CN105749758A - Coating and coagulating device and method for preparing liner-enhanced type hollow fiber composite membranes - Google Patents
Coating and coagulating device and method for preparing liner-enhanced type hollow fiber composite membranes Download PDFInfo
- Publication number
- CN105749758A CN105749758A CN201610181809.8A CN201610181809A CN105749758A CN 105749758 A CN105749758 A CN 105749758A CN 201610181809 A CN201610181809 A CN 201610181809A CN 105749758 A CN105749758 A CN 105749758A
- Authority
- CN
- China
- Prior art keywords
- coating
- coagulating
- tank
- film
- 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.)
- Granted
Links
- 230000001112 coagulating effect Effects 0.000 title claims abstract description 102
- 238000000576 coating method Methods 0.000 title claims abstract description 93
- 239000011248 coating agent Substances 0.000 title claims abstract description 89
- 239000012528 membrane Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000012510 hollow fiber Substances 0.000 title abstract description 13
- 239000002131 composite material Substances 0.000 title abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 238000005345 coagulation Methods 0.000 claims description 36
- 230000015271 coagulation Effects 0.000 claims description 36
- 238000005266 casting Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- 230000008676 import Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 4
- 206010053567 Coagulopathies Diseases 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 3
- 230000035602 clotting Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000003116 impacting effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 239000008236 heating water Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 238000003287 bathing Methods 0.000 abstract 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 20
- 239000006210 lotion Substances 0.000 description 19
- 239000010410 layer Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000010586 diagram Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229920002239 polyacrylonitrile Polymers 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 101000916532 Rattus norvegicus Zinc finger and BTB domain-containing protein 38 Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- BVPNBGBCYOYQKQ-UHFFFAOYSA-N azane;n,n-dimethylacetamide Chemical compound N.CN(C)C(C)=O BVPNBGBCYOYQKQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/26—Spraying processes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention aims at providing a coating and coagulating device and method for preparing liner-enhanced type hollow fiber composite membranes with an improved horizontal coating method. The device comprises a coating unit, a membrane forming path region, a coagulating water-bathing tank and a circulating water-bathing unit, wherein the coating unit is fixed on a machine case bottom plate with an adjustable inclined angle by a coating machine head; a main body of the coagulating device is a multi-stage cuboid water tank arranged in a line, and the height of one side of the water tank is adjustable within a certain range, so that the coating machine head keeps concentric with a braided tube; the membrane forming path region is used for controlling the environmental temperature and humidity on an air section, the air section is arranged in parallel to a coagulating tank, and accordingly, vaporized steam from the coagulating tank is prevented from being contacted with membrane fibers; grooves are formed in membrane fiber inlet and outlet sides of the coagulating water-bathing tank, and groove openings are an inlet channel and an outlet channel of the membrane fibers; meanwhile, a coagulator is conveyed back to the coagulating water-bathing tank by a pump after overflowing to a heating water tank from the groove openings. Compared with a traditional vertical liner membrane coating device, the coating and coagulating device has the advantages that the operation is easy, the process conditions are controlled easily and the productivity is high.
Description
Technical field
The present invention relates to organic hollow fiber microporous barrier preparation field, the hollow membrane tube especially strengthened by woven tube liner
And process units.Described coating and coagulation system are applied to improved level cladding process composite membrane preparation system.
Background technology
Constantly promoting along with industrialization degree and the going from bad to worse of all kinds of water resource quality, chemical stability is good, mechanical by force
Degree height, contamination resistance become by force the requirement the most universal to separation membrane performance.Simultaneously because the degree of depth of a large amount of water bodys
Polluting and the water quality type lack of water that causes, (effluent quality is poor, floor space is big, locate due to self shortcoming for traditional biological facture
Reason cycle length, impact load are low) can not meet the demand of socio-economic development, make membrane bioreactor (MBR) process become
For there being most the wastewater processing technology of market prospects, meanwhile, be applied to lining-reinforced hollow fiber composite membrane during MBR with
Quick development has been obtained by means of its superior performance.
Lining-reinforced hollow fiber composite membrane is mainly supported by the surface separation layer coated and woven tube or other types
Material is formed, and undertakes separation and two functions of high intensity respectively.The selectable membrane material of surface separation layer includes polyacrylonitrile
(PAN), polyether sulfone (PES) or Kynoar (PVDF) etc., United States Patent (USP) 4061821 discloses one and prepares liner woven tube
Polyacrylonitrile hollow fiber membrane, Chinese patent CN102389721A discloses polyacrylonitrile film and the system thereof of a kind of band backing material
Preparation Method.Prepare PAN hollow-fibre membrane by dry-wet technique, and make monofilament enter spinning head, blending preparation band from other entrances
The polyacrylonitrile hollow fiber composite membrane of backing material, the PURON MBR membrane component of KOCH company of the U.S. divides with PES for surface
Layer material (JuddS. 2006, The MBR BOOK), United States Patent (USP) 5472607 discloses a kind of PVDF solution coating tubulose
Braid to form the method for hollow-fibre membrane strengthened by braid, Chinese patent CN104117289A, CN1695777A,
CN101357303A, CN102784566B etc. disclose the lining-reinforced composite film material with PVDF as separation layer materials.
