CN111233109A - High-potassium-selectivity ion exchange membrane electrode and preparation method and application thereof - Google Patents
High-potassium-selectivity ion exchange membrane electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a high-potassium-selectivity ion exchange membrane electrode, a preparation method and application thereof. In one aspect, the invention provides a high-potassium-selectivity ion exchange membrane electrode, which has excellent electronic conductivity and ion conductivity, can realize selective separation of potassium ions, can be recycled, and has certain capacity of resisting inorganic scaling pollution; on the other hand, the invention provides a transistor electrodialysis device, which comprises the high-potassium-selectivity ion exchange membrane electrode, wherein under the action of electrode potential, an electric field is formed between the inert electrode and the high-potassium-selectivity ion exchange membrane electrode to promote the migration of ions, and the potassium ions are embedded and separated in the high-potassium-selectivity ion exchange membrane to realize the continuous selective recovery of the potassium ions. The ion exchange membrane and the transistor electrodialysis device make up the defect of poor potassium-sodium separation effect in the electrodialysis technology, and can realize selective separation of potassium ions.
Description
Technical Field
The invention belongs to the field of wastewater resource utilization, and particularly relates to a high-potassium-selectivity ion exchange membrane electrode, and a preparation method and application thereof.
Background
Potassium plays a very important role in industrial and agricultural production in China. The potash fertilizer can improve the quality of crops, increase the grain yield and meet the demand of population growth, and the potassium hydroxide, the potassium carbonate, the potassium permanganate and the like are important chemical raw materials and play an important role in national economy in China. But at present, potassium resources are in short supply in China, and 80 percent of potassium resources need to be imported. Therefore, the development of a new potassium source extraction technology is important for the industrial and agricultural development of China, especially for the agricultural development.
The waste water resource is a trend of global development and is a new direction for waste water treatment which is urgently needed to be solved in China. Pig farm wastewater, brewery wastewater, olive oil mill wastewater and the like contain high-concentration potassium salt and can be used as a potential available potassium source. However, these waste waters contain a certain amount of sodium salts, which reduces the recovery rate of potassium salts, and therefore, the separation of potassium and sodium is of great importance for the recovery of potassium salts.
The electrodialysis technology has the advantages of simple equipment, easy operation, low energy consumption and the like, and has attracted extensive attention of the academic world. The electrodialysis technique can be used to separate various nutrient salts, such as PO, from wastewater from pig farms4 3-，SO4 2-，NH4 +，K+，Mg2+And Ca2+. In addition, the electrodialysis technology can also recover heavy metal ions, such as Cr, Cu, Ni and the like, from the wastewater. The ion exchange membrane is the key of the electrodialysis technology, and the electrodialysis technology requires that the ion exchange membrane has good ion exchange capacity, selective permeability, mechanical strength and ion conductivity. However, the ion exchange membranes on the market at present have the defects of high price, lack of selectivity to specific ions, serious membrane pollution and the like, and are difficult to meet the requirement of higher wastewater resource utilization.
The electronically controlled ion exchange technology is an emerging ion exchange technology in recent years, the core of the technology is also an intermediate ion exchange membrane, and the selectivity of the ion exchange membrane determines the ion recovery efficiency and selectivity of the ion exchange membrane. However, the electric control ion exchange membrane in the current research is difficult to realize the selective separation of potassium and sodium; secondly, the system mostly adopts a three-electrode system, including a reference electrode, and a common electrode power supply is difficult to meet the requirements.
CN108996521A discloses a process and a system for producing high-purity refined salt by using selective electrodialysis to concentrate brine, wherein potassium is removed by a potassium removal system, and NaCl is concentrated by selective electrodialysis, but the process is complex and the operation is difficult.
Therefore, there is a need in the art to develop a novel potassium ion selective exchange membrane electrode which can effectively realize selective separation of potassium and sodium and has a simple preparation process.
Disclosure of Invention
Aiming at the problems that the ion exchange membrane in the market at present has high price, lacks selectivity to specific ions, particularly cannot realize effective separation of potassium ions and sodium ions, has serious membrane pollution and the like, and is difficult to meet the requirement of higher wastewater resource utilization. The invention aims to provide a high-potassium-selectivity ion exchange membrane electrode, a preparation method and application thereof. The high-potassium-selectivity ion exchange membrane electrode realizes the selective separation of potassium and sodium, and has the advantages of low recovery cost, reusable ion exchange membrane electrode, continuous process, simple equipment, simple operation, easy industrialization and the like. The high potassium selectivity ion exchange membrane electrode refers to an ion exchange membrane electrode with a potassium-sodium separation factor of more than or equal to 1.8.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a high potassium selectivity ion exchange membrane electrode, comprising: the conductive metal net comprises a conductive metal net and a polypyrrole layer distributed on the surface of the conductive metal net, wherein the dodecyl benzene sulfonate is distributed in the polypyrrole layer.
