CN105688685A - Method for preparing composite membrane through barometric pressure air plasma technology - Google Patents
Method for preparing composite membrane through barometric pressure air plasma technology Download PDFInfo
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- CN105688685A CN105688685A CN201610032008.5A CN201610032008A CN105688685A CN 105688685 A CN105688685 A CN 105688685A CN 201610032008 A CN201610032008 A CN 201610032008A CN 105688685 A CN105688685 A CN 105688685A
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- composite membrane
- membrane
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- barometric pressure
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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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/127—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction using electrical discharge or plasma-polymerisation
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- 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
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- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
- B01D2323/385—Graft polymerization involving radiation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a method for preparing a composite membrane through the barometric pressure air plasma technology and belongs to the technical field of membrane separation.The method is characterized in that a porous membrane serves as a base membrane, and a grafting monomer and an initiator stand, and are soaked and coated in advance; barometric pressure air plasma irradiation causes the grafting reaction; then the grafting reaction after irradiation is carried out to prepare the composite membrane.The method has the advantages that the composite membrane prepared through the barometric pressure air plasma technology has good selectivity and permeation flux, the preparation cost is low, and large-scale industrial production can be achieved easily.
Description
Technical field
The invention belongs to technical field of membrane separation, the preparation method relating to a kind of composite membrane, it is related specifically to a kind of method utilizing atmos low-temperature plasma technology to prepare osmosis vaporizing compound membrane。
Background technology
Infiltration evaporation or water vapour penetration are under the promotion of steam pressure difference, utilize component to dissolve in film and the difference of diffusion carrys out separating mixture, be particularly suitable for separating nearly boiling point, the constant boiling point mixture that traditional azeotropic distillation and extracting rectifying etc. are difficult to separate。Three important indicators of infiltration vaporization separation film are selectivity, permeation flux and structural stability。Suppress the excessively swelling to obtain stable membrane structure and separating property is one of the key of infiltrating and vaporizing membrane of film。
" polymerization is filled in grafting " composite membrane is to fill another kind of polymer in the fenestra of porous counterdie。The affinity of certain component in filled polymer and mixture to be separated is good, permselective property is provided, porous counterdie does not then occur swelling in Organic substance, can effectively suppress the excessively swelling of film, ensure that membrane structure is complete and separating property (selects from Macromolecules, 1991,24:5522-5527)。Zhan Jing etc. adopt low pressure glow discharge plasma, improve its antifouling property on polysulfone membrane surface by gas phase graft reaction and select from Journal of Chemical Industry and Engineering, 2004,55 (5): 747-751) Chinese patent 200410015893.3 discloses a kind of low-temperature plasma graft infiltrating and vaporizing membrane and method for making thereof, adopt low-pressure argon plasma at porous membrane surface initiation grafting, prepare infiltration vaporization separation film。But, low pressure discharge plasma technique needs vacuum and sealing device, and the cost of mass industrialized production application is high, it is difficult to continuous prodution, it is impossible to be widely used in industrialization film preparation。Wang etc. adopt dynamic pressure to drive method to be prepared for polyvinyl alcohol (PVA)-graphene oxide (GO)-polyacrylonitrile (PAN) composite membrane, this composite membrane is to the separation of 50wt% toluene/n-heptane (40 DEG C) up to 12.9, but permeation flux only has 0.027Kg/ (m2H), industrial application value little (selecting from JournalofMembraneScience, 2014,455:113 120)。Chinese patent 201010211258.8 discloses the composite membrane utilizing atmospheric low-temperature plasma technology to prepare, and using helium as discharge gas, adopts atmospheric dielectric barrier discharge plasma technology to prepare the composite membrane of " class offshore platform structure "。The preparation of this composite membrane does not need vacuum equipment, but helium is expensive, adds the manufacturing cost of composite membrane, and the manufacturing cycle of composite membrane is longer, and industrial applications is still difficult。
