CN108246128A - A kind of loose reverse osmosis membrane of fatty polyamide and its preparation method and application - Google Patents
A kind of loose reverse osmosis membrane of fatty polyamide and its preparation method and application Download PDFInfo
- Publication number
- CN108246128A CN108246128A CN201810127097.0A CN201810127097A CN108246128A CN 108246128 A CN108246128 A CN 108246128A CN 201810127097 A CN201810127097 A CN 201810127097A CN 108246128 A CN108246128 A CN 108246128A
- Authority
- CN
- China
- Prior art keywords
- reverse osmosis
- osmosis membrane
- loose reverse
- fatty
- membrane
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention discloses a kind of preparation method of the loose reverse osmosis membrane of fatty polyamide, including:It is wrapped on porous support membrane using coating or by the way of impregnating by chain fatty race amine aqueous solution, then the porous support membrane for being enclosed with chain fatty race amine aqueous solution is subjected to interfacial polymerization with alicyclic solution of acid chloride, form the loose reverse osmosis membrane of fatty polyamide.The present invention is carried out the loose reverse osmosis membrane of fatty polyamide of interfacial polymerization preparation by alicyclic acyl chlorides and chain fatty race amine, with excellent divalent ion such as Ca2+、Mg2+、SO42-Removal efficiency, splendid anti-pollution ability, high water flux, removal such as dye molecule, phenolic molecules etc. available for COD in waste water, also it can be used for the separation concentration process of material in pharmacy, food service industry, or the fields such as water softening, sea water desalination and bitter pretreatment, landfill leachate treatment, with huge application prospect.
Description
Technical field
The present invention relates to material for water treatment preparing technical fields, and in particular to a kind of loose reverse osmosis membrane of fatty polyamide
And its preparation method and application.
Background technology
Membrane separation technique solves growing water supply problem with the intensive strategy of process, has using raw material is few, energy
Source consumes less, plant bulk is small, free of contamination advantage, it is considered to be potential mode.Common membrane for water treatment is divided into micro-filtration
Film, ultrafiltration membrane, NF membrane and reverse osmosis membrane;Wherein, NF membrane is divided into two classes, and one kind is (high with highly selective NF membrane
Monovalence/divalent selectivity), referred to as highly selective NF membrane;The another kind of water for removing calcium and magnesium softens NF membrane, has high
Ca2+、Mg2+Removal rate, also known as " loose " reverse osmosis membrane.Highly selective nanofiltration retaining molecular weight between 200-1000,
Aperture is between 0.1-2nm;" loose " reverse osmosis membrane is since with excellent Ca, Mg removal rate, it is soft to can be widely used in water
Pretreatment of change, sea water desalination and brackish water desalination etc.;In short, have the advantages that using NF membrane it is unique and apparent energy saving
Effect.
With going deep into for NF membrane application, especially divide performance of the salt technology to NF membrane in technique of zero discharge in recent years
Propose requirements at the higher level:Aperture dimensions distribution is more fine, pattern thickness is controllable, the nanofiltration of high desalination selectivity, high throughput
Film becomes new developing direction.On the other hand, existing commercialization " loose " is reverse osmosis with TMC (pyromellitic trimethylsilyl chloride) and MPD
(m-phenylene diamine (MPD)) is prepared by interfacial polymerization, although with high Ca2+、Mg2+Removal rate, but the roughness of film often exists
40-200nm, antifouling property are poor.Therefore, it improves filming technology, synthesize new interfacial polymerization monomer as a new generation is prepared
The main thought of NF membrane.
Commercialized NF membrane is mostly prepared with easy interfacial polymerization, and such as DOW NF series, GE DK and DL are serial,
It is very crucial in the acyl chlorides monomer and the type of amine monomers among these, used.At present, it is commercialized the acyl chlorides list used in nanofiltration film preparation
Body is pyromellitic trimethylsilyl chloride, and amine monomers are mostly m-phenylene diamine (MPD) and piperazine, this just greatly limits the type and possibility of NF membrane
Property.The commercialized NF membrane (loose reverse osmosis membrane) for water softening is mostly used pyromellitic trimethylsilyl chloride and m-phenylene diamine (MPD), by adding
Enter various additives, such as triphenyl phosphorus, surfactant, with change in interfacial polymerization process with the amine of acyl chlorides monomer reaction
Dissolving-diffusion velocity, with the degree of cross linking, thickness of film etc. that control is formed, so as to influence the rejection of the active layer of composite membrane and
Flux.Although all divalent salts and multivalent ion can be achieved in NF membrane prepared by pyromellitic trimethylsilyl chloride and m-phenylene diamine (MPD)
More than 98% rejection, but due to m-phenylene diamine (MPD), reaction speed is excessively slow in interfacial polymerization process, causes the film surface prepared
Unique " peak valley " structure is presented, so that the loose reverse osmosis membrane surface roughness prepared is very big, low contamination resistance.The opposing party
Face, during carrying out interfacial polymerization using piperazine as water phase amine molecule, although piperazine moieties are in dissolving-diffusion process
There is high interfacial reaction speed with pyromellitic trimethylsilyl chloride, and do not need to add additional additive and remove regulation and control water phase amine molecule
Dissolving-diffusion process, the structure distorted by amine molecule can realize the structure regulating to the composite membrane active layer of preparation, but this
Often there is 90% even lower rejection in class PA membrane, divalent salts especially calcium ion, and which limits its preparations
NF membrane water softening field application.
