CN109225356B - Iodoalkane quaternized polypyrrole modified cation exchange membrane and preparation and application thereof - Google Patents
Iodoalkane quaternized polypyrrole modified cation exchange membrane and preparation and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 238000005341 cation exchange Methods 0.000 title claims abstract description 65
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 43
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 238000002791 soaking Methods 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- SKIDNYUZJPMKFC-UHFFFAOYSA-N 1-iododecane Chemical compound CCCCCCCCCCI SKIDNYUZJPMKFC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N ortho-diethylbenzene Natural products CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- LMHCYRULPLGEEZ-UHFFFAOYSA-N 1-iodoheptane Chemical compound CCCCCCCI LMHCYRULPLGEEZ-UHFFFAOYSA-N 0.000 claims description 4
- OGSJMFCWOUHXHN-UHFFFAOYSA-N 1-iodononane Chemical compound CCCCCCCCCI OGSJMFCWOUHXHN-UHFFFAOYSA-N 0.000 claims description 4
- UWLHSHAHTBJTBA-UHFFFAOYSA-N 1-iodooctane Chemical compound CCCCCCCCI UWLHSHAHTBJTBA-UHFFFAOYSA-N 0.000 claims description 4
- BLXSFCHWMBESKV-UHFFFAOYSA-N 1-iodopentane Chemical compound CCCCCI BLXSFCHWMBESKV-UHFFFAOYSA-N 0.000 claims description 4
- IQRUSQUYPCHEKN-UHFFFAOYSA-N 2-iodobutane Chemical compound CCC(C)I IQRUSQUYPCHEKN-UHFFFAOYSA-N 0.000 claims description 4
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 4
- WNPGSEJRPYSCDQ-UHFFFAOYSA-N 3-(iodomethyl)heptane Chemical compound CCCCC(CC)CI WNPGSEJRPYSCDQ-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 4
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 4
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 4
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 claims description 4
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000000909 electrodialysis Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- YAPJPSFOWOSMRG-UHFFFAOYSA-N CCCCCCCCCC.[I] Chemical compound CCCCCCCCCC.[I] YAPJPSFOWOSMRG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KBVGZIFNIBCBKH-UHFFFAOYSA-N ethanol iodomethane Chemical compound IC.CCO KBVGZIFNIBCBKH-UHFFFAOYSA-N 0.000 description 1
- MEUZEBOPFDRIBW-UHFFFAOYSA-N ethanol;1h-pyrrole Chemical compound CCO.C=1C=CNC=1 MEUZEBOPFDRIBW-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an iodoalkane quaternized polypyrrole modified cation exchange membrane and preparation and application thereof, wherein the cation exchange membrane is sequentially soaked in an alkali solution and an acid solution and washed by deionized water to obtain an acid-base activated cation exchange membrane; soaking the activated cation exchange membrane in a pyrrole solution, standing until the pyrrole solution is completely volatilized, adding an oxidant aqueous solution, oscillating, and taking out the membrane to obtain a polypyrrole modified membrane; and (3) immersing the polypyrrole modified membrane into an iodoalkane solution for 1-24h, taking out the membrane, and cleaning the membrane by using deionized water to obtain the iodoalkane quaternized polypyrrole modified cation exchange membrane. The prepared iodoalkane quaternized polypyrrole modified cation exchange membrane is used for Na+Is subjected to monovalent selective separation, is subjected to modification by iodohexane polypyrrole and then is subjected to Na+Relative to Mg2+The permselectivity value increased from 0.94 to 6.84 compared to the unmodified commercial membrane.
Description
(I) technical field
The invention relates to a single/multi-valence selective cation exchange membrane and a preparation method thereof, in particular to a monovalent selective cation exchange membrane based on quaternized polypyrrole and a preparation method thereof.
