CN107185417A - Sulfonated polyether sulfone film and preparation method thereof, sulfonated polysulfone membrane and preparation method thereof and its application - Google Patents
Sulfonated polyether sulfone film and preparation method thereof, sulfonated polysulfone membrane and preparation method thereof and its application Download PDFInfo
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
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- 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
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
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- 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
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
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Abstract
The invention provides a kind of sulfonated polyether sulfone film and preparation method thereof, sulfonated polysulfone membrane and preparation method thereof.The sulfonated polyether sulfone film that the application is provided is to be prepared by sulfonated polyether sulfone by the method for inversion of phases, and same sulfonated polysulfone membrane is to be prepared by SPSF by the method for inversion of phases.Present invention also provides a kind of bipolar membrane electrodialysis device, the cation-exchange membrane of the bipolar membrane electrodialysis device is above-mentioned sulfonated polyether sulfone film or sulfonated polysulfone membrane.Present invention also provides a kind of method using above-mentioned bipolar membrane electrodialysis device amino acid separation mixed liquor.Sulfonated polyether sulfone film and sulfonated polysulfone membrane prepared by the present invention has excellent mechanical performance, electric property, stability, and with loose structure, for bipolar membrane electrodialysis process with amino acid separation mixed liquor, positively charged amino acid molecular is easier to migrate film, so as to obtain the higher rate of recovery and current efficiency.
Description
Technical field
The present invention relates to cation exchange technical field of membrane, more particularly to sulfonated polyether sulfone film and preparation method thereof, sulfonation
The method of PS membrane and preparation method thereof, bipolar membrane electrodialysis device and amino acid separation mixed liquor.
Background technology
Amino acid is as many food and the raw material of chemicals, with important edibility and commercial value.Amino
Acid can be generated by the method for fermentation, enzymatic or chemical synthesis, and obtained span amino acid mother liquor composition is more complicated, be also had
Many accessory substance generations, it is therefore desirable to further separation and purifying.The membrane separation techniques such as traditional ultrafiltration, nanofiltration are mainly used
Membrane aperture and the difference of molecular dimension the size component that to go separation different, thus be difficult separation molecular weight very close to mixed amino
Acid.
Electrodialysis separates different mixed amino acid solutions as a kind of new membrane separation technique, but in separation
During encounter some problems.For example, due to the migration of amino acid molecular in separation process, the pH of solution can change,
And amino acid molecular there are different charges under the conditions of different pH, therefore the degree of separation for amino acids can be substantially reduced.Separately
Outside, the research of forefathers is mostly focused on separation of the commercial membranes of densification to mixed amino acid solution, but is due to fine and close business
The resistance that film is transmitted to macromolecular is very big, therefore low separation efficiency.
Bipolar membrane electrodialysis can produce H as a kind of new membrane separation technique by being electrolysed hydrone+And OH-From
Son, the H of generation+And OH-Ion can be combined with amino acid molecular, so as to keep recovery room pH stabilization, therefore can be greatly improved
The degree of separation.Fig. 1 is the structural representation of bipolar membrane electrodialysis (BMED) device, and BMED devices are by membrane stack device (1), feed liquid
Tank (2), recycling can (3), electrode flow container (4), the first peristaltic pump (5), the second peristaltic pump (6), the 3rd peristaltic pump (7), direct current
Source (8), positive plate (9) and minus plate (10) are constituted；Fig. 2 is the schematic diagram of BMED membrane stacks device (1), and membrane stack device (1) is from sun
Pole is to negative electrode successively by Bipolar Membrane (BP-1), cation-exchange membrane (C), Bipolar Membrane (BP-2), lucite spacer and silicagel pad
Piece is spaced composition, is finally fixed by anode plate and cathode plate；Battery lead plate (9 and 10) is to be mounted to Ti-Ru electrode respectively
Constituted on BMED front plates and BMED rear plates.Anode chamber is formed between positive plate (9) and Bipolar Membrane (BP-1), by Bipolar Membrane
(BP-1) feed liquid room is formed between cation-exchange membrane (C), is formed between cation-exchange membrane (C) and Bipolar Membrane (BP-2)
Lysine recovery room, cathode chamber is formed between Bipolar Membrane (BP-2) and minus plate (10)；Positive plate (9) and minus plate (10) point
It is not connected by wire with the positive pole and negative pole of dc source；Cathode chamber and anode chamber are connected, therefore, Yin/Yang pole room, material
Liquid room, lysine recovery room constitute three circulation loops.Therefore, two kinds of ammonia of close molecular weight are realized using bipolar membrane electrodialysis
Being separated into for base acid is a kind of possible.
The content of the invention
Present invention solves the technical problem that be to provide a kind of sulfonated polyether sulfone film and sulfonated polysulfone membrane, what the application was provided
Sulfonated polyether sulfone film and cation-exchange membrane of the sulfonated polysulfone membrane as bipolar membrane electrodialysis device, can be achieved two kinds of molecular weight and connect
The separation of near amino acid, and with higher the recovery of amino acid and current efficiency.
This application provides a kind of sulfonated polyether sulfone film, prepared by sulfonated polyether sulfone by the method for inversion of phases.
It is preferred that, the ion exchange capacity of the sulfonated polyether sulfone is 0.15~0.4mmol/g.
Present invention also provides a kind of preparation method of sulfonated polyether sulfone film, including：
Sulfonated polyether sulfone is subjected to inversion of phases in water, sulfonated polyether sulfone film is obtained.
It is preferred that, the process of the inversion of phases is specially：
Sulfonated polyether sulfone is mixed with organic solvent, coating liquid is obtained；
The coating liquid is coated in substrate, then is placed in water immersion, sulfonated polyether sulfone film is obtained；The organic solvent
For 1-METHYLPYRROLIDONE or the mixed liquor of 1-METHYLPYRROLIDONE and dichloromethane；The temperature of the water is 0~35 DEG C.
Present invention also provides a kind of sulfonated polysulfone membrane, prepared by SPSF by the method for inversion of phases.
It is preferred that, the ion exchange capacity of the SPSF is 0.08~0.4mmol/g.
Present invention also provides a kind of preparation method of sulfonated polysulfone membrane, including：
SPSF is subjected to inversion of phases in water, sulfonated polysulfone membrane is obtained.
It is preferred that, the process of the inversion of phases is specially：
SPSF is mixed with organic solvent, coating liquid is obtained；
The coating liquid is coated in substrate, then is placed in water immersion, sulfonated polysulfone membrane is obtained；The organic solvent is
The mixed liquor of 1-METHYLPYRROLIDONE or 1-METHYLPYRROLIDONE and dichloromethane；The temperature of the water is 0~35 DEG C.
Present invention also provides a kind of bipolar membrane electrodialysis device, the cation-exchange membrane of the bipolar membrane electrodialysis device
Described in the sulfonated polyether sulfone film or such scheme prepared by the preparation method described in described in such scheme or such scheme
Or the sulfonated polysulfone membrane prepared by the preparation method described in such scheme.
