CN104548975B - Tubular composite nanofiltration membrane - Google Patents
Tubular composite nanofiltration membrane Download PDFInfo
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- CN104548975B CN104548975B CN201510057388.3A CN201510057388A CN104548975B CN 104548975 B CN104548975 B CN 104548975B CN 201510057388 A CN201510057388 A CN 201510057388A CN 104548975 B CN104548975 B CN 104548975B
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Abstract
The invention discloses a tubular composite nanofiltration membrane which comprises four functional layers, namely a support layer, a base membrane layer, an interfacial polymerization layer and a protective layer. A tubular base ultrafiltration membrane is formed by carrying out blending modification on polyethersulfone and an inorganic nanometer material, and a tubular polyamide composite nanofiltration membrane is formed by carrying out interfacial polymerization reaction on piperazine hexahydrate as a water-phase solution and a trimesoyl chloride hexane solution. According to a preparation process, a process technology of preparing a tubular polyethersulfone ultrafiltration membrane by adopting a jelly and synchronously producing the tubular polyethersulfone ultrafiltration membrane by adopting reel pipe welding and membrane coating is adopted. The obtained tubular composite nanofiltration membrane disclosed by the invention has the advantages of different selective separation functions on a monovalent ion and a divalent ion, a higher interception rate on a small-molecular organic matter, lower requirements on the pretreatment of feed liquid, applicability on the separation of high-solubility high-granularity high-suspension matters, and very high economic values on deep separation, purification and soluble shrinkage of some specific materials.
Description
Present patent application is the divisional application of Chinese Patent Application No. 201310156264.1, the applying date of original application
For 2013-4-28, Application No. 201310156264.1, invention and created name is a kind of tubular composite nanofiltration membrane and its preparation side
Method.
Technical field
The present invention relates to a kind of polymeric membrane for separation, specifically refer to a kind of tubular composite nanofiltration membrane.
Background technology
Polymeric membrane for separation can be divided into micro-filtration membrane, ultrafilter membrane, NF membrane and reverse osmosis membrane according to its pore size.According to
Macromolecular material source is different, can be divided into the polymeric membrane for separation prepared by natural macromolecular material and by synthetic polymer system
Standby polymeric membrane for separation.Natural macromolecular material is mainly cellulose acetate and its derivant, and synthetic polymer then kind
Relatively many, main inclusion polysulfones synthetic polymer, polyamide-based synthetic polymer, polyesters synthetic polymer, polyolefin
Class synthetic polymer etc..Polymeric membrane for separation is different according to structure, and dissymmetrical structure seperation film, symmetrical structure can be divided into divide again
From film and separation membrane with composite structure；Flat board high-molecular porous film, hollow fiber polymer perforated membrane and pipe can be divided into according to profile
Shape high-molecular porous film.Different high-molecular porous films, according to differences such as its aperture, materials, has different purposes.
NF membrane is a kind of seperation film between reverse osmosis membrane and ultrafilter membrane for the aperture, because it has nano level film
On aperture, film how electrically charged it is allowed to low molecule salt by and retain Organic substance and the multivalent ion of higher molecular weight, there is uniqueness
Separating property, higher separation accuracy.Compared with other seperation films, NF membrane has that membrane flux is bigger, process infiltration is forced down,
Select to separate that ion, operating pressure be low, the low feature of power demand of system.At present, Nanofiltration-membrane technique is widely used in
Water softens and brackish water desalination, drink water purifying, feed separation purification and concentration, wastewater treatment and Treated sewage reusing, clean manufacturing
In field, achieve good economic and social benefit.
Composite nanometer filtering film is that one layer of ultrathin functional layer is deposited to the compound of the suitable porous support membrane surface in aperture
Film, depositional mode mainly has surface-coated, interfacial polycondensation, in-situ polymerization, interface-cross-linked etc..Composite membrane has many than asymmetric membrane
Advantage, but also it is all fine to have mechanical stability, heat stability and hydrolytic stability.However, current composite nanometer filtering film it is right
The rejection of small organic molecule is relatively low, and the requirement to feeding liquid is higher, in the application of traditional separating technology, needs multistage difference
The combination of membrance separation precision, just enables finer separation screening, such as dividing to part monovalent ion and divalent ion etc.
Need repeatedly to carry out from screening, high cost, and some special materials depth separate, purify, molten contracting application in not manage
Think.
