CN105646927A - Method for preparing univalent selective cation exchange membrane - Google Patents

Method for preparing univalent selective cation exchange membrane Download PDF

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Publication number
CN105646927A
CN105646927A CN201511028070.9A CN201511028070A CN105646927A CN 105646927 A CN105646927 A CN 105646927A CN 201511028070 A CN201511028070 A CN 201511028070A CN 105646927 A CN105646927 A CN 105646927A
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polyquaternium
exchange membrane
film
reaction
described step
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沈江南
赵严
李健
周玛丽
韩波
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Co Ltd Of Yiwu Scientific And Technical Research Institute Of Zhejiang Polytechnical University
Zhejiang University of Technology ZJUT
Yiwu Science and Technology Research Institute of ZJUT
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Co Ltd Of Yiwu Scientific And Technical Research Institute Of Zhejiang Polytechnical University
Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a method for preparing a univalent selective cation exchange membrane. The method comprises the steps: subjecting a cation exchange membrane with a sulfonic acid group to a reaction with thionyl chloride, so as to produce an ion exchange membrane with sulfonyl chloride; subjecting a polyquaternium-7 to hoffman degradative reaction treatment, so as to remove a carbonyl group from the quaternary ammonium salt; subjecting the degraded polyquaternium-7 to a reaction with the ion exchange membrane with sulfonyl chloride by a chemical reaction method, so as to fix degraded polyquaternium-7 with positive electricity on the surface of the membrane and then form a positive-charge thin layer on the surface of the membrane. The univalent selective cation exchange membrane prepared by the method has pore size screening and static electricity repulsing actions and can be used for effectively separating univalent and multivalent ions.

Description

The preparation method of a kind of unit price selectivity cationic exchange membrane
Technical field
The invention belongs to ion-exchange membrane field, in particular to be a kind of have one, the preparation method of the cationic exchange membrane of polyvalent ion selective separation function.
Background technology
Membrane separation technique has good using value in the world, and it maintains the rate of growth of annual 30%. Membrane separation technique has quite wide market outlook in China, and along with the quickening of China's process of industrialization, the shortage of water resources problem of China will be day by day serious. In China, entering the waste water in rivers every year increases with the speed of 1,800,000,000 tons, and wherein major part directly enters in rivers without any process, causes China's water resource pollution problem serious. More and more energy will be put into environmental protection field by China, and the attention degree of environmental problem also will can be improved and active by the environmental protection market of China very soon along with everybody. Now, the demand to product film of China is fast development attitude, and this will promote the development of China's film industry to a great extent.
Along with constantly increasing the weight of of water resources crisis, sea water desaltination and sewage disposal recycling have become the important topic of research within the scope of the world. Along with the development of science and technology, membrane separation technique has been considered as one of high-tech with development potentiality most. As an important branch of membrane separation technique, electrodialysis has been widely used in every field. But in the practical application of electrodialysis, ion exchange membrane technology still also exists certain defect, as multivalent state ion through problem, the existence of these ions can cause the reduction of electrodialyzer current efficiency, energy consumption to increase, the serious film that even can cause sinters, and unit price selectivity cationic exchange membrane can effectively address this problem.
SpringerLink periodical Ionics (2012,18:711 717) has reported and has prepared unit price selectivity cationic exchange membrane with polymine, is cross-linked with ammonium persulphate, and uses Cl-, NO3 -, SO4 2-The selection separation performance of film being analyzed etc. system, experimental result shows that the leakage rate of ion is Cl->NO3 ->SO4 2-, show that single polyvalent ion is had good separating power by modified membrane.But material modified de-attached problem is the restricted major cause of aforesaid method.
Ace Wei Er periodical Journalofmembranescience (2008,319,5-9) has been reported and has been carried out surface modification with chitosan galvanic deposit. To H+/Zn2+/Al3+Separating experiment result shows, modified membrane has significantly single multivalence and selects separating power. But it is loaded down with trivial details to there is preparation technology in the method, should not with realize the shortcomings such as industrial applications.