Initial fiber reinforcement type hollow membrane preparation technology comes from Hayano et al. (US Patent No.4061821) and carries
A kind of fiber braided tube paint-on technique gone out, this technology is the appearance that casting solution is simply coated to fiber braided tube
Face, is difficult to control casting solution infiltration capacity in woven tube, easily blocking hollow-fibre membrane inner chamber, and the most easily takes off
Fall.On this basis, Zenon company of Canada (US Patent No.5472607, US2003/0098275A1, WO 00/
78437A1) disclose one and prepare polymer composite hollow fiber membrane, by reducing the danier number of fibre bundle, increasing fiber
The count of bundle and the weaving manner of improvement fibre bundle, when making casting solution and fiber braided tube coextrusion be coated, no
As for penetrating into inside woven tube, due to this technology of preparing simply by the polymer-coated outer surface at fiber braided tube, polymerization
Thing separating layer is more weak with fiber braided tube adhesion, and the problem that separation film is prone to come off does not solves.
Supporting layer is that introducing braided fiber pipe or fibre bundle, as supporter, utilize braided fiber inside hollow-fibre membrane
Pipe or fibre bundle increase the mechanical strength of membrane material.Wherein braided fiber pipe or fibre bundle itself to have good chemistry with
Heat endurance, and superior mechanical performance, it is possible to soaked by casting solution, but can not be dissolved by solvent in casting solution, beautiful
State's patent US5472607 discloses the fibrous material used by woven tube and is polyester fiber (terylene), Fypro (nylon), gathers
Olefin(e) fibre (polypropylene fibre, polyethylene etc.), polyurethane fiber (spandex), polysulfone fibre, cellulose acetate fibre.
The membrane formation mechanism of surface separation layer, as dry-wet method submergence inversion of phases filming technology, is a dynamics double diffusion
Process, is constituted casting solution system by three kinds of main components of polymer-solvent-non-solvent.Film forming procedure is divided into two stages: liner
Material-and as woven tube becomes primary membrane layer through coating machine capitiform, experience the steam inversion of phases (of diffusion limited the most in atmosphere
One stage), spread inversion of phases (second stage) completely subsequently into coagulating bath experience.
In air section, initial being separated in moisture induction film silk surface of surrounding enviroment, solvent spreads in environment simultaneously,
The temperature of air section, humidity produce certain impact to film silk surface.F. Tasselli et al. (Journal of membrane
Science 255 (2005) 13-22) consider the relative humidity impact on film configuration of surface in air-gap, the air of its spinning
Gap temperature is 18～20 DEG C, and when relative humidity is less than 100%, in air, relative humidity is to polyether-ether-ketone hollow-fibre membrane surface
Impact is the most inconspicuous, and this is owing to nascent hollow fiber film thread residence time in air-gap only has several seconds, does not absorb
Sufficiently steam induction is separated.When relative humidity is more than 100% in air, supersaturated air exists a large amount of water droplet, when
During its contact primary membrane silk surface, defining the core that polymer is separated, therefore film surface forms macropore.When air section temperature
Higher, when relative humidity is relatively low, the solvent volatilization in air-gap of primary membrane silk is very fast, and moisture in air is less can not be abundant
Induction is separated, and this makes polymer-solvent richness phase region constantly grow up, and after immersing coagulating bath, is easily formed aperture and improves
Surface percent opening, has the surface of high opening rate simultaneously and is more beneficial for non-solvent in coagulating bath and spreads inside primary membrane silk, make
Film silk after shaping becomes asymmetrical cell shape structure.Owing to, under this kind of atmospheric condition, the film silk pore-size distribution of formation is narrower,
Average pore size is little, and macropore accounting is few, and rejection is high, in sewage disposal, fouling membrane situation be improved significantly, improve film
Resistance tocrocking.
After immersing coagulating bath, film internal solvent will spread in coagulating bath, and the non-solvent in coagulating bath then will be to film
Interior diffusion, submergence gel film forming, and cause casting solution system development of heat liquid-liquid split-phase, according to system generation liquid-liquid split-phase
Speed, be usually present the liquid-liquid split-phase behavior of two kinds of forms, it may be assumed that instantaneous liquid-liquid split-phase: preparation liquid immerses after coagulating bath fast
Speed split-phase film forming；Time delay liquid-liquid split-phase: inborn ability phase film forming after certain time in preparation liquid immersion coagulating bath.Instantaneous demixing is prone to
Form dense skin, thus hinder non-solvent and spread in film main body, cause sub-infracortical delayed demixing and macropore continuous
The result grown up, on the one hand this structure affects the mechanical performance of membrane material, on the other hand can be owing to shrinking in dry run
Stress and cause defect.Therefore composition and the temperature of coagulating bath are the biggest on the impact of membrane structure.