Invention content
In order to solve the problems, such as existing nanofiltration UF membrane present situation with preparing, the object of the present invention is to provide a kind of fat
Loose reverse osmosis membrane of fat polyamide and its preparation method and application, to solve, existing nanofiltration membrane flux is low, divalent (Ca2+、
Mg2+) rejection is low and the problem of low contamination resistance.
The technical solution that the present invention solves above-mentioned technical problem is as follows:There is provided a kind of fatty polyamide loose reverse osmosis membrane
Preparation method, including:
It is wrapped on porous support membrane, then will be wrapped up using coating or by the way of impregnating by chain fatty race amine aqueous solution
The porous support membrane and alicyclic solution of acid chloride for stating chain fatty race amine aqueous solution carry out interfacial polymerization, form fatty polyamide and dredge
Loose reverse osmosis membrane.
Beneficial effects of the present invention are:
The loose reverse osmosis membrane of the fatty polyamide carries out interface in structure by alicyclic acyl chlorides and chain fatty race amine
Polymerization is prepared, and distortion, the alicyclic acyl chlorides monomer of non-co-planar structure and chain structure aliphatic amine monomer carry out interface
Polymerization, since the aliphatic amine monomer of chain structure has the dissolving-flooding mechanism different from cyclic structure amine molecule so that raw
Into interfacial polymerization active layer there is finer and close membrane structure and weak surface charge negativity and low surface roughness, more
The film thickness generated on the supporting layer of hole is between 20-200nm;Simultaneously as the change of dissolving-flooding mechanism causes by interface
NF membrane prepared by polymerization can be to the Mg in solution2+, Ca2+Realize more than 98% retention, CUT-OFF 150-300 it
Between, to neutral molecule of the molecular weight more than 200, molecular cut off is more than 90%;Also, the loose reverse osmosis membrane tool prepared
Have a more smooth film surface, surface roughness in 2nm hereinafter, with excellent anti-pollution ability, high water flux, the fat
Fat polyamide film can be used for removal such as dye molecule, phenolic molecules etc. of COD in waste water, also available for pharmacy, food service industry
The fields such as separation concentration process or the water softening of middle material, sea water desalination and bitter pretreatment, landfill leachate treatment.
Based on the above technical solution, the present invention can also be improved as follows:
Further, after formation fatty polyamide loose reverse osmosis membrane, step is further included:
The loose reverse osmosis membrane of fatty polyamide is washed with low boiling point organic solvent, after 15-60s, then is placed in 50-90 DEG C
60s-10min is heat-treated, obtains the loose reverse osmosis membrane product of fatty polyamide;Wherein, low boiling point organic solvent for just oneself
One or more of alkane, hexamethylene, pentamethylene, normal heptane, normal octane and Isopar.
Further, a concentration of 0.01wt%-2wt% of alicyclic solution of acid chloride, chain fatty race amine aqueous solution it is a concentration of
0.01wt%-4wt%.
Further, the alicyclic solution of acid chloride is made of alicyclic acyl chlorides, oil phase solvent and additive;Wherein, alicyclic ring
The mass fraction of race's acyl chlorides is 0.01-2wt%, and the mass fraction of oil phase solvent is 96-99.98wt%, the quality of additive
Score is 0.01-2wt%;The oil phase solvent is in n-hexane, hexamethylene, pentamethylene, normal heptane, normal octane and Isopar
One or more of mixing;
Chain fatty race amine aqueous solution is made of chain fatty race amine, aqueous phase solvent and additive;Wherein, chain fatty
The mass fraction of race's amine is 0.01-4wt%, and the mass fraction of aqueous phase solvent is 46-99.98wt%, and the quality of additive is divided
Number is 0.01-50wt%;The aqueous phase solvent is water.
Further, the alicyclic solution of acid chloride is made of alicyclic acyl chlorides and oil phase solvent, the alicyclic acyl chlorides
Mass fraction is 0.01-2%, and the mass fraction of oil phase solvent is 98-99.9%.
Chain fatty race amine aqueous solution is made of chain fatty race amine and aqueous phase solvent, the matter of chain fatty race amine
Amount score is 0.01-4wt%, aqueous phase solvent 96-99.99wt%.
