CN112516809A - Preparation method of semi-homogeneous bipolar membrane - Google Patents
Preparation method of semi-homogeneous bipolar membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a semi-homogeneous bipolar membrane, which comprises the following steps: 1) melting, blending, extruding and granulating polyethylene and polyisobutylene, and carrying out polymerization reaction on the granules and polyvinyl alcohol after the granules are impregnated with styrene and divinyl benzene to obtain plastic resin powder; 2) sulfonating the plastic resin powder to obtain semi-homogeneous cation resin, chloromethylating the plastic resin powder, and quaternizing to obtain semi-homogeneous anion resin; 3) respectively and uniformly mixing the plastic anion/cation resin with ion exchange resin powder, polyethylene powder and titanium dioxide powder, and sequentially carrying out melt blending by an internal mixer and discharging by a two-roller open mill to respectively obtain single cation/anion resin membranes; 5) and (3) pasting the positive/negative resin membranes together, covering the reinforcing mesh cloth, and pressing by a hot press to obtain the semi-homogeneous bipolar membrane. The semi-homogeneous bipolar membrane prepared by the method has the advantages that the water dissociation performance is greatly superior to that of the conventional heterogeneous bipolar membrane, and meanwhile, the characteristics of low production cost and excellent mechanical property of the heterogeneous bipolar membrane are maintained.
Description
Technical Field
The invention belongs to the technical field of bipolar membrane preparation, and particularly relates to a preparation method of a semi-homogeneous bipolar membrane.
Background
The bipolar membrane is a special ion exchange membrane and is prepared by compounding a cation exchange membrane and an anion exchange membrane. The bipolar membrane can dissociate water molecules in the middle layer into H + and OH under the action of a direct current electric field-Thereby generating an acid and a base corresponding to the salt ion. In recent years, the bipolar membrane is widely applied to the fields of environmental pollution treatment, acid and alkali preparation, pharmaceutical industry, seawater desalination and the like, and contributes great force for changing the traditional industrial separation and preparation.
The existing bipolar membrane preparation methods generally comprise the following steps: (1) hot pressing, namely laminating the dried anode membrane and the dried cathode membrane in a stainless steel plate covered with a polytetrafluoroethylene film, removing bubbles, and heating and pressurizing to obtain a bipolar membrane; (2) a bonding method, namely overlapping the male membrane and the female membrane coated with the adhesive on the inner sides, removing air bubbles and vacuoles, and drying to obtain the bipolar membrane; (3) a casting method, namely covering a layer of polymer solution containing cation exchange resin on a negative membrane, or covering a layer of polymer solution containing anion exchange resin on a positive membrane, and drying to obtain the bipolar membrane; (4) an impregnation method, wherein anion and cation exchange groups are respectively introduced into two sides of a base membrane by a chemical method, so that a single-chip bipolar membrane is prepared; (5) the electrostatic spinning method comprises the steps of preparing raw materials of a positive membrane and a negative membrane into a spinning solution, and compounding the positive membrane and the negative membrane through an electrostatic spinning technology to obtain a bipolar membrane; (6) the electrodeposition method is to assemble an ion exchange membrane in an electrolytic bath, and under the action of a direct current field, the ion exchange resin with opposite charges suspended in an electrolyte is deposited on the surface of the membrane, thereby forming the bipolar membrane. Wherein the hot pressing is the simplest and the most practical, and the industrial popularization is easier.