Coagulating bath is generally made up of with water solvent, owing to the polarity of water is bigger, it usually needs add some polarity more weak
Non-solvent, or add the solvent consistent with casting solution composition or additive, purpose, in order to reduce the motive force of diffusion, makes
The form of being separated changes to time delay split-phase from instantaneous demixing, and subgrade finger gradually changes to spongy pore structure, membrane structure
Tend to overall asymmetric.Coagulation bath temperature is complex on the impact of film forming procedure, and for thermodynamics, temperature raises,
Equal phase region in polymer-solvent-non-solvent ternary phase diagrams expands, it is meant that casting solution can tolerate more non-solvent, and
Do not produce split-phase.Meanwhile, temperature raises, and significantly decreases the viscosity of casting solution, and the most synergistic effect is, diffusion speed
Degree gets a promotion relative to split-phase speed, and this is conducive to the raising of porosity.
Thus, the humidity (Ha) of air section, temperature (Ta) and the time of staying (ta), the temperature (Tc) of coagulating bath, composition with
And the time of staying (tc) is the hugest with performance impact to the structure of film, the wherein time of staying and coating apparatus structure and coating speed
(S) relevant.For the time of staying of air-gap, when S is certain, and the distance between coating head and coagulating bath is the longest, and ta is the longest, film
The average pore size of surface separation layer is the least, and pore-size distribution is the narrowest, is conducive to improving the antifouling property of film.But in actual production
Cheng Zhong, air-gap length is substantially limited by coating equipment.At present, it has been disclosed that coating equipment have two classes, one be and from
Supporting the rectilinear immersion coagulating bath application system that hollow fiber spinning is similar, this mode is the most universal, such as Chinese patent
CN1021609767A, CN102205208A, CN101357303A etc., because the film layer being coated on inner lining material solidifies completely
Before can not stress, it addition, the coagulating bath degree of depth can not too strengthen, thus coating speed is limited.Secondly, coagulating bath is volatilized
Steam also can touch with the film wire connection of air section and produce macropore.Another kind is that the level similar with cable coating method immerses coagulating bath
Application system, this mode is more rare, such as patent CN104117289A, CN104096485A, because air section is put down with coagulating bath
Row arrangement, it is to avoid affected by from the steam in coagulating tank；It extends the length of coagulating basin in principle, it is possible to improves and is coated with
Cover speed, but oversize meeting causes the film silk at air section to be bowed downward to arc-shaped, the lead of film silk and painting because of gravity
Cover head goes out interruption-forming angle, causes casting solution coating uneven.
Summary of the invention
The problem existed in view of prior art, the invention reside in offer a kind of for improved level cladding process production liner
The coating of enhancement type hollow fiber compound film and coagulation system.The coating unit of the present invention is fixed on adjustable inclination by coating head
On the chassis backplane at angle, the main body of coagulation system is the multistage cuboid tank of word order, and the height of tank side can be one
Regulation in fixed scope.Therefore, different from the level traveling mode of specification, coating is inclined in certain from front to back with coagulation system
Angle, coating head can keep concentric with woven tube, and air section is arranged in parallel with coagulating basin simultaneously, it is to avoid the steam of coagulating basin evaporation
Touch with film wire connection.Air section is controlled the epidemic disaster of environment by film forming path, the coagulator in coagulating tank by heating water tank and
Circulating pump controls temperature, and coagulating tank is slotted into and out of both sides at film silk, is the access way of film silk, solidifies simultaneously at notch
Agent overflows to heating water tank from notch, is then returned coagulating tank by transport pump.
In order to realize the technical purpose of the present invention, technical scheme is as follows:
The coating of lining-reinforced hollow-fibre membrane and coagulation system, include:
Coating unit, is used for coating casting solution and and extrudes in woven tube；
Airspace device, is arranged at the extrusion direction of coating unit, for carrying out the film silk obtained in coating unit at sky
Steam inversion of phases in gas；
Coagulating tank, is arranged at the direction of the wire vent of airspace device, is used for making film silk carry out the film forming that is separated；
The most downward-sloping set angle in extrusion direction of the coating head in coating unit.
According to an embodiment, described set angle scope is 0.1～10 °.
According to an embodiment, the level angle of described coagulating tank is adjustable.
According to an embodiment, the residing height of the film silk import of described coagulating tank is higher than the height with outlet.
According to an embodiment, the residing height of the film silk import of described coagulating tank is less than the extrusion with coating head
The height of mouth.
According to an embodiment, between film silk import and the outlet of described coagulating tank line also with the squeezing of coating head
Outgoing direction tilts towards same direction.
According to an embodiment, the film forming path district of airspace device is provided with nitrogen moisture import and gas vent,
For regulating humidity and temperature.
According to an embodiment, described nitrogen moisture import department is provided with gas distribution grid.
According to an embodiment, airspace device is additionally provided with temperature-controlled member, for controlling airspace device
The temperature in film forming path district.
According to an embodiment, described temperature-controlled member is the chuck outside the district of film forming path.
According to an embodiment, it is respectively arranged with overflow plate in the both sides within coagulating tank, inside coagulating tank also
It is provided with guiding device, for preventing the direct impact of the film silk coagulation bath by flowing out from overflow plate.
According to an embodiment, the inner passage of coagulating tank is additionally attached on circulating pump.
According to another aspect of the present invention, the coating of lining-reinforced hollow-fibre membrane and clotting method, including as follows
Step:
In woven tube, coat casting solution by coating unit and extrude, then the film silk of extrusion is sequentially passed through in airspace
Steam inversion of phases and coagulating bath in carry out be separated formed film；Extrusion direction in coating unit is the most downward-sloping
Set angle.