Present invention also provides the bipolar membrane electrodialysis device amino acid separation mixed liquor described in a kind of utilization such scheme
Method, comprise the following steps：
The mixed liquor of the first amino acid and the second amino acid is added in material liquid tank, strong electrolyte is added in electrode flow container,
The second Freamine Ⅲ is added in recycling can；First amino acid is negatively charged amino acid, second in mixed liquor
Amino acid is positively charged amino acid in mixed liquor；
The first peristaltic pump, the second peristaltic pump and the 3rd peristaltic pump are opened, is then turned on after dc source, operation in material liquid tank
Second Transport of Amino Acids is to recycling can, the first amino acid and the second amino acid separated.
It is preferred that, first amino acid is glutamic acid, and the second amino acid is lysine；The material liquid tank Glutamic Acid
Concentration is 0.02~0.1mol/L, and the concentration of lysine is 0.02~0.1mol/L in the material liquid tank, the glutamic acid and is relied
The concentration ratio of propylhomoserin is (1~5)：(1~5)；The concentration of lysine is 0.005~0.03mol/L in the recycling can.
This application provides a kind of sulfonated polyether sulfone film and a kind of sulfonated polysulfone membrane, and provide the preparation side of above two film
Method, above-mentioned sulfonated polyether sulfone film is to be prepared by sulfonated polyether sulfone by the method for inversion of phases, same above-mentioned sulfonated polysulfone membrane
It is also to be prepared by SPSF by the method for inversion of phases, the sulfonated polyether sulfone film that the application is provided has with sulfonated polysulfone membrane
There are excellent mechanical performance, electric property and stability, simultaneously because sulfonated polyether sulfone film is respectively provided with finger-type with sulfonated polysulfone membrane
Hole, therefore many hydrones can be carried inside it, and positively charged amino acid molecular was easily migrated when migrating film
Film, and amino acid molecular size is larger, resistance is smaller when by with larger finger-type hole, therefore sulfonated polyether sulfone film or
Sulfonated polysulfone membrane as bipolar membrane electrodialysis device cation-exchange membrane when, two kinds can be efficiently separated with different charged molecule amounts
Close amino acid, and with higher the recovery of amino acid and current efficiency.Further, sulfonated polysulfone membrane can film skin
Layer contains slotted eye, and nexine contains finger-type hole, further improves separative efficiency and current efficiency.
Brief description of the drawings
Fig. 1 is the structural representation of bipolar membrane electrodialysis of the present invention (BMED) device；
Fig. 2 is the structural representation of membrane stack device (1) in BMED devices of the present invention；
Fig. 3 is the infrared spectrogram of sulfonated polyether sulfone film and sulfonated polysulfone membrane in the embodiment of the present invention 1~6；
Fig. 4 is the field emission scanning electron microscope figure for the fine and close sulfonated polyether sulfone film that the embodiment of the present invention 1 is prepared；
Fig. 5 is the field emission scanning electron microscope figure for the SPES-4 films that the embodiment of the present invention 1 is prepared；
Fig. 6 is the field emission scanning electron microscope figure for the SPES-25 films that the embodiment of the present invention 3 is prepared；
Fig. 7 is the field emission scanning electron microscope figure for the SPES-D-4 films that the embodiment of the present invention 4 is prepared；
Fig. 8 is the field emission scanning electron microscope figure for the SPSf-4 films that the embodiment of the present invention 5 is prepared；
Fig. 9 is the field emission scanning electron microscope figure for the SPSf-25 films that the embodiment of the present invention 6 is prepared.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of sulfonated polyether sulfone film, it is prepared into by sulfonated polyether sulfone by the method for inversion of phases
Arrive.
For sulfonated polyether sulfone film, it is prepared by sulfonated polyether sulfone by the method for inversion of phases.The sulfonation
Polyether sulfone is well known sulfonated polyether sulfone in the prior art, and it can be bought by market, can also be prepared into according to existing method
Arrive；The sulfonation process of the polyether sulfone is specially：
Polyether sulfone is mixed with dichloromethane, the solution that mass concentration is 5%~20% is obtained, adds sulfonating agent and two
The mixed liquor of chloromethanes, obtains sulfonated polyether sulfone.
In above process, the sulfonating agent is well known to those skilled in the art, and this application is not limited particularly
System；Example, the sulfonating agent is chlorosulfonic acid and the concentrated sulfuric acid, and in a particular embodiment, the sulfonating agent is chlorosulfonic acid.The sulphur
Agent and the volume ratio of the dichloromethane are 1：(1~10), in a particular embodiment, the sulfonating agent and the dichloromethane
Volume ratio be 1：(3~8).
More specifically, the sulfonation process of the polyether sulfone is：
1.5~2.5kg polyether sulfones and 5~8L dichloromethane are added in reactor, then it are stirred, is being stirred
5~8L dichloromethane is added while mixing so that polyether sulfone can be completely dissolved；After polyether sulfone is completely dissolved, 1~2L bis-
The mixed liquor of chloromethanes and 0.2~0.8L chlorosulfonic acids is added in reactor in two batches；, will be mixed after 40 DEG C are reacted 15~25h
Close liquid to discharge from reactor bottom, be put into 20~50 DEG C of a large amount of water, obtain the sulfonated polyether sulfone of solid；By solid sulfonated polyether
Sulfone is crushed with disintegrating machine, obtains sulfonated polyether sulfone powder, be washed with water until cleaning fluid for neutrality, then by filtering and
60~100 DEG C of dry 24h, obtain sulfonated polyether sulfone finished product.
In said process, sulfonating agent be added in the solution dissolved with polyether sulfone be in order on polyether sulfone strand grafting on
Sulfonic group, obtains sulfonated polyether sulfone, so that the sulfonated polyether sulfone film bear electricity subsequently made, with ion selectivity.
The ion exchange capacity of the sulfonated polyether sulfone of the above-mentioned preparation of the application is 0.15~0.4mmol/g, in specific implementation
In example, the ion exchange capacity of the sulfonated polyether sulfone is 0.2~0.35mmol/g.
Specifically, present invention also provides a kind of preparation method of sulfonated polyether sulfone film, including：
Sulfonated polyether sulfone is subjected to inversion of phases in water, sulfonated polyether sulfone film is obtained.
During sulfonated polyether sulfone film is prepared, the preparation of sulfonated polyether sulfone has been carried out specifically in the above
It is bright, no longer repeated herein.The inversion of phases process is carried out in water, and the preparation of the sulfonated polyether sulfone film is specially：
Sulfonated polyether sulfone is mixed with organic solvent, coating liquid is obtained；
The coating liquid is coated in substrate, then is placed in water immersion, sulfonated polyether sulfone film is obtained；The organic solvent
For 1-METHYLPYRROLIDONE or the mixed liquor of 1-METHYLPYRROLIDONE and dichloromethane；The temperature of the water is 0~35 DEG C.