(II) background of the invention
The membrane separation technology is the core strength of water safety guarantee systems in China, and in the field of water treatment, a unique water treatment system comprising microfiltration, ultrafiltration, nanofiltration, reverse osmosis, electrodialysis and other methods is formed. Various membrane water treatment technologies have excellent characteristics and advantages. Among them, the electrodialysis technology is attracting attention because of its high water recovery rate, long equipment life and low operation cost, and has irreplaceable great advantages for separation of non-isotropic ions, even isotropic ions. Electrodialysis is a technology that utilizes the permselectivity of ion exchange membranes to ions to make the ions directionally migrate under the push of an external direct current electric field force, thereby achieving the separation, purification and concentration of electrolyte solution. At present, electrodialysis is widely applied to the fields of industrial production, environmental protection, biological product production and the like as a clean production technology. Although the electrodialysis technology has obvious application advantages, with the increasing difficulty of drinking water treatment, the progress of chemical production and the improvement of the requirement of aquatic product grade, the expectation of people on electrodialysis is also increased. Traditional electrodialysis processes are primarily directed at separation between ions of different polarities, while separation between ions of the same polarity but different valences is rarely involved. However, in the field of electrodialysis technology, more aqueous solutions containing ions of the same electrical type but different valency are involved. The separation technology between ions with the same electric property has great application potential in different water treatment fields, such as brackish water desalination for preparing drinking water, electrodialysis for concentrating seawater for preparing sodium chloride, and recovery of acid and alkali in waste alkali solution. This puts higher demands on the conventional electrodialysis technology: has the capability of selectively separating the same ions with different valence states. To meet the actual demands of the industry, the development of selective electrodialysis techniques is being pursued.
Disclosure of the invention
The invention aims to provide a surface modified quaternized polypyrrole cation exchange membrane prepared by quaternizing polypyrrole with iodoalkane as a quaternizing agent, which is used for preparing a single/multi-valence selective cation exchange membrane and can selectively separate monovalent ions in a salt solution, so that the separation, purification and concentration of an electrolyte solution are realized.
The technical scheme adopted by the invention is as follows:
the invention provides an iodoalkane quaternized polypyrrole modified cation exchange membrane which is prepared by the following method: 1) sequentially soaking the cation exchange membrane in an alkali solution (preferably an aqueous solution of sodium hydroxide) and an acid solution (preferably an aqueous solution of hydrochloric acid) at room temperature to remove waxy materials on the surface of the membrane, washing with deionized water, and removing redundant alkali and acid on the surface of the membrane to obtain the cation exchange membrane activated by acid and alkali;
2) soaking the activated cation exchange membrane obtained in the step 1) in a pyrrole solution at room temperature, standing for 2-4 h until the pyrrole solution is completely volatilized, adding an oxidant aqueous solution, oscillating to polymerize pyrrole (preferably 100r/min, 1h), and taking out the membrane to obtain a polypyrrole modified membrane; the oxidant in the oxidant aqueous solution is one of sodium persulfate, ferric chloride, hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate or ammonium persulfate;
3) and (3) at room temperature, immersing the polypyrrole modified membrane obtained in the step 2) into an iodoalkane solution for 1-24 hours, taking out the membrane, and washing the membrane with deionized water to obtain the iodoalkane quaternized polypyrrole modified cation exchange membrane.
Further, the concentration of the sodium hydroxide aqueous solution and the hydrochloric acid aqueous solution in the step 1) is 1 mol/L.
Further, the concentration of the pyrrole solution in the step 2) is 2mol/L, and the solvent is water, ethanol, ether or benzene.
Further, the concentration of the oxidant aqueous solution in the step 2) is 0.5 mol/L.
Further, the iodoalkane solution in the step 3) is 1-20 g/L.
Further, the iodoalkane in the iodoalkane solution in the step 3) is one of iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 1-iodohexane, 2-ethyl iodohexane, 1-iodoheptane, 1-iodooctane, 1-iodononane or 1-iododecane, and the solvent is water, ethanol, diethyl ether or benzene.