Content of the invention
It is an object of the invention to provide a kind of tubular composite nanofiltration membrane, compare conventional art, the process to feeding liquid will
Ask low, separation screening without multistage-combination, have separating property excellent, cost-effective, save energy consumption the features such as.
In order to reach above-mentioned purpose, the solution of the present invention is：
A kind of tubular composite nanofiltration membrane, in tubular construction, this tubular structure includes supporting layer, basement membrane from outside to inside successively
Layer, interfacial polymerization layer and protective layer four functional layer, wherein：
Described base membrane layer is poly (ether-sulfone) ultrafiltration membrane, the liquid preparation liquid of this poly (ether-sulfone) ultrafiltration membrane mainly by weight than following
Each material enters reactor reaction and is obtained：The polyether sulfone of 16-28%, the inorganic nano level of 0.2-2% is material modified, 57-78%
Solvent, the porogen of 1-10% and the surfactant of 0.1-5%, described solvent be N-N dimethylformamide, N-N diformazan
One or more of yl acetamide, N-Methyl pyrrolidone, triethyl phosphate, sulfolane and dimethyl sulfoxide；
Described interfacial polymerization layer is polyamide composite nanofiltration membrane, and the liquid preparation liquid of polyamide composite nanofiltration membrane is hydrated by six
Piperazine aqueous solution and organic phase solution carry out interface polymerization reaction and are obtained, and the concentration of piperazine hexahydrate aqueous solution is 0.5-3%, has
It is the sodium phosphate dodecahydrate of 0.5-3% that machine phase solution includes the pyromellitic trimethylsilyl chloride for 0.1-2% for the concentration and concentration, organic faciess
The solvent of solution is n-hexane.
Described porogen is inorganic porogen, or is organic polymer porogen, or for inorganic porogen and organic
The mixture of macromolecule porogen；Described inorganic porogen is lithium nitrate, sodium chloride, calcium chloride, Calcium Carbonate, calcium nitrate, dioxy
Change one or more of carbon, aluminium sesquioxide and Kaolin；Described organic polymer porogen is Polyethylene Glycol, polyoxy second
One or more of alkene, Polyvinylpyrrolidone, polyvinyl alcohol and methylcellulose；Described surfactant is cationic
One of surfactant, anionic surfactant, amphoteric surfactant and nonionic surfactant or
Multiple；Described inorganic nano level material modified for one or more of titanium dioxide, silicon dioxide and zinc oxide；Described
Support layer is nonwoven layer or pet layer.
Using concentration, the PVA aqueous solution for 2-10% reacts and dries system with polyamide composite nanofiltration membrane described protective layer
?.
The temperature of described reactor reaction is at 60-80 DEG C.
After such scheme, a kind of tubular composite nanofiltration membrane of the present invention, using tubular structure, by four functional layer structures
Become, particularly base membrane layer (poly (ether-sulfone) ultrafiltration membrane), the combined structure design of interfacial polymerization layer (polyamide composite nanofiltration membrane), with poly-
Ether sulfone and inorganic nano material blending and modifying have tubular ultra-filtration membrane basement membrane, with piperazine hexahydrate (P I P) as aqueous phase solution, and equal
Benzene three formyl chloride n-hexane solution interface polyreaction becomes tubular type polyamide composite nanofiltration membrane, adopts frozen glue to prepare in preparation technology
Tubular type poly (ether-sulfone) ultrafiltration membrane, using pipe crimping welding and film synchronous production tubular type poly (ether-sulfone) ultrafiltration membrane Technology.
Gained tubular composite nanofiltration membrane of the present invention has and has different choice separation function to one, divalent ion, to little point
Sub- Organic substance has higher rejection, and membrane tube diameter can prepare 5-20mm different size, relatively low to the pre-processing requirements of feeding liquid,
Can be advantageous to the separation of high solubility, high granularity, high suspended matter, it is that other film kinds (as doughnut, rolling) cannot be real
Existing, to the depth separation of some specific materials, purification, molten contracting, there is very high economic worth.Because the present invention is to feeding liquid
Requirement very low, can once carry out the separation screening to part monovalent ion and divalent ion etc. again, shorten tradition separate
Technique needs the combination of multistage difference membrance separation precision, cost-saved, energy efficient.The present invention can be applied to rubbish infiltration
On liquid process, dyeing waste water recycling, dyestuff recovery, antibiotic concentration and purification, and realize very excellent separation function.