It is above-mentioned prepare sulfonated polyether sulfone film during, coating liquid is prepared first, i.e., has been dissolved in sulfonated polyether sulfone
In machine solvent；During sulfonated polyether sulfone dissolves, when sulfonated polyether sulfone is dissolved in into 1-METHYLPYRROLIDONE, film is obtained
The mass concentration of liquid is preferably 15%~35%, in embodiment, and the mass concentration of the coating liquid is more preferably 23%~
25%；When sulfonated polyether sulfone to be dissolved in the mixed liquor of 1-METHYLPYRROLIDONE and dichloromethane, the quality for obtaining coating liquid is dense
Degree is preferably 15%~35%, and mass concentration of the dichloromethane in coating liquid is preferably 6%~18%, in embodiment, institute
The mass concentration for stating coating liquid is more preferably 23%~25%, and mass concentration of the dichloromethane in coating liquid is more preferably 11%
~13%.
According to the present invention, then by the coating liquid in substrate film, then pass through the method for inversion of phases and be film-made.The base
Bottom is preferably glass plate well known to those skilled in the art and polyfluortetraethylene plate, and this application is had no particular limits,
Polyfluortetraethylene plate is more preferably in embodiment.
Substrate after film is film-made by the method for inversion of phases, the method for described inversion of phases is specially by after film
Substrate is impregnated in film forming in the water of certain temperature.The temperature of the water is preferably 0~35 DEG C, in embodiment, more preferably 2~
6 DEG C or 23~27 DEG C.The depth of the water is preferably 300~500 times of film thickness of thin layer, in embodiment, more preferably
380~420 times.
Substrate after film is impregnated in the water of different temperatures by the application, is to obtain many of different-shape and aperture
Pore structure, with the application for the sulfonated polyether sulfone film for expanding preparation.
Present invention also offers a kind of sulfonated polysulfone membrane, prepared by SPSF by the method for inversion of phases.
Above-mentioned sulfonated polysulfone membrane is that the method for carrying out inversion of phases by SPSF is prepared.The SPSF is
SPSF known to prior art, it can be bought by market, can also be prepared according to existing method；The polysulfones
Sulfonation process is specially：
Polysulfones is mixed with dichloroethanes, the solution that mass concentration is 1%~15% is obtained, adds sulfonating agent and dichloro
The mixed liquor of ethane, obtains SPSF.
In above process, the sulfonating agent is well known to those skilled in the art, and this application is not limited particularly
System；Example, the sulfonating agent is chlorosulfonic acid and the concentrated sulfuric acid, specifically, the sulfonating agent is chlorosulfonic acid.The sulfonating agent and institute
The volume ratio for stating dichloroethanes is 1：(10~60), more specifically, the volume ratio of the sulfonating agent and the dichloroethanes is 1：
(30~50).
More specifically, the sulfonation process of the polysulfones is：
5~10g polysulfones and 50~150ml dichloroethanes are added to condenser pipe and nitrogen protection device is connected to
In the neck flasks of 250ml two, it is passed through after nitrogen 1h, the mixed liquor of 1~4ml chlorosulfonic acid and 10~30ml dichloroethanes is dripped dropwise
It is added in two neck flasks, takes 20~40 minutes.Then obtained mixed liquor is stirred 12 hours at 30 DEG C.Treat sulfonating reaction
After end, it is put into 20~50 DEG C of a large amount of water, obtains the SPSF of solid；Solid SPSF is broken with disintegrating machine
It is broken, SPSF powder is obtained, is washed with water until cleaning fluid is neutrality, then is dried in vacuo by filtering and at 40~80 DEG C
24h, obtains SPSF finished product.
In said process, sulfonating agent be added in the solution dissolved with polysulfones be in order on polysulfones strand grafting on sulfonic acid
Base, obtains SPSF, so that the sulfonated polysulfone membrane bear electricity subsequently made, with ion selectivity.
The ion exchange capacity of the SPSF of the above-mentioned preparation of the application is 0.08~0.4mmol/g, in specific embodiment
In, the ion exchange capacity of the SPSF is 0.1~0.3mmol/g.The inversion of phases process of the SPSF is ability
Inversion of phases process known to field technique personnel, has no particular limits to this application.
Specifically, present invention also provides a kind of preparation method of sulfonated polysulfone membrane, including：
SPSF is subjected to inversion of phases in water, sulfonated polysulfone membrane is obtained.
During sulfonated polysulfone membrane is prepared, the preparation of SPSF is described in detail in the above, this
Place is no longer repeated.The process of the inversion of phases carries out in water, specifically, the sulfonated polysulfone membrane is prepared as：
SPSF is mixed with organic solvent, coating liquid is obtained；
The coating liquid is coated in substrate, then is placed in water immersion, sulfonated polysulfone membrane is obtained；The organic solvent is
The mixed liquor of 1-METHYLPYRROLIDONE or 1-METHYLPYRROLIDONE and dichloromethane；The temperature of the water is 0~35 DEG C.
It is above-mentioned prepare SPSF during, coating liquid is prepared first, i.e., SPSF is dissolved in organic solvent
In；During SPSF dissolves, when SPSF is dissolved in into 1-METHYLPYRROLIDONE, the quality for obtaining coating liquid is dense
Degree is preferably 15%~35%, and in embodiment, the mass concentration of the coating liquid is more preferably 23%~25%；Sulfonation is gathered
When sulfone is dissolved in the mixed liquor of 1-METHYLPYRROLIDONE and dichloromethane, the mass concentration for obtaining coating liquid is preferably 15%~
35%, mass concentration of the dichloromethane in coating liquid is preferably 6%~18%, in embodiment, the quality of the coating liquid
Concentration is more preferably 23%~25%, and mass concentration of the dichloromethane in coating liquid is more preferably 11%~13%.
According to the present invention, then by the coating liquid in substrate film, then pass through the method for inversion of phases and be film-made.The base
Bottom is preferably glass plate well known to those skilled in the art and polyfluortetraethylene plate, and this application is had no particular limits,
Polyfluortetraethylene plate is more preferably in embodiment.
Substrate after film is film-made by the method for inversion of phases, the method for described inversion of phases is specific by the base after film
Bottom is impregnated in film forming in the water of certain temperature.The temperature of the water is preferably 0~35 DEG C, in embodiment, and more preferably 2~6
DEG C or 23~27 DEG C.The depth of the water is preferably 300~500 times of film thickness of thin layer, in embodiment, more preferably
380~420 times.
Substrate after film is impregnated in the water of different temperatures by the application, is to obtain many of different-shape and aperture
Pore structure, with the application for the sulfonated polysulfone membrane for expanding preparation.
The method that sulfonated polyether sulfone film employs inversion of phases with sulfonated polysulfone membrane is prepared in the present invention, this method is by sulphur
Change polyether sulfone or SPSF is dissolved in organic solvent, obtain coating liquid, then coating liquid is subjected to film in substrate, then will
Substrate after film is impregnated in gel bath water, occurs phase process and inversion of phases process；Phase process is coating liquid immersion water
In after organic solvent and water phase counterdiffusion will be carried out by liquid film/water termination, the exchange between organic solvent and water reaches necessarily
Degree, coating liquid becomes thermodynamic unstable system, then results in coating liquid and is separated, and determines membrane pore structure；Phase
Conversion process refers to after film liquid system split-phase that organic solvent and water are further exchanged, and there occurs the condensing of fenestra, alternate flowing
And the rich phase film forming of polymer.