Americanized institute periodical JournalofPhysicalChemistryB (2005,109,14085-14092) with Ace Wei Er periodical Journalofmembranescience (2006,280,210-218) report aniline respectively, pyrroles etc. are adsorbed in cationic surface, and then with oxygenant, it is surface-crosslinked at film, thus form the modified layer of one layer of positively charged on film surface. Film carrying out single multivalence and selects separating experiment, result shows that film has good single multivalence separating effect. But this kind of method exists material modified price height, and the problem that environment is unfriendly, therefore it is difficult to promote.
In sum, it is loaded down with trivial details generally to there is preparation technology in the preparation of current unit price selective ion exchange membrane, material modified limited, expensive, the problem that environment is unfriendly and work-ing life is short.
Summary of the invention
It is an object of the invention to provide a kind of environmental friendliness, material modified wide material sources, it may also be useful to the life-span is long, selection separation performance has the preparation method that single multivalence selects the cationic exchange membrane of separation function significantly.
The present invention provides the preparation method of a kind of unit price selectivity cationic exchange membrane, and described method comprises the following steps:
(1) utilize hoffmam to react, polyquaternium-7 is carried out pre-treatment; The sodium hydroxide solution of massfraction 10��30% (preferably 20%) drips and adds excessive bromine water, then at-15��-10 DEG C of temperature, polyquaternium-7 is added, it is warming up to 0��15 DEG C after stirring 1��2 hour at-15��-10 DEG C, continue stirring 1��2h, reacting 4��10 hours under being finally warming up to 45��60 DEG C of temperature, reaction terminates to add methyl alcohol in rear reaction solution, generates throw out, taking precipitate is dissolved in the hydrochloric acid of 0.1��1mol/L, carries out carbonyl process; And then add methyl alcohol and precipitate out by product, precipitated product is dissolved in water, then with methanol extraction, hockets washing with water, methyl alcohol, dries, and the polyquaternium-7 of obtained degraded is for subsequent use;
Described bromine water is excessive relative to polyquaternium-7, further, it is preferable that the volumetric usage of bromine water counts 1��5mL/g with the quality of polyquaternium-7, it is more preferable to 2��3mL/g; Described bromine water is saturated bromine water, is commercial preparation, is generally the saturated solution of bromine simple substance in water, and mass concentration is 3%��3.1%.
The volumetric usage of described aqueous sodium hydroxide solution generally counts 10��30mL/g with the quality of polyquaternium-7.
(2) cationic exchange membrane carries out chloride process; By the cationic exchange membrane deionized water wash containing sulfonate radical, flood 20��30 hours in toluene solvant under 30��35 DEG C of conditions after drying, take out the film after toluene dipping, add in fresh toluene solvent, drip excessive sulfur oxychloride; Drip rear temperature of reaction and it has been warmed up to 80��85 DEG C, and continued to react at 80��85 DEG C of temperature to 6-24 hour (preferably 10��24 hours); After reacted film toluene cleans, obtain the film of chloride process;
The consumption of described sulfur oxychloride is excessive, and generally 1.1-2 excessive in the loading capacity of ion-exchange membrane is doubly, and namely the amount of substance of sulfur oxychloride is 1.1��2 times of the loading capacity of the cationic exchange membrane containing sulfonate radical.
(3) by the polyquaternium-7 of degraded obtained for step (1), the aqueous solution adding highly basic is made into modification steeping fluid, the film of chloride process step (2) prepared immerses in modification steeping fluid, react 3��5 hours, taking-up deionized water rinsing, obtained described unit price selectivity cationic exchange membrane;
Described highly basic is sodium hydroxide, potassium hydroxide or sodium hydride, it is preferable that sodium hydroxide;
In described modification steeping fluid, the mass concentration of highly basic is 5%-25%, it is preferable that 10%; The mass concentration of the polyquaternium-7 of degraded is 2%-10%, it is preferable that 4%.
In described step (1), after adding polyquaternium-7, in the whole reaction process of hoffman reaction, the viscosity that should control polyquaternium-7 is 7000-15000mPas.
In above-mentioned steps (2), on cationic exchange membrane surface containing in sulfonate radical conversion process, utilize sulfur oxychloride as reaction reagent, sulfonate radical is changed into SULPHURYL CHLORIDE.