Chinese patent CN111111794A discloses a method for preparing a bipolar membrane with heterogeneous structure, which is to tightly press and separate the positive and negative membranes without mesh fabric adhesion, but the bipolar membrane prepared by the method is difficult to be widely used due to the problems of high inherent resistance, high water dissociation voltage, serious water permeation, etc. Chinese patent CN109876678A discloses a bipolar membrane and a preparation method thereof, the bipolar membrane is prepared by four steps of impregnation, polymerization, sulfonation and quaternization, the preparation process is simplified, the toxic methylation process is avoided, and the bipolar membrane has an exchange capacity and a transmembrane voltage equivalent to those of other bipolar membranes, but the patent does not explicitly show the water dissociation efficiency and the membrane surface resistance of the bipolar membrane prepared by the method. Chinese patent CN110756055A discloses a method for preparing a bipolar membrane by ultrasonic spraying, which utilizes ultrasonic spraying technology to spray a middle interface layer material on the surface of a cation exchange membrane, and then spray an anion exchange membrane to obtain the bipolar membrane. Although the bipolar membrane prepared by the method has super-hydrophilicity of the intermediate interface layer, small membrane impedance and good thermal stability, the preparation process is complex and the production cost is high.
At present, the research of the bipolar membrane focuses on how to effectively improve the water dissociation efficiency, reduce the transmembrane voltage, reduce the production cost and improve the mechanical and chemical thermal stability. Therefore, aiming at the defects of the prior art, the preparation method of the semi-homogeneous bipolar membrane with low production cost, good mechanical strength and good stability is provided.
Disclosure of Invention
The invention mainly aims to provide a novel bipolar membrane preparation method, which aims to reduce membrane preparation cost, optimize membrane water dissociation performance and improve mechanical performance of the bipolar membrane.
The preparation method of the semi-homogeneous bipolar membrane is characterized by comprising the following steps:
1) melting and blending polyethylene and polyisobutylene, then extruding and granulating, soaking the obtained particles in a mixed monomer solution consisting of styrene, divinylbenzene and an initiator, taking out the particles after impregnation, drying the particles by spinning, then putting the particles into a polyvinyl alcohol aqueous solution for polymerization reaction, and filtering and drying the particles after the polymerization reaction is finished to obtain plastic resin powder;
2) sulfonating the plastic resin powder obtained in the step 1) to obtain semi-homogeneous cation resin; chloromethylating the plastic resin powder obtained in the step 1), and quaternizing to obtain semi-homogeneous anion resin;
3) uniformly mixing the semi-homogeneous cation resin obtained in the step 2) with cation ion exchange resin powder, polyethylene powder and titanium dioxide powder, and sequentially carrying out melt blending by an internal mixer and sheet discharging by a two-roller open mill to obtain a single cation resin membrane; uniformly mixing the semi-homogeneous anion resin obtained in the step 2) with anion exchange resin powder, polyethylene powder and titanium dioxide powder, and sequentially carrying out melt blending by an internal mixer and sheet discharging by a two-roller open mill to obtain a single anion resin membrane;
4) covering the upper surface of the positive resin membrane and the lower surface of the negative resin membrane with reinforcing mesh cloth, bonding the lower surface of the positive resin membrane and the upper surface of the negative resin membrane together, and pressing by a hot press to obtain the semi-homogeneous bipolar membrane product.
Preferably, in the step 1), the mass ratio of the polyethylene to the polyisobutylene is 1: 1-10, the melt blending temperature is 140-160 ℃, and the melt blending time is 5-15 min.
Preferably, in step 1), the total mass of both styrene and divinylbenzene in the mixed monomer solution is 5 to 60% of the mass of the impregnated particles; the mass ratio of the styrene to the divinylbenzene is 10: 0.5-2, and the mass ratio of the divinylbenzene to the initiator is 3-5: 1; in the step 1), the impregnation temperature is room temperature, and the impregnation time is 1-3 h.
Preferably, in the step 1), the spun-dried particles are put into an aqueous solution of polyvinyl alcohol for polymerization, the mass ratio of the particles to the polyvinyl alcohol is 70-130:1, the polymerization temperature is 75-95 ℃, and the polymerization time is 2-20 h.
Preferably, in the step 2), before sulfonation, the plastic resin powder is added into a halogenated hydrocarbon solvent to swell for 1-4 hours at room temperature, and then sulfonation reaction is carried out, wherein the specific process of the sulfonation reaction is as follows: adding the swelled plastic resin powder into 90-98wt% concentrated sulfuric acid, reacting for 2-15h at 75-85 ℃, cooling after the reaction is finished, washing with sodium-alkali solution after 0.5-1.5M dilute sulfuric acid and deionized water in sequence, washing to neutrality with deionized water, drying, grinding and sieving to obtain the semi-homogeneous cation resin; wherein, the halogenated hydrocarbon solvent is dichloroethane, and the sodium-base solution is NaOH aqueous solution with the mass concentration of 5-10%.
