CN110327793A - A kind of ultrafiltration membrane and preparation method thereof - Google Patents
A kind of ultrafiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN110327793A CN110327793A CN201910617214.6A CN201910617214A CN110327793A CN 110327793 A CN110327793 A CN 110327793A CN 201910617214 A CN201910617214 A CN 201910617214A CN 110327793 A CN110327793 A CN 110327793A
- Authority
- CN
- China
- Prior art keywords
- ultrafiltration membrane
- film wire
- solvent
- state
- spare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- 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
Abstract
The present invention relates to the production methods of a kind of ultrafiltration membrane and ultrafiltration membrane, belong to the technical field of filter membrane.A kind of ultrafiltration membrane, it is characterized in that, the membrane micropore aperture of the ultrafiltration membrane is 0.02-0.5 microns, film thickness is 0.2-0.5 millimeters, film wire outer diameter is 1-2 millimeters, its preparation liquid includes the ingredient of following weight percent: 35%-50% active solvent 12-27% nanometer additive 0.1%-0.5% of polyvinylidene fluoride resin 15%-30% glycerol 2%-6% 1% organic additive of hydrophilic modifier, 1% main active solvent is the beneficial effects of the present invention are: technique of the invention is relatively easy to grasp, raw material is also to be easier to realize supply, hydrophilic modifier greatly promotes solute effect, organic additive then allows manufactured goods to keep the property of better organic matter, in the production that feeds intake, due to repeatedly launching and having temperature fluctuation, promote the reaction of each component, make Manufactured goods have very high performance, and full automatic production method greatly improves the purity and production efficiency of finished product.
Description
Technical field
The present invention relates to a kind of ultrafiltration membranes and preparation method thereof, belong to the technical field of filter membrane.
Background technique
With China's rapid development of economy, water resource increasingly becomes the restraining factors of economic development, therefore reduces dirty
Water discharge, the regeneration for carrying out water have become a kind of inexorable trend.There is effluent characteristics for traditional wastewater regeneration treatment technology
The disadvantages of not high, land occupation is greatly, stability is poor, has been unable to satisfy new requirement, and new technique-water treatment by membrane comes into being, should
Technique has been applied to the purification of water and the regeneration of sewage more and more.
Membrane separation technique has many advantages, such as that low energy consumption, process is simple, separative efficiency is high, non-environmental-pollution, is to solve the present age
The important new and high technology of the energy, resource and environmental problem is that other any chemical separation technologies are irreplaceable, application
Have been directed to the fields such as chemical industry, food, medicine, biochemistry, environmental protection, to it is energy saving, improve efficiency, environment purification etc. be made that it is important
Contribution, by one of the ten big new and high technologies that external referred to as 21st century is most promising.Wherein, ultrafiltration (UF) is with pressure
For the membrane separating process of motive force, it is to be separated particle from fluid with larger molecular organics matter based on selective fence effect
Out, to realize the process purified.Solute of the particles in solution partial size in 0.01 μm~1 μ m is by with special pore size distribution
The filter operation of perforated membrane retention.Ultrafiltration membrane is for larger molecular organics, colloid, algae, bacterium, virus, endotoxin, particle etc.
Substance has the removal efficiency of superelevation.Ultrafiltration membrane generally use CA, CTA, CN, PAN, PS, PES, PC, PET, PI, PE, PP, PVC,
The high molecular polymers such as PVDF (Kynoar).
And realize that the membrane separation technique of separating and filtering is a kind of current new separation technology using ultrafiltration membrane, have
It is easy to operate, efficiently and low-energy-efficiency outstanding advantages, be widely used in water resource utilization, the depollution of environment, food production with
And biological medicine preparation field.
Ultrafiltration Membrane be using ultrafiltration membrane as filter medium, under pressure, feed liquid contact membranes table to be processed
When face, only water and the small-molecule substance smaller than membrane aperture is allowed to pass through.However due to ultrafiltration membrane material or the shadow of its structure
It rings, ultrafiltration membrane in the long-term use process, is all inevitably contaminated, and pollution problem will lead to the flux of ultrafiltration membrane
With separating property sharp fall, increase use cost.How to produce the ultrafiltration membrane that low in cost, technique is easily mastered is city
The requirement of field development.Also occur the technical solution of some internal pressure ultrafiltration membrane elements in the prior art, such as application No. is
201220381871.9 Chinese patent discloses a kind of internal pressure ultrafiltration membrane elements, belongs to water correction plant field, specifically
It is related to a kind of internal pressure ultrafiltration membrane elements.Japan Patent JP1998-298298 is disclosed polyvinylidene fluoride resin poor solvent first
Infiltrate, add the method for good solvent.Therefore market and industry development now is required to a kind of production simplicity, technique is easily mastered,
The ultrafiltration membrane of save the cost.
Summary of the invention
In order to solve the above technical problems, the invention discloses a kind of technical solutions, specifically:
A kind of ultrafiltration membrane, which is characterized in that the membrane micropore aperture of the ultrafiltration membrane is 0.02-0.5 microns, film thickness is
0.2-0.5 millimeters, film wire outer diameter be 1-2 millimeters, preparation liquid includes the ingredient of following weight percent:
Polyvinylidene fluoride resin 15%-30%
Glycerol 2%-6%
Hydrophilic modifier 1%
Organic additive 1%
Main active solvent 35%-50%
Secondary active solvent 12%-27%
Nanometer additive 0.1%-0.5%.
The hydrophilic modifier is ethylene glycol.
The organic additive be fourth propyl ester, propylene glycol, polyvinyl alcohol, polyethylene glycol, triethylene glycol it is a kind of or several
Kind.
The main active solvent is N-methyl pyrrolidones.
The secondary active solvent is acetone.
The nanometer additive is silica, titanium dioxide, one of aluminum oxide or several.