Further, the additive is nano particle or organic molecule or cosolvent or hydrophilic additive or surface-active
Agent or phase transfer catalyst;
The nano particle is flake graphite alkene, elongate single wall or many walls nanotube, zeolite molecular sieve, MOF etc. are inorganic
Nano material;
The organic molecule is organic spherical, caged or colyliform porous molecular such as water wheels phenol equimolecular or is with distortion
The organic phenol of space structure is 5,5 ', 6,6 '-tetrahydroxy -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobindene is full or fluorenes -
9- bis-phenols, the phenol type structure have larger space structure, can form the block copolymerization of the polyester more distorted and polyamide
Object;
The cosolvent is acetone, polyalcohol, organic phosphorus compound or n,N-Dimethylformamide, dimethyl sulfoxide (DMSO)
(DMSO);
The hydrophilic additive is quaternary ammonium salt, hydramine, camphorsulfonic acid, triethanolamine (TEOA), N methyldiethanol amine
(MDEOA), LiBr or camphorsulfonic acid triethylamine salt;
The surfactant is PEG 200, PEG 400, PEG 600, cetyl trimethylammonium bromide, polyethylene pyrrole
It is one or more in pyrrolidone (PVP) triethyl phosphite and tetramethyl ammonium chloride.
Further, the structural formula of the alicyclic acyl chlorides is:
Wherein, A is alicyclic, is four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring;R1、R2、R3、R4For-
The number of C (O) Cl or H ,-C (O) Cl are 3-6, are ortho position or meta position between two-C (O) Cl groups;
Alicyclic acyl chlorides used is connected to for three or three or more "-C (O) Cl " on alicyclic saturated hydrocarbon, such as ring fourth
Alkane, pentamethylene or hexamethylene etc.;The present invention can select alicyclic acyl chlorides as 1,2,3,4- ring fourth, four formyl chloride, 1,2,4,5-
Four formyl chloride of hexamethylene, 1,3,5- hexamethylene, three formyl chloride, 1,2,4- ring, penta 3 formyl chloride, 1,2,3,4- ring, penta 4 formyl chloride and
It is one or more in 1,2,3,4,5,6- hexamethylene pregnancy acyl chlorides.
Further, the structural formula of chain fatty race amine is:
Wherein, n 0,1,2,3, structure can be ethylenediamineDiethylenetriamineOr trienOr
Wherein, n 0,1,2,3, structure can be three (2- amino-ethyls) amineOr
Wherein, n 0,1,2, representative configurations are ethylenediamine, (2R)-propane -1,2- diaminesOr
1,2- diamino -2- methylpropanes
Further, the porous support membrane is organic polymer ultrafiltration membrane or hollow fiber ultrafiltration membrane or inorganic ultra-filtration membrane material
Material or organic and inorganic hybridization porous support membrane;The organic polymer ultrafiltration membrane is polysulfones, polyether sulfone, polyacrylonitrile or poly-
Acid imide;The inorganic ultra-filtration membrane material is Woelm Alumina or porous ceramic film.
The invention has the advantages that:
The present invention is prepared by interfacial polymerization with excellent by using alicyclic acyl chlorides and chain fatty race amine monomers
Ca2+、Mg2+The loose reverse osmosis separating membrane of fatty polyamide of rejection, low surface roughness, under a certain optimal conditions, system
Standby NF membrane is to CaCl2、MgSO4、MgCl2、Na2SO4Rejection can reach more than 98% respectively, and monovalent salts such as NaCl
Rejection 60% hereinafter, flux be 50-70kgm- 2h- 1MPa- 1, embody excellent divalent salt rejection rate and anti-pollution
Property;Fatty polyamide NF membrane prepared by the present invention is applicable to water softening, bitter and seawater desalinization pretreatment, and dyestuff/
The separation and removing of salt, the fields such as zero discharge of industrial waste water and biological medicine.
Description of the drawings
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1:
A kind of preparation method of the loose reverse osmosis membrane of fatty polyamide, includes the following steps:
(1) first polyether sulfone ultrafiltration counterdie is immersed in chain fatty race amine aqueous solution, is taken out after 120s, gas purging ultrafiltration
Film surface to remove the extra chain fatty race amine aqueous solution of ultrafiltration film surface, wherein, chain fatty race amine aqueous solution is by diethylenetriamine
It is formed with water, the mass fraction of diethylenetriamine is 1wt%, and the mass fraction of water is 99wt%;
(2) by alicyclic solution of acid chloride be immersed in step (1) made from the surface polyethers that contains chain fatty race amine aqueous solution
Interfacial polymerization is carried out on sulfone ultrafiltration counterdie, is taken out after 60s, wherein alicyclic solution of acid chloride is by 1,3,5- hexamethylene, three acyl chlorides and oil
Phase solvent forms, and oil phase solvent is hexamethylene, and the mass fraction of oil phase solvent is 99.85wt%, 1,3,5- hexamethylene, three acyl chlorides
Mass fraction is 0.15wt%;
(3) the loose reverse osmosis membrane of fatty polyamide prepared with n-hexane rinsing step (2), washing time 15s, 60 DEG C
2min is heat-treated to get the loose reverse osmosis membrane of fatty polyamide (NF membrane) product.