Preferably, in the step 2), the specific process for preparing the semi-homogeneous anionic resin comprises the following steps:
s1: adding the plastic resin powder into a solution formed by chloromethyl ether and anhydrous zinc chloride, swelling for 1-4h at room temperature, reacting for 8-15h at 40-50 ℃, and filtering to dry the reaction solution; wherein the mass ratio of the plastic resin powder to the chloromethyl ether is 1:5-7, the unit of the mass is kg, the unit of the volume is L, and the mass ratio of the plastic resin powder to the anhydrous zinc chloride is 1: 0.5-1.5;
s2: reacting the solid obtained after the reaction liquid is drained in the step S1 with a quaternizing agent for 8-15h at the temperature of 35-45 ℃, draining the reaction liquid after the reaction is finished, washing the obtained solid with deionized water, washing with concentrated hydrochloric acid, washing with the deionized water to be neutral, drying, grinding and sieving to obtain the semi-homogeneous anion resin; wherein the quaternizing agent is trimethylamine.
Preferably, the semi-homogeneous cation resin and the semi-homogeneous anion resin prepared in the step 2) have particle sizes of less than 0.3 mm.
Preferably, in the step 3), the semi-homogeneous cation resin is uniformly mixed with cation ion exchange resin powder, polyethylene powder and titanium dioxide powder to obtain a mixture, wherein the mass fraction of the cation ion exchange resin powder is 0-65wt%, and preferably 50-60%; the weight percentage of the polyethylene powder is 5-10wt%, the weight percentage of the titanium dioxide powder is 0.5-1 wt%, and the balance is semi-homogeneous positive resin;
preferably, in the step 3), the semi-homogeneous anion resin is uniformly mixed with anion exchange resin powder, polyethylene powder and titanium dioxide powder to obtain a mixture, wherein the mass fraction of the anion exchange resin powder is 0-65wt%, and preferably 50-60%; the weight percentage of the polyethylene powder is 5-10wt%, the weight percentage of the titanium dioxide powder is 0.5-1 wt%, and the balance is semi-homogeneous negative resin.
Preferably, in the step 3), the banburying temperature and the mixing time are both 115-145 ℃ and 15-30 minutes when the positive resin membrane and the negative resin membrane are prepared; the sheet outlet temperature of the two roller open mills during the preparation of the positive resin film sheet and the negative resin film sheet is both 110-135 ℃, the sheet outlet thickness of the positive resin film sheet is 0.05-0.15mm, and the sheet outlet thickness of the negative resin film sheet is 0.03-0.1 mm.
Preferably, in the step 4), the reinforcing mesh cloth is polyester mesh cloth or nylon mesh cloth, the hot pressing temperature is 100-150 ℃, the hot pressing pressure is 5-20MPa, and the hot pressing time is 15-70 minutes.
The advantages and the beneficial effects of the invention are as follows:
1) the bipolar membrane prepared by the invention has greatly better water dissociation efficiency than a heterogeneous bipolar membrane and excellent mechanical property.
2) The bipolar membrane prepared by the invention has the production cost similar to that of the conventional heterogeneous bipolar membrane, and is greatly lower than that of a homogeneous bipolar membrane.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
1) Preparation of plastic resin powder
Weighing 40kg of polyethylene particles and 200kg of polyisobutylene particles, melting and blending for 10min at 150 ℃, melting at 150 ℃ by using a double-screw extruder, extruding, stretching and cooling by using a multi-channel filament nozzle to obtain continuous filaments with the diameter of about 1.5mm, and cutting by using a pulse cutting machine to obtain cylindrical particles with the length of 3 mm.