In this application, in order to make the perforated membrane of different shape, using changing film material type, phase transition temperature and
The mode for adding dichloromethane carries out the process of inversion of phases, so that by controlling the speed of phase process come the size of control hole,
Concrete condition refers to subsequent embodiment.
During sulfonated polyether sulfone film or sulfonated polysulfone membrane is prepared, the application is prepared preferably in 0~35 DEG C of water
The film layer of Different Pore Structures, specifically, in sulfonated polyether sulfone series membranes (SPES) made from 0~35 DEG C and SPSF series
Film (SPSf) section contains finger-type hole, but hymeniderm layer is different, for example SPES series membranes (including SPES-4 films, SPES-25 films
With SPES-D-4 films) cortex be spongiform hole, and SPSf series membranes (including SPSf-4 films and SPSf-25 films) cortex contain it is ellipse
Circular hole；Spongiform hole is more fine and close compared to the hole of ellipse, therefore carry-on hydrone is relative inside film
It is less, thus lysine molecule migrated membrane resistance can be larger, otherwise the hole of ellipse can allow it internal to carry more water
Molecule, therefore resistance can be smaller when migrating film for lysine molecule.Therefore SPSf series membranes are than SPES series membrane separation efficiencies
Higher with current efficiency, energy consumption is lower.
Separation of water content, surface resistance and the tensile strength of sulfonated polyether sulfone film or sulfonated polysulfone membrane to amino acid mixed liquor
Also influence can be produced, specifically, water content is higher, surface resistance is smaller, it is mixed applied to bipolar membrane electrodialysis device amino acid separation
Close the separative efficiency obtained during liquid and current efficiency can be higher, energy consumption can be lower；This is due to that water content is higher, is illustrated inside film
The hydrone of carrying is more, then amino acid molecular was easier when migrating film with hydrated ion；Surface resistance is smaller, illustrates same
Voltage under, current density was higher when amino acid molecular migrates film.Tensile strength is higher, illustrates that its mechanical strength is better, should
For bipolar membrane electrodialysis device so that, it is necessary to which film has higher mechanical strength, such film is not easy during amino acid separation mixed liquor
Damaged and deformation, is conducive to being recycled for multiple times.
Thus, present invention also provides a kind of bipolar membrane electrodialysis device, the cation of the bipolar membrane electrodialysis device
Exchange membrane is the sulfonated polyether sulfone film or sulfonated polysulfone membrane described in such scheme.
Herein described bipolar membrane electrodialysis (BMED) device is device well known to those skilled in the art, and the application is to this
Have no particular limits, the specific structural representation of BMED devices is as shown in Figure 1：By membrane stack device (1), material liquid tank (2), reclaim
Tank (3), electrode flow container (4), the first peristaltic pump (5), the second peristaltic pump (6), the 3rd peristaltic pump (7), dc source (8), anode
Plate (9) and minus plate (10) are constituted；Fig. 2 be BMED membrane stacks device (1) schematic diagram, membrane stack device (1) from anode to negative electrode according to
It is secondary to be spaced by Bipolar Membrane (BP-1), cation-exchange membrane (C), Bipolar Membrane (BP-2), lucite spacer and silica gel pad
Constitute, finally fixed via anode plate and cathode plate；Battery lead plate (9 and 10) is that Ti-Ru electrode is mounted into BMED fore-clamps respectively
Constituted on plate and BMED rear plates.Form anode chamber between positive plate (9) and Bipolar Membrane (BP-1), by Bipolar Membrane (BP-1) and
Feed liquid room is formed between cation-exchange membrane (C), recovery room is formed between cation-exchange membrane (C) and Bipolar Membrane (BP-2),
Cathode chamber is formed between minus plate by Bipolar Membrane (BP-2)；Positive plate (9) and minus plate (10) pass through wire and direct current respectively
The positive pole of power supply is connected with negative pole；Cathode chamber and anode chamber are connected, therefore, Yin/Yang pole room, feed liquid room, recovery room difference
Each constitute circulation loop.
Cation-exchange membrane in the BMED membrane stacks device is porous prepared by the preparation method described in such scheme
Sulfonated polyether sulfone film or sulfonated polysulfone membrane, miscellaneous part the application of bipolar membrane electrodialysis device have no particular limits, and are
This area frequently with part.Preferably, Bipolar Membrane (BP) is preferably the FBM films that German Fumatech companies provide.
In BMED devices, cathode chamber and anode chamber's series connection, therefore, Yin/Yang pole room, feed liquid room, recovery room are each independent
Constitute circulation loop；In the circulation loop, the entrance and exit of feed liquid room is passed through material liquid tank (2) via conduit, recovery room
Entrance and exit is passed through recycling can (3) via conduit, and cathode chamber is connected with anode chamber by conduit, constitutes BMED electrode chamber,
Its entrance and exit is passed through electrode flow container (4) via conduit respectively, and the material liquid tank (2), recycling can (3), electrode flow container (4) enter
Enter the power in membrane stack device (1) to be provided by the first peristaltic pump (5), the second peristaltic pump (6), the 3rd peristaltic pump (7) respectively, and warp
The volume flow of each compartment can be controlled by peristaltic pump, thus formed feed liquid room circulation loop, lysine recovery room circulation loop,
Electrode solution room circulation loop, and the respective independent loops of three circulation loops.
In consideration of it, present invention also provides a kind of side using above-mentioned bipolar membrane electrodialysis device amino acid separation mixed liquor
Method, comprises the following steps：
The mixed liquor of the first amino acid and the second amino acid is added in material liquid tank, strong electrolyte is added in electrode flow container,
The second Freamine Ⅲ is added in recycling can；First amino acid is negatively charged amino acid, second in mixed liquor
Amino acid is positively charged amino acid in mixed liquor；
The first peristaltic pump, the second peristaltic pump and the 3rd peristaltic pump are opened, is then turned on after dc source, operation in material liquid tank
Second Transport of Amino Acids is to recycling can, the first Freamine Ⅲ and the second Freamine Ⅲ separated.
In order to realize the separation of amino acid mixed liquor, the amino acid mixed liquor of the application is for two kinds in the solution with different electricity
The amino acid of lotus, is specially the first amino acid negatively charged in mixed liquor, the second positively charged amino in mixed liquor
Acid；The bipolar membrane electrodialysis device that the application is provided particularly with two kinds of close amino acid of molecular weight there is preferably separation to imitate
Really.In a particular embodiment, the application carries out the separation of two kinds of amino acid exemplified by separating glutamic acid and lysine.Specially：
Glutamic acid and lysine mixed liquor are added in material liquid tank, the lysine solution of low concentration is added in recycling can,
Strong electrolytic solution is added in electrode flow container；
The first peristaltic pump, the second peristaltic pump, the 3rd peristaltic pump are opened, lysine molecule after dc source, operation is then turned on
It will be migrated from feed liquid room to recovery room, with the operation of device, the lysine concentration in recycling can will increase, and thus achieve
Glutamic acid and lysine are efficiently separated.