According to an embodiment, the film silk of extrusion vertical height in airspace and coagulating bath reduces successively.
According to an embodiment, in the air gap, the temperature and humidity of air is adjusted.
According to an embodiment, prevent the coagulation bath flowed out from overflow plate from directly rushing by guiding device in coagulating bath
Hit to film silk.
Beneficial effect
Devise the coating machine head member that can regulate angle, when solving level coating, owing to woven tube is oversize, cause woven tube
Bending forms an angle causes coating problem of non-uniform with coating head, secondly, devise reasonably can control path length with
The film forming path of air section atmosphere, is combined prediffusion inversion of phases in air section with sovent diffusion inversion of phases process, makes overlay
Being initially formed the top layer of high aperture, the steam that final level coating method avoids coagulating tank to evaporate touches with film wire connection, simultaneously
Compared with vertical mode, horizontal mode coating processes is simple, and condition is easily controllable, improves production efficiency.
Accompanying drawing explanation
Fig. 1 is coagulating bath system general illustration；
Fig. 2 is coating unit schematic diagram；
Fig. 3 is film forming path district schematic diagram；
Fig. 4 is coagulating tank and circulator bath device schematic diagram；
Fig. 5-1 is coating unit and coagulating tank is level schematic diagram；
Fig. 5-2 is film silk schematic diagram when bending between coating unit and coagulating tank；
Fig. 5-3 is coating unit and the inclined schematic diagram of coagulating tank；
Schematic diagram when Fig. 5-4 is that film silk bends between coating unit and coagulating tank when film forming path district is shorter；
Fig. 5-5 is coating unit and the inclined schematic diagram of coagulating tank when film forming path district is shorter；
Fig. 6 is the guiding device profile of water conservancy diversion body lotion；
Fig. 7 is the guiding device stereogram of water conservancy diversion body lotion；
Fig. 8 be bottom surface be the coagulating tank front view of rectangle；
Fig. 9 is the film surface SEM figure prepared under 40% coagulating bath concentration conditions；
Figure 10 is the pvdf membrane graph of pore diameter distribution prepared in embodiment 1 and reference examples 1；
Wherein, 1, coating unit；2, airspace device；3, coagulating tank；4, circulator bath device；101, coating head；
102, angle turns screw；103, secure component；201, temperature and humidity control system；202, gas distribution grid；203, nitrogen moisture
Conveying fan；301, guiding device；302, runner；303, heating water tank；304, circulating pump；305, base adjusting nut；306、
Spiral lifting rod；307, support frame；309, hatchcover；501, body lotion outlet collecting region；502, film forming district；503, body lotion import
District；504, liquid level adjustable plate；505, overflow plate；506, body lotion race way.
Detailed description of the invention
Embodiment 1
As it is shown in figure 1, the embodiment of the present invention provides one to produce lining-reinforced doughnut for improved level cladding process
The coating of composite membrane and coagulation system, including coating unit 1, airspace device 2, coagulating tank 3 and circulator bath device 4.
As in figure 2 it is shown, described coating unit 1 part is mainly turned spiral shell by the angle of coating head 101, coating head 101
Silk 102, secure component 103 form, and coating head 101 purpose is for coating casting solution in woven tube, when woven tube is at sky
In the film forming path district of gas escapement 2 oversize, when not arriving support bar, now woven tube supporter has been arc, with painting
Cover head and become the angle (as shown in Fig. 5-2 and Fig. 5-4) of 1～2 °, cause casting solution coating uneven, turn for this design angle
Screw 102, makes coating head 101 the most at a certain angle, its exit and woven tube supporter on one face, to solve
Woven tube bending causes coating non-uniform phenomenon, described secure component purpose to be fixing coating heads so that it is with coating head
Angle is turned screw and is become a global facility.Coating machine head unit can regulate to reach on fixing base plate up and down
Best placement.Now fixing membrane tube time of staying in air-gap is 15 s.
As it is shown on figure 3, the film forming path district of airspace device 2 be in order to control to coat head 101 and coagulating tank 3 it
Between humiture, to regulate structure and the distribution of film surface holes, film forming path district is made up of stainless steel double-jacket, sidewall and the end
Face thickness 2mm, through recirculated water in chuck, the temperature of recirculated water is at 30～80 DEG C, to control the volatilization of film silk surface solvent, air
The film forming path district of escapement 2 is connected with nitrogen moisture conveying fan 203 and temperature and humidity control system 201 respectively, warm and humid control
System 201 processed is for controlling the temperature and humidity in film forming path district, and it is 40 DEG C that temperature controls, and humidity is 60%.Described nitrogen is wet
Gas conveying fan 203 is connected with gas distribution grid 202, and gas distribution grid 202 is used for being uniformly distributed nitrogen moisture conveying fan institute
The dry and wet gas that conveying comes is to reduce the air-flow disturbance to primary membrane silk.A length of 0.5 meter of film forming path, nascent membrane tube is in path
Residence time is mainly controlled by wrapping wire speed, and main wrapping wire speed controlled as 2m/min, nascent membrane tube time of staying in path
For 15s.Temperature, moisture and solvent in film forming path obtain strict control, in such a in check atmosphere
In, solvent content volatilization, the moisture that PVDF concentration somewhat raises and absorbs in path simultaneously in the casting solution of primary membrane outer surface
Preliminary generation is separated.Temperature in path affects the feature that balances each other of solvent volatile quantity and casting solution, moisture therein and molten
The content of agent mainly affects the Convention diffusion speed of solvent-nonsolvent.