It is loose using the fatty polyamide that 1,3,5- hexamethylene, three acyl chlorides and diethylenetriamine are prepared to the embodiment
Reverse osmosis membrane carries out desalting performance test, test condition:Cross-flow test, mono-salt solution be 2000ppm, 25 DEG C, 1MPa, flow
7LPM, table 1 specific as follows:
The desalting performance of the loose reverse osmosis membrane of fatty polyamide prepared by 1 embodiment 1 of table
From upper table 1, it can be seen that aliphatic poly prepared by 1,3,5- hexamethylene, three acyl chlorides and three (2- amino-ethyls) amine
The loose reverse osmosis membrane of amide has high MgSO4Rejection has reached more than 98.6%, and flux also reaches
50.14kgm- 2h- 1MPa- 1, the loose reverse osmosis membrane of fatty polyamide of the invention can be used for water to soften, sea water desalination and hardship are salty
Water pretreatment, landfill leachate treatment are medium.
Embodiment 2:
A kind of preparation method of the loose reverse osmosis membrane of fatty polyamide, includes the following steps:
(1) it coats chain fatty race amine aqueous solution on polyether sulfone ultrafiltration counterdie, after 120s, ultrafiltration membrane surface is purged with gas
To remove the chain fatty race amine aqueous solution of poly (ether-sulfone) ultrafiltration membrane excess surface, wherein, chain fatty race amine aqueous solution is by three (2- ammonia
Base ethyl) amine and water forms, and the mass fraction of three (2- amino-ethyls) amine is 1.5wt%, and the mass fraction of water is
98.5wt%;
(2) again by alicyclic solution of acid chloride be immersed in step (1) made from surface contain the poly- of chain fatty race amine aqueous solution
Interfacial polymerization is carried out on ether sulfone ultrafiltration counterdie, is taken out after 60s, wherein, alicyclic solution of acid chloride by 1,3,5- hexamethylene, three acyl chlorides and
Oil phase solvent forms, and oil phase solvent is hexamethylene, and the mass fraction of oil phase solvent is 99.85wt%, 1,3,5- hexamethylene, three acyl chlorides
Mass fraction be 0.15wt%;
(3) the loose reverse osmosis membrane of fatty polyamide prepared with n-hexane rinsing step (2), washing time 15s, 60 DEG C
2min is heat-treated to get the loose reverse osmosis membrane product of fatty polyamide.
The loose reverse osmosis membrane of fatty polyamide prepared by 1,3,5- hexamethylene, three acyl chlorides and three (2- amino-ethyls) amine
Carry out desalting performance test, test condition:Cross-flow test, mono-salt solution be 2000ppm, 25 DEG C, 1MPa, flow 7LPM, specifically
Such as the following table 2:
The desalting performance of the loose reverse osmosis membrane of fatty polyamide prepared by 2 embodiment 2 of table
From upper table 2, it can be seen that aliphatic poly prepared by 1,3,5- hexamethylene, three acyl chlorides and three (2- amino-ethyls) amine
The loose reverse osmosis membrane of amide has high MgSO4Rejection has reached more than 97.5%, and flux also reaches
39.34kgm- 2h- 1MPa- 1, the loose reverse osmosis membrane of fatty polyamide of the invention can be used for water to soften, sea water desalination and hardship are salty
Water pretreatment, landfill leachate treatment are medium.
Embodiment 3:
A kind of preparation method of the loose reverse osmosis membrane of fatty polyamide, includes the following steps:
(1) first polyether sulfone ultrafiltration counterdie is immersed in chain fatty race amine aqueous solution, is taken out after 4min, gas purging polyethers
Sulfone ultrafiltration membrane surface to remove the extra chain fatty race amine aqueous solution of ultrafiltration membrane surface, wherein, chain fatty race amine aqueous solution is by three
(2- amino-ethyls) amine, acetone and water composition, the mass fraction of three (2- amino-ethyls) amine are 1wt%, the mass fraction of water
For 98wt%, the mass fraction of acetone is 1wt%;
(2) again by alicyclic solution of acid chloride be immersed in step (1) made from poly (ether-sulfone) ultrafiltration membrane surface contain chain fatty
Carry out interfacial polymerization on the polyether sulfone ultrafiltration counterdie of race's amine aqueous solution, taken out after 90s, wherein, alicyclic solution of acid chloride by 1,2,4,
Four formyl chloride of 5- hexamethylenes and oil phase solvent composition, oil phase solvent is hexamethylene, and the mass fraction of hexamethylene is 99.85wt%, 1,
The mass fraction of 2,4,5- hexamethylene, four formyl chloride is 0.15wt%;
(3) the fatty polyamide NF membrane prepared with n-hexane rinsing step (2), washing time 30s, 60 DEG C of heat treatments
4min is to get fatty polyamide nanofiltration membrane product.
