on PAN basement membrane, drying at room temperature.Preparation
CaCl2Solution, immerses CaCl by the composite membrane of preparation subsequently2Solution cross-links.Obtain thickness after drying at room temperature and be about 350
The SA-ACM-6/PAN hybridization compounding film of nanometer.Its section SEM schemes as shown in Figure 4.
This film is carried out pervaporation ethanol dehydration test in the situation that ethanol/water is material liquid of temperature 76 DEG C, 90wt.%,
Its separation factor and permeation flux are shown in Table 1.
Embodiment 4: preparation SA-ACM-8/PAN composite membrane, comprises the following steps:
The preparation of ACM: same as in Example 1；
Composite membrane preparation and film forming: added by SA in deionized water, 50 DEG C of constant temperature stirring 1h make it fully dissolve, preparation
The SA solution becoming concentration to be 1.8wt.%.Adding a certain amount of ACM in SA solution, its consumption is the 8wt.% of SA,
Continue stirring 4h at 50 DEG C, obtain uniform casting solution, be spun on PAN basement membrane, drying at room temperature.Preparation CaCl2
Solution, immerses CaCl by the composite membrane of preparation subsequently2Solution cross-links.Obtain thickness after drying at room temperature and be about 360 nanometers
SA-ACM-8/PAN hybridization compounding film.Its section SEM schemes as shown in Figure 5.
This film is carried out pervaporation ethanol dehydration test in the situation that ethanol/water is material liquid of temperature 76 DEG C, 90wt.%,
Its separation factor and permeation flux are shown in Table 1.
Embodiment 5: preparation SA-ACM-10/PAN composite membrane, comprises the following steps:
The preparation of ACM: same as in Example 1；
Composite membrane preparation and film forming: added by SA in deionized water, 55 DEG C of constant temperature stirring 1h make it fully dissolve, preparation
The SA solution becoming concentration to be 2wt.%.Adding a certain amount of ACM in SA solution, its consumption is the 10wt.% of SA,
Continue stirring 4.5h at 55 DEG C, obtain uniform casting solution, be spun on PAN basement membrane, drying at room temperature.Preparation
CaCl2Solution, immerses CaCl by the composite membrane of preparation subsequently2Solution cross-links.Obtain thickness after drying at room temperature and be about 370
The SA-ACM-10/PAN hybridization compounding film of nanometer.Its section SEM schemes as shown in Figure 6.
This film is carried out pervaporation ethanol dehydration test in the situation that ethanol/water is material liquid of temperature 76 DEG C, 90wt.%,
Its separation factor and permeation flux are shown in Table 1.
Table 1
To sum up, the present invention prepares that SA-ACM/PAN composite membrane process simplicity is controlled, and raw material is easy to get, mild condition, prepares
SA-ACM/PAN composite membrane for ethanol/water mixture pervaporation be dehydrated, there is higher separating property.Embodiment
In 3, the SA-ACM-6/PAN composite membrane performance of preparation is optimal, separation factor and permeation flux, compared with pure SA film respectively
Improve 206% and 39%.
Although above in conjunction with figure, invention has been described, but the invention is not limited in above-mentioned detailed description of the invention,
Above-mentioned detailed description of the invention is only schematic rather than restrictive, and those of ordinary skill in the art is in the present invention
Enlightenment under, without deviating from the spirit of the invention, it is also possible to make many variations, these belong to the guarantor of the present invention
Within protecting.
Claims (3)
1. sodium alginate-amphipathic material with carbon element/polyacrylonitrile compound film, it is characterised in that: the thickness of this composite membrane is about
320-370 nanometer, is obtained by being spun on polyacrylonitrile basement membrane after physical blending with amphipathic material with carbon element by sodium alginate,
Wherein, amphipathic material with carbon element is 2～10% with the mass percent of sodium alginate.
2. a preparation method for sodium alginate as claimed in claim 1-amphipathic material with carbon element/polyacrylonitrile compound film, it is special
Levy and be, comprise the following steps:
Step one, with needle coke as raw material, use mixed acid process prepare amphipathic material with carbon element；
Step 2, weigh deionized water and sodium alginate and add in flask, be configured to the alginic acid that mass concentration is 1-2wt.%
Sodium water solution, 30-55 DEG C of constant temperature stirring 1h；
Step 3, amphipathic material with carbon element step one obtained add in the sodium alginate aqueous solution that step 2 obtains, and wherein two
Parent's property material with carbon element is 2-10% with the mass percent of sodium alginate aqueous solution, 35-55 DEG C of constant temperature stirring 2.5-4.5h, is cast
Film liquid, is spun to this casting solution on polyacrylonitrile basement membrane, drying at room temperature；
Step 4, film step 3 obtained immerse CaCl2Solution cross-links, after drying at room temperature, obtains sodium alginate-amphipathic
Material with carbon element/polyacrylonitrile compound film.