As shown in Fig. 4, Fig. 6 and Fig. 8, coagulating tank 3 and circulator bath device 4 are an overall structure, and its entirety is in film forming
After the district of path, coagulating tank 3 includes bottom surface, and is perpendicular to the side of left and right before and after bottom surface, and described bottom surface is with left front and back
Right flank surrounds the stereochemical structure of one end open, and bottom surface is rectangle or cylinder, and main material is 2～5mm stainless steel punching press welderings
Connect prepared；Coagulating tank 3 is divided into two-layer, interlayer distance to be 10～50mm, preferably 30mm, and the top of described interlayer is divided into film forming
District 502, lower floor is body lotion race way 506, and body lotion flows from film forming district 502, then turns back to circulating pump from the 506 of bottom
304, a length of 5～7 meters of coagulating tank, the degree of depth is 25～50cm, and width is 25～50cm, is simultaneously provided with a multiple word row row
Open.
Further, coagulating tank is slotted into and out of both sides at film silk, is the access way of film silk, is also solidifying at notch
Gu body lotion overflow exports, groove top is provided with hatchcover 309, and solidification liquid flows in runner 32, and hatchcover and coagulating tank main body are provided with silicon
Glue gasket seals, in order to prevent owing to coagulating tank tilts to cause coagulation bath to spill to be volatized into coagulating bath steam
The phenomenon of environment；Simultaneously in order to regulation coagulating tank is angled, it is provided with compact spiral lifting arm 306 in coagulating bath
Trench bottom, makes coagulating tank one end raise into 1～3 ° of inclination angle and has eliminated the oversize phenomenon causing bending of woven tube.
Described circulator bath device 4 is made up of circulating pump 304, heating water tank 303, coagulation bath by circulating pump 304 from bath
Liquid entrance region 503 inputs, and film silk is in film forming district 502 film forming, and body lotion is collected at body lotion outlet collecting region 501 and entered circulating pump 304,
Described circulating pump 304 is connected with heating water tank 303, and heating water tank 303 is connected by pipeline with body lotion entrance region, and flow-control exists
8.5～15L/min；Thus ensure the continuity of this equipment production operation.
Further, nascent membrane tube occurs immersion inversion of phases to precipitate in coagulating bath, and coagulation bath is solvent and water
Mixture, described solvent mainly uses 1-METHYLPYRROLIDONE or dimethylformamide or dimethylacetamide ammonia or dimethyl sulfoxide,
Described coagulation bath is mainly first step coagulating bath, and concentration is 20%～60%, and coagulation bath temperature is 30～70 DEG C；Second step coagulates
Gu the coagulation bath in bath is water.In this example, first step coagulation bath concentration is set to 30%, 40%, 50%, 60%, solidification
It is 60 DEG C that the temperature of bath controls, and second step coagulating bath is water, and temperature is 60 DEG C.
As shown in Fig. 5-1～Fig. 5-5, respectively level produces and tilts the difference schematic diagram that certain angle produces, and tilts
Produce and eliminate the oversize phenomenon causing bending of woven tube, simultaneously as tilt certain angle, make coagulation bath from membrane tube entrance point
Flow out is less, decreases the coagulation bath impact phenomenon to nascent membrane tube, and the surface making film forming is more uniform；Fig. 5-1 represents
The horizontal mode of production used when shorter air section produces with coagulating tank, Fig. 5-2 shows through longer
During air section, woven tube enters coagulating tank buckling phenomenon, uses and coats head in the inclination mode of production shown in Fig. 5-3
The height of 101 is higher than the inlet height of coagulating tank 3, and the outlet height of coagulating tank 3 is less than inlet height so that coating machine
The downward-sloping direction of 101 is consistent with the incline direction of coagulating tank 3, with eliminate woven tube air section oversize cause curved
Qu Xianxiang, Fig. 5-4 demonstrates that woven tube, through longer coagulating tank, when not up to support bar, buckling phenomenon, is adopted
By the inclination mode of production shown in Fig. 5-5 to eliminate woven tube at the buckling phenomenon caused through longer coagulating tank.
As shown in Figure 8, coagulation bath flows to coagulating tank from entrance, and liquid level slowly rises, when liquid level is higher than overflow
During plate 505 groove, coagulation bath enters body lotion outlet collecting region 503 and body lotion race way 506, and the effect of overflow plate makes coagulating bath
Liquid exits into body lotion outlet from its groove, and again circulates, overflow plate totally 4 pieces, each 2 pieces of two ends, often between 2 pieces of overflow plates of end
Distance be 2～3 centimetres, near film forming district overflow plate with away from that block overflow plate groove lowermost end differ 1～2mm, generation
Liquid level difference, to keep film forming district level stability；When circulation body lotion enters the timing of body lotion entrance region 501 flow one, liquid can be passed through
Position adjustable plate 504 regulates the height of liquid level, makes membrane tube immerse under coagulation bath liquid level, and liquid level is higher than membrane tube 5～6mm；Liquid level
Adjustable plate 504 is made up of fixed plate and adjustable plate in order to regulate the height of liquid level in coagulating tank.
