CN110394075A - A kind of preparation method of high tenacity nanofiltration membrane - Google Patents
A kind of preparation method of high tenacity nanofiltration membrane Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D71/08—Polysaccharides
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to a kind of preparation methods of high tenacity nanofiltration membrane, belong to technical field of separation membrane preparation.The present invention is by N, N '-dicyclohexyl carbodiimide is melted in solution of adipic acid to be dispersed, the heating of methoxy benzoic acid xenol monoesters is added dropwise after dispersion thereto to be mixed, drying is filtered after stirring obtains filter cake, filter cake is mixed with thionyl chloride again, heating is condensed back reaction, it is concentrated in vacuo and reflux product is made, then reflux product is stirred and is freezed with chitosan low-temperature mixed, modified filter cake is obtained by filtration in freezing, filter cake and chitosan will be finally modified, acetic acid mixing, it is applied to dry on glass plate after mixing and high tenacity nanofiltration membrane is made, the present invention utilizes polysulfones and N, N '-dicyclohexyl carbodiimide is modified chitosan, make to introduce charged group in chitosan, reinforce the interception capacity of nanofiltration membrane, and make to generate amide group in chitosan molecule by reaction, to reinforce the mechanical strength of nanofiltration membrane And chemical stability.
Description
Technical field
The present invention relates to a kind of preparation methods of high tenacity nanofiltration membrane, belong to technical field of separation membrane preparation.
Background technique
Nanofiltration be the 1980s mid-term grow up, between a kind of reverse osmosis pressure-driven between ultrafiltration
Membrane separation technique, operation pressure difference are 0.2~2.0MPa, and molecular cut off is 200~1000Da, are about for molecular size
The separation of the dissolved constituent of 1nm.Nanofiltration membrane is to carry out seawater and brackish water desalination, the softening of underground water, low in contaminated water
Molecular organic removal, in industrial wastewater recycling of utility etc. important membrane material, for water resource development and utilization, change
Philanthropists' living environment and quality of life.
The nanofiltration membrane of the overwhelming majority belongs to utilized thin film composite membranes at present, i.e., has nanoscale aperture for compound one layer on basement membrane
Ultra-thin surface layer.Research of the China in terms of nanofiltration membrane starts from the beginning of the nineties in last century, the high Xingcheng meeting from Congjie academician in 1993
It is put forward for the first time the concept of nanofiltration membrane in view, and brief introduction has been done to external nanofiltration.Since then, the research of nanofiltration membrane is at me
The hot spot of state film scientific worker research, the especially research of composite nanometer filtering film.Compared with world level, China's Nanofiltration-membrane technique
Be still in infancy, there is larger gap in terms of membrane material and membrane module: there are no the nanofiltrations of high-performance commercialization first
Film and high-performance large-scale nanofiltration membrane component, secondly Nanofiltration-membrane technique application also rest on small test and type approval test stage,
Not yet realize industrialized continuous production.
Between ultrafiltration membrane and reverse osmosis membrane, preparation method mainly has L-S phase in the aperture of nanofiltration membrane surface dense layer
Conversion method, conversion method, blending method, charged method and composite algorithm etc..It is at most also most effective system that composite algorithm, which is used at present,
The method of standby nanofiltration membrane, and production commercialization nanofiltration membrane kind is most, the maximum method of yield, this method is in ultrafiltration membranes
The upper compound one layer ultra-thin surfaces active layer with nanoscale aperture.The preparation of composite membrane includes the preparation of basement membrane, surface-active
The preparation and compound of layer.
Between 200 to 1000Da molecular weight, range just meets organic molten the size of the separation small molecule of nanofiltration membrane
Agent separates and recovers the requirement utilized, and in recent years, more and more focus of attention carry out Separation of Organic to using nanofiltration process.
Compared with traditional organic solvent separation method, the operation of nanofiltration membrane Separation of Organic compared with simple, energy consumption is lower, pollution is lower,
Occupied area is smaller, is based on above advantages, therefore obtained extensive concern.