In above process, in the material liquid tank glutamic acid and the concentration of lysine is 0.02~0.1mol/L, described
The concentration ratio of glutamic acid and lysine is (1~5)：(1~5)；In a particular embodiment, the glutamic acid and the lysine
Concentration is 0.05mol/L.Strong electrolyte in the electrode flow container be it is well known to those skilled in the art, example, it is described strong
Electrolyte is selected from sodium sulphate, sodium nitrate, potassium sulfate, sodium hydroxide or potassium hydroxide, in a particular embodiment, the strong electrolyte
For sodium sulphate, its concentration is 0.05~0.3mol/L.The concentration of the recycling can Glutamic Acid is 0.005~0.03mol/L；
In specific embodiment, the concentration of the glutamic acid is 0.01mol/L.
In above-mentioned processing procedure, the running of the bipolar membrane electrodialysis device is ripe according to those skilled in the art
The mode known is carried out, and the application has no particular limits.
During above-mentioned separation glutamic acid and lysine mixed liquor, the effect of peristaltic pump is opened before switching on power is
Circulated each compartment of the solution in material liquid tank, recycling can, electrode flow container respectively in membrane stack device, to drain compartment
Interior bubble.Bring into operation device after switching on power, and constant current terminates experiment after operating 6 hours.Described constant current is preferably
0.05~0.3A.
This application provides the preparation method of a kind of porous sulfonated polyether sulfone film and sulfonated polysulfone membrane, and as sun
Amberplex is used for bipolar membrane electrodialysis process, and to separate, molecular weight is close and two kinds of amino acid with different electric charges, so that
Solve the problem of dense film applies to separate mixed amino acid recovering rate and low current efficiency in electrodialysis.
For a further understanding of the present invention, sulfonated polysulfone membrane, the sulfonated polyether provided with reference to embodiment the present invention
Sulfone film and its application are described in detail, and protection scope of the present invention is not limited by the following examples.
The low temperature inversion of phases of embodiment 1 prepares porous sulfonated polyether sulfone film SPES-4
(1) preparation of sulfonated polyether sulfone：It is added to after 2kg polyether sulfones and the mixing of 6.7L dichloromethane in reactor, side stirring
Side, which adds 6.8L dichloromethane solutions, is completely dissolved polyether sulfone；It is divided to two after again mixing 1.5L dichloromethane and 0.5L chlorosulfonic acids
Criticize and be added in reactor, stir while adding, 20h are reacted at 40 DEG C；Then mixed liquor is discharged from reactor bottom, be put into
Precipitated in 45 DEG C of water, obtained solid is crushed with disintegrating machine, obtain sulfonated polyether sulfone powder, washing is until cleaning fluid
For neutrality, then by filtering and in 90 DEG C of dry 24h, obtain sulfonated polyether sulfone finished product.Test the ion exchange of sulfonated polyether sulfone
Capacity is 0.2mmol/g, method of testing bibliography periodical《Chemical Engineering Journal》2010 volume 160
340-350 pages of report；
(2) low temperature inversion of phases prepares porous sulfonated polyether sulfone film：40g sulfonated polyether sulfone solid powder is added to
In 123.2mL 1-METHYLPYRROLIDONE, stirring 72h obtains 24wt% coating liquid, vacuumizes to remove bubble therein；Take
2~3mL above-mentioned coating liquid is coated on above polyfluortetraethylene plate, is then kept flat the substrate after film in 4 DEG C of water and is soaked
Bubble 30~60 minutes, the depth of water is 300~500 times of film thickness of thin layer, and perforated membrane is obtained after shaping and SPES- is named as
4 films.
As a comparison, sulfonated polyether sulfone dense film is also prepared for, detailed process is：
The coating liquid obtained after above sulfonated polyether sulfone is dissolved is coated on above glass plate, then is kept flat in baking oven, is pressed
According to 40 DEG C of -4h, 60 DEG C of -4h, 80 DEG C of -4h heat-treating methods are heat-treated, then by the film of shaping slowly from glass plate
Face is peeled, and with standby in immersion sodium chloride solution, is designated as sulfonated polyether sulfone dense film, dense SPES are named as with English
membrane。
(3) sign of film：Water content, tensile strength, surface resistance, infrared spectrum and Flied emission are carried out to SPES-4 films to sweep
Sign and the observation of Electronic Speculum are retouched, it is as a result as follows：The water content of SPES-4 films is 214.0%, and tensile strength is 3.30MPa, face electricity
Hinder for 4.51 Ω cm2。
The infrared spectrum of SPES-4 films is as shown in figure 3, the curve a in Fig. 3 is the infrared spectrum curve of SPES-4 films, by scheming
3 understand, in 3000-3300cm-1Place occurs in that the characteristic absorption peak of-OH in sulfonic group；In~1025cm-1With~1180cm-1Point
Wei not sulfonic symmetrical and asymmetric stretching vibration absworption peak；In~1240cm-1With 714~725cm-1Absworption peak difference
Caused by vibration for C-O-C and C=C；Result above shows that the sulfonation to polyether sulfone produces a desired effect, and has obtained sulphur
Change poly (ether sulfone) film.
The field emission scanning electron microscope figure of SPES-4 films is as shown in figure 5, scheme the section close-up view (amplification of (a-1) for film in Fig. 5
300 times), figure (a-2) is the partial enlarged drawing (5000 times of amplification) of film section, and figure (a-3) (is put for the partial enlarged drawing of film section
It is big 50000 times), as shown in Figure 5, the section of film contains a large amount of finger-type holes, shows to be successfully prepared porous sulfonated polyether sulfone film.
The water content of sulfonated polyether sulfone dense film as a comparison is 4.1%, and tensile strength is 46.48MPa, and surface resistance is big
In 80 Ω cm2.Fig. 4 is the field emission scanning electron microscope figure of sulfonated polyether sulfone dense film, and figure (a-1) is complete for the section of film in Fig. 4
Looks figure (300 times of amplification), figure (a-2) is the partial enlarged drawing (5000 times of amplification) of film section, and figure (a-3) is the part of film section
Enlarged drawing (50000 times of amplification), as shown in Figure 4, obvious hole is not observed in the inside of film, shows to be made by heat treatment
Be dense film.