As shown in Figure 6 and Figure 7, in order to prevent coagulation bath from touching with coagulating tank two ends, bottom when two ends notch flows out
Hit and produce the phenomenon that primary membrane silk is affected by fluid spills, be provided with guiding device 301；Guiding device by a hollow cylinder with
The semicylinder composition of top end opening, when coagulation bath is before the notch end of membrane tube import department flows to body lotion outlet collecting region,
The semicylinder of top end opening in guiding device, its purpose is to water conservancy diversion coagulation bath and does not allow it splash, and membrane tube is from sky
Through entering in coagulating bath in heart cylinder, hollow cylinder acts primarily as the steam that isolation body lotion collecting region produces.
In some other embodiments, heating water tank 303 is provided with heater, can make coagulating in recirculated water bath
Gu body lotion heating is in optimal state of temperature, described heater is electric heater unit, and its heating-up temperature is 0～100 DEG C, adopts
With base adjusting nut 5, it is used for regulating the level of coagulating tank.
Using above-mentioned device to prepare pvdf membrane, formed film after coagulating bath solidifies, film external diameter is 2.0mm, coating
For cavernous structure, obtained film soaks 8 hours in the water of 40 DEG C, is then placed in sodium hypochlorite rinsing and goes unnecessary little
The PVP of molecular weight, places in 30% glycerine and soaks 8 hours, taken out by film silk and dry, measure its flux, bubble point, burst pressure
(cohesive force between overlay and a stay tube), Electronic Speculum figure.
Table 1 produces the pure water flux of membrane, bubble point, burst pressure
Reference examples 1
Difference with embodiment 1 is: the angle of coating head 101 does not tilt, and uses 40% coagulating bath concentration to prepare PVDF
Film, the membrane aperture obtained is distributed as shown in Figure 10, it can be seen that the pore-size distribution prepared in embodiment is significantly narrower than comparison
Example.
Table 2 produces the pure water flux of membrane, bubble point, burst pressure
Reference examples 2
Difference with embodiment 1 is: be not provided with guiding device 301 at overflow plate 505, and the coagulation bath at overflow there will be and spatters
Situation on film silk, result in film-formation result bad, through the membrane aperture distribution of the film that test prepares than embodiment 1
Width, and bubble point is less for 0.143MPa, and macropore is described.
Embodiment 2
In this example, under certain wrapping wire speed, it is considered to the air-gap impact on film formation surface, stop it is arranged in air-gap
Time be respectively 5,10,15,20 seconds, owing to woven tube distance of process in the district of film forming path is oversize, if now according to
Common horizontal mode produces, and hollow fiber film tube will necessarily bend, cause casting solution at a certain angle with coating head
Coat uneven, to this end, arrange coating head to deflect down the angle of 1～2 °, improve the upright position of coating head simultaneously, with
Time by described compact spiral lifting arm (306), coagulating tank one end is improved 1～2cm, so that nascent membrane tube is entered obliquely
Entering coagulating tank generation liquid liquid phase separation, the concentration of the first coagulating tank is 40%, and temperature is 45 DEG C, and the second gelation groove is water,
Temperature is 60 DEG C；
Film forming path district purpose is to control to coat the humiture between head and coagulating bath device, to regulate film surface holes
Structure and distribution, film forming path district is made up of stainless steel double-jacket, and sidewall and bottom surface thickness 2mm, through overheated circulation in chuck
Water, the temperature of recirculated water is at 60～80 DEG C, and preferably 80 DEG C, to control the volatilization of film silk surface solvent, district 2, film forming path is respectively
Being connected with nitrogen moisture conveying fan 202 and temperature and humidity control system 201, warm and humid control system 201 is used for controlling film forming path
The temperature and humidity in district, it is 40 DEG C that temperature controls, and relative humidity is 60%；Formed film after coagulating bath solidifies, film external diameter is
2.0mm, coating is cavernous structure, soaks 8 hours in obtained film water in 40 DEG C, is then placed in sodium hypochlorite drift
Wash away the PVP of unnecessary small-molecular-weight, place in 30% glycerine and soak 8 hours, film silk is taken out and dries, measure its flux, bubble
Point, burst pressure (cohesive force between overlay and a stay tube), Electronic Speculum figure.
Table 3 coats out the different pure water flux of film, bubble point, burst pressure under different air residence time
Claims (10)
1. the coating of lining-reinforced hollow-fibre membrane and coagulation system, includes:
Coating unit (1), is used for coating casting solution and and extrudes in woven tube；
Airspace device (2), is arranged at the extrusion direction of coating unit (1), for the film silk that will obtain in coating unit (1)
Carry out aerial steam inversion of phases；
Coagulating tank (3), is arranged at the direction of the wire vent of airspace device (2), is used for making film silk carry out the film forming that is separated；
It is characterized in that: the most downward-sloping set angle in extrusion direction of the coating head (101) in coating unit (1)
Degree.
