CN109012236A - Casting solution, ultrafiltration membrane and the method for preparing ultrafiltration membrane - Google Patents
Casting solution, ultrafiltration membrane and the method for preparing ultrafiltration membrane Download PDFInfo
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- CN109012236A CN109012236A CN201810892619.6A CN201810892619A CN109012236A CN 109012236 A CN109012236 A CN 109012236A CN 201810892619 A CN201810892619 A CN 201810892619A CN 109012236 A CN109012236 A CN 109012236A
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- ultrafiltration membrane
- polyamide
- casting solution
- sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
Abstract
The present invention provides casting solution, ultrafiltration membrane and the methods for preparing ultrafiltration membrane.Wherein, casting solution includes: polyamide；At macroporous additive；And solvent, wherein the relative molecular mass of the polyamide is 20-30 ten thousand.The viscosity of the casting solution is more appropriate as a result, almost without bubble in casting solution, is conducive to film forming.
Description
Technical field
The present invention relates to masking technique fields, specifically, being related to casting solution, ultrafiltration membrane and the method for preparing ultrafiltration membrane.
Background technique
Membrane separation technique is broadly divided into four kinds of reverse osmosis (RO), nanofiltration (NF), ultrafiltration (UF), micro-filtration (MF) isolation technics,
Wherein, Ultrafiltration Membrane is low due to having the pressure used, and water yield is larger, the advantages such as is more convenient to operate and is widely used
In water process, health care industry and food industry etc., development speed quickly, has a extensive future.In Ultrafiltration Membrane extensively at present
The practical performance of the ultrafiltration membrane of application, such as compression resistance performance, high temperature resistant and resistance to acid and alkali are still to be improved.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of casting solution, the compression resistance performance of the ultrafiltration membrane being prepared using the casting solution, high temperature resistant or
Person's resistance to acid and alkali is preferable, and water flux is larger, and film-strength is higher, has preferable practicability.
In one aspect of the invention, the present invention provides a kind of casting solutions.According to an embodiment of the invention, the casting solution
It include: polyamide；At macroporous additive；And solvent, wherein the relative molecular mass of the polyamide is 20-30 ten thousand.As a result,
The viscosity of the casting solution is more appropriate, almost without bubble in casting solution, is conducive to film forming, the ultrafiltration membrane obtained using the casting solution
Have preferable resistance to acid and alkali, force resistance and high temperature resistance, and the water flux of ultrafiltration membrane is larger, rejection is higher, especially
More harsh feed separation field is required it is suitable for sewage treatment or to separation condition.
According to an embodiment of the invention, the polyamide includes in meta-aromatic polyamide and contraposition aromatic polyamide
At least one of.Meta-aromatic polyamide and contraposition aromatic polyamide resistance to acid and alkali, heat resistance are preferable as a result, into
And make the resistance to acid and alkali of ultrafiltration membrane, heat resistance preferable, and utilize meta-aromatic polyamide and contraposition aromatic series polyamides
The ultrafiltration membrane that at least one of amine is prepared has excellent pressure-resistant performance, in highly difficult sewage treatment or to separation
The more harsh feed separation field of the requirement of condition (such as high temperature, high pressure or high pH value) has advantage outstanding.
According to an embodiment of the invention, the meta-aromatic polyamide includes poly, it is described
Aligning aromatic polyamide includes poly(p-phenylene terephthalamide).Poly and poly- to benzene as a result,
Two formyl p-phenylenediamine resistance to acid and alkali, heat resistance more preferably so that the resistance to acid and alkali of ultrafiltration membrane, heat resistance are more preferably, and
Have preferably pressure-resistant performance, is more suitable for the material of highly difficult sewage treatment or the requirement more harshness to separation condition
Separation field.
It at macroporous additive include polyvinylpyrrolidone, polyethylene glycol, ethyl alcohol, third according to an embodiment of the invention, described
At least one of alcohol, lithium chloride and phosphoric acid.Added in casting solution as a result, it is above-mentioned at macroporous additive be conducive to preparation ultrafiltration
Increase the pore structure in ultrafiltration membrane during film, and pore size is more appropriate so that the water flux of ultrafiltration membrane and
Rejection is higher, and service performance is preferable.
