CN109173756B - Bromine alkyl quaternized polypyrrole modified cation exchange membrane and preparation and application thereof - Google Patents
Bromine alkyl quaternized polypyrrole modified cation exchange membrane and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a modified cation exchange membrane of brominated alkyl quaternized polypyrrole 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 at room temperature until the pyrrole solution is volatilized, then adding an oxidant aqueous solution, shaking, and taking out the membrane to obtain a polypyrrole modified membrane; and (3) soaking the polypyrrole modified membrane into a bromoalkane solution for 1-24h at room temperature, taking out the membrane, and washing with deionized water to obtain the bromoalkane quaternized polypyrrole modified cation exchange membrane. The modified cation exchange membrane of the bromine alkyl quaternized polypyrrole of the invention is used for Na+Monovalent selective separation of.
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 importance of water as a source of life is self-evident. However, nowadays, with the increasing exhaustion of global resources, the problem of water resource shortage comes first and becomes increasingly serious, and the pollution of water resources is also increased, which is undoubtedly the frosting on snow. The scarcity of drinking water is also a global problem, and a unique water treatment system comprising microfiltration, ultrafiltration, nanofiltration, reverse osmosis, electrodialysis and other methods is formed in the field of water treatment at present. 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 aspects of sewage treatment, food processing, medicine health and the like as a membrane separation 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. 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 bromoalkane as a quaternizing agent, which is used for preparing a mono/multivalent selective cation exchange membrane, and has great irreplaceable advantages in separation of non-isotropic ions and even isotropic ions, so that the cation exchange membrane is concerned.
The technical scheme adopted by the invention is as follows:
the invention provides a bromine alkyl 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 cation exchange membrane activated in the step 1) in a pyrrole solution at room temperature, standing at room temperature until the pyrrole solution is dried (preferably for 2-6h), adding an oxidant aqueous solution, vibrating to polymerize pyrrole (preferably for 100 times/min, vibrating for 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, peroxyacetic acid, sodium dichromate, chromic acid, potassium permanganate or ammonium persulfate;
3) and (3) at room temperature, immersing the polypyrrole modified membrane obtained in the step 2) into a bromoalkane solution for 1-24 hours, taking out the membrane, and washing the membrane with deionized water to obtain the bromoalkane 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, step 3) is 1 to 20g/L of the bromoalkane solution, wherein the bromoalkane in the bromoalkane solution is ethyl bromide, 1-bromopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, 1-bromopentane, 2-bromopentane, 3-bromopentane, 1-bromohexane, 2-bromohexane, 3-bromohexane, 1-bromoheptane, 2-bromoheptane, 3-bromoheptane, 4-bromoheptane, 1-bromooctane, 2-bromooctane, 1-bromononane or 1-bromodecane, 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 bromoalkane 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 until the pyrrole solution is completely volatilized, adding an oxidant aqueous solution (preferably 0.5mol/L), shaking (preferably 100 times/min, shaking for 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, 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 of bromoalkane solution for 24 hours, taking out the membrane, and washing the membrane with deionized water to obtain a bromoalkane polypyrrole modified cation exchange membrane; the bromoalkane structural formula Br- (CH) in the bromoalkane solution2)n-CH3(n ═ 0 to 12), preferably ethyl bromide, 1-propyl bromide, 2-propyl bromide, 1-butyl bromide, 2-butyl bromide, 1-pentyl bromide, 2-pentyl bromide, 3-pentyl bromide, 1-hexyl bromide, 2-hexyl bromide, 3-hexyl bromide, 1-heptyl bromide, 2-heptyl bromide, 3-heptyl bromide, 4-heptyl bromide, 1-octyl bromide, 2-octyl bromide, 1-nonyl bromide or 1-decyl bromide, more preferably ethyl bromide, 1-hexyl bromide or decyl bromide, and the solvent is water, ethanol, ethyl ether or benzene.
Further, the step 2) is carried out in a beaker, the volume of the added pyrrole solution is 5-30% of the total volume of the beaker, and the volume of the added oxidant solution is 5-30% of the total volume of the beaker.