The invention also provides a preparation method of the modified cation exchange membrane of the iodoalkane quaternized polypyrrole, which comprises the following steps: 1) soaking a cation exchange membrane in a sodium hydroxide aqueous solution (preferably 1mol/L) for 2h at room temperature, washing with deionized water to remove alkali on the surface of the membrane, then soaking in a hydrochloric acid aqueous solution (preferably 1mol/L) for 2h, and washing with deionized water to remove acid on the surface of the membrane, thereby obtaining the cation exchange membrane activated by acid and alkali;
2) soaking the cation exchange membrane activated in the step 1) in a pyrrole solution (preferably 2mol/L) at room temperature, standing for 90min until the pyrrole solution is completely volatilized, adding an oxidant aqueous solution (preferably 0.5mol/L), shaking (100r/min, 1h), taking out the membrane, and obtaining a polypyrrole modified membrane; the oxidant in the oxidant aqueous solution is one of sodium persulfate, ferric chloride, hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate or ammonium persulfate, and preferably sodium persulfate or ferric chloride;
3) at room temperature, soaking the polypyrrole modified membrane obtained in the step 2) into 1-20g/L iodoalkane solution for 1-24h, taking out the membrane, and washing the membrane with deionized water to obtain an iodoalkane quaternized polypyrrole modified cation exchange membrane; the iodoalkane structural formula Br- (CH) in the iodoalkane solution2)n-CH3(n ═ 0 to 12), preferably methyl iodide, ethyl iodide, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 1-iodohexane, 2-ethyl iodohexane, 1-iodoheptane, 1-iodooctane, 1-iodononane or 1-iododecane, more preferably methyl iodide, 1-iodohexane or iododecane, and the solvent is water, ethanol, diethyl ether or benzene.
Further, the soaking in the step 2) is carried out in a beaker, the adding volume of the pyrrole solution is 5-30% of the volume of the beaker, and the adding volume of the oxidant solution is 5-30% of the volume of the beaker.
The invention also provides an application of the iodoalkane quaternized polypyrrole modified cation exchange membrane in preparation of a monovalent or polyvalent selective cation exchange membrane.
The cation exchange membrane of the present invention may be any commercially available or self-wiped cation exchange membrane, preferably a CM-1Y cation exchange membrane. The room temperature of the invention is 25-30 ℃.
Compared with the prior art, the invention has the following beneficial effects: the prepared iodoalkane quaternized polypyrrole modified cation exchange membrane is used for Na+Is subjected to monovalent selective separation, is subjected to modification by iodohexane polypyrrole and then is subjected to Na+Relative to Mg2+Commercial membranes with a lower permselectivity value than unmodified membranes0.94 to 6.84. Cation exchange membrane modified by the invention, Na+/Mg2+The selectivity coefficient (flux ratio) of (a) can be improved by up to 7 times compared with that before modification, which is 2.5 times that of two commercially available products in Japan (CSV of Astom and CSO of Astom).
(IV) description of the drawings
FIG. 1 is a schematic diagram of the preparation process of the iodoalkane polypyrrole modified cation exchange membrane of the present invention.
FIG. 2 is an electron microscope image of the surface (a) of the modified cation exchange membrane of iodoalkane polypyrrole and a section (a1), and an electron microscope image of the surface (b) of the unmodified cation exchange membrane and a section (b 1).
FIG. 3 is a schematic diagram showing the flux of sodium ions relative to magnesium ions and the monovalent selectivity of an unmodified cation exchange membrane and an iodoalkane quaternized polypyrrole modified cation exchange membrane in a concentration chamber in a monovalent selective electrodialysis experiment for 1h, wherein C-1 represents the iodomethane quaternized polypyrrole modified cation exchange membrane of example 1, C-2 represents the iodohexane quaternized polypyrrole modified cation exchange membrane of example 2, C-3 represents the iododecane quaternized polypyrrole modified cation exchange membrane of example 3, and C-4 represents an unmodified cation exchange membrane (i.e., CM-1Y cation exchange membrane).