The preparation method includes the following steps:
1) baking material ----high molecular polymer raw material are easy to absorb moisture, need to dry raw material before ingredient
Processing carries out drying and processing according to the baking material time of different raw materials and temperature in baking oven, by polyvinylidene fluoride resin particle
Crystal is put into dryer, and it is spare that 30-40min is dried in the state of 45 DEG C -50 DEG C；
2) automatic blending --- Full automatic material preparation device is utilized, according to the raw material ratio requirement set, carries out ingredient；
3) feed intake production --- it is fed intake using full-automatic charging device according to the addition step set；
A, the primary slurry lotion of production --- utilize spray gun by 1) spare polyvinylidene fluoride resin granule crystal and main activity
Solvent sprays mutually mixing simultaneously carrying out being sufficiently stirred 30min after importing reaction kettle in the state of 55 DEG C -65 DEG C, is formed warm
Degree starches lotion for 55 DEG C -65 DEG C of primary, and the state for being cooled to 30 DEG C -40 DEG C is spare；
B, first mixing stirring, is added whole glycerol, hydrophilic modifier in A, the secondary active solvent of half weight, and
It carries out that 20min is sufficiently stirred in the state of 55 DEG C -65 DEG C, and the state for being cooled to 30 DEG C -40 DEG C is spare；
C, rerolling stirs, and whole organic additive is added in B and is left the secondary active solvent of the other half weight,
And carry out that 10min is sufficiently stirred in the state of 55 DEG C -65 DEG C, additive is added and is stirred for 5min, so that each component substance is equal
It is dissolved into solvent evenly, obtains uniform casting solution；
4) standing air-cooled --- the casting solution that will be obtained is statically placed in reaction kettle, and takes air-cooled cooling, is cooled to 30 DEG C -40
DEG C state it is spare；
5) deaeration --- effect is will to dissolve the bubble removing brought into casting solution in whipping process, it is ensured that is spun out
Film wire surface does not have the phenomenon that minute bubbles retain and cause gas leakage；
6) spinning --- the casting solution prepared is pressurizeed by metering pump and is exported, is uniformly coated on internal lining pipe, so
The evaporation for passing through one section of air bath afterwards, enters back into solidification liquid, the solvent and perforating agent in casting solution are dissolved into rapidly solidification
In liquid, high molecular polymer solidifies and forms the process of filtering micropore, to prepare hollow fiber ultrafiltration membrane；
7) impregnate ----impregnated using pure water, 6 sink parallel combinations, reach the film that different water tanks impregnate different length
Silk and guarantee soaking time；
8) moisturizing --- it using 2 sink combinations, is used alternatingly, i.e., film wire is dipped into moisturizing from taking-up in sink is impregnated
Sink；
9) dry --- this process is made of transfer robot and rotary drying room, and film wire surface moisture is dried, to protect
Demonstrate,prove the adhesive effect of subsequent sealing, film wire is moved in rotary drying room under 35 DEG C of -45 DEG C of states by transfer robot and dried
10min obtains finished product.
The beneficial effects of the present invention are: technique of the invention is relatively easy to grasp, raw material is also to be easier to realize supply,
Hydrophilic modifier greatly promotes solute effect, and organic additive then allows manufactured goods to keep the property of better organic matter,
Feed intake production, due to repeatedly launching and having temperature fluctuation, promotes the reaction of each component, manufactured goods is made to have very high property
Can, and full automatic production method, greatly improve the purity and production efficiency of finished product.
Detailed description of the invention
Fig. 1 is production technological process of the invention
Specific embodiment
Embodiment 1:
Polyvinylidene fluoride resin:
It is Piezoelectricity under Kynoar (PVDF) normality, crystallinity is about 50%.Hitherto reported have α, β, γ,
5 kinds of crystal forms such as 6 and ε, they are formed under different conditions, under certain condition (effect of heat, electric field, machinery and radiation energy)
It can mutually convert again.In this 5 kinds of crystal forms, beta crystal is mostly important, and the PVDF applied as piezoelectricity and pyroelectricity mainly contains
There is beta crystal.1, PVDF has excellent chemical corrosion resistance, excellent high temperature resistant color distortion and oxidative resistance.2, PVDF has
Excellent wearability, flexibility, very high anti-rise intensity and impact resistance intensity.
PVDF application is concentrated mainly on petrochemical industry, the electric and big field of fluorocarbon coating three, since PVDF is good
Chemical resistance, processability and antifatigue and creep properties are pump, the valve of petrochemical equipment fluid handling system entirety or lining
One of door, pipeline, pipe line parts, storage tank and optimal material of heat exchanger.The good chemical stability of PVDF, electrical insulating property
Can, so that the equipment of production is able to satisfy TOCS and flame-retardancy requirements, is widely used in the storage of high-purity chemicals in semi-conductor industry
Deposit and convey, using perforated membrane, gel, the diaphragm etc. of the production of PVDF resin, apply in the lithium secondary battery, at present the purposes at
For most fast one of the market of PVDF demand growth.PVDF is one of main raw material of fluorocarbon coating, using it as the fluorine of raw material preparation
Carbon coating had evolved to for the 6th generation, due to PVDF resin weatherability with super strength, can be used for a long time outdoors, without protecting
It supports, such coating is widely used in power station, airport, highway, skyscraper etc..In addition PVDF resin can also and its
His resin alloy is modified, if PVDF is blended to obtain composite material with ABS resin, has been widely used for building, automobile decoration, family
Electric shell etc..With good chemical stability, do not corroded at room temperature by acid, alkali, strong oxidizer and halogen, oleum
The continuous a small number of chemicals of acid, highly basic, ketone, ether can make it be swollen or be partly dissolved, and dimethyl acetamide and dimethyl sulfoxide etc. are strong
Polar organic solvent can make it dissolve into colloidal solution.The most common technique is emulsion polymerization and suspension polymerization.