50kg of the prepared cylindrical particles were immersed in 60.6kg of a mixed monomer solution prepared by mixing 55.5 parts by weight of styrene, 4.5 parts by weight of divinylbenzene as a crosslinking agent and 0.6 part by weight of benzoyl peroxide (BPO as an initiator) and imbibed at room temperature for 2 hours; taking out the cylindrical particles, spin-drying by a centrifuge, putting into a solution formed by 0.6kg of polyvinyl alcohol (used as a dispersing agent) and 600L of deionized water, uniformly stirring, polymerizing for 2h at 75 ℃, polymerizing for 3h at 85 ℃, then polymerizing for 10h at 95 ℃, filtering and drying to obtain 69.5kg of plastic resin powder.
2) Preparation of semi-homogeneous cation resin powder
50kg of the plastic resin powder prepared in the step 1) is put into a sulfonation reaction kettle of 1000L, 300L of dichloroethane is added, swelling is carried out for 2 hours at room temperature, then pumping is carried out, and redundant solvent is removed; adding 300L of 98% concentrated sulfuric acid, reacting at 75 ℃ for 2 hours, heating to 85 ℃, and continuing to react for 10 hours to finish the sulfonation reaction. After cooling, discharging to a washing kettle, washing for three times by using 1M dilute sulfuric acid and deionized water, and then washing for 1 hour by using NaOH aqueous solution with the mass concentration of 8% to convert into a sodium type; washing with deionized water to neutral, filtering, air drying at 110 deg.C, grinding with a mill, sieving with a vibrating sieve to obtain 46.5kg of cation resin powder with particle size less than 0.15 mm.
3) Preparation of semi-homogeneous anion resin powder
50kg of the plastic resin powder prepared in the step 1) is put into a 1000L chlorination reactor, 300L of chloromethyl ether and 50kg of anhydrous zinc chloride are added, the mixture is swelled at room temperature for 2 hours, and after the mixture is reacted at 45 ℃ for 10 hours, the reaction solution is filtered to be dried. Washing the solid obtained by filtering and drying the reaction solution for 3 times by methylal, discharging the material into an amination kettle, adding 300L of trimethylamine aqueous solution with the mass concentration of 30%, reacting for 10 hours at the temperature of 38-40 ℃, and filtering and drying the reaction solution; discharging the obtained solid to a washing kettle, washing for three times, adding 30L of concentrated hydrochloric acid with the mass concentration of 37%, and pickling for 1 hour to convert the solid into a chlorine type; washing with deionized water to neutral, filtering, air drying at 90 deg.C, grinding with a mill, and sieving with a vibrating sieve to obtain 46kg of anion resin powder with particle size less than 0.15 mm.
4) Preparation of cation membrane
Weighing 40kg of the cation resin powder prepared in the step 2), 76.5kg of commercial cation exchange resin powder (model 001 × 7, available from anhui rong sanden environmental protection water treatment limited company), 10kg of polyethylene powder and 1kg of titanium dioxide, directly putting into an internal mixer, and premixing for 5 minutes. Then heating to 125 ℃ and banburying for 20min, discharging, and pulling out the positive membrane with the thickness of 0.12mm by a two-roller open mill at about 120 ℃.
5) Preparation of negative membrane
Weighing 40kg of the anion resin powder prepared in the step 3), 76.5kg of commercial anion exchange resin powder (model number 201 multiplied by 7, purchased from Anhui Sancheng environmental protection water treatment Co., Ltd.), 10kg of polyethylene powder and 1kg of titanium dioxide, directly putting into an internal mixer, and premixing for 5 minutes. Then the mixture is heated to 125 ℃ and banburied for 20min, and the discharge is carried out, and a negative diaphragm is pulled out by a two-roller open mill at about 120 ℃ and the thickness of the diaphragm is about 0.06 mm.