Summary of the invention
The technical problems to be solved by the invention: low efficiency is retained for current nanofiltration membrane, the insufficient defect of toughness provides
A kind of preparation method of high tenacity nanofiltration membrane.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
The specific preparation step of high tenacity nanofiltration membrane are as follows:
It weighs the acetic acid solution that organic modifiers, chitosan and mass fraction are 8~10% to put into beaker, with blender with 600
The revolving speed of~620r/min, which is mixed, is made mixing casting solution, mixing casting solution is uniformly applied on glass plate, by glass plate
It is placed in baking oven, 13~14h is placed under conditions of temperature is 65~75 DEG C, discharge up to high tenacity nanofiltration membrane.
The specific preparation step of organic modifiers are as follows:
(1) it weighs in methoxy benzoic acid xenol monoesters, tetrahydrofuran and pyridine investment beaker, places the beaker bath temperature
For 50~60min system is mixed under conditions of revolving speed is 500~520r/min with blender in 60~64 DEG C of water-baths
Obtain prefabricated mixed liquor；
(2) mixed solution is put into conical flask, is dripped into conical flask with the drop rate of 15~17mL/min into conical flask
Add prefabricated mixed liquor, will react conical flask as the obtained reaction product of 3~5h is vibrated in shaking table, under room temperature after completion of dropwise addition
Product investment suction filtration machine in filter obtains filter cake, with washes of absolute alcohol filter cake 3~5 times, put into baking oven in temperature be 105~
It is dried under conditions of 115 DEG C；
(3) filter cake and thionyl chloride investment are inserted in the three-necked flask of condensing reflux pipe, three-necked flask is placed in bath temperature
It is 60~80Pa, temperature in vacuum degree to be heated to reflux 9~10h, then put into vacuum oven in 95~100 DEG C of water-baths
Reflux product is made in 4~5h of vacuum concentration under conditions of degree is 105~115 DEG C；
(4) by chitosan and Loprazolam investment reaction kettle, 40 are mixed under conditions of revolving speed is 500~520r/min
Mixed emulsion is made in~50min, and reactor temperature is reduced to 2~4 DEG C, reflux product is added into reaction kettle, in revolving speed
For 60~80min is mixed under conditions of 500~520r/min, stirring is placed in household freezer, is -30~-26 in temperature
3~4h is freezed under conditions of DEG C, is filtered after frost and is obtained modified filter cake, with ammonia scrubbing filter cake 3~5 times to get organically-modified
Agent；
The specific preparation step of mixed solution are as follows:
By in adipic acid and distilled water investment three-necked flask, 100 are mixed with blender with the revolving speed of 500~520r/min~
Mixed liquor is made in 120min, weighs mixed liquor, N, and N '-dicyclohexyl carbodiimide, 4-dimethylaminopyridine, tetrahydrofuran are thrown
Enter and is uniformly mixed obtained mixed solution in beaker.
Preferably according to parts by weight, organic modifiers are 5~7 parts, chitosan is 6~8 parts, mass fraction is 8~10%
Acetic acid solution be 7~9 parts.
In the specific preparation step (1) of organic modifiers preferably according to parts by weight, methoxy benzoic acid xenol list
Ester is 13~15 parts, tetrahydrofuran is 40~42 parts, pyridine is 8~10 parts.
The quality for the prefabricated mixed liquor being added dropwise in the specific preparation step (2) of organic modifiers into conical flask is that mixing is molten
The 30~40% of liquid quality.
The mass ratio of filter cake and thionyl chloride is 1:3 in the specific preparation step (3) of organic modifiers.
The mass ratio of chitosan and Loprazolam is 1:10 in the specific preparation step (4) of organic modifiers.
The quality for the reflux product being added in the specific preparation step (4) of organic modifiers into reaction kettle is mixed emulsion
The 30~40% of quality.
The mass ratio of adipic acid and distilled water is 1:5 in the specific preparation step of mixed solution.