Glycerol:
Glycerine, national standard is known as glycerol, colourless, odorless, sweet, and appearance is in clear and bright viscous liquid state, is a kind of organic
Object.It is commonly called as glycerol.Glycerine can absorb moisture from air, can also absorb hydrogen sulfide, hydrogen cyanide and sulfur dioxide.It is insoluble in
Benzene, chloroform, carbon tetrachloride, carbon disulfide, petroleum ether and oils.Glycerine is the framework ingredient of triglycerides molecule.It is relatively close
Degree 1.26362.17.8 DEG C of fusing point.290.0 DEG C of boiling point (decomposition).Index of refraction 1.4746.176 DEG C of flash-point (opening cup).Acute toxicity:
LD50:31500mg/kg (rat oral).Colourless, transparent, odorless, thick liquid, it is sweet, there is hygroscopicity.With water and alcohols,
Amine, phenols are miscible in any proportion, and aqueous solution is neutrality.It is dissolved in 11 times of ethyl acetate, about 500 times of ether.It does not dissolve in
Benzene, chloroform, carbon tetrachloride, carbon disulfide, petroleum ether, oils, long-chain fatty alcohol.It is flammable, meet the strong oxygen such as chromium dioxide, potassium chlorate
Agent can cause to burn and explode.It is also the good solvent of many inorganic salts and gas.It is non-corrosive to metal, make as solvent
Used time can be oxidized to methacrylaldehyde.Chemical property: esterification occurs with acid, such as with phthalic acid ester metaplasia at alkyd resin.
Ester exchange reaction occurs with ester.Chlorhydrin is generated with hcl reaction.There are two types of modes for dehydrating glycerin: intermolecular dehydration obtains two
Glycerol and polyglycereol；Intramolecular dehydration obtains methacrylaldehyde.Glycerol is reacted with alkali generates alcoholates.Acetal is generated with aldehyde, reactive ketone
With ketal.It is aoxidized with dust technology and generates glyceraldehyde and dihydroxyacetone (DHA)；Formic acid and formaldehyde are generated with periodate oxidation.With Strong oxdiative
Agent such as chromic anhybride, potassium chlorate or potassium permanganate contact, can cause to burn or explode.Glycerol can also play the work such as nitrification and acetylation
With.
Ethylene glycol:
Ethylene glycol (ethylene glycol) also known as " glycol ", " 1,2- ethylidene glycol ", abbreviation EG.Chemical formula is
(CH2OH) 2, it is simplest dihydric alcohol.Ethylene glycol is no color or smell, pleasantly sweet liquid, mankind lethal agent toxic to animal
Amount is about 1.6g/kg.Ethylene glycol can dissolve each other with water, acetone, but solubility is smaller in ethers.As solvent, antifreezing agent and
Synthesize the raw material of terylene.The high polymer polyethylene glycol (PEG) of ethylene glycol is a kind of phase transfer catalyst, is also used for cell fusion；
Its nitrate is a kind of explosive.Since molecular weight is low, property is active, can play esterification, etherificate, alcoholization, oxidation, acetal, dehydration etc.
Reaction.
Fourth propyl ester:
Propyl butyrate, English name: n-propyl butyrate
Appearance and character: colourless liquid has fruit aroma, banana and pineapple sample note.
Main application has: the mixed solvent of cellulose and ether processed and be used for composition.
N-methyl pyrrolidones:
N-methyl pyrrolidones is a kind of chemical substance, and molecular formula is C5H9NO.Solubility property and water, alcohol, ether, ester, ketone,
Halogenated hydrocarbons, aromatic hydrocarbons dissolve each other.It under certain conditions can be with water, toluene hierarchical.
Purposes: advanced lubrication oil refining, the synthesis of polymer, insulating materials, pesticide, pigment and cleaning agent are widely used in
Deng.
This product is important industrial chemicals, is the polar solvent that a kind of selectivity is strong and stability is good, boiling low with toxicity
Point is high, dissolving power is strong, nonflammable, biodegradable, recoverable, using safe and to be suitable for multiple formulations purposes etc. excellent
Point.N-Methyl pyrrolidone (NMP) is a kind of polar aprotic solvent.Go out with small toxicity, boiling point height, dissolving power
It is many.The advantage that selectivity is strong and stability is good.It is widely used in the purifying of aromatic hydrocarbons extraction, acetylene, alkene, alkadienes, gathers inclined difluoro
The solvent of ethylene.
Acetone:
Acetone, English name are acetone, molecular formula CH3COCH3.Also known as dimethyl ketone, it is simplest saturated ketone.
It is a kind of colourless transparent liquid, there are special acrid odors.Soluble easily in water and methanol, ethyl alcohol, ether, chloroform, pyridine etc. are organic
Solvent.Inflammable, volatile, chemical property is more active.The industrial production of acetone is based on cumene method.Acetone is industrially main
As solvent in the industries such as explosive, plastics, rubber, fiber, process hides, grease, spray painting, also can be used as synthesis ketenes, aceticanhydride,
The important source material of the substances such as iodoform, polyisoprene rubber, methyl methacrylate, chloroform, epoxy resin.Also usually illegal
Molecule does the raw material bromo propiophenone of drugs.Acetone is important organic synthesis raw material, for producing epoxy resin, poly- carbonic acid
Ester, organic glass, medicine, pesticide etc..It also is good solvent, for coating, adhesive, steel cylinder acetylene etc..Diluent is also served as,
Cleaning agent, extractant.Or manufacture aceticanhydride, diacetone alcohol, chloroform, iodoform, epoxy resin, polyisoprene rubber, methyl-prop
The important source material of e pioic acid methyl ester etc..It is used as solvent in the industry such as cordite, celluloid, acetate fiber, spray painting.In grease etc.
It is used as extractant in industry.
For producing organic hyaline monomer, bisphenol-A, diacetone alcohol, hexylene glycol, methyl iso-butyl ketone (MIBK), methyl-isobutyl first
The important Organic Chemicals such as alcohol, phorone, isophorone, chloroform, iodoform.In coating, acetate fiber spinning process, steel cylinder storage
It deposits acetylene, petroleum refining industry's dewaxing etc. and is used as excellent solvent.