In the invention, the polypyrrole layer is distributed on two sides of the stainless steel mesh, and dodecyl benzene sulfonate in the polypyrrole layer is combined with polypyrrole through electrostatic attraction. In neutral aqueous solution, aniline or thiophene can not be subjected to the process of oxidizing and doping dodecylbenzene sulfonate, and pyrrole can be subjected to the reaction of oxidizing and doping dodecylbenzene sulfonate to obtain a polypyrrole electrode with high conductivity. The porous structure formed by the polypyrrole layer is beneficial to the diffusion of potassium ions, and the diffusion coefficient is 1.7 multiplied by 10-6cm2S, and the diffusion coefficient of sodium ions is 3.65X 10-7cm2And s. Secondly, based on the density functional theory, the bonding energy of dodecylbenzene sulfonate and potassium ions in the polypyrrole layer is 4.53eV, while the sodium ions are 4.33eV, the larger the bonding energy is, the easier dodecylbenzene sulfonate is to be bonded with cations electrostatically, and therefore, potassium ions are more easily bonded with dodecylbenzene sulfonate in the polypyrrole layer to show the selectivity of potassium ions.
The high-potassium-selectivity ion exchange membrane electrode has excellent electronic conductivity and ionic conductivity, can realize selective separation of potassium ions, and makes up the defect of poor potassium-sodium separation effect of an electrodialysis technology; and the high-potassium-selectivity ion exchange membrane electrode can be recycled, and has certain capacity of resisting inorganic scaling pollution.
Preferably, the thickness of the polypyrrole layer is 40-70 μm, such as 42 μm, 44 μm, 46 μm, 48 μm, 50 μm, 52 μm, 54 μm, 56 μm, 58 μm, 60 μm, 62 μm, 64 μm, 66 μm, or 68 μm.
The thickness of the polypyrrole layer influences the potassium ion exchange process, the thickness of the film is too small, and the potassium ion exchange capacity is small; when the thickness of the membrane is too large, the potassium ion exchange capacity increases, but the distance of potassium ions passing through the membrane increases, and migration of potassium ions is hindered, so that the ion exchange amount decreases.
Preferably, the polypyrrole layer contains 6 to 9 wt% of dodecylbenzene sulfonate, for example, 6.5 wt%, 7 wt%, 7.2 wt%, 7.5 wt%, 7.8 wt%, 8 wt%, 8.5 wt%, 8.8 wt%, or the like, based on the mass of S.
The content of dodecyl benzene sulfonate in the polypyrrole layer is 6-9 wt% (by mass S), and with the increase of the concentration of the dodecyl benzene sulfonate, the conductivity of the polypyrrole ion exchange membrane electrode can be improved, and the ion exchange rate is accelerated; but excessive dopant can not be combined with polypyrrole continuously, and the conductivity of the membrane electrode is not obviously changed.
Preferably, in the polypyrrole layer, the content of polypyrrole is 5-7 mg/cm2E.g. 5.2mg/cm2、5.5mg/cm2、5.8mg/cm2、6mg/cm2、6.2mg/cm2、6.5mg/cm2Or 6.8mg/cm2And the like.
Preferably, the polypyrrole layer is obtained by electrochemical synthesis.
Preferably, the conductive metal mesh comprises a stainless steel mesh, a titanium mesh or a copper mesh.
Preferably, the mesh number of the stainless steel mesh is 3000-4000 meshes, such as 3100 meshes, 3200 meshes, 3300 meshes, 3400 meshes, 3500 meshes, 3600 meshes, 3700 meshes, 3800 meshes, 3900 meshes and the like.
The mesh number of the stainless steel mesh influences the ion exchange process, and the mesh number is too low, so that the concentration diffusion of ions cannot be prevented by the synthesized polypyrrole layer, and the selectivity of potassium ions is reduced. With the increase of the mesh number, the concentration diffusion of ions is slowed down, and the electrodialysis effect is enhanced.
The second purpose of the invention is to provide a preparation method of the high potassium selectivity ion exchange membrane electrode according to the first purpose, which comprises the following steps:
(1) mixing dodecyl benzene sulfonate with water to obtain a water phase solution A;
(2) mixing a pyrrole monomer with the aqueous phase solution A to obtain an aqueous phase solution B;
(3) and placing the three-electrode system in the aqueous phase solution B for electrochemical synthesis to obtain the high-potassium-selectivity ion exchange membrane electrode.
The traditional preparation method of the ion exchange membrane is a monomer polymerization method, a base membrane introduces a functional group, a hot pressing method, a melt extrusion method, a salivation method and the like, but the traditional preparation method has the problems of complicated preparation method, environmental unfriendliness, higher price, limited application environment and the like. The electrochemical synthesis ion exchange membrane electrode has the advantages of simple equipment, simple operation, low cost and economic advantage. In addition, conductive polypyrrole (PPy) is known as the most attractive and promising material in conductive polymers because of its advantages of easy synthesis, no toxicity, high conductivity, good environmental stability, and the like.
The high-potassium selective ion exchange membrane electrode prepared by the method realizes the selective separation of potassium and sodium, and makes up the defect of poor potassium and sodium separation effect of an electrodialysis technology. The dodecylbenzene sulfonate in step (1) of the present invention is a material containing dodecylbenzene sulfonate, and is exemplified by sodium dodecylbenzene sulfonate.