The present invention's raw material used is the cationic exchange membrane containing sulfonate radical, directly buys the cationic exchange membrane containing sulfonate radical of commercialization.
Preparation method described in above-mentioned steps (2), in preparation with in the ion-exchange membrane process of SULPHURYL CHLORIDE, temperature of reaction is warmed up to 80��85 DEG C, and general control temperature rate of growth is warmed up to 80��85 DEG C with the heat-up rate of 10��15 DEG C per hour (preferably 10 DEG C per hour).
In described step (2), drip rear temperature of reaction and it is warmed up to 80��85 DEG C, and continue to react at 80��85 DEG C of temperature to 6-24 hour (preferably 10��24 hours), here react and it was meant to 6-24 hour, after dripping sulfur oxychloride, the time that temperature raises also counted in the reaction times, and timing from intensification is initial, reacting total time after being warmed up to 80��85 DEG C is 6-24 hour.
Compared with prior art, the useful effect of the present invention is:
(1) the present invention adopts material modified as conventional ion-exchange membrane unit price selective separation performance of polyquaternium-7, and this kind of material source is very extensive, cheap, and environmental friendliness.
(2) owing to polyquaternium-7 has very high electric density, its use can effectively increase film surface charge density, thus strengthen unit price and select separation performance.
(3) the present invention adopts chemical graft process, carbonyl is sloughed in polyquaternium-7 degraded, the ion-exchange film reaction with SULPHURYL CHLORIDE after processing with sulfur oxychloride, generates the modified layer combined in chemical bond mode, thus effectively extends the life-span of unit price selective ion exchange membrane.
(4) the unit price selectivity cationic exchange membrane prepared has aperture screening and electrostatic repulsion concurrently, it is possible to be effectively separated by single polyvalent ion. Embodiment of the present invention data show, at H+/Zn2+,Na+/Mg2+/Ca2+Etc. in system, utilize the surface reforming layer of unit price selectivity cationic exchange membrane prepared by the present invention and do not allow electrostatic repulsion difference and aperture sieving action between valency state positively charged ion, it is possible to well realize the selective separation of a polyvalent cation.
Cationic exchange membrane with sulfonic acid group is reacted by the present invention with sulfur oxychloride, generates the ion-exchange membrane with SULPHURYL CHLORIDE; By polyquaternium-7 through hoffman degradation treatment, remove the carbonyl in quaternary ammonium salt; By chemical reaction method, the polyquaternium-7 of degraded is reacted with SULPHURYL CHLORIDE, the degraded polyquaternium-7 of positively charged is fixed on film surface, thus form one layer of positive charge thin layer on film surface. The electrodialysis experiment of modified film shows, modified membrane prepared by the present invention in sepn process, by the aperture sieving action of functional layer and the difference of electrostatic repulsion, it is possible to realize the selective separation of single polyvalent cation.
Accompanying drawing explanation
Fig. 1 is cationic exchange membrane step (2) chloride process and the chemical equation schematic diagram of step (3) membrane modifying process.
Fig. 2 is environmental microbes comparison diagram before and after membrane modifying process, in Fig. 2, a figure is the SEM figure of commodity homogeneous phase cation exchange film before modified in embodiment 1, b figure is the SEM figure of unit price selectivity cationic exchange membrane prepared by embodiment 1, c figure is the AFM figure of commodity homogeneous phase cation exchange film before modified, d figure is the AFM figure of unit price selectivity cationic exchange membrane.
Fig. 3 is infrared spectrogram before and after membrane modifying.
Fig. 4 is the selective separation schematic diagram in the electrodialysis process of electrodialysis unit figure and embodiment 2.
Embodiment
Below in conjunction with accompanying drawing and further describe the present invention by specific embodiment, but the protection scheme of the present invention is not limited to this.