According to an embodiment of the invention, the solvent includes dimethylformamide, dimethyl acetamide, N- crassitude
At least one of ketone, dimethyl sulfoxide and chloroform.Polyamide can be completely dissolved in above-mentioned solvent as a result, after being conducive to
The preparation of continuous ultrafiltration membrane.
According to an embodiment of the invention, casting solution includes the polyamide of 15~25 parts by weight；The institute of 4~10 parts by weight
State into macroporous additive；The solvent of 65~81 parts by weight.The viscosity of casting solution is more appropriate as a result, polyamide and pore-forming
Additive dispersion more uniformly, have in the ultrafiltration membrane for being conducive to the preparation of subsequent ultrafiltration film, and being formed more and aperture compared with
For suitable pore structure, be conducive to the water flux and rejection that improve ultrafiltration membrane.
In another aspect of this invention, the present invention provides a kind of ultrafiltration membranes.According to an embodiment of the invention, the ultrafiltration membrane
It is to be prepared by mentioned-above casting solution.As a result, the ultrafiltration membrane have preferable resistance to acid and alkali, force resistance or
High temperature resistance, and water flux is larger, rejection is higher, is particularly suitable for sewage treatment or requirement to separation condition more
Harsh feed separation field.
According to an embodiment of the invention, the ultrafiltration membrane is prepared by immersion precipitation phase conversion method.As a result,
Preparation method is simply, conveniently, it is easy to accomplish, it is suitble to large-scale production.
In another aspect of this invention, the present invention provides a kind of sewage water treatment methods.According to an embodiment of the invention, should
Method is that sewage to be processed is made to pass through mentioned-above ultrafiltration membrane.
According to an embodiment of the invention, hydrionic concentration may be up to 3mol/L or described in the sewage to be processed
The concentration of hydroxide ion may be up to 1mol/L in sewage to be processed.It is suitable for requiring more sewage treatment condition as a result,
Harsh feed separation field, separative efficiency are higher.
According to an embodiment of the invention, the sewage in image recording material coating production process the sewage that generates or
Person's printing material manufactures at least one of generated waste water.The type of the sewage handled as a result, is more, the application of ultrafiltration membrane
It is relatively broad, it is suitable for the industrially above-mentioned sewage of large scale processing.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram that ultrafiltration membrane is prepared in one embodiment of the invention.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In one aspect of the invention, the present invention provides a kind of casting solutions.According to an embodiment of the invention, the casting solution
It include: polyamide；At macroporous additive；And solvent, wherein the relative molecular mass of the polyamide is 20-30 ten thousand.As a result,
The viscosity of the casting solution is more appropriate, almost without bubble in casting solution, is conducive to film forming, the ultrafiltration membrane obtained using the casting solution
Have preferable resistance to acid and alkali, force resistance and high temperature resistance, and the water flux of ultrafiltration membrane is larger, rejection is higher, especially
More harsh feed separation field is required it is suitable for sewage treatment or to separation condition.When the average molecular matter of polyamide
When measuring excessive, difficulty will be caused to its course of dissolution, and the viscosity of dissolved casting solution is larger, dispersion is not enough,
There are a large amount of bubbles in casting solution, so that film apparently easily forms apparent disadvantage, so that the ultrafiltration membrane obtained can not normal use；
When the relative molecular mass of polyamide is too small, the mechanical strength for using it as the ultrafiltration membrane of high molecular material formation is insufficient,
Ultrafiltration membrane is higher damaged to leak using being easy under pressure, therefore the compressive property of the ultrafiltration membrane obtained is bad,
Service performance is bad.
According to an embodiment of the invention, the polyamide includes in meta-aromatic polyamide and contraposition aromatic polyamide
At least one of.Meta-aromatic polyamide and contraposition aromatic polyamide resistance to acid and alkali, heat resistance are preferable as a result, in turn
So that the resistance to acid and alkali of ultrafiltration membrane, heat resistance are preferable, and utilize meta-aromatic polyamide and contraposition aromatic polyamide
At least one of the ultrafiltration membrane that is prepared have excellent pressure-resistant performance, in highly difficult sewage treatment or to lightning strip
The more harsh feed separation field of the requirement of part (such as high temperature, high pressure or high pH value) has advantage outstanding.At this
In some embodiments of invention, meta-aromatic polyamide includes poly, aligns aromatic polyamide
Including poly(p-phenylene terephthalamide).Poly and poly(p-phenylene terephthalamide) are resistance to as a result,
More preferably, so that the resistance to acid and alkali of ultrafiltration membrane, heat resistance, which is also equipped with more preferably resistance to for acid-base property, heat resistance
Performance is pressed, the feed separation field of highly difficult sewage treatment or the requirement more harshness to separation condition is more suitable for.