Preferably, the concentration of the aqueous phase solution A in the step (1) is 0.05-0.2 mol/L, such as 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L, 0.15mol/L, 0.16mol/L, 0.17mol/L, 0.18mol/L or 0.19mol/L, etc.
The concentration of the aqueous phase solution A is 0.05-0.2 mol/L, the concentration is too high, pyrrole is uniformly dispersed, and redundant dopant ions cause waste; if the concentration is too low, the pyrrole monomer cannot be uniformly dispersed in the solution, and the deposition rate is slowed down.
Preferably, the water in step (1) is ultrapure water.
Preferably, in the aqueous phase solution B in the step (2), the concentration of pyrrole monomer is 0.05-0.2 mol/L, such as 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, 0.14mol/L, 0.15mol/L, 0.16mol/L, 0.17mol/L, 0.18mol/L or 0.19mol/L, etc.
The concentration of pyrrole monomers in the aqueous phase solution B is 0.05-0.2 mol/L, and the concentration is too high, so that the deposition rate of polypyrrole on a stainless steel net is too high, and the polypyrrole layer is not uniform; too low a concentration, too slow a reaction rate.
Preferably, after the step (2) and before the step (3), the process of stirring, ultrasound and nitrogen gas aeration of the aqueous phase solution B is further included.
Preferably, the stirring time is 20-40 min, such as 21min, 23min, 25min, 27min, 29min, 30min, 31min, 33min, 35min, 37min or 39 min.
Preferably, the stirring frequency is 300-700 rpm, such as 330rpm, 360rpm, 390rpm, 420rpm, 450rpm, 480rpm, 510rpm, 540rpm, 570rpm, 600rpm, 630rpm, 660rpm or 690rpm, and the like.
Preferably, the time of the ultrasonic treatment is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min or 28 min.
Preferably, the frequency of the ultrasound is 20-40 kHz, such as 22kHz, 24kHz, 26kHz, 28kHz, 30kHz, 32kHz, 34kHz, 36kHz or 38kHz and the like.
Preferably, the nitrogen exposure time is 10-25 min, such as 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min or 24 min.
Preferably, in the three-electrode system in the step (3), the working electrode is a conductive metal mesh, preferably a stainless steel mesh, and further preferably, the mesh number of the stainless steel mesh is 3000-4000 meshes.
The mesh number of the stainless steel mesh influences the ion exchange process, and the mesh number is too low, so that the concentration diffusion of ions cannot be prevented by the synthesized polypyrrole layer, and the selectivity of potassium ions is reduced. With the increase of the mesh number, the concentration diffusion of ions is slowed down, and the electrodialysis effect is enhanced.
Preferably, in the three-electrode system, the counter electrode is a platinum sheet electrode.
Preferably, in the three-electrode system, the reference electrode is an Ag/AgCl electrode.
Preferably, the potential of the electrochemical synthesis in the step (3) is 0.6-0.7V, such as 0.61V, 0.62V, 0.63V, 0.64V, 0.65V, 0.66V, 0.67V, 0.68V or 0.69V.
Preferably, the time of the electrochemical synthesis in the step (3) is 1800-7200 s, such as 2000s, 2500s, 3000s, 3500s, 4000s, 4500s, 5000s, 5500s, 6000s, 6500s or 7000 s.
The potential of the electrochemical synthesis is 0.6-0.7V, the time is 1800-7200 s, the synthesis potential is too low, and the polypyrrole is difficult to synthesize or the synthesis rate is too slow; when the synthesis potential is too high, polypyrrole can generate peroxidation, the conjugated structure of the polypyrrole is damaged, and the conductivity is reduced. The synthesis time affects the thickness of the polypyrrole layer, and is too short, so that the thickness of the polypyrrole layer is too small to prevent concentration diffusion of ions; and the synthesis time is too long, so that the thickness of the polypyrrole layer is too large, the ion migration resistance is increased, and the ion exchange capacity is reduced.
Preferably, after the step (3), the obtained high-potassium selectivity ion exchange membrane electrode is washed, preferably by using ultra-pure water.
It is a further object of the present invention to provide a transistor electrodialysis unit comprising the high potassium selectivity ion exchange membrane electrode of one of the objects.
Preferably, the transistor electrodialysis device further comprises a reaction chamber, an inert electrode, a power supply and a relay.
Preferably, in the transistor electrodialysis device, the high potassium selectivity ion exchange membrane electrode divides the reaction chamber into a chamber A and a chamber B, wherein the chamber A stores the raw material liquid, and the chamber B stores the receiving liquid.
Preferably, the power supply is divided into an a-chamber side power supply and a B-chamber side power supply.
The transistor electrodialysis device consists of the high-potassium-selectivity ion exchange membrane electrode, a reaction chamber, an inert electrode, a power supply and a relay; the high potassium selectivity ion exchange membrane electrode has selectivity to potassium ions; an electric field is formed between the inert electrode and the ion exchange membrane electrode to promote the migration of ions; a power supply supplies a transistor electrodialysis system current; the relay controls the switch of the power supply to be closed, and continuous selective recovery of potassium ions is realized.