The porous sulfonated polyether sulfone film SPES-4 of embodiment 2 passes through bipolar membrane electrodialysis (BMED) amino acid separation
The SPES-4 films obtained to embodiment 1 carry out BMED experiments, and BMED devices illustrate such as Fig. 1, and BMED devices are by membrane stack
Device (1), material liquid tank (2), recycling can (3), electrode flow container (4), the first peristaltic pump (5), the second peristaltic pump (6), the 3rd are wriggled
Pump (7), dc source (8), positive plate (9) and minus plate (10) are constituted；Bipolar Membrane (BP-1) used in membrane stack device (1) and
(BP-2) it is FBM films that German Fumatech companies provide, cation-exchange membrane (C) is SPES-4 films prepared by embodiment 1；
The placement order of different films is as shown in Fig. 2 successively by Bipolar Membrane (BP-1), cation-exchange membrane (C), bipolar from anode to negative electrode
Film (BP-2), lucite spacer and silica gel pad are spaced composition, are finally fixed via anode plate and cathode plate.Membrane stack is filled
The single film effective area put in (1) is 20cm2.Wherein the entrance and exit of feed liquid room is passed through material liquid tank (2) via conduit,
The entrance and exit of lysine recovery room is passed through recycling can (3) via conduit, and cathode chamber is connected with anode chamber by conduit, constitutes
BMED electrode chamber, its entrance and exit is passed through electrode flow container (4) via conduit respectively, the material liquid tank (2), recycling can (3),
The power that electrode flow container (4) enters in membrane stack device (1) is wriggled by the first peristaltic pump (5), the second peristaltic pump (6), the 3rd respectively
Pump (7) is provided, and via peristaltic pump the volume flow of each compartment can be controlled to be 300mL/min, so as to form the circulation of feed liquid room
The respective independent loops of loop, recovery room circulation loop, electrode solution room circulation loop, and three circulation loops.By the membrane stack device
(1) positive plate (9) and minus plate (10) connects the positive pole and negative pole of dc source (8) by wire respectively.
Glutamic acid and lysine mixed liquor are handled using the BMED devices of the above, glutamic acid and lysine is realized separation.
250mL 0.05mol/L glutamic acid and the mixed liquor of 0.05mol/L lysines are added into material liquid tank (2)；To recycling can (3)
Middle addition 250mL 0.01mol/L lysine solution；250mL 0.1mol/L Na is added into electrode flow container (4)2SO4
Solution；The flow of peristaltic pump (5), (6) and (7) is adjusted for 300mL/min, the bubble in each circulation compartment is eliminated after 10min, with
Opening dc source (8) afterwards makes BMED devices be run under conditions of constant current 0.07A, the lysine molecule of recovery room after 6h
Concentration is increased to 0.043mol/L by initial 0.01mol/L, now stops experiment.
As a result show：Under conditions of constant current 0.07A, the rate of recovery of lysine molecule is 76.7%, and energy consumption is
6.43kWh/kg, current efficiency is 62.0%.Test in running, recovery room pH changes very little, stable in 9.88-9.96
In the range of.Experiment detects after terminating to the purity of lysine, as a result about 100%.
As a comparison, Japanese Asahi Glass Company companies provide CMX films and the sulfonated polyether sulfone film of densification
BMED processes are also used for, BMED process of its operating method with SPES-4 films.According to literature periodical《Desalination》2015
The report in 38-46 pages of volume 373 of year understands that the water content of CMX films is 25%~30%, and surface resistance is 2.0~3.5 Ω cm2, from
Sub- exchange capacity is 1.5~1.8mmol/g.
Using CMX reference films carry out BMED experiments result be：The rate of recovery of lysine is 48.1%, and purity is about
100%, energy consumption is 8.16kWh/kg, and current efficiency is 40.1%.Test in running, recovery room pH changes very little, surely
It is scheduled in the range of 9.85-9.98.
When carrying out BMED experiments using sulfonated polyether sulfone dense film, voltage needed for finding is excessive, more than the range of power supply
(60V), so can not go to carry out BMED experiments under identical condition.This is due to sulfonated polyether sulfone dense film without obvious hole
Gap, causes water content very little and with very big surface resistance.
The above analysis result is understood, relative to reference film CMX, and the preparation-obtained SPES-4 films of embodiment 1 are relying
The rate of recovery, the current efficiency aspect of propylhomoserin are all significantly improved, because the finger-type pore structure that SPES-4 films possess can
Substantially reduce the resistance of lysine molecule migration；And the lysine product of high-purity is also can obtain using SPES-4 films.As
Contrast, fine and close sulfonated polyether sulfone film can not be applied to BMED processes in this experiment, further the advantage of checking film loose structure.
The normal temperature inversion of phases of embodiment 3 prepares porous sulfonated polyether sulfone film SPES-25
The preparation of SPES-4 films in the present embodiment preparation method be the same as Example 1, difference is：Substrate after film is in water
It it is 25 DEG C by lower water temperature, obtained film is named as SPES-25 films during middle carry out inversion of phases.
To the SPES-4 films in the characterization method be the same as Example 1 of SPES-25 films.Test result indicates that, SPES-25 films contain
Water is 237.80%, and tensile strength is 3.69MPa, and surface resistance is 18.62 Ω cm2。
Shown in the infrared spectrum of SPES-25 films such as Fig. 3 (b), the SPES-4 films in its characteristic absorption peak be the same as Example 1.
The field emission scanning electron microscope figure of SPES-25 films (is put as shown in fig. 6, scheming (a-1) in Fig. 6 for the section close-up view of film
It is big 300 times), figure (a-2) is the partial enlarged drawing (5000 times of amplification) of film section, and figure (a-3) is the partial enlarged drawing of film section
(50000 times of amplification), it will be appreciated from fig. 6 that the section of film contains finger-type hole, shows what is prepared in 25 DEG C of water by inversion of phases
SPES-25 films also have porous structure；And the thickness ratio SPES-4 films of SPES-25 films are higher, illustrate made from 25 DEG C
SPES-25 films are more loose.
BMED devices and running be the same as Example 2, as a result show：Under conditions of constant current 0.07A, lysine molecule
The rate of recovery is 52.0%, and purity is about 100%, and current efficiency is 44.1%, and energy consumption is 8.74kWh/kg.Test running
In, recovery room pH changes very little, stable in the range of 9.95-10.03.
The above analysis result understands that sulfonated polyether sulfone can also obtain having referring in the water of normal temperature by phase inversion
The perforated membrane in shape hole.Contrast reference film CMX, SPES-25 film is all improved in terms of the rate of recovery, current efficiency of lysine, and
And both lysine purity is all close to 100%, the migration that the loose structure of this and SPES-25 films can reduce lysine molecule hinders
Power is relevant.
Inversion of phases process of the low temperature of embodiment 4 containing dichloromethane prepares porous sulfonated polyether sulfone film SPES-D-4
The preparation of film：40g sulfonated polyether sulfone powder is added to 103.76mL 1-METHYLPYRROLIDONE and 15.08mL
In dichloromethane mixed liquor, stirring 72h obtains 24wt% coating liquid, and mass concentration of the dichloromethane in coating liquid is
12%, vacuumize to remove bubble therein；2~3mL coating liquid is taken to be coated on above polyfluortetraethylene plate, then by film
Substrate afterwards, which is kept flat in 4 DEG C of water, soaks 30~60 minutes, and the depth of water is 300~500 times of film thickness of thin layer, shaping
After obtain perforated membrane and be named as SPES-D-4 films.
Test result shows：The water content of SPES-D-4 films is 197.9%, and tensile strength is 4.45MPa, and surface resistance is
7.90Ω·cm2；Shown in the infrared spectrum of film such as Fig. 3 (c), the SPES-4 films in its characteristic absorption peak be the same as Example 1.