It is stored according to an embodiment of the invention, polyamide can be placed in be protected from light at dry, if the polyamide moisture absorption, not by pole
It is dissolved in conducive to it in solvent of dimethyl acetamide etc., is placed in and is protected from light dry place and can store polyamide for a long time, keep polyamide
It is dry, it is beneficial to polyamide and is dissolved in organic solvent.
It at macroporous additive include polyvinylpyrrolidone, polyethylene glycol, ethyl alcohol, third according to an embodiment of the invention, described
At least one of alcohol, lithium chloride and phosphoric acid.Added in casting solution as a result, it is above-mentioned at macroporous additive be conducive to preparation ultrafiltration
Increase the pore structure in ultrafiltration membrane during film, and pore size is more appropriate so that the water flux of ultrafiltration membrane and
Rejection is higher, and service performance is preferable.
According to an embodiment of the invention, the solvent includes dimethylformamide, dimethyl acetamide, N- crassitude
At least one of ketone, dimethyl sulfoxide and chloroform.Polyamide can be completely dissolved in above-mentioned solvent as a result, after being conducive to
The preparation of continuous ultrafiltration membrane.
According to an embodiment of the invention, casting solution includes the polyamide of 15~25 parts by weight；The institute of 4~10 parts by weight
State into macroporous additive；The solvent of 65~81 parts by weight.The viscosity of casting solution is more appropriate as a result, polyamide and pore-forming
Additive dispersion more uniformly, have in the ultrafiltration membrane for being conducive to the preparation of subsequent ultrafiltration film, and being formed more and aperture compared with
For suitable pore structure, be conducive to the water flux and rejection that improve ultrafiltration membrane.When the too high levels of polyamide, can make
The porosity of ultrafiltration membrane is relatively low, so that the water flux of ultrafiltration membrane is relatively low, the requirement of actual use is not achieved, and
And the viscosity that will also result in casting solution is relatively bigger than normal, bubble can not empty, relatively easy to generate the apparent disadvantage of ultrafiltration membrane；Work as polyamides
When the content of amine is too low, cause the viscosity of casting solution too low, when casting solution is coated on porous non-woven cloth base material, casting solution can
It can leak into the hole of non-woven fabrics, be not easy to form a film on the surface of non-woven fabrics base material.As macroporous additive too high levels when,
Big finger-like pore is then easily formed in ultrafiltration membrane, so that the rejection and resistance to pressure of ultrafiltration membrane are relatively low；As macroporous additive
When content is too low, the pore structure of ultrafiltration membrane is less, so that its water flux is relatively low.
In another aspect of this invention, the present invention provides a kind of ultrafiltration membranes.According to an embodiment of the invention, the ultrafiltration membrane
It is to be prepared by mentioned-above casting solution.As a result, the ultrafiltration membrane have preferable resistance to acid and alkali, force resistance or
High temperature resistance, and water flux is larger, rejection is higher, is particularly suitable for sewage treatment or requires separation condition more severe
The feed separation field at quarter.
According to an embodiment of the invention, the ultrafiltration membrane is prepared by immersion precipitation phase conversion method.As a result,
Preparation method simply, conveniently, and can obtain the preferable ultrafiltration membrane of service performance.
According to an embodiment of the invention, referring to Fig.1, the method for preparing ultrafiltration membrane includes:
S100: it is dried to polyamide and at the solid material in macroporous additive.
According to an embodiment of the invention, polyamide and consistent with the description of front at macroporous additive, no longer excessive herein
It repeats.Polyamide is solid material (such as can be polyamide powder), need to save, be dissolved in a dry environment
It also needs to be dried before in solvent, in order to which it is completely dissolved in solvent.At component in macroporous additive
It is also solid material (such as molecular weight polyethylene glycol when being more than 600 in solid-state) when molecular weight is larger.