In actual production when for following components:
Polyvinylidene fluoride resin (30%), glycerol (3%), ethylene glycol (1%), fourth propyl ester (1%), N-methyl pyrrolidones
(44%), acetone (21%), silica (0.3%):
1) baking material ----high molecular polymer raw material are easy to absorb moisture, need to dry raw material before ingredient
Otherwise processing influences proportion scale because containing moisture when feeding intake, to influence product quality.In order to guarantee product quality,
Drying and processing is carried out according to the baking material time of different raw materials and temperature, equipment used is baking oven.High molecular polymer former material
Material is easy to absorb moisture, needs to carry out drying and processing to raw material before ingredient, according to the baking material of different raw materials in baking oven
Time and temperature carry out drying and processing, polyvinylidene fluoride resin granule crystal are put into dryer, in the state of 45 DEG C -50 DEG C
It is spare to dry 30-40min；
2) automatic blending ----this system uses the processes such as the metering of computer full-automatic process control, blanking, vibration and alarm,
According to the raw material ratio requirement set, by man-machine configuration monitoring system and PLC program to being loaded into weighing and burden funnel
Material carry out weight, flow measurement control, equipment used be electronic scale and Full automatic material preparation device.
3) automatic charging --- screw rod feeding device is used, by industrial chemicals that automatic doser prepares by the speed set
Degree and frequency are transported in agitator tank.The whole process of automatic feeding system is to complete in a sealed meter environment, and without dust pollution is not unrestrained
Take raw material, raw material tentatively can be mixed uniformly on batch charger, and rate of feeding is controllable, and equipment used is electronic scale and full automatic feeding
Expect device.
In terms of stirring --- by industrial chemicals by heating and stirring so that high molecular polymer be equably dissolved into it is molten
In agent, uniform casting solution is made.This equipment using PLC Single-chip Microprocessor Auto control, temperature control precisely, mixing speed and when
Between it is controllable, to guarantee product quality, equipment used is reaction kettle.
Feed intake production --- it is fed intake using full-automatic charging device according to the addition step set；
A, the primary slurry lotion of production --- utilize spray gun by 1) spare polyvinylidene fluoride resin granule crystal and main activity
Solvent sprays mutually mixing simultaneously carrying out being sufficiently stirred 30min after importing reaction kettle in the state of 55 DEG C -65 DEG C, is formed warm
Degree starches lotion for 55 DEG C -65 DEG C of primary, and the state for being cooled to 30 DEG C -40 DEG C is spare；
B, first mixing stirring, is added whole glycerol, hydrophilic modifier (ethylene glycol) in A, and the secondary of half weight is lived
Property solvent, and carry out that 20min is sufficiently stirred in the state of 55 DEG C -65 DEG C, and the state for being cooled to 30 DEG C -40 DEG C is spare；
C, rerolling stirs, and whole organic additive (fourth propyl ester) and time activity of the other half weight are added in B
Solvent, and carry out that 10min is sufficiently stirred in the state of 55 DEG C -65 DEG C, additive (silica) is added and is stirred for 5min, makes
It obtains each component substance to be equably dissolved into solvent, obtains uniform casting solution；
4) standing air-cooled --- the casting solution that will be obtained is statically placed in reaction kettle, and takes air-cooled cooling, is cooled to 30 DEG C -40
DEG C state it is spare；
5) deaeration --- effect is will to dissolve the bubble removing brought into casting solution in whipping process, it is ensured that is spun out
Film wire surface does not have the phenomenon that minute bubbles retain and cause gas leakage, is controlled using PLC Single-chip Microprocessor Auto, temperature and vacuum degree control
System is precisely, automatic pressure-maintaining, non-maintaining and pollution-free to feed liquid.
6) spinning --- it is controlled by computer system and frequency conversion system, controls the accurate and stability of coat thickness,
The casting solution prepared is pressurizeed by metering pump and is exported, is uniformly coated on internal lining pipe, one section of air bath is then passed through
Evaporation, enters back into solidification liquid, and the solvent and perforating agent in casting solution are dissolved into solidification liquid rapidly, and high molecular polymer is solidifying
Consolidate and form the process of filtering micropore, to prepare hollow fiber ultrafiltration membrane.
7) impregnate ----impregnated using pure water, 6 sink parallel combinations, reach the film that different water tanks impregnate different length
Silk and guarantee soaking time.The film wire taken off from hollow fiber spinning machine, there are also a small amount of solvent and perforating agent etc. are non-molten
Agent is not completely dissolved out, and at this moment film wire intensity is also insufficient, and filtering micropore also not sizing completely needs to be dipped into again in water and continue
Solvent and perforating agent is precipitated, to improve the intensity and effluent flux of film wire.
8) moisturizing ----soaked film wire needs dry after could sealing, but film wire is dried rear fenestra and is shunk, and influences
Water flux needs to carry out moisturizing processing before film wire is dried.It is combined, is used alternatingly using 2 sinks, i.e., by film wire from soaking water
It is taken out in slot and is dipped into moisturizing sink, prepare moisture retention liquid in slot, play the moisture displaced in ultrafiltration membrance filter micropore and do not made
Obtain the effect that micropore is shunk.
9) dry ----this process is made of transfer robot and rotary drying room, and film wire surface moisture is dried, with
Guarantee the adhesive effect of subsequent sealing.Film wire is moved in rotary drying room under 35 DEG C of -45 DEG C of states by transfer robot and is dried
10min obtains finished product.
10) chopping --- film wire is cut off according to specification.
11) silk is filled --- this process is configured with film wire conveying pipeline and makes corresponding frock clamp, according to product film surface
Product requires to arrange film wire quantity, cuts flat with both ends by length requirement, and blocked up land plaster.
12) it is packed and stored ----this process is equipped with product conveying belt, and to detection, qualified MBR diaphragm finished product is wrapped
Dress, protection, are put in storage and are stored in drying, in the warehouse of without sunlight direct projection, play sealing and protective action.
Finished product can be obtained according to the above production method.