The present invention is using air as discharge gas, use composite membrane prepared by atmos low-temperature plasma technology, do not need the helium of vacuum and sealing system and costliness as discharge gas, can effectively reduce and disclosed in Chinese patent 201010211258.8, utilize normal pressure helium gas plasma technology to prepare the cost of composite membrane, and air-channel system that need not be complicated, equipment and technique are more simple, and industrial prospect is also better。
Summary of the invention
The invention provides a kind of method utilizing atmos low-temperature plasma technology to prepare composite membrane, composite membrane has aromatic selective permeability, can economical and efficient ground aromatics separation/paraffins mixture, and preparation method is simple, cost is low, has obvious industrial application value。
Technical scheme is as follows:
A kind of method that atmos low-temperature plasma technology prepares composite membrane, it is characterised in that perforated membrane precoating grafted monomers and initiator；Perforated membrane after atmos plasma irradiation precoating, the irradiation of trigger monomer synchronizes graft reaction；After carrying out irradiation, graft reaction prepares composite membrane。
Described perforated membrane can be the polymeric material insoluble in aromatic hydrocarbons such as polyacrylonitrile, fluoropolymer, polyolefin, polyyne and prepared by the inorganic material such as pottery, charcoal。
Described monomer and the affinity of aromatic hydrocarbons are stronger, it is possible to for containing CH2-CH2The acrylic ester compound of-O structure, one or more mixture in Polyoxyethylene Methyl acryate compounds, monomer concentration is 0.1～1.0mol/L, and solvent is water, methanol, ethanol；
Described initiator is radical polymerization initiator, more optimizedly peroxide, persulfate, oxidation-reduction trigger system, optimum is dibenzoyl peroxide/DMA, potassium peroxydisulfate/sodium sulfite etc.；
Described atmos low-temperature plasma, discharging condition can be:
Discharge gas: air；
Irradiance power density: 1～50W/cm2；
Exposure time: 10～300s；
The composite membrane of preparation is applied to aromatics separation/alkane compound, sulfide/hydrocarbon mixture。
The invention has the beneficial effects as follows: the present invention uses and is standing and soak for method precoating perforated membrane, using air as discharge gas, utilizing atmos low-temperature plasma to excite initiator, grafted monomers to carry out graft reaction, the composite membrane of preparation has higher selectivity, permeation flux and structural stability。Further, air is adopted to replace expensive helium as discharge gas, it is not necessary to complicated air-channel system and vacuum system, equipment and operation are also all simpler。Relative to the composite membrane utilizing disclosed in Chinese patent 201010211258.8 normal pressure helium gas plasma technology to prepare, the present invention is without using the helium of costliness, and cost is low, is more beneficial for large-scale industrial and produces。
Detailed description of the invention
The present invention uses Flat Membrane to be example, it is therefore intended that clearly describes the present invention concisely, but does not limit the invention to Flat Membrane。
Below in conjunction with specific embodiment, the present invention is elaborated。
Embodiment 1
Asymmetric polyacrylonitrile (PAN) ultrafilter membrane is as perforated membrane, and Polyoxyethylene Methyl acryate (PEO500OHMA) is grafted monomers, and the preparation process of composite membrane is as follows:
Being placed in by PAN ultrafilter membrane in 0.5mol/LPEO500OHMA monomer/methanol precoating solution, at 45 DEG C, constant temperature is standing and soak for 2 hours, carries out monomer precoating；Inserting in plasma reactor by the PAN ultrafilter membrane of precoating, open radio-frequency power supply, control irradiance power density is 30W/cm2, the low temperature atomsphere plasma initiation grafting reaction of generation。Plasma radiation time 90s, after completing synchronization irradiation grafting reaction, closes power supply；Monomer after degassed/methanol solution is imported in reactor, carries out graft reaction after irradiation。Taking out film after reaction 30min, with the monomer of deionized water eluting film surface attachment and homopolymer, vacuum drying obtains composite membrane。
The composite membrane of above-mentioned preparation carries out separating property evaluation test on infiltration evaporation evaluating apparatus。The pressure of membrane permeation side is 200Pa, and raw material is toluene/n-heptane (mass ratio 1:4) mixed solution of 80 DEG C, and the toluene/n-heptane separation of composite membrane is 1.0, it does not have arenes selectivity。