Preferably, the raw material liquid includes potassium ions and sodium ions.
Preferably, the receiving solution is an acid, preferably hydrochloric acid, and more preferably 0.05 to 0.15mol/L hydrochloric acid, such as 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, 0.11mol/L, 0.12mol/L, 0.13mol/L, or 0.14 mol/L.
A fourth object of the present invention is to provide a method for using the transistor electrodialysis device according to the third object, the method comprising: and (3) enabling the high-potassium-selectivity ion exchange membrane electrode to be negatively charged, then enabling the high-potassium-selectivity ion exchange membrane electrode to be neutral in electricity, and enabling potassium ions to enter a chamber B to realize selective separation of potassium ions and sodium ions.
The method reduces the recovery cost of potassium ions, reduces the consumption by 37 percent compared with the traditional electrodialysis method, and has the advantages of continuous process, simple equipment, simple operation, easy industrialization and the like.
Preferably, the time for the high potassium selectivity ion exchange membrane electrode to be negatively charged is 10-20 s, such as 10s, 12s, 14s, 16s, 18s or 20 s.
The time of the negative charge of the high-potassium-selectivity ion exchange membrane electrode is 10-20 s, the shorter the time of the negative charge is, the more potassium ion embedding processes occur in the same interval time, and the larger the ion exchange amount is; the longer the negative charge time, the less potassium intercalation process occurs in the same interval time and the smaller the amount of ion exchange. In addition, the shorter the negative charge time is, the higher the pulse frequency is, which is beneficial to destroying the concentration polarization phenomenon of the polypyrrole layer and slowing down the membrane pollution.
Preferably, the high potassium selectivity ion exchange membrane electrode has the charge neutrality time of 10-20 s, such as 10s, 12s, 14s, 16s, 18s or 20 s.
The time for the electrode of the high-potassium selective ion exchange membrane to be neutral is 10-20 s, the shorter the time for the electrode to be neutral is, the more potassium ion removal processes occur in the same interval time, and the larger the ion exchange amount is; the longer the electroneutrality time, the less potassium intercalation process occurs at the same interval time and the smaller the amount of ion exchange.
Preferably, the high potassium selectivity ion exchange membrane electrode is negatively charged in the following manner: and starting a power supply on the side of the A chamber, connecting the negative electrode of the power supply on the side of the A chamber with the high-potassium-selectivity ion exchange membrane electrode, and applying 1.5-2.5V of voltage, such as 1.6V, 1.7V, 1.8V, 1.9V, 2.0V, 2.1V, 2.2V, 2.3V or 2.4V.
The applied voltage is 1.5-2.5V, and when the voltage is too high, the cathode can generate hydrogen evolution reaction to destroy the process that potassium ions are embedded into the polypyrrole layer; the voltage is too low, the polarization rate is slow, and the rate of potassium ions embedded into the polypyrrole layer is slow.
Preferably, the high potassium selectivity ion exchange membrane electrode is in a charge neutral mode as follows: and closing the power supply on the side of the A chamber, opening the power supply on the side of the B chamber, connecting the positive electrode of the power supply on the side of the B chamber with the high-potassium-selectivity ion exchange membrane electrode, and applying a voltage of 0.6-1.2V (such as 0.7V, 0.8V, 0.9V, 1V or 1.1V).
The applied voltage is 0.6-1.2V, and the polypyrrole layer can generate peroxidation reaction when the voltage is too large, so that the structure of the polypyrrole layer is damaged, and the ion exchange performance is lost; the voltage is too small, the polarization rate is slow, and the rate of potassium ions escaping from the polypyrrole layer is slow.
The schematic diagram of the transistor electrodialysis device is shown in fig. 1, wherein a left chamber A is a raw material solution (containing potassium and sodium ions in an equimolar ratio), and a right chamber B is a receiving solution (0.05-0.15 mol/L hydrochloric acid). The working process comprises the following steps: firstly, a power supply on the side of an A chamber is started through relay control, 1.5-2.5V voltage is applied to enable a high-potassium selective ion exchange membrane (marked by polypyrrole in the figure) to be negatively charged, potassium ions in a raw material liquid can be selectively embedded into the high-potassium selective ion exchange membrane, after 10-20 s, the power supply on the side of the A chamber is closed through relay control, the power supply on the side of a B chamber on the right side is opened to enable the high-potassium selective ion exchange membrane to be electrically neutral, potassium ions just embedded into the high-potassium selective ion exchange membrane are separated from a membrane electrode, and enter the B chamber under the action of a receiving liquid electric field to realize selective separation of potassium ions and sodium ions.