Embodiment 1
The NaOH aqueous solution of 100mL massfraction 20% is added in the there-necked flask of 250mL, slowly drip the bromine water adding 30mL. Under-15 DEG C of conditions, the polyquaternium-7 of 10g is added to above-mentioned mixing solutions, and continues to stir 1h. Temperature is increased to 0 DEG C and continues to stir 1h, finally when 45 DEG C, continue reaction 4 hours. Reacted polyquaternium-7 is precipitated after terminating by reaction with methyl alcohol, and throw out is dissolved in 0.1MHCl and carries out carbonyl process; And then add methyl alcohol and precipitate out by product, gained precipitated product is dissolved in water again, then with methanol extraction, hockets washing with water, methyl alcohol, dries, and the polyquaternium-7 of obtained degraded is for subsequent use.
Commodity homogeneous phase cation exchange film 7 �� 7cm (loading capacity is about 0.05mmol for Beijing Ting Run membrane technique company limited, JAM-II-10) is washed with deionized water under ultrasound condition, removes the salinity in film. Take out film, after surface thieving paper is cleaned, the 24 hours moisture to remove in film is flooded in toluene under 30 DEG C of conditions, then the film immersion after toluene dipping is taken out in the there-necked flask containing 40mL toluene, there-necked flask is equipped with reflux, drip 4mL sulfur oxychloride, dripped rear temperature of reaction and be warmed up to 80 DEG C with the speed of 10 DEG C per hour, at 80 DEG C, then continue reaction to 24h. Take out film toluene wash 3 times, remove the unreacting substance on surface, obtain the film of chloride process. Film chloride processed immerses in modification steeping fluid, described modification steeping fluid is the sodium hydroxide solution of the polyquaternium-7 of degraded, the massfraction of the polyquaternium-7 wherein degraded is 4%, the concentration of sodium hydroxide is 10%, reaction 3h, with deionized water rinsing, remove surface impurity, obtain unit price selectivity cationic exchange membrane. The configuration of surface figure and Infrared Characterization figure of film is respectively as shown in Figures 2 and 3.
In Fig. 2, a figure is the SEM figure of commodity homogeneous phase cation exchange film before modified in embodiment 1, b figure is the SEM figure of unit price selectivity cationic exchange membrane prepared by embodiment 1, c figure is the AFM figure of commodity homogeneous phase cation exchange film before modified, d figure is the AFM figure of unit price selectivity cationic exchange membrane. As shown in Figure 2, it is smooth that film surface becomes, and illustrates that modified material is deposited on film surface; After the infrared spectrogram of Fig. 3 shows membrane modifying, there is the characteristic peak of sulphonamide in film surface, illustrates that surface mass is present in film surface with the form of chemical bond. Fig. 2 and Fig. 3 together illustrates the successful modification of film.
Embodiment 2
Film is placed in four compartment electrodialysis units, and as shown in Figure 4, M-CEM represents unit price selectivity cationic exchange membrane prepared by embodiment 1, and AEM represents anion-exchange membrane, and the useful area of film is 5cm �� 5cm.In device, light room is 200mL0.5MH2SO4, dense room be 200mL containing 15g/LZnSO40.5MH2SO4In solution. Pole liquid is 0.5MK2SO4. Electrodialysis time controling is 100min, and current density is 50mA/cm2. Experimental installation is as shown in Figure 4.
H+/Zn2+System shows, Zn2+Leakage rate drop to 14% from 22%.
Embodiment 3
The film that embodiment 1 prepares is used for during concentrated seawater electrodialysis tests, four compartment electrodialysis units such as Fig. 4, institute the difference is that, dense room and light room add 200mL concentrated seawater respectively, are 50mA/cm in current density2When run 100min, Ca2+And Mg2+Leakage rate drop to modified 38% and 32.8% from the 53.1% of product film JAM-II-10 before modified and 81.7% respectively. By commodity homogeneous ion-exchange membrane (Japan, Asahi, CSO) with to same sampling device, it is 50mA/cm in current density2When run 100min. Experimental result display Ca2+And Mg2+Leakage rate respectively 32.4% and 23.6%. The application prepares performance and the homogeneous ion-exchange membrane (Japan of modified film, Asahi, CSO) suitable, but performance is more stable than product film, there is the problem that modified layer comes off in product film, and the modified layer of the present invention combines in chemical bond mode, effectively extending the life-span of unit price selective ion exchange membrane, stability is higher.