3. the application of sodium alginate-amphipathic material with carbon element/polyacrylonitrile compound film, it is characterised in that will be such as claim
Sodium alginate described in 1-amphipathic material with carbon element/polyacrylonitrile compound film is used as the separation film of pervaporation ethanol dehydration, in temperature
76 DEG C, in the case of the ethanol/water of 90wt.% is material liquid, its separation factor is 1066～1816, and permeation flux is
1359～1778g/m2h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610096675.XA CN105727762A (en) | 2016-02-22 | 2016-02-22 | Sodium alginate-amphipathy carbon material/polyacrylonitrile composite film, preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610096675.XA CN105727762A (en) | 2016-02-22 | 2016-02-22 | Sodium alginate-amphipathy carbon material/polyacrylonitrile composite film, preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105727762A true CN105727762A (en) | 2016-07-06 |
Family
ID=56242007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610096675.XA Pending CN105727762A (en) | 2016-02-22 | 2016-02-22 | Sodium alginate-amphipathy carbon material/polyacrylonitrile composite film, preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105727762A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107551830A (en) * | 2017-08-04 | 2018-01-09 | 天津大学 | Sulfonated gilsonite/sodium alginate hybridized film and preparation and application |
| CN113062120A (en) * | 2021-04-09 | 2021-07-02 | 南京信息工程大学 | Sodium alginate modified amphiphilic feather and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045062B1 (en) * | 2003-01-21 | 2006-05-16 | Seventy-Seventh Meridian Corporation, Llc | Pervaporation membranes and methods of use |
| CN104772043A (en) * | 2015-04-07 | 2015-07-15 | 天津大学 | Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane |
| CN104785133A (en) * | 2015-04-07 | 2015-07-22 | 天津大学 | Sodium alginate-zwitterion modified graphene oxide hybrid composite membrane, preparation and application |
| CN104785121A (en) * | 2015-03-30 | 2015-07-22 | 天津大学 | Three-layer composite membrane of sodium alginate, polydopamine-polyethyleneimine and polyacrylonitrile, and preparation and application of three-layer composite membrane |
-
2016
- 2016-02-22 CN CN201610096675.XA patent/CN105727762A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045062B1 (en) * | 2003-01-21 | 2006-05-16 | Seventy-Seventh Meridian Corporation, Llc | Pervaporation membranes and methods of use |
| CN104785121A (en) * | 2015-03-30 | 2015-07-22 | 天津大学 | Three-layer composite membrane of sodium alginate, polydopamine-polyethyleneimine and polyacrylonitrile, and preparation and application of three-layer composite membrane |
| CN104772043A (en) * | 2015-04-07 | 2015-07-15 | 天津大学 | Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane |
| CN104785133A (en) * | 2015-04-07 | 2015-07-22 | 天津大学 | Sodium alginate-zwitterion modified graphene oxide hybrid composite membrane, preparation and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107551830A (en) * | 2017-08-04 | 2018-01-09 | 天津大学 | Sulfonated gilsonite/sodium alginate hybridized film and preparation and application |
| CN113062120A (en) * | 2021-04-09 | 2021-07-02 | 南京信息工程大学 | Sodium alginate modified amphiphilic feather and preparation method and application thereof |
| CN113062120B (en) * | 2021-04-09 | 2022-12-06 | 南京信息工程大学 | Sodium alginate modified amphiphilic feather and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104117297B (en) | A kind of preparation method of hydrophobically modified nanon calcium carbonatefilled osmosis vaporizing compound membrane | |
| CN105295265B (en) | A kind of modified polyvinilidene fluoride super hydrophobic material and preparation method thereof | |
| CN113769593B (en) | Nanofiltration membrane for extracting lithium from salt lake and preparation method thereof | |
| CN109126469B (en) | Preparation method and application of polyimide/inorganic particle pervaporation hybrid membrane | |
| CN104084052B (en) | A kind of preparation method of silicone rubber composite hollow fiber membrane | |
| CN102580560A (en) | Method for preparing nano-material-doped polymer film | |
| CN102755841A (en) | Preparation method and product of hydrophobic PVDF (Polyvinylidene Fluoride) microporous membrane with beta crystalline phase structure | |
| CN104084059B (en) | A kind of preparation method of hydrophobically modified nanon calcium carbonatefilled composite silicone rubber membrane | |
| CN102689018A (en) | Production method of nanometer silver wire material | |
| CN104963098A (en) | Method for preparing electrostatic spinning perfluocarbon polymer nanofiber membrane | |
| CN112726028B (en) | Super-hydrophilic composite nanofiber membrane with coarse structure and preparation and application thereof | |
| CN103785309B (en) | A kind of polyether sulfone/polymethyl methacrylate alloy plate milipore filter and preparation method thereof | |
| Zhao et al. | High-performance PVDF water treatment membrane based on IL-Na+ MMT for simultaneous removal of dyes and oil-water emulsions | |
| CN104923089B (en) | A kind of method preparing polyvinylidene fluoride porous film | |
| CN107081068B (en) | Infiltrating and vaporizing membrane and preparation method thereof | |
| CN105727762A (en) | Sodium alginate-amphipathy carbon material/polyacrylonitrile composite film, preparation and application | |
| CN114904404A (en) | Mixed matrix forward osmosis membrane based on MOF-808(Zr) and preparation method thereof | |
| CN104107644B (en) | A kind of preparation method of alcohol permselective silicon rubber composite membrane | |
| CN109173731A (en) | A kind of method that Freeze Drying Technique prepares metal organic framework@graphene oxide hybridized film | |
| CN117181004A (en) | Hydrophilic anti-pollution MXene/PVDF composite membrane and preparation method and application thereof | |
| CN106345316B (en) | A kind of miillpore filter of acid-resisting corrosion | |
| CN112717697A (en) | Biomass-based carbon nanomaterial/polysulfone ultrafiltration membrane and preparation method thereof | |
| CN110938897A (en) | Technology for rapidly preparing fibrous porous material | |
| CN103933868A (en) | Preparation method of methanol-water ceramic-based hollow-fiber-penetrated vaporized composite membrane | |
| Jiang et al. | High performance bimetallic ZIF-CoZn@ PVDF-HFP composite nanofiber membrane for membrane distillation based on coaxial electrospinning technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160706 |
|
| WD01 | Invention patent application deemed withdrawn after publication |