The coating of lining-reinforced hollow-fibre membrane the most according to claim 1 and coagulation system, it is characterised in that: described
Set angle scope be 0.1～10 °.
The coating of lining-reinforced hollow-fibre membrane the most according to claim 2 and coagulation system, it is characterised in that: described
The level angle of coagulating tank (3) adjustable.
The coating of lining-reinforced hollow-fibre membrane the most according to claim 3 and coagulation system, it is characterised in that: described
Coagulating tank (3) film silk import residing height higher than and outlet height.
The coating of lining-reinforced hollow-fibre membrane the most according to claim 4 and coagulation system, it is characterised in that: described
Coagulating tank (3) film silk import residing height less than and the height of extrusion of coating head (101).
The coating of lining-reinforced hollow-fibre membrane the most according to claim 1 and coagulation system, it is characterised in that: described
Coagulating tank (3) film silk import and outlet between line also with coating head (101) extrusion direction towards same direction
Tilt.
The coating of lining-reinforced hollow-fibre membrane the most according to claim 1 and coagulation system, it is characterised in that: air
The film forming path district of escapement (2) is provided with nitrogen moisture import and gas vent, is used for regulating humidity and temperature；Described
Nitrogen moisture import department is provided with gas distribution grid (202)；Airspace device is additionally provided with temperature-controlled member on (2), is used for controlling
The temperature in the film forming path district of airspace processed device；Described temperature-controlled member is the chuck outside the district of film forming path.
The coating of lining-reinforced hollow-fibre membrane the most according to claim 1 and coagulation system, it is characterised in that: solidifying
Gu the both sides of bath (3) inside are respectively arranged with overflow plate (505), it is additionally provided with guiding device in coagulating tank (3) inside
(301), for preventing the direct impact of the film silk coagulation bath by flowing out from overflow plate；The inner passage of coagulating tank (2)
On be additionally attached on circulating pump (304).
9. the coating of lining-reinforced hollow-fibre membrane and clotting method, comprise the steps: by coating unit in woven tube
Upper coating casting solution is also extruded, then is sequentially passed through in the steam inversion of phases in airspace and coagulating bath by the film silk of extrusion
Carry out being separated and form film；It is characterized in that, the most downward-sloping set angle in extrusion direction in coating unit.
The coating of lining-reinforced hollow-fibre membrane the most according to claim 9 and clotting method, it is characterised in that: squeeze
The film silk gone out vertical height in airspace and coagulating bath reduces successively；The temperature and humidity of air is entered by the air gap
Row regulation；Prevent the coagulation bath flowed out from overflow plate from directly impacting to film silk by guiding device in coagulating bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610181809.8A CN105749758B (en) | 2016-03-28 | 2016-03-28 | A kind of coating preparing lining-reinforced hollow fiber composite membrane and coagulation system and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610181809.8A CN105749758B (en) | 2016-03-28 | 2016-03-28 | A kind of coating preparing lining-reinforced hollow fiber composite membrane and coagulation system and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105749758A true CN105749758A (en) | 2016-07-13 |
| CN105749758B CN105749758B (en) | 2019-04-19 |
Family
ID=56346626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610181809.8A Active CN105749758B (en) | 2016-03-28 | 2016-03-28 | A kind of coating preparing lining-reinforced hollow fiber composite membrane and coagulation system and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105749758B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670512A (en) * | 2017-10-16 | 2018-02-09 | 苏州富淼膜科技有限公司 | A kind of Pvdf Microporous Hollow Fiber Membrane and preparation method thereof |
| CN107913603A (en) * | 2017-10-09 | 2018-04-17 | 李亮 | Woven tube enhancement type hollow fiber film and its preparation facilities and production technology |
| CN109277002A (en) * | 2018-09-11 | 2019-01-29 | 碧菲分离膜（大连）有限公司 | A kind of manufacturing equipment and technique of modularization ultrafiltration membrane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000202256A (en) * | 1999-01-12 | 2000-07-25 | Toyobo Co Ltd | Production of composite hollow fiber membrane, apparatus therefor and composite hollow fiber membrane |
| CN202376918U (en) * | 2011-12-27 | 2012-08-15 | 北京美华博大环境技术研究院有限公司 | Spinning nozzle of porose double-layer hollow fiber membrane |
| CN103831018A (en) * | 2014-01-20 | 2014-06-04 | 天津工业大学 | Continuously-super-hydrophobic hollow fiber membrane and preparation method thereof |
| CN104096485A (en) * | 2014-07-29 | 2014-10-15 | 枫科(北京)膜技术有限公司 | Equipment for preparing enhanced compound supporting hollow fiber film |
| CN104707767A (en) * | 2014-12-30 | 2015-06-17 | 杨峥雄 | Production method for reverse osmosis membrane and device |
-
2016