Claims (10)

1. the preparation method of a unit price selectivity cationic exchange membrane, it is characterised in that described method comprises the following steps:
(1) polyquaternium-7 pre-treatment; The sodium hydroxide solution of massfraction 10��30% drips and adds excessive bromine water, then at-15��-10 DEG C of temperature, polyquaternium-7 is added, it is warming up to 0��15 DEG C after stirring 1��2 hour at-15��-10 DEG C, continue stirring 1��2h, reacting 4��10 hours under being finally warming up to 45��60 DEG C of temperature, reaction terminates to add methyl alcohol in rear reaction solution, generates throw out, taking precipitate is dissolved in the hydrochloric acid of 0.1��1mol/L, carries out carbonyl process; And then add methyl alcohol and precipitate out by product, precipitated product is dissolved in water, then with methanol extraction, hockets washing with water, methyl alcohol, dries, and the polyquaternium-7 of obtained degraded is for subsequent use;
(2) cationic exchange membrane carries out chloride process; By the cationic exchange membrane deionized water wash containing sulfonate radical, flood 20��30 hours in toluene solvant under 30��35 DEG C of conditions after drying, take out the film after toluene dipping, add in fresh toluene solvent, drip excessive sulfur oxychloride; Drip rear temperature of reaction and it has been warmed up to 80��85 DEG C, and continued to react to 6-24 hour at 80��85 DEG C of temperature; After reacted film toluene cleans, obtain the film of chloride process;
(3) by the polyquaternium-7 of degraded obtained for step (1), the aqueous solution adding highly basic is made into modification steeping fluid, the film of chloride process step (2) prepared immerses in modification steeping fluid, react 3��5 hours, taking-up deionized water rinsing, obtained described unit price selectivity cationic exchange membrane.
2. the method for claim 1, it is characterised in that in described step (1), described bromine water is excessive relative to polyquaternium-7.
3. method as claimed in claim 2, it is characterised in that in described step (1), the volumetric usage of described bromine water counts 1��5mL/g with the quality of polyquaternium-7.
4. the method for claim 1, it is characterised in that in described step (1), the volumetric usage of described aqueous sodium hydroxide solution counts 10��30mL/g with the quality of polyquaternium-7.
5. the method for claim 1, it is characterised in that in described step (2), the amount of substance of described sulfur oxychloride is 1.1��2 times of the loading capacity of the cationic exchange membrane containing sulfonate radical.
6. the method for claim 1, it is characterised in that in described step (3), described highly basic is sodium hydroxide, potassium hydroxide or sodium hydride.
7. method as claimed in claim 6, it is characterised in that in described step (3), described highly basic is sodium hydroxide.
8. the method for claim 1, it is characterised in that in described step (3), in described modification steeping fluid, the mass concentration of highly basic is 5%-25%; The mass concentration of the polyquaternium-7 of degraded is 2%-10%.
9. method as claimed in claim 8, it is characterised in that in described step (3), in described modification steeping fluid, the mass concentration of highly basic is 10%; The mass concentration of the polyquaternium-7 of degraded is 4%.
10. the method for claim 1, it is characterised in that in described step (1), after adding polyquaternium-7, controls in whole reaction process, and the viscosity of polyquaternium-7 is 7000-15000mPas.
CN201511028070.9A 2015-12-31 2015-12-31 Method for preparing univalent selective cation exchange membrane Pending CN105646927A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108097069A (en) * 2017-11-24 2018-06-01 浙江工业大学 A kind of method that polypyrrole Monovalent selectivity cation-exchange membrane is prepared in situ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIAN LI, ET AL.: "Mono-valent cation selective membranes for electrodialysis by introducing polyquaternium-7 in a commercial cation exchange membrane", 《JOURNAL OF MEMBRANE SCIENCE》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108097069A (en) * 2017-11-24 2018-06-01 浙江工业大学 A kind of method that polypyrrole Monovalent selectivity cation-exchange membrane is prepared in situ
CN108097069B (en) * 2017-11-24 2021-05-11 浙江工业大学 Method for in-situ preparation of polypyrrole monovalent selective cation exchange membrane

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