Embodiment 2:
In actual production when for following components:
Polyvinylidene fluoride resin (28%), glycerol (3%), ethylene glycol (1%), propylene glycol (1%), N-methyl pyrrolidones
(50%), acetone (27%), titanium dioxide (0.2%):
1) baking material ----high molecular polymer raw material are easy to absorb moisture, need to dry raw material before ingredient
Otherwise processing influences proportion scale because containing moisture when feeding intake, to influence product quality.In order to guarantee product quality,
Drying and processing is carried out according to the baking material time of different raw materials and temperature, equipment used is baking oven.High molecular polymer former material
Material is easy to absorb moisture, needs to carry out drying and processing to raw material before ingredient, according to the baking material of different raw materials in baking oven
Time and temperature carry out drying and processing, polyvinylidene fluoride resin granule crystal are put into dryer, in the state of 45 DEG C -50 DEG C
It is spare to dry 30-40min；
2) automatic blending ----this system uses the processes such as the metering of computer full-automatic process control, blanking, vibration and alarm,
According to the raw material ratio requirement set, by man-machine configuration monitoring system and PLC program to being loaded into weighing and burden funnel
Material carry out weight, flow measurement control, equipment used be electronic scale and Full automatic material preparation device.
3) automatic charging --- screw rod feeding device is used, by industrial chemicals that automatic doser prepares by the speed set
Degree and frequency are transported in agitator tank.The whole process of automatic feeding system is to complete in a sealed meter environment, and without dust pollution is not unrestrained
Take raw material, raw material tentatively can be mixed uniformly on batch charger, and rate of feeding is controllable, and equipment used is electronic scale and full automatic feeding
Expect device.
In terms of stirring --- by industrial chemicals by heating and stirring so that high molecular polymer be equably dissolved into it is molten
In agent, uniform casting solution is made.This equipment using PLC Single-chip Microprocessor Auto control, temperature control precisely, mixing speed and when
Between it is controllable, to guarantee product quality, equipment used is reaction kettle.
Feed intake production --- it is fed intake using full-automatic charging device according to the addition step set；
A, the primary slurry lotion of production --- utilize spray gun by 1) spare polyvinylidene fluoride resin granule crystal and main activity
Solvent sprays mutually mixing simultaneously carrying out being sufficiently stirred 30min after importing reaction kettle in the state of 55 DEG C -65 DEG C, is formed warm
Degree starches lotion for 55 DEG C -65 DEG C of primary, and the state for being cooled to 30 DEG C -40 DEG C is spare；
B, first mixing stirring, is added whole glycerol, hydrophilic modifier (ethylene glycol) in A, and the secondary of half weight is lived
Property solvent, and carry out that 20min is sufficiently stirred in the state of 55 DEG C -65 DEG C, and the state for being cooled to 30 DEG C -40 DEG C is spare；
C, rerolling stirs, and whole organic additive (propylene glycol) and time activity of the other half weight are added in B
Solvent, and carry out that 10min is sufficiently stirred in the state of 55 DEG C -65 DEG C, additive (titanium dioxide) is added and is stirred for 5min, makes
It obtains each component substance to be equably dissolved into solvent, obtains uniform casting solution；
4) standing air-cooled --- the casting solution that will be obtained is statically placed in reaction kettle, and takes air-cooled cooling, is cooled to 30 DEG C -40
DEG C state it is spare；
5) deaeration --- effect is will to dissolve the bubble removing brought into casting solution in whipping process, it is ensured that is spun out
Film wire surface does not have the phenomenon that minute bubbles retain and cause gas leakage, is controlled using PLC Single-chip Microprocessor Auto, temperature and vacuum degree control
System is precisely, automatic pressure-maintaining, non-maintaining and pollution-free to feed liquid.
6) spinning --- it is controlled by computer system and frequency conversion system, controls the accurate and stability of coat thickness,
The casting solution prepared is pressurizeed by metering pump and is exported, is uniformly coated on internal lining pipe, one section of air bath is then passed through
Evaporation, enters back into solidification liquid, and the solvent and perforating agent in casting solution are dissolved into solidification liquid rapidly, and high molecular polymer is solidifying
Consolidate and form the process of filtering micropore, to prepare hollow fiber ultrafiltration membrane.
7) impregnate ----impregnated using pure water, 6 sink parallel combinations, reach the film that different water tanks impregnate different length
Silk and guarantee soaking time.The film wire taken off from hollow fiber spinning machine, there are also a small amount of solvent and perforating agent etc. are non-molten
Agent is not completely dissolved out, and at this moment film wire intensity is also insufficient, and filtering micropore also not sizing completely needs to be dipped into again in water and continue
Solvent and perforating agent is precipitated, to improve the intensity and effluent flux of film wire.
8) moisturizing ----soaked film wire needs dry after could sealing, but film wire is dried rear fenestra and is shunk, and influences
Water flux needs to carry out moisturizing processing before film wire is dried.It is combined, is used alternatingly using 2 sinks, i.e., by film wire from soaking water
It is taken out in slot and is dipped into moisturizing sink, prepare moisture retention liquid in slot, play the moisture displaced in ultrafiltration membrance filter micropore and do not made
Obtain the effect that micropore is shunk.
9) dry ----this process is made of transfer robot and rotary drying room, and film wire surface moisture is dried, with
Guarantee the adhesive effect of subsequent sealing.Film wire is moved in rotary drying room under 35 DEG C of -45 DEG C of states by transfer robot and is dried
10min obtains finished product.
10) chopping --- film wire is cut off according to specification.
11) silk is filled --- this process is configured with film wire conveying pipeline and makes corresponding frock clamp, according to product film surface
Product requires to arrange film wire quantity, cuts flat with both ends by length requirement, and blocked up land plaster.
12) it is packed and stored ----this process is equipped with product conveying belt, and to detection, qualified MBR diaphragm finished product is wrapped
Dress, protection, are put in storage and are stored in drying, in the warehouse of without sunlight direct projection, play sealing and protective action.
Finished product can be obtained according to the above production method.