6) Preparation of bipolar membrane
Covering the upper surface of the positive membrane prepared in the step 4) with a nylon mesh cloth with the thickness of 120nm, covering the lower surface of the negative membrane prepared in the step 5) with a nylon mesh cloth with the thickness of 120nm, pasting the lower surface of the positive membrane with the upper surface of the negative membrane (namely pasting the two membranes with one surface without the mesh cloth), and hot-pressing at the hot-pressing temperature of 115 ℃ and under the pressure of 8MPa for 20min to prepare the bipolar membrane.
The bipolar membrane prepared in example 1 was subjected to an electrolytic performance test using the following experimental setup: the electrolytic test was carried out in an electrolytic cell in which a cation exchange membrane (Type FUJI-Type1, available from hangzhou kojiu environmental energy technologies co., ltd.), the bipolar membrane prepared in example 1, and a cation exchange membrane (Type FUJI-Type1, available from hangzhou kojiu environmental energy technologies co., ltd.) were disposed in this order from left to right to divide the electrolytic cell into 4 polar compartments, namely, a first, a second, a third, and a fourth polar compartment from left to right. 0.3M sodium sulfate solution is contained in the first pole chamber and the fourth pole chamber, 0.1M sodium chloride solution is contained in the second pole chamber and the third pole chamber, a negative pole and a positive pole during electrolysis are respectively arranged in the first pole chamber and the fourth pole chamber, and the negative pole and the positive pole are connected with a power supply through a lead.
The bipolar membrane prepared in example 1 was subjected to a current-voltage curve measurement by the above experimental apparatus, and the bipolar membrane potential at different current densities was measured by a multimeter under a constant current condition, and the performance indexes of the membrane products are shown in table 1.
The bipolar membrane prepared in example 1 was subjected to mechanical property test: the bipolar membranes were tested for tensile strength and elongation at break using a universal stretcher (HPB, leqing idelberg). When in test, the sample is cut into 4 cm multiplied by 1 cm, and the test is carried out for 3 times, and the average value is taken. The performance specifications of the film products are listed in table 1.
Comparative example 1
Comparative example 1 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "in step 5) of comparative example 1, the thickness of the prepared negative electrode sheet was changed to 0.12 mm", and other operations were performed in the same manner as in example 1 to obtain a bipolar membrane.
Comparative example 2
Comparative example 2 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "in step 4) of comparative example 2, the thickness of the obtained anode sheet was changed to 0.06 mm", and other operations were performed in the same manner as in example 1 to obtain a bipolar membrane.
Comparative example 3
Comparative example 3 experimental process for preparing a bipolar membrane example 1 was repeated except that in "step 6) of comparative example 3), nylon mesh cloth covered with both the positive membrane sheet and the negative membrane sheet was replaced with polyester mesh cloth having the same thickness", and other operations were the same as those in example 1 to obtain a bipolar membrane.
The bipolar membranes prepared in comparative examples 1 to 3 were subjected to the electrolytic performance test and the mechanical performance test in the same manner as in example 1, and the performance indexes of the membrane products are shown in table 1.
Example 2
Example 2 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "step 1) was changed from 2h to 3h in the room-temperature imbibition time", and other operations were the same as in example 1 to obtain a bipolar membrane.
Example 3
Example 3 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "step 1) was performed in which the room-temperature imbibition time was changed from 2h to 4 h", and other operations were performed as in example 1 to obtain a bipolar membrane.
Example 4
Example 4 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "step 1) was changed from 2h to 5 h" for the room-temperature soaking time, and other operations were the same as in example 1 to obtain a bipolar membrane.
Example 5
Example 5 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "in step 1), the procedure of dipping 2 hours at room temperature was changed to dipping 1 hour at 40" and other procedures were the same as in example 1 to obtain a bipolar membrane.
Example 6
Example 6 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "in step 1), the procedure of dipping 2 hours at room temperature was changed to dipping 1 hour at 50" and other procedures were the same as in example 1 to obtain a bipolar membrane.
Example 7
Example 7 experimental procedure for preparation of bipolar membrane example 1 was repeated except that "in step 1), the procedure of dipping 2 hours at room temperature was changed to dipping 1 hour at 60" and other procedures were the same as in example 1 to obtain a bipolar membrane.