Embodiment 2
Adding dibenzoyl peroxide/DMA initiator in PEO500OHMA monomer/methanol solution, other condition is identical with embodiment 1。The toluene/n-heptane separation of prepared composite membrane is 5.8, and permeation flux is 0.9kg/m2·h。
Embodiment 3
Control irradiance power density is 1W/cm2, exposure time 300s, PEO500OHMA monomer concentration is 0.1mol/L, and other condition is identical with embodiment 2。The toluene/n-heptane separation of prepared composite membrane is 1.2, and permeation flux is 3.5kg/m2·h。
Embodiment 4
Control irradiance power density is 50W/cm2, exposure time 10s, PEO500OHMA monomer concentration is 1.0mol/L, and other condition is identical with embodiment 2。The toluene/n-heptane separation of prepared composite membrane is 3.6, and permeation flux is 2.6kg/m2·h。
Embodiment 5
The solvent of monomer solution is water, and other condition is identical with embodiment 1。The toluene/n-heptane separation of prepared composite membrane is 1.0, it does not have arenes selectivity。
Embodiment 6
Adding potassium peroxydisulfate in monomer solution, other condition is identical with embodiment 5。The toluene/n-heptane separation of prepared composite membrane is 3.6, and permeation flux is 4.0kg/m2·h。
Embodiment 7
Adding potassium peroxydisulfate/sodium sulfite initiator in monomer solution, other condition is identical with embodiment 5。The toluene/n-heptane separation of prepared composite membrane is 4.6, and permeation flux is 2.0kg/m2·h。
Claims (6)
1. the method that an atmospheric air plasma technique prepares composite membrane, it is characterised in that with perforated membrane for counterdie, is placed on counterdie in monomer and initiator solution and is standing and soak for precoating；With air for discharge gas, the counterdie after coating being carried out plasma irradiation, initiation grafting reacts；After carrying out irradiation, graft reaction prepares composite membrane。
2. the perforated membrane described in can be the polymeric material insoluble in aromatic hydrocarbons such as polyacrylonitrile, fluoropolymer, polyolefin, polyyne and prepared by the inorganic material such as pottery, charcoal。
3. monomer and the affinity of aromatic hydrocarbons described in are stronger, it is possible to for containing CH2-CH2The acrylic ester compound of-O structure, one or more mixture in Polyoxyethylene Methyl acryate compounds, monomer concentration is 0.1～1.0mol/L, and solvent is water, methanol。
4. the initiator described in is radical polymerization initiator, more optimizedly peroxide, persulfate, oxidation-reduction trigger system, optimum is dibenzoyl peroxide/DMA, potassium peroxydisulfate/sodium sulfite etc.。
5. the atmos low-temperature plasma described in, discharging condition can be:
Discharge gas: air；
Irradiance power density: 1～50W/cm2；
Exposure time: 10～300s。
6. the composite membrane of preparation is applied to aromatics separation/alkane compound。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610032008.5A CN105688685B (en) | 2016-01-18 | 2016-01-18 | The method that atmospheric air plasma technique prepares composite membrane |
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| CN201610032008.5A CN105688685B (en) | 2016-01-18 | 2016-01-18 | The method that atmospheric air plasma technique prepares composite membrane |
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| CN105688685A true CN105688685A (en) | 2016-06-22 |
| CN105688685B CN105688685B (en) | 2018-07-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390762A (en) * | 2016-10-27 | 2017-02-15 | 启迪清源（北京）科技有限公司 | Preparation method of plasma grafted FEVE fluororesin nanofiltration membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179183A (en) * | 2010-06-28 | 2011-09-14 | 大连理工大学 | Composite membrane prepared by low-temperature plasma technology under normal pressure |
| CN103831027A (en) * | 2014-02-28 | 2014-06-04 | 东华大学 | Method for improving pollution resistance of PVDF (polyvinylidene fluoride) porous membrane based on plasmas technology |
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2016
- 2016-01-18 CN CN201610032008.5A patent/CN105688685B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179183A (en) * | 2010-06-28 | 2011-09-14 | 大连理工大学 | Composite membrane prepared by low-temperature plasma technology under normal pressure |
| CN103831027A (en) * | 2014-02-28 | 2014-06-04 | 东华大学 | Method for improving pollution resistance of PVDF (polyvinylidene fluoride) porous membrane based on plasmas technology |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390762A (en) * | 2016-10-27 | 2017-02-15 | 启迪清源（北京）科技有限公司 | Preparation method of plasma grafted FEVE fluororesin nanofiltration membrane |
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| CN105688685B (en) | 2018-07-20 |
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