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1
1. Iodoalkane polypyrrole modified cation exchange membrane
Step 1: soaking a piece of CM-1Y cation exchange membrane of Tokuyama (Riben mountain Caucao company) in 1mol/L sodium hydroxide aqueous solution for 2h at room temperature (25-30 ℃, the same is applied below), taking out, repeatedly washing the membrane with deionized water for 5 times to remove redundant alkali on the surface, then soaking the membrane in 1mol/L hydrochloric acid aqueous solution for 2h, taking out, repeatedly washing the membrane with deionized water for 5 times to remove redundant acid on the surface, and obtaining the cation exchange membrane activated by acid and alkali.
Step 2: as shown in fig. 1, soaking the activated cation exchange membrane in a 500ml beaker containing 20ml of 2mol/L pyrrole ethanol solution at room temperature, standing for 90min until the pyrrole solution is volatilized, adding 20ml of 0.5mol/L ferric chloride aqueous solution, placing the mixture in an oscillator, oscillating for 1h (frequency is 100 times/min), and taking out the membrane to obtain the polypyrrole modified membrane.
And step 3: at room temperature, the polypyrrole modified cation exchange membrane is placed in 5g/L of methyl iodide ethanol solution, the membrane is taken out after being soaked for 24 hours, deionized water is used for repeatedly cleaning for 5 times to remove methyl iodide on the surface, and the iodoalkane quaternized polypyrrole mono-modified cation exchange membrane is obtained, wherein a is shown in a surface electron microscope picture in fig. 2, and a is shown in a cross-sectional electron microscope picture in fig. 2 as 1. Meanwhile, by taking a common cation exchange membrane as a contrast, a surface electron microscope is shown as b in fig. 2, and a cross-sectional electron microscope is shown as b1 in fig. 2.
The difference between the modified and unmodified films is evident from a in fig. 2 and b in fig. 2, and the presence of the modified layer is evident from a1 in fig. 2 and b1 in fig. 2.
2. Divalent cation selective electrodialysis experiment
The test method according to the reference (Recovery of chemically degraded polyethylene by a re-modification method: modifying the lifetime of the location exchange membranes (DOI:10.1039/C5RA27916J) wherein the test system was modified with Na+/Mg2+The system was tested and the initial concentrations were all 0.05mol/L, wherein after 1h the solution in the desalting chamber was taken and analyzed by ion chromatography for Na+And Mg2+And calculating Na+Relative to Mg2+A permselectivity value. In the same way, the common cation exchange membrane is used as a contrast. The results are shown in FIG. 3, from which it can be seen in FIG. 3 that Na is modified with quaternized polypyrrole+Relative to Mg2+The permselectivity value increased from 0.94 to 4.64 compared to the unmodified commercial membrane.
Example 2
The same procedure as in example 1 was repeated except that the 5g/L ethanol solution obtained in step 3 of example 1 was changed to 20g/L ethanol solution of 1-iodohexane, thereby obtaining an iodoalkane-quaternized polypyrrole-modified cation exchange membrane.
Na was determined by the same method+/Mg2+Monovalent selectivity of the system via iodohexaneModified by alkylpyrrole Na+Relative to Mg2 +The permselectivity value increased from 0.94 to 6.84 compared to the unmodified commercial membrane.
Example 3
The same procedure as in example 1 was repeated except that the ethanol solution of methyl iodide 5g/L in step 3 of example 1 was changed to ethanol solution of decane 1g/L to obtain an iodoalkane-quaternized polypyrrole mono/polyvalent selective cation exchange membrane.
Na was determined by the same method+/Mg2+The monovalent selectivity of the system is Na after the iodine decane quaternization polypyrrole modification+Relative to Mg2+The permselectivity value increased from 0.94 to 4.37 compared to the unmodified commercial membrane.