The working principle of the transistor electrodialysis device is as follows: under the action of electrode potential, the high-potassium-selectivity ion exchange membrane can perform ion embedding and ion removing processes, so that a dialysis membrane penetrating process for ions in a solution is realized. The specific principle is as follows: under the reduction potential, the high potassium selectivity ion exchange membrane is negatively charged, and cations in the solution can be embedded into the membrane to supplement positive charges; and then applying an oxidation potential to the high-potassium selective ion exchange membrane, wherein the high-potassium selective ion exchange membrane is electrically neutral, and ions just embedded into the membrane are separated from the high-potassium selective ion exchange membrane and return to the solution. The operation principle diagram of the transistor electrodialysis device is shown in fig. 2, wherein 1 is a side power supply of a chamber A, 2 is a side power supply of a chamber B, 3 is a relay, 4,5 are inert electrodes (platinum electrodes), and 6 is a high-potassium-selectivity ion exchange membrane.
The fifth object of the present invention is to provide a use of the transistor electrodialysis device of the third object for extracting potassium ions from wastewater, preferably any one or a combination of at least two of piggery wastewater, brewery wastewater and olive oil factory wastewater.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention realizes the selective separation of potassium and sodium, and makes up the defect of poor potassium and sodium separation effect of the traditional electrodialysis technology;
(2) the recovery cost of potassium ions is low, and the consumption is reduced by 37 percent compared with the traditional electrodialysis;
(3) the ion exchange membrane electrode can be repeatedly used and has certain capacity of resisting inorganic scaling pollution;
(4) the continuous process has simple equipment, simple operation and easy industrialization.
Drawings
Fig. 1 is a schematic view of a transistor electrodialysis unit provided by the present invention;
fig. 2 is a schematic diagram of the operation of the transistor electrodialysis apparatus provided by the present invention, wherein 1 is a side power supply of a chamber a, 2 is a side power supply of a chamber B, 3 is a relay, 4,5 are inert electrodes (platinum electrodes), and 6 is a high potassium selectivity ion exchange membrane.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the high potassium selectivity ion exchange membrane electrode comprises the following steps:
(1) 1.7424g of sodium dodecyl benzene sulfonate is dissolved in 50mL of ultrapure water to prepare a solution A with the concentration of 0.1 mol/L;
(2) adding 350 mu L of pyrrole into the solution A to prepare a solution B with the pyrrole content of 0.1 mol/L;
(3) stirring the solution B at 500rpm for 30min, performing ultrasonic treatment at 40kHz for 10min, and aerating nitrogen for 10 min;
(4) placing the three-electrode system in an aqueous phase solution B, and carrying out electrochemical synthesis, wherein the working electrode is a stainless steel mesh (3500 meshes), the counter electrode is a platinum sheet electrode, the reference electrode is an Ag/AgCl electrode, the electrochemical synthesis potential is 0.7V, and the electrochemical synthesis time is 3600s, so as to obtain the high-potassium-selectivity ion exchange membrane electrode;
(5) and (4) taking out the high-potassium selective ion exchange membrane electrode obtained in the step (4), washing with ultrapure water for a plurality of times, and then putting into the ultrapure water for storage for later use.
In the high-potassium-selectivity ion-exchange membrane electrode obtained in this example, the thickness of the polypyrrole layer was 43 μm, and the surface density was 5.67mg/cm2The content of dodecylbenzenesulfonate was 7.57% by mass as S.
Example 2
The preparation method of the high potassium selectivity ion exchange membrane electrode comprises the following steps:
(1) 1.7424g of sodium dodecyl benzene sulfonate is dissolved in 50mL of ultrapure water to prepare a solution A with the concentration of 0.1 mol/L;
(2) adding 350 mu L of pyrrole into the solution A to prepare a solution B with the pyrrole content of 0.1 mol/L;
(3) stirring the solution B at a frequency of 600rpm for 30min, performing ultrasonic treatment at a frequency of 30kHz for 10min, and aerating nitrogen for 10 min;
(4) placing the three-electrode system in the aqueous phase solution B, and carrying out electrochemical synthesis, wherein the working electrode is a stainless steel mesh (2500 meshes), the counter electrode is a platinum sheet electrode, the reference electrode is an Ag/AgCl electrode, the electrochemical synthesis potential is 0.7V, and the electrochemical synthesis time is 3600s, so as to obtain the high-potassium-selectivity ion exchange membrane electrode;
(5) and (4) taking out the high-potassium selective ion exchange membrane electrode obtained in the step (4), washing with ultrapure water for a plurality of times, and then putting into the ultrapure water for storage for later use.
This example givesIn the high potassium selectivity ion exchange membrane electrode, the thickness of the polypyrrole layer is 20 mu m, and the surface density is 5.54mg/cm2The content of dodecylbenzenesulfonate was 7.86% by mass as S.
Example 3
The preparation method of the high potassium selectivity ion exchange membrane electrode comprises the following steps:
(1) 1.7424g of sodium dodecyl benzene sulfonate is dissolved in 50mL of ultrapure water to prepare a solution A with the concentration of 0.1 mol/L;
(2) adding 350 mu L of pyrrole into the solution A to prepare a solution B with the pyrrole content of 0.1 mol/L;
(3) stirring the solution B at 500rpm for 30min, performing ultrasonic treatment at 40kHz for 10min, and aerating nitrogen for 10 min;
(4) placing the three-electrode system in an aqueous phase solution B, and carrying out electrochemical synthesis, wherein the working electrode is a stainless steel mesh (3500 meshes), the counter electrode is a platinum sheet electrode, the reference electrode is an Ag/AgCl electrode, the electrochemical synthesis potential is 0.8V, and the electrochemical synthesis time is 3600s, so as to obtain the high-potassium-selectivity ion exchange membrane electrode;
(5) and (4) taking out the high-potassium selective ion exchange membrane electrode obtained in the step (4), washing with ultrapure water for a plurality of times, and then putting into the ultrapure water for storage for later use.