Specific embodiment
Embodiment 1
A kind of tubular composite nanofiltration membrane, in tubular construction, this tubular structure includes supporting layer, basement membrane from outside to inside successively
Layer, interfacial polymerization layer and protective layer four functional layer, wherein：
Supporting layer is nonwoven layer or pet layer；
Base membrane layer is poly (ether-sulfone) ultrafiltration membrane, and the raw material of the liquid preparation liquid of this poly (ether-sulfone) ultrafiltration membrane includes weight than following
Each material：16% polyether sulfone, 0.2% inorganic nano level is material modified, 74% N-N solvent, 9.7% porogen and
0.1% surfactant；
Interfacial polymerization layer is polyamide composite nanofiltration membrane, and the raw material of the liquid preparation liquid of polyamide composite nanofiltration membrane includes six
Piperzine Hexahydrate aqueous solution and organic phase solution, the concentration of piperazine hexahydrate aqueous solution is 0.5%, and organic phase solution includes concentration and is
0.1% pyromellitic trimethylsilyl chloride and the sodium phosphate dodecahydrate that concentration is 0.5%, the solvent of organic phase solution is n-hexane.
Described 74% solvent is intensive polar solvent, the mixture of specially following one or more solvent：N-N dimethyl methyl
Amide, N-N dimethyl acetylamide, N-Methyl pyrrolidone, triethyl phosphate, sulfolane and dimethyl sulfoxide.
The preparation method of corresponding tubular composite nanofiltration membrane, comprises the following steps：
(1) preparation constitutes the liquid preparation liquid of base membrane layer, and the raw material preparing above is entered reactor reaction, reactor
The temperature of reaction is 60 DEG C, waits to be completely dissolved prepared liquid preparation liquid；This liquid preparation liquid has extruding strings device to squeeze after filtering again
Go out, finally enter the film device in rolling machine, in order to following and pipe crimping simultaneously operating；
(2) prepare the tubular type poly (ether-sulfone) ultrafiltration membrane being made up of supporting layer and base membrane layer, the supporting layer of lamellar is passed through pipe crimping
And pipe crimping shapes, ultrasonic welding machine is recycled to be welded into the supporting layer of tubular structure, the liquid system simultaneously (1) step being obtained
Film liquid synchronously carries out basement membrane coating in the inner surface of the described supporting layer in tubular structure, enters coagulation bath tank afterwards and is frozen
Adhesive curing, that is, be obtained tubular type poly (ether-sulfone) ultrafiltration membrane；This in type tubular type poly (ether-sulfone) ultrafiltration membrane is rinsed by pure water and soaks, will
Solvent is cleaned up with porogen；
(3) the interfacial polymerization step of interfacial polymerization layer, the tubular type poly (ether-sulfone) ultrafiltration membrane being obtained in (2) step immersion is prepared
Good piperazine hexahydrate aqueous solution, makes inner surface fully infiltrate (infiltrating time is 45S), removes unnecessary water-soluble in pipe after taking-up
Liquid；Afterwards, react in the organic phase solution immersion of the described tubular type poly (ether-sulfone) ultrafiltration membrane infiltrating being prepared, reaction one timing
Between after take out dry, obtain final product tubular type polyamide composite nanofiltration membrane；
(4) making step of protective layer, will be resistant to pollution for the tubular type polyamide composite nanofiltration membrane being obtained in (3) step immersion
The protective agent PVA reactant aqueous solution of concentration 5%, reaction is taken out after 8 hours and is dried, that is, tubular composite nanofiltration membrane is obtained.
Performance test (1)：Under operating pressure 0.4Mpa, room temperature condition, to 2g/L MgSO4The flux of aqueous solution is surveyed
Examination, up to 38.2L/ (.n), rejection is 90.5%.
Performance test (2)：Take printing and dyeing waste liquid, through activated sludge reaction, using cross-current flow, make the tubular type of internal diameter 10mm
Polyamide composite nanofiltration membrane assembly, without pretreatment, through booster pump supercharging, operating pressure 0.4Mpa, entering water conductivity is
2500 μ s/m, permeability electrical conductivity is 500 μ s/m, and salt rejection rate is 80%, and flux reaches 38.2L/ (.n).Because passage is wider,
Therefore no clogging.