- 2016-03-28 CN CN201610181809.8A patent/CN105749758B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000202256A (en) * | 1999-01-12 | 2000-07-25 | Toyobo Co Ltd | Production of composite hollow fiber membrane, apparatus therefor and composite hollow fiber membrane |
| CN202376918U (en) * | 2011-12-27 | 2012-08-15 | 北京美华博大环境技术研究院有限公司 | Spinning nozzle of porose double-layer hollow fiber membrane |
| CN103831018A (en) * | 2014-01-20 | 2014-06-04 | 天津工业大学 | Continuously-super-hydrophobic hollow fiber membrane and preparation method thereof |
| CN104096485A (en) * | 2014-07-29 | 2014-10-15 | 枫科(北京)膜技术有限公司 | Equipment for preparing enhanced compound supporting hollow fiber film |
| CN104707767A (en) * | 2014-12-30 | 2015-06-17 | 杨峥雄 | Production method for reverse osmosis membrane and device |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107913603A (en) * | 2017-10-09 | 2018-04-17 | 李亮 | Woven tube enhancement type hollow fiber film and its preparation facilities and production technology |
| CN107913603B (en) * | 2017-10-09 | 2023-05-09 | 李亮 | Braided tube reinforced hollow fiber membrane, and preparation device and production process thereof |
| CN107670512A (en) * | 2017-10-16 | 2018-02-09 | 苏州富淼膜科技有限公司 | A kind of Pvdf Microporous Hollow Fiber Membrane and preparation method thereof |
| CN107670512B (en) * | 2017-10-16 | 2021-05-04 | 苏州富淼膜科技有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
| CN109277002A (en) * | 2018-09-11 | 2019-01-29 | 碧菲分离膜（大连）有限公司 | A kind of manufacturing equipment and technique of modularization ultrafiltration membrane |
| CN109277002B (en) * | 2018-09-11 | 2021-07-20 | 碧菲分离膜（大连）有限公司 | Manufacturing equipment and process of modular ultrafiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105749758B (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102160967B (en) | Lining-reinforced hollow fiber membrane tube as well as preparation device and preparation method thereof | |
| Arthanareeswaran et al. | Preparation, characterization and performance studies of ultrafiltration membranes with polymeric additive | |
| CN105749758A (en) | Coating and coagulating device and method for preparing liner-enhanced type hollow fiber composite membranes | |
| CN108097071A (en) | A kind of preparation method of improved polyvinylidene fluoride NF membrane | |
| CN107913603B (en) | Braided tube reinforced hollow fiber membrane, and preparation device and production process thereof | |
| CN103691327B (en) | An a kind of stay tube with high-peeling strength strengthens the preparation method of polymer hollow fiber membrane | |
| CN103055721B (en) | Preparation method for high-flux high-strength polytetrafluoroethylene hollow fibrous membrane | |
| CN106731897A (en) | A kind of pollution-resistant polyvinylidene fluoride hollow fiber ultrafiltration membrane high, preparation method and device | |
| CN107970791A (en) | A kind of preparation method and preparation system of enhanced hollow fiber microfiltration membrane | |
| CN101641148A (en) | Vinylidene fluoride resin hollow-fiber porous membrane and process for production of the same | |
| CN105854625A (en) | Preparation method of unpowered PVDF hollow fiber membrane | |
| CN105561813A (en) | Method for preparing polyacrylonitrile (PAN)-based microporous membrane through thermally induced phase separation | |
| CN113117538A (en) | Sulfone polymer filter membrane and preparation method thereof | |
| CN215539887U (en) | Preparation device of poly 4-methyl-1-pentene hollow fiber membrane for ECMO | |
| CN106256414A (en) | A kind of preparation method of the hollow fiber film assembly of Selective Separation metal ion | |
| CN105435655A (en) | Separating membrane material with low cost and solvent resistance as well as preparation method thereof | |
| CN107670504B (en) | A method of the organic tubular nanofiltration membrane of solvent resistant is prepared using bidirectional circulating perfusion | |
| CN106237870B (en) | A kind of flat plate ultrafiltration ripple membrane preparation method | |
| CN109847595A (en) | A kind of preparation method of the big compound polyvinylidene fluoride hollow fiber ultrafiltration membrane of flux inner support | |
| CN104069744B (en) | There is the enhancement type hollow fiber film of hydrophily honeycomb, its preparation method and process units | |
| CA2789016C (en) | Apparatus for conditioning an airstream | |
| Qin et al. | Preparation of poly (phthalazinone ether sulfone ketone) asymmetric ultrafiltration membrane: II. The gelation process | |
| CN104437092B (en) | A kind of water process membrane separation plant | |
| CN108854600A (en) | Graphene oxide/polyurethane hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN207929014U (en) | A kind of preparation system of enhanced hollow fiber microfiltration membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170714 Address after: 211800 Nanjing District, Jiangsu, Pukou garden ideas No. 1 Applicant after: Nanjing Co., Ltd of membrane material industrial technology research institute Address before: 210009 Gulou District, Jiangsu, Nanjing new model road, No. 5 Applicant before: Nanjing University of Technology |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200715 Address after: 211808 Nanjing City, Jiangsu Province, Jiangbei new District Garden train of thought No. 1 Patentee after: NANJING JIUYING MEMBRANE TECHNOLOGIES Co.,Ltd. Address before: 211800, Pukou District, Jiangsu City, Nanjing Province Park No. 1 Patentee before: NANJING MEMBRANE MATERIAL INDUSTRY TECHNOLOGY INSTITUTE Co.,Ltd. |