In the high-potassium-selectivity ion exchange membrane electrode obtained in this example, the thickness of the polypyrrole layer was 12 μm, and the surface density was 3.01mg/cm2The content of dodecylbenzenesulfonate was 4.53% by mass as S.
Example 4
The preparation method of the high potassium selectivity ion exchange membrane electrode comprises the following steps:
(1) dissolving sodium dodecyl benzene sulfonate in 50mL of ultrapure water to prepare a solution A of 0.05 mol/L;
(2) adding pyrrole into the solution A to prepare a solution B with the pyrrole content of 0.05 mol/L;
(3) stirring the solution B at 500rpm for 20min, performing ultrasonic treatment at 40kHz for 20min, and introducing nitrogen for 10 min;
(4) placing the three-electrode system in an aqueous phase solution B, and carrying out electrochemical synthesis, wherein the working electrode is a stainless steel mesh (3500 meshes), the counter electrode is a platinum sheet electrode, the reference electrode is an Ag/AgCl electrode, the electrochemical synthesis potential is 0.6V, and the electrochemical synthesis time is 7200s to obtain the high-potassium-selectivity ion exchange membrane electrode;
(5) and (4) taking out the high-potassium selective ion exchange membrane electrode obtained in the step (4), washing with ultrapure water for a plurality of times, and then putting into the ultrapure water for storage for later use.
In the ion exchange membrane electrode with high potassium selectivity obtained in this example, the thickness of the polypyrrole layer was 62 μm, and the surface density was 6.11mg/cm2The content of dodecylbenzenesulfonate was 8.33% by mass as S.
Example 5
The preparation method of the high potassium selectivity ion exchange membrane electrode comprises the following steps:
(1) dissolving sodium dodecyl benzene sulfonate in 50mL of ultrapure water to prepare a solution A with the concentration of 0.2 mol/L;
(2) adding pyrrole into the solution A to prepare a solution B with the pyrrole content of 0.2 mol/L;
(3) stirring the solution B at 500rpm for 40min, performing ultrasonic treatment at 40kHz for 10min, and aerating nitrogen for 20 min;
(4) placing the three-electrode system in an aqueous phase solution B, and carrying out electrochemical synthesis, wherein the working electrode is a stainless steel mesh (3500 meshes), the counter electrode is a platinum sheet electrode, the reference electrode is an Ag/AgCl electrode, the electrochemical synthesis potential is 0.6V, and the electrochemical synthesis time is 3600s, so as to obtain the high-potassium-selectivity ion exchange membrane electrode;
(5) and (4) taking out the high-potassium selective ion exchange membrane electrode obtained in the step (4), washing with ultrapure water for a plurality of times, and then putting into the ultrapure water for storage for later use.
In the high-potassium-selectivity ion-exchange membrane electrode obtained in this example, the thickness of the polypyrrole layer was 48 μm, and the surface density was 6.67mg/cm2The content of dodecylbenzenesulfonate was 6.97% by mass as S.
Comparative example 1
The difference from example 1 is that in step (1), sodium dodecylbenzenesulfonate is replaced with an equal amount of sodium dodecylsulfate.
Comparative example 2
The difference from example 1 is that in step (2) the pyrrole is replaced by an equivalent amount of aniline.
Comparative example 3
The difference from example 1 is that step (1) does not add sodium dodecylbenzenesulfonate.
Application example 1
An electrodialysis device as shown in figure 1 is adopted, wherein the chamber A contains 0.1mol/L NaCl and 0.1mol/L KCl solution, and the volume of the solution is 60 mL; the chamber B contains 0.1mol/L HCl solution; the middle diaphragm is the high potassium selectivity ion exchange membrane electrode in example 1;
firstly, starting a side power supply of the A chamber, applying 2V voltage to enable the high potassium selective ion exchange membrane to be negatively charged, and keeping the duration for 10 s; the power supply on the side of the A chamber is turned off and the power supply on the side of the B chamber is turned on through the control of a relay, the voltage is 1V, the high-potassium selective ion exchange membrane is neutral, and the duration time is 10 s; then the relay controls to close the power supply of the chamber B, and the power supply of the chamber A is started, so as to circulate;
after a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 0.86mmol/L, Na+The concentration is 0.48mmol/L, and the potassium-sodium separation factor is 1.84.