The loose reverse osmosis of fatty polyamide prepared by 1,2,4,5- hexamethylene, four formyl chloride and three (2- amino-ethyls) amine
Permeable membrane carries out desalting performance test, test condition:Cross-flow test, mono-salt solution be 2000ppm, 25 DEG C, 1MPa, flow 7LPM,
Table 3 specific as follows:
The desalting performance of the loose reverse osmosis membrane of fatty polyamide prepared by 3 embodiment 3 of table
From upper table 3, it can be seen that fat prepared by 1,2,4,5- hexamethylene, four formyl chloride and three (2- amino-ethyls) amine
The loose reverse osmosis membrane of polyamide has high MgCl2Rejection has reached more than 98%, and flux also reaches
49.68kgm- 2h- 1MPa- 1, the loose reverse osmosis membrane of fatty polyamide of the invention can be used for water to soften, sea water desalination and hardship are salty
Water pretreatment, landfill leachate treatment are medium.
Embodiment 4:
A kind of preparation method of the loose reverse osmosis membrane of fatty polyamide, includes the following steps:
(1) first polyacrylonitrile ultrafiltration counterdie is immersed in chain fatty race amine aqueous solution, is taken out after 4min, gas purging is super
Filter membrane surface to remove the extra chain fatty race amine aqueous solution of ultrafiltration film surface, wherein, chain fatty race amine aqueous solution is by three (2- ammonia
Base ethyl) amine aqueous solution and water forms, and the mass fraction of three (2- amino-ethyls) amine is 1wt%, and the mass fraction of water is
99wt%;
(2) again by alicyclic solution of acid chloride be immersed in step (1) made from surface contain the poly- of chain fatty race amine aqueous solution
Interfacial polymerization is carried out on ether sulfone ultrafiltration counterdie, is taken out after 60s, wherein, alicyclic solution of acid chloride is by 1,2,3,4- ring fourth, four formyl
Chlorine, oil phase solvent and additive composition, additive is acetone, and oil phase solvent is normal heptane, wherein 1,2,3,4- ring fourth, four formyl
The mass fraction of chlorine is 0.12wt%, and the mass fraction of acetone is 1wt%, and the mass fraction of normal heptane is 98.88wt%;
(3) polyamide nanofiltration membrane prepared with n-hexane rinsing step (2), washing time 15s, 60 DEG C of heat treatment 4min,
Up to the loose reverse osmosis membrane product of fatty polyamide.
The loose reverse osmosis of fatty polyamide prepared by 1,2,3,4- ring fourth, four formyl chloride and three (2- amino-ethyls) amine
Permeable membrane carries out desalting performance test, test condition:Cross-flow test, mono-salt solution be 2000ppm, 25 DEG C, 1MPa, flow 7LPM,
Table 4 specific as follows:
The desalting performance of the loose reverse osmosis membrane of fatty polyamide prepared by 4 embodiment 4 of table
From upper table 4, it can be seen that fat prepared by 1,2,3,4- ring fourth, four formyl chloride and three (2- amino-ethyls) amine
The loose reverse osmosis membrane of polyamide has high CaCl2Rejection has reached more than 98%, and flux also reaches
50.31kgm- 2h- 1MPa- 1, the loose reverse osmosis membrane of fatty polyamide of the invention can be used for water to soften, sea water desalination and hardship are salty
Water pretreatment, landfill leachate treatment are medium.
Embodiment 5:
A kind of preparation method of the loose reverse osmosis membrane of fatty polyamide, includes the following steps:
(1) first polyimides ultrafiltration counterdie is immersed in chain fatty race amine aqueous solution, is taken out after 4min, gas purging is super
Filter membrane surface to remove the extra chain fatty race amine aqueous solution of ultrafiltration film surface, wherein, chain fatty race amine aqueous solution by 1- methyl-
1,2- ethylenediamine is formed with water, 1- methyl-1s, and the mass fraction of 2- ethylenediamines is 1wt%, and the mass fraction of water is
99wt%;
(2) again by alicyclic solution of acid chloride be immersed in step (1) made from surface contain the poly- of chain fatty race amine aqueous solution
On ether sulfone ultrafiltration counterdie, taken out after 60s, wherein, alicyclic solution of acid chloride is made of four formyl chloride of ring fourth and oil phase solvent, oil phase
Solvent is n-hexane, and the mass fraction of n-hexane is 99.84wt%, and the mass fraction of four formyl chloride of ring fourth is 0.16wt%;
(3) the loose reverse osmosis membrane of fatty polyamide prepared with n-hexane rinsing step (2), washing time 15s, 60 DEG C
4min is heat-treated to get the loose reverse osmosis membrane product of fatty polyamide.