The bipolar membranes prepared in examples 2 to 7 were subjected to the methods of the electrolytic performance test and the mechanical performance test in the same manner as in example 1, and the performance indexes of the membrane products are shown in table 2.
Examples 8 to 14
Example 8 experimental procedure for preparation of bipolar membrane example 1 was repeated except that the following two points "1, step 1) were changed to dipping at 60 ℃ for 1 hour in the procedure of dipping at room temperature for 2 hours; 2. the addition amount of the commercial cation exchange resin powder in the step 4) was changed to 0, the addition amount of the commercial anion exchange resin powder in the step 5) was changed to 0 ", and the other operations were the same as in example 1 to obtain a bipolar membrane.
Experimental procedures for preparation of bipolar membranes in examples 9 to 14 example 8 was repeated except that "the amount of addition of the commercial cation exchange resin powder in step 4) was changed and the amount of addition of the commercial anion exchange resin powder in step 5) was changed" and bipolar membranes were respectively obtained by performing the same operations as in example 8.
Wherein, in the experimental procedures for preparing bipolar membranes of examples 9 to 14, the amounts of addition of the commercial cation exchange resin powders in step 4) were 5kg, 15 kg, 25 kg, 35 kg, 45 kg and 55 kg, respectively, and the amounts of addition of the commercial anion exchange resin powders in step 5) were 5kg, 15 kg, 25 kg, 35 kg, 45 kg and 55 kg, respectively.
The bipolar membranes prepared in examples 8 to 14 were subjected to the electrolytic performance test and the mechanical performance test in the same manner as in example 1, and the performance indexes of the membrane products are shown in Table 3.
Examples 15 to 18
Example 15 experimental procedure for preparation of bipolar membrane example 1 was repeated except that the following three points "1), the operation procedure of soaking at room temperature for 2 hours in step 1) was changed to soaking at 60 ℃ for 1 hour; 2. the addition amount of the commercial cation exchange resin powder in the step 4) and the addition amount of the commercial anion exchange resin in the step 5) are changed to 25 kg; 3. and (5) changing the addition amount of the polyethylene powder in the steps 4) and 5) to 0', and performing the same operation as in the example 1 to obtain the bipolar membrane.
Experimental procedures for preparing Bipolar membranes in examples 16-18 example 15 was repeated except that "the amount of polyethylene powder added in step 4) and step 5)" was changed, and other operations were performed in the same manner as in example 15 to obtain bipolar membranes, respectively.
In the experimental procedures for preparing bipolar membranes of examples 16 to 18, the amounts of polyethylene powder added in step 4) and step 5) were the same. The amounts of the polyethylene powder added in step 4) and step 5) of example 16 were 2.5kg, 5kg in example 17 and 7.5kg in example 18, respectively.
The bipolar membranes prepared in examples 15 to 18 were subjected to the electrolytic performance test and the mechanical performance test in the same manner as in example 1, and the performance indexes of the membrane products are shown in Table 4.
Examples 19 to 23
Example 19 an experimental procedure for preparing a bipolar membrane in which example 17 was repeated except that "the amount of titanium dioxide added in step 4) was changed to 0 and the amount of titanium dioxide added in step 5) was changed to 0", and the other operations were the same as in example 17, thereby obtaining a bipolar membrane.
In the experimental procedures for preparing bipolar membranes in examples 20 to 23, example 19 was repeated except that "the amount of titanium dioxide added in step 4) and step 5) was changed", and other operations were performed in the same manner as in example 19 to obtain bipolar membranes, respectively.
In the experimental processes for preparing bipolar membranes in examples 20 to 23, the amounts of titanium dioxide added in step 4) and step 5) were the same. Wherein, the addition amount of the titanium dioxide in the step 4) and the step 5) of the embodiment 20 is 0.2kg, while the addition amount of the titanium dioxide in the embodiment 21 is 0.4kg, the addition amount of the titanium dioxide in the embodiment 22 is 0.6kg, and the addition amount of the titanium dioxide in the embodiment 23 is 0.8 kg.