Application example 2
The difference from application example 1 is that the duration of the negative charge of the high potassium selectivity ion exchange membrane is 30 s; the duration time of the electroneutrality of the high-potassium selective ion exchange membrane is 30 s;
after a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 0.76mmol/L, Na+The concentration is 0.39mmol/L, the potassium-sodium separation factor is 1.99, and the application example shows that when the duration of the negative charge of the high-potassium-selectivity ion exchange membrane is longer (30s), the concentration of cations in the receiving solution is reduced, the ion exchange amount is reduced, but the potassium ion selectivity is not obviously influenced.
Application example 3
The difference from application example 1 is that the duration of the negative charge of the high potassium selectivity ion exchange membrane is 60 s; the duration time of the electroneutrality of the high-potassium selective ion exchange membrane is 60 s;
after a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 0.33mmol/L, Na+The concentration is 0.17mmol/L, the potassium-sodium separation factor is 1.92, and the application example shows that the duration of the negative charge of the high-potassium-selectivity ion exchange membrane is further prolonged (60s), the concentration of cations in the receiving solution is further reduced, the ion exchange amount is reduced, but the potassium ion selectivity is not obviously influenced.
Application example 4
The difference from application example 1 is that the high potassium selectivity ion exchange membrane electrode obtained in example 2 was used.
After a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 0.78mmol/L, Na+The concentration is 0.57mmol/L, the potassium-sodium separation factor is 1.61, and through the application example, the mesh number of the stainless steel mesh in the example 2 is 2500 meshes, which leads to the increase of the concentration of the cations in the receiving liquid, but the increase of the concentration of the ions is the result of the combined action of the ion concentration difference diffusion and the electrodialysis, which also leads to the reduction of the potassium-sodium separation factor in the receiving liquid to 1.61, and the separation effect is poor.
Application example 5
The difference from application example 1 was that the high potassium selectivity ion exchange membrane electrode obtained in example 3 was used.
After a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 5.24mmol/L, Na+The concentration is 5.13mmol/L, the potassium-sodium separation factor is 1.02, and it can be seen from this application example that the electrochemical synthesis potential in example 3 is 0.8V, so that the polypyrrole membrane electrode undergoes peroxidation, the polypyrrole layer structure is destroyed, and the concentration diffusion of ions cannot be effectively prevented, so that ions in the raw material liquid equally diffuse into the receiving solution, and the selective separation of potassium and sodium ions cannot be realized.
Application example 6
The difference from application example 1 is that the high potassium selectivity ion exchange membrane electrode obtained in example 4 was used.
After a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 0.59mmol/L, Na+The concentration is 0.29mmol/L, and the potassium-sodium separation factor is2.08. Due to the increase of the thickness of the polypyrrole layer, the ion migration distance is prolonged, the concentration of cations in the receiving solution is reduced, the ion exchange amount is reduced, and the selectivity of potassium ions is not changed significantly.
Application example 7
The difference from application example 1 was that the high potassium selectivity ion exchange membrane electrode obtained in example 5 was used.
After a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 0.96mmol/L, Na+The concentration was 0.44mmol/L and the potassium-sodium separation factor was 2.19. The increase of the electrolyte concentration during the synthesis of the membrane electrode is beneficial to improving the surface density of the polypyrrole layer and improving the ion exchange capacity, but does not cause obvious influence on the selectivity of potassium ions.
Comparative example 1
The difference from application example 1 is that the high potassium selectivity ion exchange membrane electrode obtained in comparative example 1 was used.
After a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 0.60mmol/L, Na+The concentration is 0.63mmol/L, the potassium-sodium separation factor is 0.95, and the comparison example shows that the polypyrrole layer doped with dodecyl sulfate radical can not realize the selective separation of potassium and sodium. Because the dodecyl sulfate radical doped polypyrrole layer forms a pore channel structure which is not favorable for the diffusion of potassium ions.
Comparative example 2
The difference from application example 1 is that the high potassium selectivity ion exchange membrane electrode obtained in comparative example 2 was used.
After a two-hour electrodialysis experiment, K in the receiver liquid+The concentration is 3.24mmol/L, Na+The concentration was 3.33mmol/L and the potassium-sodium separation factor was 0.97, and it can be seen from this comparative example that the membrane electrode could not effectively prevent the concentration diffusion of ions and could not achieve the selective separation of potassium and sodium because sufficient polyaniline could not be synthesized on the stainless steel mesh.
Comparative example 3
The difference from application example 1 is that the high potassium selectivity ion exchange membrane electrode obtained in comparative example 3 was used.
ThroughTwo hour electrodialysis experiment, K in the receiver+The concentration is 10.22mmol/L, Na+The concentration is 10.02mmol/L, the potassium-sodium separation factor is 1.02, and the comparison example shows that when the dodecylbenzene sulfonate is not present in the electrolyte, the conductive polypyrrole can not be subjected to electropolymerization on a stainless steel mesh, so that the membrane electrode can not prevent the concentration diffusion of ions, and the selective separation of potassium and sodium can not be realized.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A high potassium selectivity ion exchange membrane electrode, comprising: the conductive metal net comprises a conductive metal net and a polypyrrole layer distributed on the surface of the conductive metal net, wherein the dodecyl benzene sulfonate is distributed in the polypyrrole layer.