To four formyl chloride of ring fourth and 1- methyl-1s, the loose reverse osmosis membrane of fatty polyamide prepared by 2- ethylenediamines into
Row desalting performance is tested, test condition:Cross-flow test, mono-salt solution be 2000ppm, 25 DEG C, 1MPa, flow 7LPM, specifically such as
The following table 5:
The desalting performance of the loose reverse osmosis membrane of fatty polyamide prepared by 5 embodiment 5 of table
From upper table 5, it can be seen that four formyl chloride of ring fourth and 1- methyl-1s, aliphatic polyamides prepared by 2- ethylenediamines
The loose reverse osmosis membrane of amine has high CaCl2Rejection has reached more than 98%, and flux has also reached 50.31kgm2h- 1MPa- 1, the loose reverse osmosis membrane of this fatty polyamide can be used for water to soften, sea water desalination and bitter pretreatment, rubbish are oozed
Filtrate processing is medium.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the loose reverse osmosis membrane of fatty polyamide, it is characterized in that, including:
It is wrapped on porous support membrane, then the chain will be enclosed with using coating or by the way of impregnating by chain fatty race amine aqueous solution
The porous support membrane of shape aliphatic amine solution carries out interfacial polymerization with alicyclic solution of acid chloride, and it is loose anti-to form fatty polyamide
Permeable membrane.
2. the preparation method of the loose reverse osmosis membrane of fatty polyamide according to claim 1, it is characterized in that, when formation fat
After the loose reverse osmosis membrane of fat polyamide, step is further included:
With the loose reverse osmosis membrane of organic solvent washing fatty polyamide, after 15-60s, then it is placed in 50-90 DEG C of heat treatment
60s-10min obtains the loose reverse osmosis membrane product of fatty polyamide.
3. according to the preparation method of the loose reverse osmosis membrane of claim 1 to 2 any one of them fatty polyamide, feature
It is a concentration of 0.01wt%-2wt% of alicyclic solution of acid chloride, a concentration of 0.01wt%- of chain fatty race amine aqueous solution
4wt%.
4. the preparation method of the loose reverse osmosis membrane of fatty polyamide according to claim 3, it is characterized in that, the alicyclic ring
Race's solution of acid chloride is made of alicyclic acyl chlorides, oil phase solvent and additive;Wherein, the mass fraction of alicyclic acyl chlorides is 0.01-
2wt%, the mass fraction of oil phase solvent is 96-99.98wt%, and the mass fraction of additive is 0.01-2wt%;The oil
Phase solvent is one or more of n-hexane, hexamethylene, pentamethylene, normal heptane, normal octane and Isopar mixing;
Chain fatty race amine aqueous solution is made of chain fatty race amine, aqueous phase solvent and additive;Wherein, chain fatty race amine
Mass fraction for 0.01-4wt%, the mass fraction of aqueous phase solvent is 46-99.98wt%, and the mass fraction of additive is
0.01-50wt%;The aqueous phase solvent is water.
5. the preparation method of the loose reverse osmosis membrane of fatty polyamide according to claim 3, it is characterized in that, the alicyclic ring
Race's solution of acid chloride is made of alicyclic acyl chlorides and oil phase solvent, and the mass fraction of the alicyclic acyl chlorides is 0.01-2wt%, oily
The mass fraction of phase solvent is 98-99.99wt%;
Chain fatty race amine aqueous solution is made of chain fatty race amine and aqueous phase solvent, the quality point of chain fatty race amine
Number is 0.01-4wt%, aqueous phase solvent 96-99.99wt%.
6. the preparation method of the loose reverse osmosis membrane of fatty polyamide according to claim 3, it is characterized in that, the addition
Agent for nano particle or the organic molecule with distortion space structure or cosolvent or hydrophilic additive or surfactant or
Phase transfer catalyst;
The nano particle is inorganic nano material, is flake graphite alkene, elongate single wall or many walls nanotube, zeolite molecules
Sieve or MOF;
The organic molecule is or organic spherical, caged or colyliform porous molecular or for the organic phenol with distortion space structure
It is 5,5 ', 6,6 '-tetrahydroxy -3,3,3 ', 3 '-tetramethyl -1,1 '-spirobindene are expired or fluorenes -9- bis-phenols;
The cosolvent is acetone, polyalcohol, organic phosphorus compound, n,N-Dimethylformamide or dimethyl sulfoxide (DMSO);
The hydrophilic additive is quaternary ammonium salt, hydramine, camphorsulfonic acid, triethanolamine, N methyldiethanol amine, LiBr or camphor tree
Brain sulfonic acid triethylamine salt;
The surfactant is PEG200, PEG400, PEG600, cetyl trimethylammonium bromide, polyvinylpyrrolidone
It is one or more in triethyl phosphite, camphorsulfonic acid triethylamine salt and tetramethyl ammonium chloride.