In the specific preparation step of mixed solution preferably according to parts by weight, mixed liquor is 50~52 parts, N ,-two ring of N '
Hexyl carbodiimides is 13~15 parts, 4-dimethylaminopyridine is 20~22 parts, tetrahydrofuran is 0.4~0.6 part.
The method have the benefit that:
(1) present invention is first by N, and N '-dicyclohexyl carbodiimide melts dispersion in solution of adipic acid, after dispersion thereto
The heating of methoxy benzoic acid xenol monoesters is added dropwise to be mixed, drying is filtered after stirring and obtains filter cake, then by filter cake and dichloro
Sulfoxide mixing, heating are condensed back reaction, are concentrated in vacuo and reflux product is made, then by reflux product and chitosan low-temperature mixed
It stirs and is freezed, modified filter cake is obtained by filtration in freezing, finally mix modified filter cake with chitosan, acetic acid, after mixing
It is applied to dry on glass plate and high tenacity nanofiltration membrane is made,
The present invention using chitosan as substrate be made filter membrane, using in chitosan organo-functional group generate hydrogen bond, covalently
Each ingredient in key and other Chemical bondings absorption nanofiltration membrane, reinforces the crosslinking degree in nanofiltration membrane between each structure, thus
The mechanical strength for reinforcing nanofiltration membrane, improves the toughness of nanofiltration membrane, and the present invention utilizes polysulfones modification of chitosan, makes to introduce in chitosan
Band charged group, band charged group can form positive and negative charge attraction between each ingredient in nanofiltration membrane around and ionic bond is inhaled
It is attached, to further increase the structural strength of nanofiltration membrane, makes the mechanical property and toughness enhancing of nanofiltration membrane, make the hydrophilic of chitosan
Performance is improved, and ion selectivity can be strengthened, and reinforces the rejection effect to high valence ion；
(2) present invention is with N, and N '-dicyclohexyl carbodiimide is that raw material introduces amide group into nanofiltration membrane, amide group with
Each group in the form protection nanofiltration membrane of branch, makes the chemical stability of nanofiltration membrane be strengthened, while itself has benzene
Base, amino and other organo-functional groups can be crosslinked mutually, to be formed with amide group formation covalent bond, Hydrogen Binding Adsorption
Stable space structure further strengthens the mechanical strength of nanofiltration membrane, so that the toughness of nanofiltration membrane is further strengthened, then pass through
The chemical stability of nanofiltration membrane is reinforced in the protection of amide group, phenyl, is difficult to nanofiltration membrane in conjunction with fine and close structural network rotten
Erosion, has broad application prospects.
Specific embodiment
Adipic acid and distilled water 1:5 in mass ratio are put into three-necked flask, with blender turning with 500~520r/min
Speed is mixed the obtained mixed liquor of 100~120min and weighs 50~52 portions of mixed liquors, 13~15 parts of N, N '-according to parts by weight
Mixing is equal in dicyclohexyl carbodiimide, 0.4~0.6 part of 4-dimethylaminopyridine and 20~22 parts of tetrahydrofuran investment beakers
Even obtained mixed solution, it is spare；According to parts by weight, 13~15 parts of methoxy benzoic acid xenol monoesters, 40~42 parts are weighed
In tetrahydrofuran and 8~10 parts of pyridine investment beakers, place the beaker in the water-bath that bath temperature is 60~64 DEG C, with stirring
Device 50~60min is mixed under conditions of revolving speed is 500~520r/min, prefabricated mixed liquor is made；Spare mixing is molten
Liquid is put into conical flask, and spare mixed solution is added dropwise into conical flask for the drop rate into conical flask with 15~17mL/min
The above-mentioned prefabricated mixed liquor of quality 30~40%, it is after completion of dropwise addition that conical flask is obtained as 3~5h is vibrated in shaking table, under room temperature
Reaction product is put into suction filtration in suction filtration machine and obtains filter cake, with washes of absolute alcohol filter cake 3~5 times, puts into baking oven by reaction product