2. The high potassium selectivity ion exchange membrane electrode of claim 1, wherein the thickness of the polypyrrole layer is 40 to 70 μm;
preferably, in the polypyrrole layer, the content of dodecyl benzene sulfonate is 6-9 wt% in terms of S mass;
preferably, in the polypyrrole layer, the content of polypyrrole is 5-7 mg/cm2；
Preferably, the polypyrrole layer is obtained by electrochemical synthesis;
preferably, the conductive metal mesh comprises a stainless steel mesh, a titanium mesh or a copper mesh;
preferably, the mesh number of the stainless steel mesh is 3000-4000 meshes.
3. A method for preparing the high potassium selectivity ion exchange membrane electrode according to claim 1 or 2, comprising the steps of:
(1) mixing dodecyl benzene sulfonate with water to obtain a water phase solution A;
(2) mixing a pyrrole monomer with the aqueous phase solution A to obtain an aqueous phase solution B;
(3) and placing the three-electrode system in the aqueous phase solution B for electrochemical synthesis to obtain the high-potassium-selectivity ion exchange membrane electrode.
4. The method according to claim 3, wherein the concentration of the aqueous phase solution A in the step (1) is 0.05-0.2 mol/L;
preferably, the water in step (1) is ultrapure water;
preferably, in the aqueous phase solution B in the step (2), the concentration of the pyrrole monomer is 0.05-0.2 mol/L.
5. The method according to claim 3 or 4, wherein after the step (2) and before the step (3), the method further comprises the steps of stirring, ultrasonic treatment and nitrogen gas aeration of the aqueous phase solution B;
preferably, the stirring time is 20-40 min;
preferably, the stirring frequency is 300-700 rpm;
preferably, the time of the ultrasonic treatment is 10-30 min;
preferably, the frequency of the ultrasonic wave is 20-40 kHz;
preferably, the time for exposing the nitrogen is 10-25 min.
6. The method according to any one of claims 3 to 5, wherein in the three-electrode system in the step (3), the working electrode is a conductive metal mesh, preferably a stainless steel mesh, and further preferably the mesh number of the stainless steel mesh is 3000-4000 mesh;
preferably, in the three-electrode system, the counter electrode is a platinum sheet electrode;
preferably, in the three-electrode system, the reference electrode is an Ag/AgCl electrode.
7. The method according to any one of claims 3 to 6, wherein the potential of the electrochemical synthesis in step (3) is 0.6 to 0.7V;
preferably, the time of the electrochemical synthesis in the step (3) is 1800-7200 s;
preferably, after the step (3), the obtained high-potassium selectivity ion exchange membrane electrode is washed, preferably by using ultra-pure water.
8. A transistor electrodialysis unit, characterized in that it comprises the high potassium selectivity ion exchange membrane electrode of claim 1 or 2;
preferably, the transistor electrodialysis device further comprises a reaction chamber, an inert electrode, a power supply and a relay;
preferably, in the transistor electrodialysis device, the high potassium selectivity ion exchange membrane electrode divides the reaction chamber into a chamber A and a chamber B, wherein the chamber A is used for storing the raw material liquid, and the chamber B is used for storing the receiving liquid;
preferably, the power supply is divided into an a-chamber side power supply and a B-chamber side power supply;
preferably, the raw material liquid comprises potassium ions and sodium ions;
preferably, the receiving solution is acid, preferably hydrochloric acid, and more preferably 0.05-0.15 mol/L hydrochloric acid.
9. A method of using a transistor electrodialysis unit according to claim 8, comprising: enabling the high-potassium-selectivity ion exchange membrane electrode to be negatively charged, enabling the high-potassium-selectivity ion exchange membrane electrode to be neutral in electricity, enabling potassium ions to enter a chamber B, and realizing selective separation of potassium ions and sodium ions;
preferably, the time for the negative charge of the high-potassium selective ion exchange membrane electrode is 10-20 s;
preferably, the time for the high-potassium-selectivity ion exchange membrane electrode to be neutral is 10-20 s;
preferably, the high potassium selectivity ion exchange membrane electrode is negatively charged in the following manner: starting a power supply on the side of the A chamber, connecting the negative electrode of the power supply on the side of the A chamber with the high-potassium-selectivity ion exchange membrane electrode, and applying 1.5-2.5V voltage;
preferably, the high potassium selectivity ion exchange membrane electrode is in a charge neutral mode as follows: and closing the power supply on the side of the chamber A, opening the power supply on the side of the chamber B, connecting the positive electrode of the power supply on the side of the chamber B with the high-potassium-selectivity ion exchange membrane electrode, and applying a voltage of 0.6-1.2V.
10. Use of a transistor electrodialysis unit according to claim 8 for extracting potassium ions from wastewater, preferably any one or a combination of at least two of piggery wastewater, brewery wastewater and olive oil plant wastewater.
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| DE102009058766A1 (en) * | 2009-12-15 | 2011-06-16 | Finatep Ag | Multifunctional liquid treatment device (device) for the electrochemical treatment (electrolysis) of water and water solutions |
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