Embodiment 3:
Polyvinylidene fluoride resin (28%), glycerol (3%), ethylene glycol (1%), polyvinyl alcohol (1%), N-methyl pyrrolidines
Ketone (50%), acetone (27%), aluminum oxide (0.2%):
1) baking material ----high molecular polymer raw material are easy to absorb moisture, need to dry raw material before ingredient
Otherwise processing influences proportion scale because containing moisture when feeding intake, to influence product quality.In order to guarantee product quality,
Drying and processing is carried out according to the baking material time of different raw materials and temperature, equipment used is baking oven.High molecular polymer former material
Material is easy to absorb moisture, needs to carry out drying and processing to raw material before ingredient, according to the baking material of different raw materials in baking oven
Time and temperature carry out drying and processing, polyvinylidene fluoride resin granule crystal are put into dryer, in the state of 45 DEG C -50 DEG C
It is spare to dry 30-40min；
2) automatic blending ----this system uses the processes such as the metering of computer full-automatic process control, blanking, vibration and alarm,
According to the raw material ratio requirement set, by man-machine configuration monitoring system and PLC program to being loaded into weighing and burden funnel
Material carry out weight, flow measurement control, equipment used be electronic scale and Full automatic material preparation device.
3) automatic charging --- screw rod feeding device is used, by industrial chemicals that automatic doser prepares by the speed set
Degree and frequency are transported in agitator tank.The whole process of automatic feeding system is to complete in a sealed meter environment, and without dust pollution is not unrestrained
Take raw material, raw material tentatively can be mixed uniformly on batch charger, and rate of feeding is controllable, and equipment used is electronic scale and full automatic feeding
Expect device.
In terms of stirring --- by industrial chemicals by heating and stirring so that high molecular polymer be equably dissolved into it is molten
In agent, uniform casting solution is made.This equipment using PLC Single-chip Microprocessor Auto control, temperature control precisely, mixing speed and when
Between it is controllable, to guarantee product quality, equipment used is reaction kettle.
Feed intake production --- it is fed intake using full-automatic charging device according to the addition step set；
A, the primary slurry lotion of production --- utilize spray gun by 1) spare polyvinylidene fluoride resin granule crystal and main activity
Solvent sprays mutually mixing simultaneously carrying out being sufficiently stirred 30min after importing reaction kettle in the state of 55 DEG C -65 DEG C, is formed warm
Degree starches lotion for 55 DEG C -65 DEG C of primary, and the state for being cooled to 30 DEG C -40 DEG C is spare；
B, first mixing stirring, is added whole glycerol, hydrophilic modifier (ethylene glycol) in A, and the secondary of half weight is lived
Property solvent, and carry out that 20min is sufficiently stirred in the state of 55 DEG C -65 DEG C, and the state for being cooled to 30 DEG C -40 DEG C is spare；
C, rerolling stirs, and whole organic additive (polyvinyl alcohol) is added in B and the secondary of the other half weight is lived
Property solvent, and carry out in the state of 55 DEG C -65 DEG C that 10min is sufficiently stirred, additive (aluminum oxide) be added and is stirred for
5min obtains uniform casting solution so that each component substance is equably dissolved into solvent；
4) standing air-cooled --- the casting solution that will be obtained is statically placed in reaction kettle, and takes air-cooled cooling, is cooled to 30 DEG C -40
DEG C state it is spare；
5) deaeration --- effect is will to dissolve the bubble removing brought into casting solution in whipping process, it is ensured that is spun out
Film wire surface does not have the phenomenon that minute bubbles retain and cause gas leakage, is controlled using PLC Single-chip Microprocessor Auto, temperature and vacuum degree control
System is precisely, automatic pressure-maintaining, non-maintaining and pollution-free to feed liquid.
6) spinning --- it is controlled by computer system and frequency conversion system, controls the accurate and stability of coat thickness,
The casting solution prepared is pressurizeed by metering pump and is exported, is uniformly coated on internal lining pipe, one section of air bath is then passed through
Evaporation, enters back into solidification liquid, and the solvent and perforating agent in casting solution are dissolved into solidification liquid rapidly, and high molecular polymer is solidifying
Consolidate and form the process of filtering micropore, to prepare hollow fiber ultrafiltration membrane.
7) impregnate ----impregnated using pure water, 6 sink parallel combinations, reach the film that different water tanks impregnate different length
Silk and guarantee soaking time.The film wire taken off from hollow fiber spinning machine, there are also a small amount of solvent and perforating agent etc. are non-molten
Agent is not completely dissolved out, and at this moment film wire intensity is also insufficient, and filtering micropore also not sizing completely needs to be dipped into again in water and continue
Solvent and perforating agent is precipitated, to improve the intensity and effluent flux of film wire.
8) moisturizing ----soaked film wire needs dry after could sealing, but film wire is dried rear fenestra and is shunk, and influences
Water flux needs to carry out moisturizing processing before film wire is dried.It is combined, is used alternatingly using 2 sinks, i.e., by film wire from soaking water
It is taken out in slot and is dipped into moisturizing sink, prepare moisture retention liquid in slot, play the moisture displaced in ultrafiltration membrance filter micropore and do not made
Obtain the effect that micropore is shunk.
9) dry ----this process is made of transfer robot and rotary drying room, and film wire surface moisture is dried, with
Guarantee the adhesive effect of subsequent sealing.Film wire is moved in rotary drying room under 35 DEG C of -45 DEG C of states by transfer robot and is dried
10min obtains finished product.
10) chopping --- film wire is cut off according to specification.
11) silk is filled --- this process is configured with film wire conveying pipeline and makes corresponding frock clamp, according to product film surface
Product requires to arrange film wire quantity, cuts flat with both ends by length requirement, and blocked up land plaster.
12) it is packed and stored ----this process is equipped with product conveying belt, and to detection, qualified MBR diaphragm finished product is wrapped
Dress, protection, are put in storage and are stored in drying, in the warehouse of without sunlight direct projection, play sealing and protective action.
Finished product can be obtained according to the above production method.