In temperature be 105~115 DEG C under conditions of dry；Above-mentioned filter cake and thionyl chloride 1:3 in mass ratio investment are inserted with condensation
In the three-necked flask of return pipe, three-necked flask be placed in bath temperature be in 95~100 DEG C of water-bath be heated to reflux 9~
10h, then put into vacuum oven, it is concentrated in vacuo 4 under conditions of vacuum degree is 60~80Pa, temperature is 105~115 DEG C~
Reflux product is made in 5h；Chitosan and Loprazolam 1:10 in mass ratio are put into reaction kettle, are 500~520r/ in revolving speed
40~50min is mixed under conditions of min, mixed emulsion is made, reactor temperature is reduced to 2~4 DEG C, to reaction kettle
The middle above-mentioned reflux product that mixed emulsion quality 30~40% is added, is mixed under conditions of revolving speed is 500~520r/min
60~80min, stirring are placed in household freezer, and 3~4h is freezed under conditions of temperature is -30~-26 DEG C, is filtered after frost
To modified filter cake, with ammonia scrubbing filter cake 3~5 times to get organic modifiers；According to parts by weight, weighing 5~7 parts above-mentioned has
The acetic acid solution that machine modifying agent, 6~8 parts of chitosans and 7~9 parts of mass fractions are 8~10% is put into beaker, with blender with
The revolving speed of 600~620r/min, which is mixed, is made mixing casting solution, mixing casting solution is uniformly applied on glass plate, by glass
Plate is placed in baking oven, and 13~14h is placed under conditions of temperature is 65~75 DEG C, is discharged up to high tenacity nanofiltration membrane.
Example 1
The preparation of mixed solution:
By in adipic acid and distilled water 1:5 in mass ratio investment three-necked flask, stirred with blender with the revolving speed mixing of 500r/min
It mixes 100min and mixed liquor is made, according to parts by weight, weigh 50 portions of mixed liquors, 13 parts of N, N '-dicyclohexyl carbodiimide,
It is uniformly mixed obtained mixed solution in 0.4 part of 4-dimethylaminopyridine and 20 parts of tetrahydrofuran investment beakers, it is spare.
The preparation of prefabricated mixed liquor:
According to parts by weight, 13 parts of methoxy benzoic acid xenol monoesters, 40 parts of tetrahydrofurans and 8 parts of pyridine investment beakers are weighed
In, it places the beaker in the water-bath that bath temperature is 60 DEG C, is mixed and stirred under conditions of revolving speed is 500r/min with blender
It mixes 50min and prefabricated mixed liquor is made.
The preparation of reflux product:
By in spare mixed solution investment conical flask, it is added dropwise into conical flask with the drop rate of 15mL/min into conical flask
The above-mentioned prefabricated mixed liquor of spare mixed solution quality 30%, vibrates 3h under room temperature as in shaking table for conical flask after completion of dropwise addition
Reaction product is made, reaction product is put into suction filtration in suction filtration machine and obtains filter cake, with washes of absolute alcohol filter cake 3 times, investment is dried
It is dried under conditions of temperature is 105 DEG C in case；Above-mentioned filter cake and thionyl chloride 1:3 in mass ratio investment are inserted with condensing reflux
In the three-necked flask of pipe, three-necked flask is placed in the water-bath that bath temperature is 95 DEG C, is heated to reflux 9h, then put into vacuum and do
In dry case, 4h is concentrated in vacuo under conditions of vacuum degree is 60Pa, temperature is 105 DEG C, reflux product is made.
The preparation of organic modifiers:
By in chitosan and Loprazolam 1:10 in mass ratio investment reaction kettle, mixing is stirred under conditions of revolving speed is 500r/min
It mixes 40min and mixed emulsion is made, reactor temperature is reduced to 2 DEG C, the upper of mixed emulsion quality 30% is added into reaction kettle
Reflux product to be stated, is mixed 60min under conditions of revolving speed is 500r/min, stirring is placed in household freezer, be in temperature-
3h is freezed under conditions of 30 DEG C, is filtered after frost and is obtained modified filter cake, with ammonia scrubbing filter cake 3 times to get organic modifiers.