The bipolar membranes prepared in examples 19 to 23 were subjected to the electrolytic performance test and the mechanical performance test in the same manner as in example 1, and the performance indexes of the membrane products are shown in Table 5.
Example 24
Example 24 experimental procedure for preparation of bipolar membrane example 21 was repeated except that "the hot-pressing temperature in step 6) was changed to 130 ℃, the pressure was 10 mpa, and the hot-pressing time was 15 minutes", and otherwise the same operation as in example 21 was performed to obtain a bipolar membrane.
Comparative example 4
Comparative example 4 experimental procedure for preparation of bipolar membrane example 24 was repeated except that "the hot pressing pressure in step 6) was changed to 15 mpa", and other operations were performed in the same manner as in example 24 to obtain a bipolar membrane.
Comparative example 5
Example 24 experimental procedure for preparation of bipolar membrane example 24 was repeated except that "hot pressing time in step 6) was 30 minutes", and other operations were the same as in example 24 to obtain a bipolar membrane.
The bipolar membranes prepared in example 24 and comparative examples 4 to 5 were subjected to the electrolytic performance test and the mechanical performance test in the same manner as in example 1, and the performance indexes of the membrane products are shown in table 6.
Comparative example 6
Example 1 was repeated to carry out both the electrolytic performance test and the mechanical performance test of a commercial bipolar membrane (BPU, available from hangzhou blue technologies ltd.) except for "replacing the bipolar membrane prepared in example 1 with the commercial bipolar membrane", the other operations were the same as those of example 1, and the performance indexes of the membrane products are shown in table 6.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (10)
1. A preparation method of a semi-homogeneous bipolar membrane is characterized by comprising the following steps:
1) melting and blending polyethylene and polyisobutylene, then extruding and granulating, soaking the obtained particles in a mixed monomer solution consisting of styrene, divinylbenzene and an initiator, taking out the particles after impregnation, drying the particles by spinning, then putting the particles into a polyvinyl alcohol aqueous solution for polymerization reaction, and filtering and drying the particles after the polymerization reaction is finished to obtain plastic resin powder;
2) sulfonating the plastic resin powder obtained in the step 1) to obtain semi-homogeneous cation resin; chloromethylating the plastic resin powder obtained in the step 1), and quaternizing to obtain semi-homogeneous anion resin;
3) uniformly mixing the semi-homogeneous cation resin obtained in the step 2) with cation ion exchange resin powder, polyethylene powder and titanium dioxide powder, and sequentially carrying out melt blending by an internal mixer and sheet discharging by a two-roller open mill to obtain a single cation resin membrane; uniformly mixing the semi-homogeneous anion resin obtained in the step 2) with anion exchange resin powder, polyethylene powder and titanium dioxide powder, and sequentially carrying out melt blending by an internal mixer and sheet discharging by a two-roller open mill to obtain a single anion resin membrane;
4) covering the upper surface of the positive resin membrane and the lower surface of the negative resin membrane with reinforcing mesh cloth, bonding the lower surface of the positive resin membrane and the upper surface of the negative resin membrane together, and pressing by a hot press to obtain the semi-homogeneous bipolar membrane product.
2. The method for preparing a semi-homogeneous bipolar membrane according to claim 1, wherein in step 1), the mass ratio of the polyethylene to the polyisobutylene is 1: 1-10, the melt blending temperature is 140 ℃ and 160 ℃, and the melt blending time is 5-15 min.
3. The method according to claim 1, wherein in step 1), the total mass of styrene and divinylbenzene in said mixed monomer solution is 5 to 60% of the mass of said impregnated particles; the mass ratio of the styrene to the divinylbenzene is 10: 0.5-2, and the mass ratio of the divinylbenzene to the initiator is 3-5: 1; in the step 1), the impregnation temperature is room temperature, and the impregnation time is 1-3 h.