7. the preparation method of the loose reverse osmosis membrane of fatty polyamide according to claim 3, it is characterized in that, the alicyclic ring
The structural formula of race's acyl chlorides is:
Wherein, A is alicyclic, is four-membered ring, five-membered ring, hexatomic ring, heptatomic ring or octatomic ring;R1、R2、R3、R4For-C (O)
The number of Cl or H ,-C (O) Cl are 3-6, are ortho position or meta position between two-C (O) Cl groups.
8. the preparation method of the loose reverse osmosis membrane of fatty polyamide according to claim 3, it is characterized in that, the chain
The structural formula of aliphatic amine is:
Wherein, n 0,1,2,3;Or
Wherein, n 0,1,2,3;Or
Wherein, n 0,1,2.
9. the preparation method using the loose reverse osmosis membrane of claim 1-8 any one of them fatty polyamides is prepared
The loose reverse osmosis membrane of fatty polyamide.
10. application of the loose reverse osmosis membrane of fatty polyamide in water treatment field described in claim 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810127097.0A CN108246128A (en) | 2018-02-07 | 2018-02-07 | A kind of loose reverse osmosis membrane of fatty polyamide and its preparation method and application |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810127097.0A CN108246128A (en) | 2018-02-07 | 2018-02-07 | A kind of loose reverse osmosis membrane of fatty polyamide and its preparation method and application |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108246128A true CN108246128A (en) | 2018-07-06 |
Family
ID=62744841
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810127097.0A Pending CN108246128A (en) | 2018-02-07 | 2018-02-07 | A kind of loose reverse osmosis membrane of fatty polyamide and its preparation method and application |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108246128A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109289543A (en) * | 2018-10-26 | 2019-02-01 | 中国石油大学(华东) | One kind is from micropore high-flux nanofiltration composite membrane and preparation method thereof |
CN109847585A (en) * | 2018-12-20 | 2019-06-07 | 时代沃顿科技有限公司 | The preparation method of composite nanometer filtering film and composite nanometer filtering film prepared therefrom |
CN110201559A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of big flux Enhanced type hollow fiber film and preparation method thereof |
CN110201558A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of reinforced PVDF of big flux not belt material ultrafiltration membrane and preparation method thereof |
CN110201557A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of reinforced ultrafiltration membrane of big flux and preparation method thereof |
CN110385046A (en) * | 2018-12-29 | 2019-10-29 | 启成(江苏)净化科技有限公司 | A method of big flux RO membrane is prepared with more acyl chlorides substituted cyclic macromoleculars |
CN110548400A (en) * | 2019-09-04 | 2019-12-10 | 杭州易膜环保科技有限公司 | Large-flux reverse osmosis membrane and preparation method thereof |
CN112246110A (en) * | 2020-10-28 | 2021-01-22 | 湖南澳维环保科技有限公司 | Double-functional-layer composite reverse osmosis membrane and preparation method thereof |
CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
CN114832627A (en) * | 2022-05-30 | 2022-08-02 | 浙江工业大学 | High-flux high-interception composite polyamide separation membrane containing divalent metal ions and alcohol activating agent and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101934201A (en) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | High-selectivity composite nanofiltration membrane and preparation method thereof |
CN103785307A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Attapulgite-contaiing composite nanofiltration membrane and making method thereof |
CN104010718A (en) * | 2011-10-18 | 2014-08-27 | 帝国创新有限公司 | Membranes for separation |
JP2016190213A (en) * | 2015-03-31 | 2016-11-10 | 東レ株式会社 | Composite semipermeable membrane |
CN107126850A (en) * | 2017-05-23 | 2017-09-05 | 中国石油大学(华东) | A kind of polysulfonamide nanofiltration or reverse osmosis composite membrane and preparation method thereof |
-
2018
- 2018-02-07 CN CN201810127097.0A patent/CN108246128A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101934201A (en) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | High-selectivity composite nanofiltration membrane and preparation method thereof |
CN104010718A (en) * | 2011-10-18 | 2014-08-27 | 帝国创新有限公司 | Membranes for separation |
CN103785307A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Attapulgite-contaiing composite nanofiltration membrane and making method thereof |
JP2016190213A (en) * | 2015-03-31 | 2016-11-10 | 東レ株式会社 | Composite semipermeable membrane |
CN107126850A (en) * | 2017-05-23 | 2017-09-05 | 中国石油大学(华东) | A kind of polysulfonamide nanofiltration or reverse osmosis composite membrane and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
张兴英: "《高分子化学》", 30 June 2000 * |
李孟 等: "《给水处理原理》", 31 December 2013, 武汉理工大学出版社 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109289543A (en) * | 2018-10-26 | 2019-02-01 | 中国石油大学(华东) | One kind is from micropore high-flux nanofiltration composite membrane and preparation method thereof |