The field emission scanning electron microscope figure of SPES-D-4 films (is put as shown in fig. 7, scheming (a-1) in Fig. 7 for the section close-up view of film
It is big 300 times), figure (a-2) is the partial enlarged drawing (5000 times of amplification) of film section, and figure (a-3) is the partial enlarged drawing of film section
(50000 times of amplification), as shown in Figure 7, the section of film also containing a large amount of finger-type holes and have finer and close spongiform hole, this
Cause delayed demixing relevant with the dichloromethane contained in coating liquid.
BMED devices and running be the same as Example 2, as a result show：Under conditions of constant current 0.07A, lysine molecule
The rate of recovery is 63.0%, and purity is about 100%, and current efficiency is 51.0%, and energy consumption is 9.53kWh/kg.Test running
In, recovery room pH changes very little, stable in the range of 9.78-9.91.
The above analysis result understands that the SPES-D-4 films that the present embodiment is obtained also contain finger-type pore structure, therefore phase
Than in reference film CMX, SPES-D-4 films still improve a lot in terms of the rate of recovery, current efficiency of lysine.
The low temperature inversion of phases of embodiment 5 prepares porous sulfonated polysulfone membrane SPSf-4
SPES-4 films in the present embodiment preparation method be the same as Example 1, difference is：Sulfonated polyether sulfone powder is changed to sulphur
Change polysulfones powder, the ion exchange capacity of sulfonated polyether sulfone is 0.1mmol/g, and obtained film is named as SPSf-4 films.
As a comparison, the sulfonated polyether sulfone being also prepared in SPSF dense film, its preparation method be the same as Example 1 is fine and close
Film, difference is：Sulfonated polyether sulfone powder is changed to SPSF powder, obtained film is named as SPSF dense film.
Test shows that the water content of SPSf-4 films is 289.1%；Tensile strength is 2.61MPa, and surface resistance is 0.35 Ω
cm2。
Shown in the infrared spectrum of SPSf-4 films such as Fig. 3 (d), in 2800-3200cm-1Place occurs in that-CH characteristic absorption peak；
In~1030cm-1And 1170-1190cm-1Respectively sulfonic symmetrical and asymmetric stretching vibration absworption peak；In~1240cm-1And 714-725cm-1Peak value be respectively C-O-C and C=C vibration caused by；Result above shows that SPSF material contains
There are-SO3- groups.
The field emission scanning electron microscope figure of SPSf-4 films is as shown in figure 8, scheme the section close-up view (amplification of (a-1) for film in Fig. 8
300 times), figure (a-2) is the partial enlarged drawing (5000 times of amplification) of film section, and figure (a-3) (is put for the partial enlarged drawing of film section
It is big 50000 times), as shown in Figure 8, the section of film also contains finger-type hole, but the top cortex of film section contains the hole of ellipse.
BMED devices and running be the same as Example 2, as a result show：Under conditions of constant current 0.07A, lysine molecule
The rate of recovery is 74.4%, and purity is 86.1%, and current efficiency is 63.1%, and energy consumption is 4.82kWh/kg.Test running
In, recovery room pH changes smaller, stable in the range of 9.30-9.83.
The water content of SPSF dense film as a comparison is 5.8%；Tensile strength is 49.97MPa, and surface resistance is more than
80Ω·cm2.When carrying out BMED experiments using sulfonated polyether sulfone dense film, voltage needed for finding is excessive, more than the range of power supply
(60V), so can not go to carry out BMED experiments under identical condition.
The above analysis result understands that the SPSf-4 films that the present embodiment is obtained also contain finger-type pore structure, therefore are relying
Had an enormous advantage in terms of the rate of recovery, current efficiency and the energy consumption of propylhomoserin than business CMX films；And containing due to SPSf-4 films
Water is bigger than SPES-4 film, and its top cortex contains big oval hole, therefore lysine molecule is easier migration
Film is crossed, thus it is more more advantageous than SPES-4 film in terms of the rate of recovery, current efficiency, energy consumption of lysine；But top cortex
Oval macroporous structure will also result in the leakage of a certain amount of glutamate molecule, therefore the purity of lysine product has dropped
It is low.
The normal temperature inversion of phases of embodiment 6 prepares porous sulfonated polysulfone membrane (SPSf-25)
The preparation of SPSf-4 films in the present embodiment preparation method be the same as Example 5, difference is：Substrate after film is in water
During middle carry out inversion of phases, water temperature is 25 DEG C, and obtained film is named as SPSf-25.
Test shows that the water content of SPSf-25 films is 370.1%；Tensile strength is 1.77MPa, and surface resistance is 0.81
Ω·cm2.Shown in the infrared spectrum of film such as Fig. 3 (e), its characteristic absorption peak is with the SPSf-4 films in example 5.
The field emission scanning electron microscope of SPSf-25 films is as shown in figure 9, scheme the section close-up view (amplification of (a-1) for film in Fig. 9
300 times), figure (a-2) is the partial enlarged drawing (5000 times of amplification) of film section, and figure (a-3) (is put for the partial enlarged drawing of film section
It is big 50000 times), as shown in Figure 9, film section also contains finger-type hole, but the oval boring ratio SPSf- that contains of top cortex of film
The Kong Yao little of 4 films, shows that the size of sulfonated polysulfone membrane epithelial layer fenestra is relevant with the water temperature during inversion of phases.
BMED devices and running be the same as Example 2, apply to BMED processes by SPSf-25 films, as a result show：Constant current
Under conditions of 0.07A, the rate of recovery of lysine molecule is 71.6%, and purity is 84.7%, and current efficiency is 54.3%, and energy consumption is
6.52kW·h/kg.Test in running, recovery room pH changes very little, stable in the range of 9.51-9.82.
The above analysis result understands that the SPSf-25 films that the present embodiment is obtained also contain finger-type pore structure, therefore are relying
Had an enormous advantage in terms of the rate of recovery, current efficiency and the energy consumption of propylhomoserin than business CMX films.Further, since on SPSf-25 films
The oval boring ratio SPSf-4 films of cortex are small, so being slightly poorer than in terms of the rate of recovery, current efficiency, energy consumption of lysine
SPSf-4 films.
To homemade SPES-4, SPES-25, SPES-D-4, SPSf-4 and SPSf-25 film and business in above example
The BMED experimental results of CMX films are summarized, as shown in table 1：
Porous sulfonated polyether sulfone film, sulfonated polysulfone membrane and commercial membranes CMX prepared by the embodiment of the present invention of table 1 BMED
Result data table
Table 1 shows, it is same under conditions of after operation 6h, the recovery for the lysine that homemade porous sulfonated polyether sulfone film is obtained
Rate and current efficiency ratio business CMX films are much higher, and lysine purity is about 100%.It follows that sulfonation prepared by the present invention
Poly (ether sulfone) film lysine molecule when separating glutamic acid and lysine mixed liquor is easier to migrate to recovery room, and this is due to sulfonation
The loose structure of poly (ether sulfone) film can reduce resistance when lysine molecule migrated film.Homemade porous sulfonated polysulfone membrane exists
In BMED applications, relative to commercial membranes CMX, with the higher lysine rate of recovery and current efficiency, and lower energy consumption；Say
Sulfonated polysulfone membrane prepared by the bright present invention is separating glutamic acid and had than commercial membranes CMX during lysine mixed liquor very big excellent
Gesture.