The invention also provides an application of the bromine alkane 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 modified cation exchange membrane of the bromine alkyl quaternized polypyrrole of the invention is used for Na+Is subjected to univalent selective separation, modified by bromine hexane quaternized polypyrrole and then Na+Relative to Mg2+Comparison of permselectivityUnmodified commercial membranes increased from 0.94 to 4.13; cation exchange membrane modified by the patent, Na+/Mg2+The selectivity factor (flux ratio) of (A) can be increased by up to 4 times compared with that before modification, which is 1.5 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 a modified cation exchange membrane of bromoalkane quaternized polypyrrole of the invention.
FIG. 2 is an electron microscope image of the surface (a) of a cation exchange membrane modified by the brominated alkyl quaternized polypyrrole, a section (a1), an electron microscope image of the surface (b) of an unmodified cation exchange membrane, and an electron microscope image of 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 a bromoethane quaternized polypyrrole modified cation exchange membrane in a concentration chamber in a monovalent selective electrodialysis experiment for 1h, wherein C-1 represents the bromoethane quaternized polypyrrole modified cation exchange membrane of example 1, C-2 represents the bromohexane polypyrrole modified cation exchange membrane of example 2, C-3 represents the bromodecane polypyrrole modified cation exchange membrane of example 3, and C-4 represents an unmodified cation exchange membrane (i.e., a 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. Cation exchange membrane modified by bromine alkyl quaternized polypyrrole
Step 1: soaking a 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 the cation exchange membrane, repeatedly washing the cation exchange membrane by deionized water to remove redundant alkali on the surface, then soaking the cation exchange membrane in 1mol/L hydrochloric acid aqueous solution for 2h, taking out the cation exchange membrane, repeatedly washing the cation exchange membrane by deionized water 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, in step 1, soaking the activated cation exchange membrane in a beaker containing 20ml of 2mol/L pyrrole ethanol solution and 500ml of pyrrole ethanol solution at room temperature, standing for 90min until the pyrrole solution is completely volatilized, adding 20ml of 0.5mol/L ferric chloride aqueous solution, placing the beaker in an oscillator, oscillating for 1h (the frequency is 100 times/min), and taking out the membrane to obtain the polypyrrole modifying membrane.
And step 3: at room temperature, putting the polypyrrole modified membrane into 5g/L ethanol solution of bromoethane, soaking for 24h, taking out the membrane, and repeatedly washing away the bromoethane on the surface by using deionized water to obtain the bromoalkane quaternized polypyrrole mono/multivalent selective cation exchange membrane, wherein a surface electron microscope picture is shown in a figure 2, and a cross-sectional electron microscope picture is shown in a figure 2, a 1. Meanwhile, the CM-1Y cation exchange membrane is used as a contrast, and the surface electron microscope picture is shown as b in figure 2, and the cross-sectional electron microscope picture is shown as b1 in figure 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 area-modification method: modifying the lifetime of the location exchange membranes (DOI:10.1039/C5RA27916J) wherein the test system was changed to Na+/Mg2+To test the system, and the initial concentrations were all 0.05mol/L, wherein the solution in the desalting chamber was taken after 1h and analyzed by ion chromatography for Na+And Mg2+And calculating Na+Relative to Mg2+A permselectivity value. Meanwhile, CM-1Y cation exchange membrane is used as a control. 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 3.67 compared to the unmodified commercial membrane.
Example 2
The ethanol solution of 2mol/L pyrrole in the step 2 of the example 1 is changed into 2mol/L pyrrole aqueous solution, the ethanol solution of 5g/L ethyl bromide in the step 3 is 20 g/L1-bromohexane ethanol solution, and the oxidant is 0.5mol/L FeCl3The aqueous solution was changed to 0.5mol/L aqueous sodium persulfate solution, and the remainder was conducted in the same manner as in example 1 to obtainObtaining the bromine alkyl 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 polypyrrole is modified by bromine hexane quaternization+Relative to Mg2+The permselectivity value increased from 0.94 to 4.13 compared to the unmodified commercial membrane.