Claims (7)
1. An iodoalkane quaternized polypyrrole modified cation exchange membrane is characterized in that the exchange membrane is prepared by the following method:
1) sequentially soaking the cation exchange membrane in an alkali solution and an acid solution, washing with deionized water, and removing redundant alkali and acid on the surface of the membrane to obtain an acid-base activated cation exchange membrane;
2) soaking the activated cation exchange membrane in the step 1) in 2mol/L pyrrole solution, standing until the pyrrole solution is volatilized, adding an oxidant aqueous solution, shaking, and taking out the membrane to obtain a polypyrrole modified membrane; the pyrrole solution solvent is water, ethanol, diethyl ether or benzene; the oxidant in the oxidant aqueous solution is one of sodium persulfate, ferric chloride, hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid or potassium permanganate;
3) and (3) immersing the polypyrrole modified membrane obtained in the step 2) into an iodoalkane solution for 1-24 hours, taking out the membrane, and cleaning with deionized water to obtain the iodoalkane quaternized polypyrrole modified cation exchange membrane.
2. The modified cation exchange membrane of iodoalkane quaternized polypyrrole according to claim 1, wherein the alkali solution in step 1) is 1mol/L aqueous solution of sodium hydroxide, and the acid solution is 1mol/L aqueous solution of hydrochloric acid.
3. The modified cation exchange membrane of iodoalkane quaternized polypyrrole according to claim 1, wherein the concentration of the aqueous solution of the oxidizing agent in step 2) is 0.5 mol/L.
4. The modified cation exchange membrane of iodoalkane quaternized polypyrrole of claim 1, wherein the concentration of the iodoalkane solution in step 3) is 1-20 g/L.
5. The modified cation exchange membrane of iodoalkane quaternized polypyrrole and recited in claim 1, wherein in the iodoalkane solution of step 3), the iodoalkane is one of iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 1-iodohexane, 2-ethyl iodohexane, 1-iodoheptane, 1-iodooctane, 1-iodononane and 1-iododecane, and the solvent is water, ethanol, diethyl ether or benzene.
6. A method for preparing an iodoalkane quaternized polypyrrole modified cation exchange membrane according to claim 1, characterized in that the method is performed according to the following steps:
1) soaking a cation exchange membrane in a sodium hydroxide aqueous solution for 2 hours at room temperature, washing with deionized water to remove alkali on the surface of the membrane, then soaking with a hydrochloric acid aqueous solution for 2 hours, washing with deionized water to remove acid on the surface of the membrane, and obtaining the cation exchange membrane activated by acid and alkali;
2) soaking the cation exchange membrane activated in the step 1) in 2mol/L pyrrole solution at room temperature, standing until the pyrrole solution is volatilized, then adding 0.5mol/L oxidant aqueous solution, shaking, and taking out the membrane to obtain a polypyrrole modified membrane; the pyrrole solution solvent is water, ethanol, diethyl ether or benzene; the oxidant in the oxidant aqueous solution is one of sodium persulfate, ferric chloride, hydrogen peroxide, peracetic acid, sodium dichromate, chromic acid, nitric acid, potassium permanganate or ammonium persulfate;
3) at room temperature, soaking the polypyrrole modified membrane obtained in the step 2) into 1-20g/L iodoalkane solution for 1-24h, taking out the membrane, and washing the membrane with deionized water to obtain an iodoalkane quaternized polypyrrole modified cation exchange membrane; the iodoalkane in the iodoalkane solution is one of iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane, 2-iodobutane, 1-iodopentane, 1-iodohexane, 2-ethyl iodohexane, 1-iodoheptane, 1-iodooctane, 1-iodononane or 1-iododecane, and the solvent is water, ethanol, diethyl ether or benzene.
7. Use of an iodoalkane quaternized polypyrrole modified cation exchange membrane according to claim 1 in the preparation of monovalent or polyvalent selective cation exchange membranes.
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