The preparation of high tenacity nanofiltration membrane:
According to parts by weight, the acetic acid solution that 5 parts of above-mentioned organic modifiers, 6 parts of chitosans and 7 parts of mass fractions are 8% is weighed to throw
Enter in beaker, be mixed with blender with the revolving speed of 600r/min and mixing casting solution is made, mixing casting solution is uniformly applied to
On glass plate, glass plate is placed in baking oven, places 13h under conditions of temperature is 65 DEG C, is discharged up to high tenacity nanofiltration membrane.
Example 2
The preparation of mixed solution:
By in adipic acid and distilled water 1:5 in mass ratio investment three-necked flask, stirred with blender with the revolving speed mixing of 510r/min
It mixes 110min and mixed liquor is made, according to parts by weight, weigh 51 portions of mixed liquors, 14 parts of N, N '-dicyclohexyl carbodiimide,
It is uniformly mixed obtained mixed solution in 0.5 part of 4-dimethylaminopyridine and 21 parts of tetrahydrofuran investment beakers, it is spare.
The preparation of prefabricated mixed liquor:
According to parts by weight, 1 part of methoxy benzoic acid xenol monoesters, 41 parts of tetrahydrofurans and 9 parts of pyridine investment beakers are weighed
In, it places the beaker in the water-bath that bath temperature is 62 DEG C, is mixed and stirred under conditions of revolving speed is 510r/min with blender
It mixes 55min and prefabricated mixed liquor is made.
The preparation of reflux product:
By in spare mixed solution investment conical flask, it is added dropwise into conical flask with the drop rate of 16mL/min into conical flask
The above-mentioned prefabricated mixed liquor of spare mixed solution quality 35%, vibrates 4h under room temperature as in shaking table for conical flask after completion of dropwise addition
Reaction product is made, reaction product is put into suction filtration in suction filtration machine and obtains filter cake, with washes of absolute alcohol filter cake 4 times, investment is dried
It is dried under conditions of temperature is 110 DEG C in case；Above-mentioned filter cake and thionyl chloride 1:3 in mass ratio investment are inserted with condensing reflux
In the three-necked flask of pipe, three-necked flask is placed in the water-bath that bath temperature is 98 DEG C, is heated to reflux 10h, then put into vacuum
In drying box, 5h is concentrated in vacuo under conditions of vacuum degree is 70Pa, temperature is 110 DEG C, reflux product is made.
The preparation of organic modifiers:
By in chitosan and Loprazolam 1:10 in mass ratio investment reaction kettle, mixing is stirred under conditions of revolving speed is 510r/min
It mixes 45min and mixed emulsion is made, reactor temperature is reduced to 3 DEG C, the upper of mixed emulsion quality 35% is added into reaction kettle
Reflux product to be stated, is mixed 70min under conditions of revolving speed is 510r/min, stirring is placed in household freezer, be in temperature-
4h is freezed under conditions of 28 DEG C, is filtered after frost and is obtained modified filter cake, with ammonia scrubbing filter cake 4 times to get organic modifiers.
The preparation of high tenacity nanofiltration membrane:
According to parts by weight, the acetic acid solution that 6 parts of above-mentioned organic modifiers, 7 parts of chitosans and 8 parts of mass fractions are 9% is weighed to throw
Enter in beaker, be mixed with blender with the revolving speed of 610r/min and mixing casting solution is made, mixing casting solution is uniformly applied to
On glass plate, glass plate is placed in baking oven, places 14h under conditions of temperature is 70 DEG C, is discharged up to high tenacity nanofiltration membrane.
Example 3
The preparation of mixed solution:
By in adipic acid and distilled water 1:5 in mass ratio investment three-necked flask, stirred with blender with the revolving speed mixing of 520r/min
It mixes 120min and mixed liquor is made, according to parts by weight, weigh 52 portions of mixed liquors, 15 parts of N, N '-dicyclohexyl carbodiimide,
It is uniformly mixed obtained mixed solution in 0.6 part of 4-dimethylaminopyridine and 22 parts of tetrahydrofuran investment beakers, it is spare.