4. The method of claim 1, wherein in step 1), the spun-dried particles are put into an aqueous solution of polyvinyl alcohol for polymerization, the mass ratio of the particles to the polyvinyl alcohol is 70-130:1, the polymerization temperature is 75-95 ℃, and the polymerization time is 2-20 h.
5. The method of claim 1, wherein in step 2), the plastic resin powder is added into the halogenated hydrocarbon solvent to swell for 1-4h at room temperature before sulfonation, and then sulfonation is performed, wherein the sulfonation is performed by: adding the swelled plastic resin powder into 90-98wt% concentrated sulfuric acid, reacting for 2-15h at 75-85 ℃, cooling after the reaction is finished, washing with sodium-alkali solution after 0.5-1.5M dilute sulfuric acid and deionized water in sequence, washing to neutrality with deionized water, drying, grinding and sieving to obtain the semi-homogeneous cation resin; wherein, the halogenated hydrocarbon solvent is dichloroethane, and the sodium-base solution is NaOH aqueous solution with the mass concentration of 5-10%.
6. The method for preparing a semi-homogeneous bipolar membrane according to claim 1, wherein in step 2), the semi-homogeneous anionic resin is prepared by a specific process comprising the following steps:
s1: adding the plastic resin powder into a solution formed by chloromethyl ether and anhydrous zinc chloride, swelling for 1-4h at room temperature, reacting for 8-15h at 40-50 ℃, and filtering to dry the reaction solution; wherein the mass ratio of the plastic resin powder to the chloromethyl ether is 1:5-7, the unit of the mass is kg, the unit of the volume is L, and the mass ratio of the plastic resin powder to the anhydrous zinc chloride is 1: 0.5-1.5;
s2: reacting the solid obtained after the reaction liquid is drained in the step S1 with a quaternizing agent for 8-15h at the temperature of 35-45 ℃, draining the reaction liquid after the reaction is finished, washing the obtained solid with deionized water, washing with concentrated hydrochloric acid, washing with the deionized water to be neutral, drying, grinding and sieving to obtain the semi-homogeneous anion resin; wherein the quaternizing agent is trimethylamine.
7. The method of claim 1, wherein the semi-homogeneous cationic resin and the semi-homogeneous anionic resin obtained in step 2) have a particle size of less than 0.3 mm.
8. A method of preparing a semi-homogeneous bipolar membrane according to claim 1, wherein:
in the step 3), the semi-homogeneous cation resin is uniformly mixed with cation ion exchange resin powder, polyethylene powder and titanium dioxide powder to obtain a mixture, wherein the mass fraction of the cation ion exchange resin powder is 0-65wt%, and preferably 50-60%; the weight percentage of the polyethylene powder is 5-10wt%, the weight percentage of the titanium dioxide powder is 0.5-1 wt%, and the balance is semi-homogeneous positive resin;
in the step 3), the semi-homogeneous anion exchange resin is uniformly mixed with anion exchange resin powder, polyethylene powder and titanium dioxide powder to obtain a mixture, wherein the mass fraction of the anion exchange resin powder is 0-65wt%, and preferably 50-60%; the weight percentage of the polyethylene powder is 5-10wt%, the weight percentage of the titanium dioxide powder is 0.5-1 wt%, and the balance is semi-homogeneous negative resin.
9. The method according to claim 1, wherein in step 3), the banburying temperature for preparing the positive resin membrane and the negative resin membrane is 115-145 ℃, and the mixing time is 15-30 min; the sheet outlet temperature of the two roller open mills during the preparation of the positive resin film sheet and the negative resin film sheet is both 110-135 ℃, the sheet outlet thickness of the positive resin film sheet is 0.05-0.15mm, and the sheet outlet thickness of the negative resin film sheet is 0.03-0.1 mm.
10. The method of claim 1, wherein in step 4), the reinforcing mesh fabric is a polyester mesh fabric or a nylon mesh fabric, the hot-pressing temperature is 100 ℃ to 150 ℃, the hot-pressing pressure is 5 MPa to 20MPa, and the hot-pressing time is 15 minutes to 70 minutes.
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