Those skilled in the art will readily recognize that above-mentioned each preferred embodiment can be free under the premise of not conflicting
Ground combination, superposition.It should be appreciated that above-mentioned embodiment is merely exemplary, and not restrictive, without departing from of the invention
In the case where basic principle, those skilled in the art can be for the various apparent or equivalent modification that above-mentioned details is made
Or replacement, all it is included in scope of the presently claimed invention.
Claims (7)
1. a kind of ultrafiltration membrane, which is characterized in that the membrane micropore aperture of the ultrafiltration membrane is 0.02-0.5 microns, film thickness is
0.2-0.5 millimeters, film wire outer diameter be 1-2 millimeters, preparation liquid includes the ingredient of following weight percent:
Polyvinylidene fluoride resin 15%-30%
Glycerol 2%-6%
Hydrophilic modifier 1%
Organic additive 1%
Main active solvent 35%-50%
Secondary active solvent 12%-27%
Nanometer additive 0.1%-0.5%.
2. ultrafiltration membrane according to claim 1, which is characterized in that the hydrophilic modifier is ethylene glycol.
3. ultrafiltration membrane according to claim 1, which is characterized in that the organic additive is fourth propyl ester, and propylene glycol is gathered
Vinyl alcohol, polyethylene glycol, the one or several kinds of triethylene glycol.
4. ultrafiltration membrane according to claim 1, which is characterized in that the main active solvent is N-methyl pyrrolidones.
5. ultrafiltration membrane according to claim 1, which is characterized in that the secondary active solvent is acetone.
6. ultrafiltration membrane according to claim 1, which is characterized in that the nanometer additive is silica, titanium dioxide
Titanium, one of aluminum oxide or several.
7. the preparation method of -6 any ultrafiltration membranes according to claim 1, which is characterized in that the preparation method includes
Following steps:
1) baking material ----high molecular polymer raw material are easy to absorb moisture, need to carry out at drying raw material before ingredient
Reason carries out drying and processing according to the baking material time of different raw materials and temperature in baking oven, and polyvinylidene fluoride resin particle is brilliant
Body is put into dryer, and it is spare that 30-40min is dried in the state of 45 DEG C -50 DEG C；
2) automatic blending --- Full automatic material preparation device is utilized, according to the raw material ratio requirement set, carries out ingredient；
3) feed intake production --- it is fed intake using full-automatic charging device according to the addition step set；
A, the primary slurry lotion of production --- utilize spray gun by 1) spare polyvinylidene fluoride resin granule crystal and main active solvent
Simultaneously carrying out that 30min is sufficiently stirred in the state of 55 DEG C -65 DEG C after importing reaction kettle, formation temperature is for spray mixing mutually
55 DEG C -65 DEG C of primary slurry lotion, and the state for being cooled to 30 DEG C -40 DEG C is spare；
B, first mixing stirring, is added whole glycerol, hydrophilic modifier in A, the secondary active solvent of half weight, and 55
It in the state of DEG C -65 DEG C carries out that 20min is sufficiently stirred, and the state for being cooled to 30 DEG C -40 DEG C is spare；
C, rerolling stirs, and whole organic additive is added in B and is left the secondary active solvent of the other half weight, and
It carries out that 10min is sufficiently stirred in the state of 55 DEG C -65 DEG C, additive is added and is stirred for 5min, so that each component substance is equably
It is dissolved into solvent, obtains uniform casting solution；
4) standing air-cooled --- the casting solution that will be obtained is statically placed in reaction kettle, and takes air-cooled cooling, is cooled to 30 DEG C -40 DEG C
State is spare；
5) deaeration --- effect is will to dissolve the bubble removing brought into casting solution in whipping process, it is ensured that spins out the film wire come
Surface does not have the phenomenon that minute bubbles retain and cause gas leakage；
6) spinning --- the casting solution prepared is pressurizeed by metering pump and is exported, is uniformly coated on internal lining pipe, then leads to
The evaporation for crossing one section of air bath, enters back into solidification liquid, and the solvent and perforating agent in casting solution are dissolved into solidification liquid rapidly,
High molecular polymer solidifies and forms the process of filtering micropore, to prepare hollow fiber ultrafiltration membrane；
7) impregnate ----impregnated using pure water, 6 sink parallel combinations, reach different water tanks impregnate the film wire of different lengths with
And guarantee soaking time；
8) moisturizing --- it using 2 sink combinations, is used alternatingly, i.e., film wire is dipped into moisture retention water from taking-up in sink is impregnated
Slot；
9) dry --- this process is made of transfer robot and rotary drying room, and film wire surface moisture is dried, after guaranteeing
The adhesive effect of continuous sealing, film wire, which by transfer robot moves in rotary drying room and dries 10min under 35 DEG C of -45 DEG C of states, to be obtained
To finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617214.6A CN110327793A (en) | 2019-07-08 | 2019-07-08 | A kind of ultrafiltration membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617214.6A CN110327793A (en) | 2019-07-08 | 2019-07-08 | A kind of ultrafiltration membrane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110327793A true CN110327793A (en) | 2019-10-15 |
Family
ID=68145008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910617214.6A Pending CN110327793A (en) | 2019-07-08 | 2019-07-08 | A kind of ultrafiltration membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110327793A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228308A (en) * | 2022-06-15 | 2022-10-25 | 广西国宏智鸿环保科技集团股份有限公司 | Hollow PVDF ultrafiltration membrane and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422708A (en) * | 2008-11-26 | 2009-05-06 | 北京碧水源膜科技有限公司 | Recovery method of polyvinylidene fluoride hollow fiber membrane |