The preparation of prefabricated mixed liquor:
According to parts by weight, 15 parts of methoxy benzoic acid xenol monoesters, 42 parts of tetrahydrofurans and 10 parts of pyridine investments are weighed to burn
In cup, places the beaker in the water-bath that bath temperature is 64 DEG C, mixed under conditions of revolving speed is 520r/min with blender
Prefabricated mixed liquor is made in stirring 60min.
The preparation of reflux product:
By in spare mixed solution investment conical flask, it is added dropwise into conical flask with the drop rate of 17mL/min into conical flask
The above-mentioned prefabricated mixed liquor of spare mixed solution quality 40%, vibrates 5h under room temperature as in shaking table for conical flask after completion of dropwise addition
Reaction product is made, reaction product is put into suction filtration in suction filtration machine and obtains filter cake, with washes of absolute alcohol filter cake 5 times, investment is dried
It is dried under conditions of temperature is 115 DEG C in case；Above-mentioned filter cake and thionyl chloride 1:3 in mass ratio investment are inserted with condensing reflux
In the three-necked flask of pipe, three-necked flask is placed in the water-bath that bath temperature is 100 DEG C, is heated to reflux 10h, then put into vacuum
In drying box, 5h is concentrated in vacuo under conditions of vacuum degree is 80Pa, temperature is 115 DEG C, reflux product is made.
The preparation of organic modifiers:
By in chitosan and Loprazolam 1:10 in mass ratio investment reaction kettle, mixing is stirred under conditions of revolving speed is 520r/min
It mixes 50min and mixed emulsion is made, reactor temperature is reduced to 4 DEG C, the upper of mixed emulsion quality 40% is added into reaction kettle
Reflux product to be stated, is mixed 80min under conditions of revolving speed is 520r/min, stirring is placed in household freezer, be in temperature-
4h is freezed under conditions of 26 DEG C, is filtered after frost and is obtained modified filter cake, with ammonia scrubbing filter cake 5 times to get organic modifiers.
The preparation of high tenacity nanofiltration membrane:
According to parts by weight, the acetic acid solution that 7 parts of above-mentioned organic modifiers, 8 parts of chitosans and 9 parts of mass fractions are 10% is weighed
It puts into beaker, is mixed with blender with the revolving speed of 620r/min and mixing casting solution is made, mixing casting solution is uniformly applied
In on glass plate, glass plate is placed in baking oven, places 14h under conditions of temperature is 75 DEG C, is discharged up to high tenacity nanofiltration
Film.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that mixed solution is not added.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that organic modifiers are not added.
Comparative example 3: the nanofiltration membrane of company, Ningbo City production.To high tenacity nanofiltration membrane produced by the present invention and comparative example
In nanofiltration membrane carry out performance detection, testing result is as shown in table 1:
Test method:
Rejection test
Each nanofiltration membrane is placed in the sodium-chloride water solution that mass fraction is 13~16%, one film device, control are set every 1m
Pressure is 3.5~3.7MPa, and temperature is 35~37 DEG C, measures the sodium chloride mass fraction of the liquid after nanofiltration, calculates
To rejection.
Toughness test
Each group nanofiltration membrane is respectively placed in electronic tensile machine, the length of nanofiltration membrane when measuring fracture is stretched, divided by original length
Obtain elongation at break.
1 performance measurement result of table
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Rejection (%) | 81 | 83 | 86 | 75 | 72 | 74 |
| Elongation at break (%) | 142 | 145 | 148 | 136 | 124 | 113 |
It is high-efficient according to above-mentioned detection data high tenacity nanofiltration membrane good toughness produced by the present invention, retention, have wide
Application prospect.