In summary the porous sulfonated polyether sulfone film and sulfonated polysulfone membrane prepared in experimental result, the present invention is as bipolar
The cation-exchange membrane of EDBM device has obvious excellent in terms of separation glutamic acid and lysine mixed liquor than business CMX films
Gesture.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (11)
1. a kind of sulfonated polyether sulfone film, it is characterised in that prepared by sulfonated polyether sulfone by the method for inversion of phases.
2. sulfonated polyether sulfone film according to claim 1, it is characterised in that the ion exchange capacity of the sulfonated polyether sulfone
For 0.15~0.4mmol/g.
3. a kind of preparation method of sulfonated polyether sulfone film, including：
Sulfonated polyether sulfone is subjected to inversion of phases in water, sulfonated polyether sulfone film is obtained.
4. preparation method according to claim 3, it is characterised in that the process of the inversion of phases is specially：
Sulfonated polyether sulfone is mixed with organic solvent, coating liquid is obtained；
The coating liquid is coated in substrate, then is placed in water immersion, sulfonated polyether sulfone film is obtained；The organic solvent is N-
The mixed liquor of methyl pyrrolidone or 1-METHYLPYRROLIDONE and dichloromethane；The temperature of the water is 0~35 DEG C.
5. a kind of sulfonated polysulfone membrane, it is characterised in that prepared by SPSF by the method for inversion of phases.
6. sulfonated polysulfone membrane according to claim 5, it is characterised in that the ion exchange capacity of the SPSF is
0.08~0.4mmol/g.
7. a kind of preparation method of sulfonated polysulfone membrane, including：
SPSF is subjected to inversion of phases in water, sulfonated polysulfone membrane is obtained.
8. preparation method according to claim 7, it is characterised in that the process of the inversion of phases is specially：
SPSF is mixed with organic solvent, coating liquid is obtained；
The coating liquid is coated in substrate, then is placed in water immersion, sulfonated polysulfone membrane is obtained；The organic solvent is N- first
The mixed liquor of base pyrrolidones or 1-METHYLPYRROLIDONE and dichloromethane；The temperature of the water is 0~35 DEG C.
9. a kind of bipolar membrane electrodialysis device, it is characterised in that the cation-exchange membrane of the bipolar membrane electrodialysis device is power
Profit requires the sulfonated polyether sulfone film prepared by the preparation method described in described in 1~2 any one or any one of claim 3~4
Described in any one of claim 5~6 or any one of claim 7~8 described in preparation method prepared by SPSF
Film.
10. a kind of method of the bipolar membrane electrodialysis device amino acid separation mixed liquor described in utilization claim 9, its feature exists
In comprising the following steps：
The mixed liquor of the first amino acid and the second amino acid is added in material liquid tank, strong electrolyte is added in electrode flow container, is being returned
The second Freamine Ⅲ is added in closed cans；First amino acid is negatively charged amino acid, the second amino in mixed liquor
Acid is positively charged amino acid in mixed liquor；
The first peristaltic pump, the second peristaltic pump and the 3rd peristaltic pump are opened, second after dc source, operation in material liquid tank is then turned on
Transport of Amino Acids is to recycling can, the first amino acid and the second amino acid separated.
11. method according to claim 10, it is characterised in that first amino acid is glutamic acid, the second amino acid
For lysine；The concentration of the material liquid tank Glutamic Acid is that the concentration of lysine in 0.02~0.1mol/L, the material liquid tank is
0.02~0.1mol/L, the concentration ratio of the glutamic acid and lysine is (1~5)：(1~5)；Lysine in the recycling can
Concentration is 0.005~0.03mol/L.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108295677A (en) * | 2018-04-11 | 2018-07-20 | 山东科技大学 | A kind of modification of chitosan/sulfonated polyether sulfone cation-exchange membrane and preparation method thereof |
| CN109012180A (en) * | 2018-07-18 | 2018-12-18 | 天津大学 | A kind of preparation method with the clever structure composite forward osmosis membrane of figure |
| CN109758917A (en) * | 2018-09-18 | 2019-05-17 | 张伟 | A kind of preparation method of bivalent cation selective ion exchange membrane |
| CN110026086A (en) * | 2019-03-18 | 2019-07-19 | 衢州蓝然新材料有限公司 | Using hollow fiber porous film as the diffusion dialysis film and its manufacturing method of matrix |
| CN112473395A (en) * | 2020-11-20 | 2021-03-12 | 中国海洋大学 | Bipolar membrane based on pre-modified metal-organic framework material and preparation method and application thereof |
| CN109192922B (en) * | 2018-08-07 | 2021-06-29 | 格林美（无锡）能源材料有限公司 | Solid-state lithium ion battery anode with special structure and preparation method thereof |
| CN116059841A (en) * | 2022-12-29 | 2023-05-05 | 南开大学 | Asymmetric composite ion exchange membrane for electrodialysis desalination and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108295677A (en) * | 2018-04-11 | 2018-07-20 | 山东科技大学 | A kind of modification of chitosan/sulfonated polyether sulfone cation-exchange membrane and preparation method thereof |
| CN108295677B (en) * | 2018-04-11 | 2019-06-11 | 山东科技大学 | A kind of modification of chitosan/sulfonated polyether sulfone cation-exchange membrane and preparation method thereof |
| CN109012180A (en) * | 2018-07-18 | 2018-12-18 | 天津大学 | A kind of preparation method with the clever structure composite forward osmosis membrane of figure |
| CN109192922B (en) * | 2018-08-07 | 2021-06-29 | 格林美（无锡）能源材料有限公司 | Solid-state lithium ion battery anode with special structure and preparation method thereof |
| CN109758917A (en) * | 2018-09-18 | 2019-05-17 | 张伟 | A kind of preparation method of bivalent cation selective ion exchange membrane |
| CN109758917B (en) * | 2018-09-18 | 2021-07-02 | 张伟 | Preparation method of divalent cation selective ion exchange membrane |
| CN110026086A (en) * | 2019-03-18 | 2019-07-19 | 衢州蓝然新材料有限公司 | Using hollow fiber porous film as the diffusion dialysis film and its manufacturing method of matrix |
| CN110026086B (en) * | 2019-03-18 | 2021-08-27 | 衢州蓝然新材料有限公司 | Diffusion dialysis membrane using hollow fiber porous membrane as substrate and method for producing same |
| CN112473395A (en) * | 2020-11-20 | 2021-03-12 | 中国海洋大学 | Bipolar membrane based on pre-modified metal-organic framework material and preparation method and application thereof |
| CN116059841A (en) * | 2022-12-29 | 2023-05-05 | 南开大学 | Asymmetric composite ion exchange membrane for electrodialysis desalination and preparation method thereof |
| CN116059841B (en) * | 2022-12-29 | 2024-03-29 | 南开大学 | Asymmetric composite ion exchange membrane for electrodialysis desalination and preparation method thereof |
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