According to an embodiment of the invention, the temperature of the drying process is 40~100 degrees Celsius, the time is 2~6 hours.
Thus, it is possible to which moisture content minimal amount of in polyamide is removed in time, be conducive to be completely dissolved in solvent.
S200: the polyamide, described mix at macroporous additive and solvent are dissolved by heating later, dissolution is completed
Afterwards, standing and defoaming processing is to obtain casting solution.
According to an embodiment of the invention, casting solution is consistent with the description of front, no longer excessively repeat herein.
According to an embodiment of the invention, can also include to polyamide, pore-forming addition before carrying out standing and defoaming
The step of mixed solution of agent and solvent is filtered, can make mixed solution finer and smoother, be conducive at subsequent film forming
Reason.
According to an embodiment of the invention, the heating for dissolving temperature is 50~80 degrees Celsius, dissolution time is 5~6 hours,
The temperature of standing and defoaming is 25~80 degrees Celsius, and the time is 2~6 hours.Aforesaid operations help to obtain the comparison of mixing as a result,
Uniform casting solution, and be conducive to be conducive to the bubble discharge in casting solution to improve ultrafiltration membrane by above-mentioned standing and defoaming
The uniformity of thickness, and the pore structure of ultrafiltration membrane can be made relatively stable, be conducive to the water flux for improving ultrafiltration membrane and cut
Stay rate.
S300: the casting solution is coated on carrier to form nascent state film, by the nascent state film in air bath
Being placed in coagulating bath for middle evaporation carries out gel film process to form the ultrafiltration membrane.
Casting solution is uniformly scratched in non-woven fabrics base material according to an embodiment of the invention, can use knife type coater
Surface is simple to operate as a result, be easily achieved to form nascent state film, and is conducive to the progress of subsequent step.
According to an embodiment of the invention, the time that the nascent state film is evaporated in air bath is 10~20 seconds.As a result,
Being conducive to nascent state film becomes fine and close, can slow down the diffusion rate of water during coagulating bath, reduce the formation of macropore, improve
The rejection of ultrafiltration membrane.When the time of air bath evaporation is too short, the rejection of ultrafiltration membrane is relatively low；When air bath evaporation
When overlong time, then nascent state film becomes excessively fine and close, and water flux is lower, and is unable to reach the requirement used.
According to an embodiment of the invention, the temperature of the coagulating bath is 5~60 degrees Celsius.Be conducive to improve ultrafiltration as a result,
The porosity of film can obtain flux or the higher ultrafiltration membrane of rejection.
According to an embodiment of the invention, the coagulating bath is water-bath.Pollution of the coagulating bath to environment is used water as a result,
It is smaller, have higher practicability.In some embodiments of the invention, described in order to further increase the performance of ultrafiltration membrane
A small amount of organic solvent can be added in water-bath.Addition organic solvent is conducive to control immersion precipitation inversion of phases in a water bath as a result,
It is more preferable, surface layer proper pore size to form permeability so as to improve the pore structure of ultrafiltration membrane for split-phase velocity and time in method
High flux and high retention ratio ultrafiltration membrane.In some embodiments of the invention, the organic solvent includes dimethyl acetamide, diformazan
At least one of base formamide, N-Methyl pyrrolidone and dimethyl sulfoxide.It is more advantageous to the hole knot for improving ultrafiltration membrane as a result,
Structure forms the high flux and high retention ratio ultrafiltration membrane that permeability is more preferable, surface layer pore size is preferably.
According to an embodiment of the invention, the above-mentioned method for preparing ultrafiltration membrane is simple, convenient, it is easy to accomplish, and can be with
It obtains resistance to acid and alkali, force resistance or the preferable ultrafiltration membrane of high temperature resistance, and the water throughput of the ultrafiltration membrane and cuts
Stay rate higher.
In another aspect of this invention, the present invention provides a kind of sewage water treatment methods.According to an embodiment of the invention, should
Method is that sewage to be processed is made to pass through ultrafiltration membrane noted earlier.It is simple, convenient as a result, it is easy to accomplish.