Example 3
The ethanol solution of 2mol/L pyrrole in the step 2 of the example 1 is changed into 2mol/L pyrrole aqueous solution, the ethanol solution of 5g/L bromoethane in the step 3 is changed into the ethanol solution of 1g/L bromodecane, and the oxidant is changed from 0.5mol/L FeCl3The aqueous solution was changed to 0.5mol/L aqueous sodium persulfate solution, and the following example 1 was repeated to obtain a bromoalkane-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 bromine decane quaternization polypyrrole modification+Relative to Mg2+The permselectivity value increased from 0.94 to 3.56 compared to the unmodified commercial membrane.
Claims (9)
1. A bromine alkyl 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 cation exchange membrane activated in the step 1) in 2mol/L pyrrole solution, standing at room temperature until the pyrrole solution is completely volatilized, adding an oxidant aqueous solution, carrying out oscillation polymerization, 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 and potassium permanganate; the pyrrole solution solvent is water, ethanol, diethyl ether or benzene;
3) and (3) at room temperature, immersing the polypyrrole modified membrane obtained in the step 2) into a bromoalkane solution for 1-24 hours, taking out the membrane, and washing the membrane with deionized water to obtain the bromoalkane quaternized polypyrrole modified cation exchange membrane.
2. The modified cation exchange membrane of bromoalkane 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 bromoalkane quaternized polypyrrole of claim 1, wherein the concentration of the aqueous oxidant solution in step 2) is 0.5 mol/L.
4. The modified cation exchange membrane of bromoalkane quaternized polypyrrole of claim 1, wherein in step 3) the bromoalkane solution is 1-20 g/L.
5. The modified cation exchange membrane of bromoalkane quaternized polypyrrole of claim 1, wherein in the bromoalkane solution of step 3), the bromoalkane is bromoethane, 1-bromopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, 1-bromopentane, 2-bromopentane, 3-bromopentane, 1-bromohexane, 2-bromohexane, 3-bromohexane, 1-bromoheptane, 2-bromoheptane, 3-bromoheptane, 4-bromoheptane, 1-bromooctane, 2-bromooctane, 1-bromononane or 1-bromodecane, and the solvent is water, ethanol, diethyl ether or benzene.
6. A method for preparing a modified cation exchange membrane of bromoalkane quaternized polypyrrole according to claim 1, which is characterized in that the method comprises 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 a pyrrole solution at room temperature, standing until the pyrrole solution is volatilized, adding an oxidant aqueous solution, carrying out vibration polymerization, 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, peroxyacetic acid, sodium dichromate, chromic acid, potassium permanganate or ammonium persulfate;
3) at room temperature, soaking the polypyrrole modified membrane obtained in the step 2) into 1-20g/L of bromoalkane solution for 1-24h, taking out the membrane, and washing the membrane with deionized water to obtain a bromoalkane quaternized polypyrrole modified cation exchange membrane; in the bromoalkane solution, bromoalkane is bromoethane, 1-bromopropane, 2-bromopropane, 1-bromobutane, 2-bromobutane, 1-bromopentane, 2-bromopentane, 3-bromopentane, 1-bromohexane, 2-bromohexane, 3-bromohexane, 1-bromoheptane, 2-bromoheptane, 3-bromoheptane, 4-bromoheptane, 1-bromooctane, 2-bromooctane, 1-bromononane or 1-bromodecane, and a solvent is water, ethanol, diethyl ether or benzene.
7. The method according to claim 6, wherein the concentrations of the aqueous sodium hydroxide solution and the aqueous hydrochloric acid solution in step 1) are 1 mol/L.
8. The method according to claim 7, wherein the concentration of the pyrrole solution in step 2) is 2mol/L, and the solvent is water, ethanol, diethyl ether or benzene; the concentration of the oxidant aqueous solution is 0.5 mol/L.
9. Use of a bromoalkane 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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| 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 |
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| 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 |
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| A modified coating method for preparing a mono-valent perm-selective cation exchange membrane: I. The evolution of membrane property corresponding to different preparing stage;Ting-Ting Yao, et.al;《Desalination and Water Treatment》;20130402;第51卷;第2740-2748页 * |
| Preparation and characterization of mono-valent ion selective polypyrrole composite ion-exchange membranes;G.S. Gohil, et.al;《 Journal of Membrane Science》;20060213;第280卷;第210-218页 * |
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