Embodiment 2
A kind of tubular composite nanofiltration membrane, in tubular construction, this tubular structure includes supporting layer, basement membrane from outside to inside successively
Layer, interfacial polymerization layer and protective layer four functional layer, wherein：
Supporting layer is nonwoven layer or pet layer；
Base membrane layer is poly (ether-sulfone) ultrafiltration membrane, and the raw material of the liquid preparation liquid of this poly (ether-sulfone) ultrafiltration membrane includes weight than following
Each material：25% polyether sulfone, 2% inorganic nano level is material modified, 61% solvent, 10% porogen and 2% table
Face activating agent；
Interfacial polymerization layer is polyamide composite nanofiltration membrane, and the raw material of the liquid preparation liquid of polyamide composite nanofiltration membrane includes six
Piperzine Hexahydrate aqueous solution and organic phase solution, the concentration of piperazine hexahydrate aqueous solution is 3%, and organic phase solution includes concentration and is
2% pyromellitic trimethylsilyl chloride and the sodium phosphate dodecahydrate that concentration is 3%, the solvent of organic phase solution is n-hexane.
Described solvent is intensive polar solvent, the mixture of specially following one or more solvent：N-N dimethyl formyl
Amine, N-N dimethyl acetylamide, N-Methyl pyrrolidone, triethyl phosphate, sulfolane and dimethyl sulfoxide.
The preparation method of corresponding tubular composite nanofiltration membrane, comprises the following steps：
(1) preparation constitutes the liquid preparation liquid of base membrane layer, and the raw material preparing above is entered reactor reaction, reactor
The temperature of reaction is 80 DEG C, waits to be completely dissolved prepared liquid preparation liquid；This liquid preparation liquid has extruding strings device to squeeze after filtering again
Go out, finally enter the film device in rolling machine, in order to following and pipe crimping simultaneously operating；
(2) prepare the tubular type poly (ether-sulfone) ultrafiltration membrane being made up of supporting layer and base membrane layer, the supporting layer of lamellar is passed through pipe crimping
And pipe crimping shapes, ultrasonic welding machine is recycled to be welded into the supporting layer of tubular structure, the liquid system simultaneously (1) step being obtained
Film liquid synchronously carries out basement membrane coating in the inner surface of the described supporting layer in tubular structure, enters coagulation bath tank afterwards and is frozen
Adhesive curing, that is, be obtained tubular type poly (ether-sulfone) ultrafiltration membrane；This in type tubular type poly (ether-sulfone) ultrafiltration membrane is rinsed by pure water and soaks, will
Solvent is cleaned up with porogen；
(3) the interfacial polymerization step of interfacial polymerization layer, the tubular type poly (ether-sulfone) ultrafiltration membrane being obtained in (2) step immersion is prepared
Good piperazine hexahydrate aqueous solution, makes inner surface fully infiltrate (infiltrating time is 45S), removes unnecessary water-soluble in pipe after taking-up
Liquid；Afterwards, react in the organic phase solution immersion of the described tubular type poly (ether-sulfone) ultrafiltration membrane infiltrating being prepared, reaction one timing
Between after take out dry, obtain final product tubular type polyamide composite nanofiltration membrane；
(4) making step of protective layer, will be resistant to pollution for the tubular type polyamide composite nanofiltration membrane being obtained in (3) step immersion
The protective agent PVA reactant aqueous solution of concentration 10%, reaction is taken out after 10 hours and is dried, that is, tubular composite nanofiltration membrane is obtained.
Performance test (1)：Operating pressure 0.4Mpa, under room temperature condition, to 2g/L MgSO4The flux of aqueous solution is surveyed
Examination, up to 35L (.n), rejection is 95%.
Performance test (2)：Take printing and dyeing waste liquid, through activated sludge reaction, using cross-current flow, make the tubular type of internal diameter 12mm
Polyamide composite nanofiltration membrane assembly, without pretreatment, through booster pump supercharging, operating pressure 0.4Mpa, entering water conductivity is
2500 μ s/m, permeability electrical conductivity is 375 μ s/m, and salt rejection rate is 85%, and flux reaches 35.2L/ (.n).Because passage is wider,
Therefore no clogging.
Embodiment 3
A kind of tubular composite nanofiltration membrane, in tubular construction, this tubular structure includes supporting layer, basement membrane from outside to inside successively
Layer, interfacial polymerization layer and protective layer four functional layer, wherein：
Supporting layer is nonwoven layer or pet layer；
Base membrane layer is poly (ether-sulfone) ultrafiltration membrane, and the raw material of the liquid preparation liquid of this poly (ether-sulfone) ultrafiltration membrane includes weight than following
Each material：20% polyether sulfone, 1% inorganic nano level is material modified, 71% solvent, 5% porogen and 3% surface
Activating agent；
Interfacial polymerization layer is polyamide composite nanofiltration membrane, and the raw material of the liquid preparation liquid of polyamide composite nanofiltration membrane includes six
Piperzine Hexahydrate aqueous solution and organic phase solution, the concentration of piperazine hexahydrate aqueous solution is 1.7%, and organic phase solution includes concentration and is
1.1% pyromellitic trimethylsilyl chloride and the sodium phosphate dodecahydrate that concentration is 1.7%, the solvent of organic phase solution is n-hexane.
Described solvent is intensive polar solvent, the mixture of specially following one or more solvent：N-N dimethyl formyl
Amine, N-N dimethyl acetylamide, N-Methyl pyrrolidone, triethyl phosphate, sulfolane and dimethyl sulfoxide.
The preparation method of corresponding tubular composite nanofiltration membrane, comprises the following steps：
(1) preparation constitutes the liquid preparation liquid of base membrane layer, and the raw material preparing above is entered reactor reaction, reactor
The temperature of reaction is 70 DEG C, waits to be completely dissolved prepared liquid preparation liquid；This liquid preparation liquid has extruding strings device to squeeze after filtering again
Go out, finally enter the film device in rolling machine, in order to following and pipe crimping simultaneously operating；
(2) prepare the tubular type poly (ether-sulfone) ultrafiltration membrane being made up of supporting layer and base membrane layer, the supporting layer of lamellar is passed through pipe crimping
And pipe crimping shapes, ultrasonic welding machine is recycled to be welded into the supporting layer of tubular structure, the liquid system simultaneously (1) step being obtained
Film liquid synchronously carries out basement membrane coating in the inner surface of the described supporting layer in tubular structure, enters coagulation bath tank afterwards and is frozen
Adhesive curing, that is, be obtained tubular type poly (ether-sulfone) ultrafiltration membrane；This in type tubular type poly (ether-sulfone) ultrafiltration membrane is rinsed by pure water and soaks, will
Solvent is cleaned up with porogen；
(3) the interfacial polymerization step of interfacial polymerization layer, the tubular type poly (ether-sulfone) ultrafiltration membrane being obtained in (2) step immersion is prepared
Good piperazine hexahydrate aqueous solution, makes inner surface fully infiltrate (infiltrating time is 45S), removes unnecessary water-soluble in pipe after taking-up
Liquid；Afterwards, react in the organic phase solution immersion of the described tubular type poly (ether-sulfone) ultrafiltration membrane infiltrating being prepared, reaction one timing
Between after take out dry, obtain final product tubular type polyamide composite nanofiltration membrane；
(4) making step of protective layer, will be resistant to pollution for the tubular type polyamide composite nanofiltration membrane being obtained in (3) step immersion
The protective agent PVA reactant aqueous solution of concentration 5%, reaction is taken out after 10 hours and is dried, that is, tubular composite nanofiltration membrane is obtained.
Performance test (1)：Operating pressure 0.4Mpa, under room temperature condition, to 2g/L MgSO4The flux of aqueous solution is surveyed
Examination, is 98.5% up to 30L/ (.n) rejection.
Performance test (2)：Take printing and dyeing waste liquid, through activated sludge reaction, using cross-current flow, make the tubular type of internal diameter 8mm
Polyamide composite nanofiltration membrane assembly, without pretreatment, through booster pump supercharging, operating pressure 0.4Mpa, entering water conductivity is
2500 μ s/m, permeability electrical conductivity is 250 μ s/m, and salt rejection rate is 90%, and flux reaches 30.2L/ (.n).Because passage is wider,
Therefore no clogging.
In various embodiments above, it is to be filtered using 100 mesh stainless (steel) wire filters that described liquid preparation liquid filters, and filters mesh
Be to remove the granule not being completely dissolved and impurity, filter is connected at reactor feed opening.
In various embodiments above, described porogen can be inorganic porogen, or is organic polymer porogen, or
For the mixture of inorganic porogen and organic polymer porogen, wherein inorganic porogen can be lithium nitrate, sodium chloride, chlorination
One or more of calcium, Calcium Carbonate, calcium nitrate, carbon dioxide, aluminium sesquioxide and Kaolin, organic polymer porogen can
Think one or more of Polyethylene Glycol, polyoxyethylene, Polyvinylpyrrolidone, polyvinyl alcohol and methylcellulose.Described
Surfactant can for cationic surface active agent, anionic surfactant, amphoteric surfactant and non-from
One or more of subtype surfactant, wherein anionic surfactant can be sodium lauryl sulphate or ten
Dialkyl benzene sulfonic acids sodium or this mixture of the two.Described inorganic nano level is material modified can be titanium dioxide, titanium dioxide
One or more of silicon and zinc oxide.The material modified preferable employing inorganic nano level of described inorganic nano level is hydrophilically modified
Material.
Claims (3)
1. a kind of tubular composite nanofiltration membrane it is characterised in that：In tubular construction, this tubular structure includes supporting from outside to inside successively
Layer, base membrane layer, interfacial polymerization layer and protective layer four functional layer, wherein：
Described supporting layer is nonwoven layer or pet layer；Described base membrane layer is poly (ether-sulfone) ultrafiltration membrane, described poly (ether-sulfone) ultrafiltration membrane
The raw material of liquid preparation liquid includes weight than following each material：16% polyether sulfone, 0.2% inorganic nano level modification material
Material, 74% solvent, 9.7% porogen and 0.1% surfactant；Described interfacial polymerization layer is polyamides amine composite nanofiltration
Film, the raw material of the liquid preparation liquid of described polyamide composite nanofiltration membrane includes piperazine hexahydrate aqueous solution and organic phase solution, institute
The concentration stating piperazine hexahydrate aqueous solution is 0.5%, described organic phase solution include pyromellitic trimethylsilyl chloride that concentration is 0.1% and
Concentration is 0.5% sodium phosphate dodecahydrate, and the solvent of described organic phase solution is normal hexane；Described solvent is N-N dimethyl
One of Methanamide, N-N dimethyl acetylamide, N-Methyl pyrrolidone, triethyl phosphate, sulfolane and dimethyl sulfoxide or
Multiple；
Described porogen is inorganic porogen, or is organic polymer porogen, or is inorganic porogen and organic high score
The mixture of sub- porogen；Described inorganic porogen be lithium nitrate, sodium chloride, calcium chloride, Calcium Carbonate, calcium nitrate, three oxidation two
One or more of aluminum and Kaolin；Described organic polymer porogen is polyoxyethylene, Polyvinylpyrrolidone, polyethylene
One or more of alcohol and methylcellulose；Described surfactant is cationic surface active agent, anionic surface
One or more of activating agent, amphoteric surfactant and nonionic surfactant, live in described anionic surface
Property agent be one of sodium lauryl sulphate and dodecylbenzene sodium sulfonate or two kinds；Described inorganic nano level is material modified to be
One or more of titanium dioxide, silicon dioxide and zinc oxide；The PVA that described protective layer adopts concentration to be 2-10% is water-soluble
Liquid is reacted with polyamide composite nanofiltration membrane and dries prepared.
2. a kind of tubular composite nanofiltration membrane it is characterised in that：In tubular construction, this tubular structure includes supporting from outside to inside successively
Layer, base membrane layer, interfacial polymerization layer and protective layer four functional layer, wherein：
Described supporting layer is nonwoven layer or pet layer；Described base membrane layer is poly (ether-sulfone) ultrafiltration membrane, described poly (ether-sulfone) ultrafiltration membrane
The raw material of liquid preparation liquid includes weight than following each material：25% polyether sulfone, 2% inorganic nano level is material modified,
61% solvent, 10% porogen and 2% surfactant；Described interfacial polymerization layer is polyamide composite nanofiltration membrane, institute
The raw material stating the liquid preparation liquid of polyamide composite nanofiltration membrane includes piperazine hexahydrate aqueous solution and organic phase solution, described six water
The concentration closing piperazine aqueous solution is 3%, and it is 3% that described organic phase solution includes pyromellitic trimethylsilyl chloride that concentration is 2% and concentration
Sodium phosphate dodecahydrate, the solvent of described organic phase solution is normal hexane；Described solvent is N-N dimethylformamide, N-N bis-
One or more of methylacetamide, N-Methyl pyrrolidone, triethyl phosphate, sulfolane and dimethyl sulfoxide；
Described porogen is inorganic porogen, or is organic polymer porogen, or is inorganic porogen and organic high score
The mixture of sub- porogen；Described inorganic porogen be lithium nitrate, sodium chloride, calcium chloride, Calcium Carbonate, calcium nitrate, three oxidation two
One or more of aluminum and Kaolin；Described organic polymer porogen is polyoxyethylene, Polyvinylpyrrolidone, polyethylene
One or more of alcohol and methylcellulose；Described surfactant is cationic surface active agent, anionic surface
One or more of activating agent, amphoteric surfactant and nonionic surfactant, live in described anionic surface
Property agent be one of sodium lauryl sulphate and dodecylbenzene sodium sulfonate or two kinds；Described inorganic nano level is material modified to be
One or more of titanium dioxide, silicon dioxide and zinc oxide；The PVA that described protective layer adopts concentration to be 2-10% is water-soluble
Liquid is reacted with polyamide composite nanofiltration membrane and dries prepared.
3. a kind of tubular composite nanofiltration membrane it is characterised in that：In tubular construction, this tubular structure includes supporting from outside to inside successively
Layer, base membrane layer, interfacial polymerization layer and protective layer four functional layer, wherein：
Described supporting layer is nonwoven layer or pet layer；Described base membrane layer is poly (ether-sulfone) ultrafiltration membrane, described poly (ether-sulfone) ultrafiltration membrane
The raw material of liquid preparation liquid includes weight than following each material：20% polyether sulfone, 1% inorganic nano level is material modified,
71% solvent, 5% porogen and 3% surfactant；Described interfacial polymerization layer is polyamide composite nanofiltration membrane, described
The raw material of the liquid preparation liquid of polyamide composite nanofiltration membrane includes piperazine hexahydrate aqueous solution and organic phase solution, described six hydrations
The concentration of piperazine aqueous solution is 1.7%, and described organic phase solution includes pyromellitic trimethylsilyl chloride that concentration is 1.1% and concentration is
1.7% sodium phosphate dodecahydrate, the solvent of described organic phase solution is normal hexane；Described solvent be N-N dimethylformamide,
One or more of N-N dimethyl acetylamide, N-Methyl pyrrolidone, triethyl phosphate, sulfolane and dimethyl sulfoxide；
Described porogen is inorganic porogen, or is organic polymer porogen, or is inorganic porogen and organic high score
The mixture of sub- porogen；Described inorganic porogen be lithium nitrate, sodium chloride, calcium chloride, Calcium Carbonate, calcium nitrate, three oxidation two
One or more of aluminum and Kaolin；Described organic polymer porogen is polyoxyethylene, Polyvinylpyrrolidone, polyethylene
One or more of alcohol and methylcellulose；Described surfactant is cationic surface active agent, anionic surface
One or more of activating agent, amphoteric surfactant and nonionic surfactant；Live in described anionic surface
Property agent be one of sodium lauryl sulphate and dodecylbenzene sodium sulfonate or two kinds；Described inorganic nano level is material modified to be
One or more of titanium dioxide, silicon dioxide and zinc oxide；The PVA that described protective layer adopts concentration to be 2-10% is water-soluble
Liquid is reacted with polyamide composite nanofiltration membrane and dries prepared.
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| JP2019501019A (en) * | 2015-12-23 | 2019-01-17 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Porous membrane containing silicate |
| CN106178969A (en) * | 2016-07-28 | 2016-12-07 | 湖南沁森环保高科技有限公司 | The preparation method of a kind of high-performance complex reverse osmosis membrane and prepared reverse osmosis membrane thereof |
| CN107875859A (en) * | 2017-12-02 | 2018-04-06 | 天津海普尔膜科技有限公司 | A kind of tubular composite nanofiltration membrane production system and the composite nanometer filtering film using its production |
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| CN108854581B (en) * | 2018-03-28 | 2021-03-30 | 湖北瑞滤膜科技有限公司 | Preparation method of high-strength composite tubular membrane |
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