According to an embodiment of the invention, hydrionic concentration may be up to 3mol/L (such as institute in the sewage to be processed
Stating hydrionic concentration in sewage to be processed can be 10-7mol/L、10-6mol/L、10-5mol/L、10-4mol/L、10- 3mol/L、10-2mol/L、10-1mol/L、1mol/L、1.2mol/L、1.4mol/L、1.6mol/L、1.8mol/L、2mol/L、
2.2mol/L, 2.4mol/L, 2.6mol/L, 2.8mol/L, 3mol/L etc.) or the sewage to be processed in hydroxide ion
Concentration may be up to 1mol/L (such as hydrogen-oxygen can be for 10 with the concentration of ion in the sewage to be processed-7mol/L、10- 6mol/L、10-5mol/L、10-4mol/L、10-3mol/L、10-2mol/L、10-1Mol/L, 1mol/L etc.).As a result, be suitable for pair
Sewage treatment condition requires more harsh feed separation field, and separative efficiency is higher.
According to an embodiment of the invention, the sewage is the waste water generated under the conditions of high temperature, high pressure or high pH value.?
In some specific embodiments of the present invention, sewage or printing that sewage generates in image recording material coating production process
Material manufactures at least one of generated waste water.The type of the sewage handled as a result, is more, and the application of ultrafiltration membrane is more wide
It is general, it is suitable for the industrially above-mentioned sewage of large scale processing.
Embodiments herein is described below.
Embodiment
Unless otherwise instructed, in embodiment below, the performance of ultrafiltration membrane is tested through the following steps.
The performance test of ultrafiltration membrane
1, water flux
Test method: ultrafiltration membrane is fitted into membrane cisterna, under the pressure of 0.2MPa after precompressed 0.5 hour, is in pressure
0.1MPa, temperature measures the transit dose Q of water in 1 hour under conditions of being 25 DEG C, and is calculated by the following formula to obtain water flux
J:
J=Q/ (St)
Wherein, the meaning that J, Q, S, t are respectively represented are as follows:
J: water flux, unit are L/m2h；
Q: water transit dose, unit are L；
S: ultrafiltration membrane area, unit are m2；
T: time, unit are h.
2, rejection
Test method: ultrafiltration membrane is fitted into membrane cisterna, under the pressure of 0.2MPa after precompressed 0.5 hour, is in pressure
0.1MPa, temperature test bovine serum albumin in the original liquid concentration and permeate of bovine serum albumin(BSA) respectively under conditions of being 25 DEG C
White concentration is calculated by the following formula to obtain rejection:
R=(Cp-Cf)/Cp× 100%
Wherein, R, Cp、Cf、CpThe meaning respectively represented are as follows:
R: rejection, unit are %；
Cp: the concentration of bovine serum albumin(BSA) in raw water, unit are mg/L；
Cf: the concentration of bovine serum albumin(BSA) in permeate, unit are mg/L.
3, resistance to pressure
Test method: at 0.1MPa and 0.5MPa, ultrafiltration membrane is tested to bovine serum albumin(BSA) rejection, before rejection
The pressure-resistant performance of variation characterization ultrafiltration membrane afterwards (wherein, variation is bigger before and after rejection, and the pressure-resistant performance of ultrafiltration membrane is poorer).Its
The test method of middle bovine serum albumin(BSA) rejection is shown in 2.
4, acid-proof alkaline
Test method: ultrafiltration membrane is separately immersed in pure water under conditions of temperature is 25 DEG C, the alkali soluble that pH value is 13.0
24 hours in the acid solution that liquid and pH are 1, the variation of ultrafiltration membrane flux and rejection is then tested, wherein water flux
Test method is shown in 1, and the test method of rejection is shown in 2.
Casting solution includes the polyamide of 15~25 parts by weight；4~10 parts by weight it is described at macroporous additive；65~81
The solvent of parts by weight.
Embodiment 1
Weigh 15 grams of raw material of dry poly (relative molecular mass is 250,000), 4 grams of poly- second two
Alcohol (relative molecular mass 400), is added in the solvent of 81 grams of dimethyl acetamides, is stirred immersion 1 hour at room temperature,
It then heats to 80 DEG C to dissolve by heating 6 hours, the casting solution being made into includes the additive of the polyamide of 15 parts by weight, 4 parts by weight
And the solvent of surplus, standing and defoaming after filtering.
It is pasted onto non-woven fabrics is smooth on bright and clean glass plate, humid control temperature in 40%, casting film room in casting film room
Control falls deaeration complete casting solution on non-woven fabrics in clean casting film room, at 25 DEG C with slot scraping with a thickness of 0.25mm's
Stainless steel spatula striking film forming, nascent state film is evaporated 10 seconds in air bath, is put into rapidly in the coagulating bath that temperature is 25 DEG C,
Solidification is taken out after 24 hours, and ultrafiltration membrane can be obtained.
Embodiment 2
Weigh 15 grams of raw material of dry poly (relative molecular mass is 250,000), 10 grams of poly- second two
Alcohol (relative molecular mass 400), is added in the solvent of 75 grams of dimethyl acetamides, is stirred immersion 1 hour at room temperature,
It then heats to 80 DEG C to dissolve by heating 6 hours, the casting solution being made into includes the additive of the polyamide of 15 parts by weight, 10 parts by weight
And the solvent of surplus, standing and defoaming after filtering.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
Embodiment 3
Weigh 15 grams of raw material of dry poly (relative molecular mass is 250,000), 4 grams of polyethylene
Base pyrrolidones is added in 81 grams of dimethyl acetamide of solvent, is stirred immersion 1 hour at room temperature, is then heated to
80 DEG C dissolve by heating 6 hours, and the casting solution being made into includes the polyamide of 15 parts by weight, the additive of 4 parts by weight and surplus
Solvent, standing and defoaming after filtering.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
Embodiment 4
Weigh 15 grams of raw material of dry poly (relative molecular mass is 250,000), polyvinyl pyrrole
It 10 grams of pyrrolidone, is added in 75 grams of dimethyl acetamide of solvent, is stirred immersion 1 hour at room temperature, then heats to
80 DEG C dissolve by heating 6 hours, and the casting solution being made into includes the polyamide of 15 parts by weight, the additive of 10 parts by weight and surplus
Solvent, standing and defoaming after filtering.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
Embodiment 5
Weigh 25 grams of dry poly (relative molecular mass is 200,000), polyvinylpyrrolidone
It 8 grams of ketone, is added in 67 grams of dimethyl acetamide of solvent, is stirred immersion 1 hour at room temperature, then heat to 80 DEG C and add
Heat of solution 6 hours, the casting solution being made into included the solvent of the polyamide of 25 parts by weight, the additive of 8 parts by weight and surplus, mistake
Standing and defoaming after filter.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
Embodiment 6
Weigh 20 grams of raw material of dry poly (relative molecular mass is 300,000), polyvinyl pyrrole
It 10 grams of pyrrolidone, is added in 70 grams of dimethyl acetamide of solvent, is stirred immersion 1 hour at room temperature, then heats to
80 DEG C dissolve by heating 6 hours, and the casting solution being made into includes the polyamide of 20 parts by weight, the additive of 10 parts by weight and surplus
Solvent, standing and defoaming after filtering.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
Embodiment 7
The raw material and condition for preparing ultrafiltration membrane with embodiment 1, the difference is that, polyamide in the present embodiment is poly- pair
Phenylene terepthalamide (relative molecular mass is 250,000).
Comparative example 1
Weigh 15 grams of dry poly (relative molecular mass is 150,000), 4 grams of polyethylene glycol (phases
It is 400) to be added in 81 grams of dimethyl acetamide of solvent to molecular mass, is stirred immersion 1 hour at room temperature, then rises
Temperature dissolves by heating 6 hours to 80 DEG C, and the casting solution being made into contains the polyamide of 15 parts by weight, the additives of 4 parts by weight with
And the solvent of surplus, standing and defoaming after filtering.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
Comparative example 2
Weigh 15 grams of dry poly (relative molecular mass is 350,000), 4 grams of polyethylene glycol (phases
It is 400), to be added in 81 grams of dimethyl acetamide of solvent to molecular mass, is stirred immersion 1 hour at room temperature, then
It is warming up to 80 DEG C to dissolve by heating 6 hours, the casting solution being made into contains the polyamide of 15 parts by weight, the additive of 4 parts by weight
And the solvent of surplus, closed standing and defoaming after filtering.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
Comparative example 3
15 grams of polysulfones (relative molecular mass is 80,000) is weighed, 10 grams of polyvinylpyrrolidone, is added to 75 grams of diformazan
In yl acetamide solvent, it is stirred immersion 1 hour at room temperature, then heats to 80 DEG C and dissolves by heating 6 hours, the casting film being made into
Liquid contains the polyamide of 15 parts by weight, the additive of 10 parts by weight and the solvent of surplus, closed standing and defoaming after filtering.
The preparation condition of ultrafiltration membrane is the same as embodiment 1.
The performance test data of embodiment 1-7 and comparative example 1-3 are shown in Table 1.
Table 1
Embodiment and comparative example 3 is compared and is found, with same rejection, the ultrafiltration membrane containing polyamide
With higher water flux.The ultrafiltration membrane of embodiment is resistant to the pressure of 0.5MPa, under the conditions of high pressure, flux simultaneously
It is increased, but rejection does not change substantially.And the flux of the ultrafiltration membrane of comparative example 3 is with pressure rise and while raising,
But rejection sharp fall is no longer satisfied requirement to 14%.By acid soak 24 hours (pH=1), contain
The flux and rejection of the ultrafiltration membrane of polysulfones have dropped 40% or so, and the ultrafiltration membrane containing polyamide then presents preferably
Acid-proof alkaline.
It, can be normal when it is 150,000 that the relative molecular mass of polyamide is less than 200,000 by embodiment compared with comparative example 1
Film forming has normal flux and rejection performance under preferable acid-proof alkaline and 0.1MPa, but when pressure rise to 0.5MPa
When, because of its mechanical strength deficiency, film layer is easy damaged to leak ultrafiltration membrane, causes its flux high, and do not have
Cutoff performance, therefore, the force resistance of the ultrafiltration membrane obtained when polyamide molecular weight is smaller are poor.
Embodiment is compared with comparative example 2, and the relative molecular mass of polyamide is greater than 300,000 when being 350,000, and casting film fluid viscosity is inclined
Greatly, a large amount of bubbles are formed, thus cannot normal film, film apparently easily forms apparent disadvantage, under 0.1MPa pressure, Wu Fazheng
It is often used.
In conclusion ultrafiltration membrane prepared by the present invention not only has high-throughput, high rejection and high temperature tolerance, have simultaneously
There are good resistance to pressure and resistance to acid and alkali, is highly suitable for sewage treatment and separation condition requires harsh industrial material or waste liquid
Separation field.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of casting solution characterized by comprising
Polyamide；
At macroporous additive；And
Solvent,
Wherein, the relative molecular mass of the polyamide is 20-30 ten thousand.
2. casting solution according to claim 1, which is characterized in that the polyamide includes meta-aromatic polyamide and right
At least one of position aromatic polyamide.
3. casting solution according to claim 2, which is characterized in that the meta-aromatic polyamide includes poly- isophthalic diformazan
Acyl m-phenylene diamine (MPD), the contraposition aromatic polyamide includes poly(p-phenylene terephthalamide).
4. casting solution according to claim 1, which is characterized in that it is described at macroporous additive include polyvinylpyrrolidone,
At least one of polyethylene glycol, ethyl alcohol, propyl alcohol, lithium chloride and phosphoric acid；
The solvent includes in dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and chloroform
At least one.
5. casting solution described in any one of -4 according to claim 1 characterized by comprising
The polyamide of 15~25 parts by weight；
4~10 parts by weight it is described at macroporous additive；
The solvent of 65~81 parts by weight.
6. a kind of ultrafiltration membrane, which is characterized in that the ultrafiltration membrane is formed by the described in any item casting solutions of Claims 1 to 5
's.
7. ultrafiltration membrane according to claim 6, the ultrafiltration membrane is prepared by immersion precipitation phase conversion method.
8. a kind of sewage water treatment method, which is characterized in that sewage to be processed is made to pass through ultrafiltration described in claim 6 or 7
Film.
9. according to the method described in claim 8, it is characterized in that, hydrionic concentration may be up in the sewage to be processed
The concentration of hydroxide ion may be up to 1mol/L in 3mol/L or the sewage to be processed.
10. according to the method described in claim 8, it is characterized in that, the sewage was produced selected from image recording material coating
The sewage or printing material generated in journey manufactures at least one of generated waste water.
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| CN109966928A (en) * | 2019-03-18 | 2019-07-05 | 浙江泰林生命科学有限公司 | A kind of preparation method of high-throughput high-intensitive polyamide flat micro-filtration |
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