CN109847585A (en) * | 2018-12-20 | 2019-06-07 | 时代沃顿科技有限公司 | The preparation method of composite nanometer filtering film and composite nanometer filtering film prepared therefrom |
CN110385046A (en) * | 2018-12-29 | 2019-10-29 | 启成(江苏)净化科技有限公司 | A method of big flux RO membrane is prepared with more acyl chlorides substituted cyclic macromoleculars |
CN110201559B (en) * | 2019-06-04 | 2021-11-09 | 泉州碧蓝膜科技有限责任公司 | Large-flux reinforced hollow fiber membrane and preparation method thereof |
CN110201557A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of reinforced ultrafiltration membrane of big flux and preparation method thereof |
CN110201558A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of reinforced PVDF of big flux not belt material ultrafiltration membrane and preparation method thereof |
CN110201559A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of big flux Enhanced type hollow fiber film and preparation method thereof |
CN110201558B (en) * | 2019-06-04 | 2021-11-09 | 泉州碧蓝膜科技有限责任公司 | Large-flux reinforced PVDF unlined ultrafiltration membrane and preparation method thereof |
CN110201557B (en) * | 2019-06-04 | 2021-11-09 | 泉州碧蓝膜科技有限责任公司 | Large-flux reinforced ultrafiltration membrane and preparation method thereof |
CN110548400A (en) * | 2019-09-04 | 2019-12-10 | 杭州易膜环保科技有限公司 | Large-flux reverse osmosis membrane and preparation method thereof |
CN112246110A (en) * | 2020-10-28 | 2021-01-22 | 湖南澳维环保科技有限公司 | Double-functional-layer composite reverse osmosis membrane and preparation method thereof |
CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
CN114832627A (en) * | 2022-05-30 | 2022-08-02 | 浙江工业大学 | High-flux high-interception composite polyamide separation membrane containing divalent metal ions and alcohol activating agent and preparation method thereof |
CN114832627B (en) * | 2022-05-30 | 2024-01-12 | 浙江工业大学 | High-flux high-retention composite polyamide separation membrane containing divalent metal ions and alcohol activating agent and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108246128A (en) | A kind of loose reverse osmosis membrane of fatty polyamide and its preparation method and application | |
US10780401B2 (en) | Highly selective alicyclic polyamide nanofiltration membrane and making method thereof | |
CN107158980B (en) | Thin-layer composite membrane based on gas/liquid interface reaction and preparation method and application thereof | |
Gao et al. | Creation of active-passive integrated mechanisms on membrane surfaces for superior antifouling and antibacterial properties | |
Ismail et al. | Thin film composite membrane—Recent development and future potential | |
CN104941461B (en) | Nanofiltration membrane for seawater desalination and preparation method thereof | |
Tang et al. | Enhancing the permeance and antifouling properties of thin-film composite nanofiltration membranes modified with hydrophilic capsaicin-mimic moieties | |
CN106999870A (en) | The molecule of polysulfonamide nanofiltration or reverse osmosis composite membrane process for assembly preparing layer by layer | |
CN104245100B (en) | There is excellent seperation film of antifouling property and preparation method thereof for water process | |
CN108325389B (en) | Azlactone-based polyamide membrane and preparation method thereof | |
CN113041840B (en) | Preparation method of nanofiltration membrane and nanofiltration membrane prepared by same | |
CN106582299B (en) | A kind of graphene-based 3D modified by nano particles organic separation membrane preparation method of ammoxidation | |
CN113856501A (en) | Composite nanofiltration membrane and preparation method and application thereof | |
CN106345323A (en) | Preparation method for anti-pollution hydrophilic positive permeable membrane | |
CN1243600C (en) | High permeability composite reverse osmosis film and its producing method | |
CN108159891A (en) | A kind of N- sulfenamides based polyamide water softens loose reverse osmosis composite membrane and preparation method thereof | |
Ji et al. | Performance evaluation of nanofiltration polyamide membranes based from 3, 3′-diaminobenzidine | |
KR20150049273A (en) | Preparation method of nanofiltration composite membrane impregnated graphene oxide and the nanofiltration composite membrane thereby | |
CN103260731B (en) | The polysulfonamide film obtained by interfacial polymerization | |
JP2018520847A (en) | Water treatment separation membrane and method for producing the same | |
Yang et al. | Engineering a separation membrane containing a gel layer with backbone support effect and bionic-inspired capillary effect for the efficient separation of dyes/salts | |
CN116328565A (en) | Preparation method of composite nanofiltration membrane and composite nanofiltration membrane prepared by same | |
KR20180113350A (en) | Method for preparation of high flux polyamide composite membrane | |
KR101487764B1 (en) | Preparation method of polyamide nanofiltration composite membrane and the polyamide nanofiltration composite membrane thereby | |
KR20180108208A (en) | Coating composition having selective removal of divalent cation and filtration membrane using the same |
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 |