Claims (10)
1. a kind of preparation method of high tenacity nanofiltration membrane, it is characterised in that specific preparation step are as follows:
It weighs the acetic acid solution that organic modifiers, chitosan and mass fraction are 8~10% to put into beaker, with blender with 600
The revolving speed of~620r/min, which is mixed, is made mixing casting solution, mixing casting solution is uniformly applied on glass plate, by glass plate
It is placed in baking oven, 13~14h is placed under conditions of temperature is 65~75 DEG C, discharge up to high tenacity nanofiltration membrane.
The specific preparation step of organic modifiers described in 2. are as follows:
(1) it weighs in methoxy benzoic acid xenol monoesters, tetrahydrofuran and pyridine investment beaker, places the beaker bath temperature
For 50~60min system is mixed under conditions of revolving speed is 500~520r/min with blender in 60~64 DEG C of water-baths
Obtain prefabricated mixed liquor；
(2) mixed solution is put into conical flask, is dripped into conical flask with the drop rate of 15~17mL/min into conical flask
Add prefabricated mixed liquor, will react conical flask as the obtained reaction product of 3~5h is vibrated in shaking table, under room temperature after completion of dropwise addition
Product investment suction filtration machine in filter obtains filter cake, with washes of absolute alcohol filter cake 3~5 times, put into baking oven in temperature be 105~
It is dried under conditions of 115 DEG C；
(3) filter cake and thionyl chloride investment are inserted in the three-necked flask of condensing reflux pipe, three-necked flask is placed in bath temperature
It is 60~80Pa, temperature in vacuum degree to be heated to reflux 9~10h, then put into vacuum oven in 95~100 DEG C of water-baths
Reflux product is made in 4~5h of vacuum concentration under conditions of degree is 105~115 DEG C；
(4) by chitosan and Loprazolam investment reaction kettle, 40 are mixed under conditions of revolving speed is 500~520r/min
Mixed emulsion is made in~50min, and reactor temperature is reduced to 2~4 DEG C, reflux product is added into reaction kettle, in revolving speed
For 60~80min is mixed under conditions of 500~520r/min, stirring is placed in household freezer, is -30~-26 in temperature
3~4h is freezed under conditions of DEG C, is filtered after frost and is obtained modified filter cake, with ammonia scrubbing filter cake 3~5 times to get organically-modified
Agent；
The specific preparation step of the mixed solution are as follows:
By in adipic acid and distilled water investment three-necked flask, 100 are mixed with blender with the revolving speed of 500~520r/min~
Mixed liquor is made in 120min, weighs mixed liquor, N, and N '-dicyclohexyl carbodiimide, 4-dimethylaminopyridine, tetrahydrofuran are thrown
Enter and is uniformly mixed obtained mixed solution in beaker.
3. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: preferably by weight
Number meter, the acetic acid solution that the organic modifiers are 5~7 parts, chitosan is 6~8 parts, mass fraction is 8~10% is 7~9
Part.
4. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: the tool of organic modifiers
In preparation step (1) preferably according to parts by weight, the methoxy benzoic acid xenol monoesters is 13~15 parts, tetrahydro
Furans is 40~42 parts, pyridine is 8~10 parts.
5. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: the tool of organic modifiers
The quality for the prefabricated mixed liquor being added dropwise described in preparation step (2) into conical flask is the 30~40% of mixed solution quality.
6. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: the tool of organic modifiers
The mass ratio of filter cake described in preparation step (3) and thionyl chloride is 1:3.
7. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: the tool of organic modifiers
The mass ratio of chitosan described in preparation step (4) and Loprazolam is 1:10.
8. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: the tool of organic modifiers
The quality for the reflux product being added described in preparation step (4) into reaction kettle is the 30~40% of mixed emulsion quality.
9. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: mixed solution it is specific
The mass ratio of adipic acid described in preparation step and distilled water is 1:5.
10. a kind of preparation method of high tenacity nanofiltration membrane according to claim 1, it is characterised in that: the tool of mixed solution
In preparation step preferably according to parts by weight, the mixed liquor is 50~52 parts, N, N '-dicyclohexyl carbodiimide
For 13~15 parts, 4-dimethylaminopyridine be 20~22 parts, tetrahydrofuran is 0.4~0.6 part.
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