| WO2009143734A1 (en) * | 2008-05-27 | 2009-12-03 | 广州美能材料科技有限公司 | A polyvinylidene fluoride hollow fiber membrane and process for producing the same |
| CN102114390A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院生态环境研究中心 | Reinforced type polyvinylidene fluoride hollow fiber hydrophobic membrane and preparation method thereof |
| CN102430348A (en) * | 2011-12-09 | 2012-05-02 | 西安建筑科技大学 | Preparation method for polyethylene terephthalate (PET) braided tube/polymer composite hollow fiber microporous membrane |
| CN103331107A (en) * | 2013-06-18 | 2013-10-02 | 常州大学 | Polyvinylidene fluoride (PVDF) separation film and preparation method thereof |
| CN103657447A (en) * | 2013-12-17 | 2014-03-26 | 常熟丽源膜科技有限公司 | Polyvinylidene fluoride porous hollow-fiber membrane |
| CN103752178A (en) * | 2014-01-08 | 2014-04-30 | 宁波恺谱瑞膜科技有限公司 | Hollow fibre membrane and preparation method thereof |
| CN104667763A (en) * | 2013-11-28 | 2015-06-03 | 上海一鸣过滤技术有限公司 | Supported hydrophilic polyvinylidene fluoride microporous membrane and preparation method thereof |
| CN105413487A (en) * | 2015-11-19 | 2016-03-23 | 福州顺升科技有限公司 | Polypropylene hollow fiber microporous film and preparation method thereof |
| CN109675447A (en) * | 2019-01-03 | 2019-04-26 | 广州超禹膜分离技术有限公司 | A kind of enhancement type hollow fiber film and preparation method thereof for being not easy to strip off |
-
2019
- 2019-07-08 CN CN201910617214.6A patent/CN110327793A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009143734A1 (en) * | 2008-05-27 | 2009-12-03 | 广州美能材料科技有限公司 | A polyvinylidene fluoride hollow fiber membrane and process for producing the same |
| CN101422708A (en) * | 2008-11-26 | 2009-05-06 | 北京碧水源膜科技有限公司 | Recovery method of polyvinylidene fluoride hollow fiber membrane |
| CN102114390A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院生态环境研究中心 | Reinforced type polyvinylidene fluoride hollow fiber hydrophobic membrane and preparation method thereof |
| CN102430348A (en) * | 2011-12-09 | 2012-05-02 | 西安建筑科技大学 | Preparation method for polyethylene terephthalate (PET) braided tube/polymer composite hollow fiber microporous membrane |
| CN103331107A (en) * | 2013-06-18 | 2013-10-02 | 常州大学 | Polyvinylidene fluoride (PVDF) separation film and preparation method thereof |
| CN104667763A (en) * | 2013-11-28 | 2015-06-03 | 上海一鸣过滤技术有限公司 | Supported hydrophilic polyvinylidene fluoride microporous membrane and preparation method thereof |
| CN103657447A (en) * | 2013-12-17 | 2014-03-26 | 常熟丽源膜科技有限公司 | Polyvinylidene fluoride porous hollow-fiber membrane |
| CN103752178A (en) * | 2014-01-08 | 2014-04-30 | 宁波恺谱瑞膜科技有限公司 | Hollow fibre membrane and preparation method thereof |
| CN105413487A (en) * | 2015-11-19 | 2016-03-23 | 福州顺升科技有限公司 | Polypropylene hollow fiber microporous film and preparation method thereof |
| CN109675447A (en) * | 2019-01-03 | 2019-04-26 | 广州超禹膜分离技术有限公司 | A kind of enhancement type hollow fiber film and preparation method thereof for being not easy to strip off |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228308A (en) * | 2022-06-15 | 2022-10-25 | 广西国宏智鸿环保科技集团股份有限公司 | Hollow PVDF ultrafiltration membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103601703B (en) | The method of epoxidation methyl eleostearate is prepared by tung oil | |
| CN101580549B (en) | Method for preparing cellulose acetate propionate or cellulose acetate butyrate | |
| JP2009079220A (en) | Dissolution and processing of cellulose using ionic liquids | |
| ATE14894T1 (en) | PREPARATION OF A LIQUID COMPOSITION WITH A PERFLUORINATED ION EXCHANGE POLYMER AND THE USE OF SUCH POLYMER. | |
| CN101880411B (en) | Method for preparing functionalized regenerated cellulose membranes by using bagasse celluloses | |
| CN103012747A (en) | Degradable mixed polyamine epoxy resin curing agent, and preparation and composite material recovery thereof | |
| CN107376666A (en) | A kind of modified cellulose acetate film and preparation method and application | |
| CN110327793A (en) | A kind of ultrafiltration membrane and preparation method thereof | |
| CN109224638A (en) | A kind of sewage treatment hydrophilic and oleophobic modified fibrous globule filtering material and preparation method | |
| CN107459460A (en) | A kind of process for purification of the tricaprylate of triethylene glycol two | |
| CN110591133A (en) | Environment-friendly production process for improving strength of regenerated cellulose membrane | |
| CN103977717A (en) | Hollow polyethersulfone fiber ultrafiltration membrane capable of resisting biological pollution and preparation method of membrane | |
| CN103435504A (en) | Preparation method of degradable primary amine curing agents | |
| CN105233703A (en) | Preparation method of high flux cellulose microfiltration membrane | |
| CN106237870B (en) | A kind of flat plate ultrafiltration ripple membrane preparation method | |
| CN106750302A (en) | A kind of preparation method of heat resistance, corrosion resistant HMW poly arylidene thio-ester sulfone | |
| CN114672925B (en) | Polylactic acid melt-blown cloth and preparation method and application thereof | |
| CN102357346B (en) | Polyvinylidene fluoride hollow fiber membrane, preparation method and application | |
| CN105214527A (en) | A kind of preparation technology of ultra-hydrophobic polyvinylidene fluoride hexafluoropropene perforated membrane | |
| CN103205002B (en) | A kind of low stain synthetic method of super high cross-linked adsorbing resin | |
| CN113634134A (en) | Carbon fiber composite filtering membrane for sewage treatment and preparation method thereof | |
| CN104710285A (en) | Method for recycling ethylene glycol monomethyl ether | |
| CN102766116B (en) | Dehydroabietylamine-based epoxy resin and preparation method and application thereof | |
| CN103554060A (en) | Catalyst used for synthesizing glycidol from glycerol and dimethyl carbonate by employing one-step method | |
| CN110368822A (en) | A kind of high temperature resistant semi-aromatic seperation film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |