Practical method suitable for chemical reaction electric field catalysis of various solution systems

Abstract

The invention provides a practical method suitable for chemical reaction electric field catalysis of various solution systems, and belongs to the field of catalytic reaction in the chemical reaction process. The method is mainly characterized in that positive and negative electrode plates with opposite surfaces are placed in a solution system, voltage is applied to the positive and negative electrode plates, and positive and negative electrode phase interface double-electrode layers are respectively formed by positive and negative charge layers on the inner surfaces of the positive and negative electrode plates and anions and cations in a solution electrically adsorbed on the outer surfaces; an electrode phase interface electric field is formed in the phase interface electric double layer, and ions, polarized molecules, molecules and other microscopic particles adsorbed on the outer surface of the electrode are activated through the electrode phase interface electric field and comprise ions, polarized molecules, molecules and other microscopic particles participating in chemical reaction in a solution system. In combination with other technologies provided by the invention, the invention respectively provides an electric field catalysis system applicable to the seed decomposition process of the sodium aluminate solution in the aluminum industry; the electric field catalysis system can be suitable for the process of degrading tetracycline-polluted wastewater by an environment-friendly industrial hydrogen peroxide aqueous solution system; and the electric field catalysis system can be suitable for ammonia synthesis reaction in a liquid ammonia solution system dissolved with nitrogen and hydrogen in the chemical industry.

Description

Technical Field

[0001] The invention belongs to the field of catalytic reactions in chemical reaction processes, and mainly relates to an electric field catalysis method. Background Art

[0002] As early as the 1960s and 1970s, people tried to reveal the specific effects of external electric fields on chemical reactions. This electric field effect is completely different from the electrocatalytic form of electrochemistry involved in patents [1,2]. In 1970, Pocker [3] and his colleagues used the specialized term "electrostatic catalysis". Electric field, as a special form of "catalyst", has unique advantages that ordinary catalysts do not have. Generally speaking, it is not very difficult to create a certain electric field, and the use of electric field catalytic reaction systems will not have such thorny problems as polluting the original chemical reaction system. More importantly, unlike the specificity of ordinary catalysts, theoretically speaking, electric field catalysis has a certain versatility and can be applied to almost all chemical reactions, because all chemical bonds are essentially various electric field interaction forces between charged particles. Therefore, a lot of research on electric field catalysis has been conducted at home and abroad. The research can be roughly divided into the following categories. The first category is theoretical research on electric field catalysis. [4-9] The second category is for local electric fields from various sources, such as electrostatic catalysis caused by intramolecular salt effects. [10,11] , electrostatic catalysis caused by the solvent [12,13] , catalyzing electrostatic catalysis within enzymes [14-16] The third type uses a special method to control the orientation of the applied external electric field at the microscopic scale to construct a directional external electric field catalysis [17-21] The fourth type uses the electrostatic field catalysis of surface adsorbed ions

[22] , or using the electric field on the surface of the metal electrode in electrochemistry to catalyze the reaction [23-25] However, after half a century of research, electric field catalysis research is still mainly limited to the theoretical and experimental research stage at the microscopic level.

[25] , and the research object is mainly molecular reaction system. [26,27,28] It has also been reported that the macroscopic external electrostatic field generated by electrodes can be used to enhance the chemical reaction of organic molecules. However, due to various conditions, the maximum electric field strength used in these studies is only 10 6 At the V / m level, electric field catalysis can only affect chemical reactions but cannot achieve true electric field catalysis. In short, electric field catalysis, which is theoretically universal, has not yet been widely applied to various chemical reaction systems, especially electrolyte solution systems, and lacks practicality.

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[28] Song Hongbo; He Hong; An Fengping; Huang Qun; Jia Shirong; Kong Yuting. Agar oligosaccharide iron and its preparation method[P]. Fujian Agriculture and Forestry University , invention patent CN 109293802, granted on November 3, 2020. Summary of the Invention

[0031] The main purpose of the present invention is to provide a practical method that can obtain an electric field of sufficient intensity in a microscopic environment under macroscopic controllable conditions and is applicable to electric field catalysis of chemical reactions in various solution systems.

[0032] The inventors have found that according to the current scientific research viewpoints on electric field catalysis [8] The prerequisite for the implementation of electric field catalysis is to use the electric field to act on the chemical bonds of the chemical reaction microparticles, so that the chemical bonds produce electric field-induced chemical bond ionicity, thereby activating the microparticles under the action of the electric field. According to the classical transition state theory of chemical reaction kinetics, after the microparticles of the reactants are activated, they will reduce the activation energy or activation entropy of the chemical reaction, and ultimately accelerate the rate of the chemical reaction. However, the electric field strength required to activate the microparticles is very strong, and it can often only be obtained through some kind of micro-environment. According to the literature [8] It is reported that the electric field strength of chemical bonds can usually reach 10 10 At the same time, if we approximate a single chemical bond as the electric field interaction between two cations and anion with unit charge at a distance of bond length, then according to the basic principles of physical electricity and the length of chemical bonds, it can be estimated that when the electric field interaction strength between the anion and cation is 1×10 10 ~10×10 10 V / m range, the electric field interaction energy between them is approximately in the range of 360~1160 kJ / mol. At the same time, we know that most chemical bonds are not pure ionic bonds, but are affected by covalent bonds, which results in the actual interaction strength of a single chemical bond being only equivalent to the electrostatic field interaction between two ions with partial unit charge, anion and cation, at a distance from the bond length. Therefore, the bond energy and electric field interaction strength of the actual chemical bond will be less than the corresponding interaction energy and electric field interaction strength calculated according to the pure electrostatic interaction force theory. Therefore, the actual chemical bond field interaction strength can be converted according to the ratio of the theoretically calculated interaction energy and the actual chemical bond bond energy based on the theoretically calculated electric field interaction strength, that is, when the actual chemical bond bond energy is less than the theoretical interaction energy, the corresponding actual electric field interaction strength is less than the theoretically calculated electric field interaction strength. The actual bond energy of most chemical bonds does not exceed the range of 360~1160 kJ / mol. Therefore, it can be considered that the normal chemical bond electric field strength is approximately 10 10 V / m level. If the external electric field is required to induce chemical bond ionicity, then the external electric field strength should be at least 1% of the chemical bond strength. In other words, if the external electric field is able to activate microscopic particles, the electric field strength should be at least 10 8The electric field strength is above the V / m level. This level of electric field strength exceeds that achievable under typical macroscopic conditions. Even if an electric field of this strength could be established within the bulk of a chemical reaction system under macroscopic conditions, it could still cause electrical breakdown in the bulk of the system. Therefore, the difficulty in achieving an electric field of sufficient strength, similar to that achieved in a microscopic environment, under macroscopically controllable conditions is a significant obstacle to the practical application of current electric field catalysis methods. Furthermore, there are currently few reports domestically and internationally on the application of electric field catalysis to electrolyte solution systems. In addition to the aforementioned difficulties, another important reason arises: charged ions within an electrolyte solution system migrate under the action of an external electric field, thereby establishing an internal reverse electric field within the electrolyte solution to offset the external electric field, preventing the external electric field from directly acting on any charged particles within the solution system. Using a variable electric field could generate an alternating current within the electrolyte solution, thereby reducing the effect of the applied electric field. Therefore, to overcome the various obstacles currently encountered in the practical application of electric field catalysis and thereby enable the widespread and practical application of electric field catalysis methods to a variety of solution-based chemical reactions, particularly those in electrolyte solution systems, the present invention is proposed, the details of which are as follows.

[0033] The inventors' research has shown that applying voltage to two facing positive and negative electrode plates can generate an electrostatic field between the two electrode plates. However, this method is difficult to establish an external electric field of sufficient strength within the bulk phase of a chemical reaction system. Therefore, we can consider bringing the facing positive and negative electrode plates that generate the external electric field into contact with a solution system (the solution system here is a broad solution that can include a gas phase solution system) and establishing an external electric field of sufficient strength at the interface between the positive and negative electrode plates and the solution system. E 外 This electric field is also the electrode interface electric field E 相界面 , that is, E 相界面 = E 外 The electric field through the electrode interface E 相界面 To activate the various ions, polarized molecules, molecules and other microscopic particles adsorbed on the outer surface of the inner side of the electrode plate, including ions, polarized molecules or molecules and other microscopic particles participating in the chemical reaction. Then these activated ions, polarized molecules or molecules and other microscopic particles will react faster on the outer surface of the electrode to generate product ions, polarized molecules or molecules and other microscopic particles. The principle diagram is as follows Figure 1 The inventors' research shows that for electrolyte solution system, under external electric field E 外Under the action of the positive and negative electrode plates, the anions and cations in the solution system on the inner side will migrate and gather towards the two electrode plates with positive and negative charges that generate the electric field, including the anions or cations that participate in the chemical reaction, and finally electrically adsorb on the outer surface of the inner side of the electrode plate with opposite charges, forming a Figure 1 The "polarized charge layer electrically adsorbed on the inner and outer surfaces of the electrode plate" is shown in the figure. At the same time, the surface charge density of this "polarized charge layer" is σ 极化 The charge density on the inner surface of the electrode plate σ 内表面 If it is a non-electrolyte system, then the various molecules and other microscopic particles in the solution system between the positive and negative electrode plates, including the molecules and other microscopic particles involved in the chemical reaction, will be polarized into polarized molecules under the action of the external electric field, and generate polarized charges of opposite charges on the inner and outer surfaces of the electrode plates, forming the same Figure 1 The "polarized charge layer electrically adsorbed on the inner and outer surfaces of the electrode plates" is shown in the figure. However, the surface charge density of this "polarized charge layer" is σ 极化 It is not equal to the charge density on the inner surface of the electrode plate. σ 内表面 , but the relative dielectric constant of the solution system ε r According to the basic principles of physical electricity, there is σ 极化 =(1-1 / ε r ) σ 内表面 Obviously, for the electrolyte solution system, due to its relative dielectric constant ε r is infinite, that is, σ 极化 = σ 内表面 At the same time, Figure 1 As shown, the "polarization charge" layer and the "inner surface charge of the electrode plate" layer together form the "interface double layer". Let the double layer capacitance be C 双电层 The inventors' research shows that the macroscopic interface between the electrode plate and the solution phase is actually the interface of direct electric field interaction between the charged particles on the inner surface of the electrode plate and the microscopic particles such as ions, polarized molecules or molecules adsorbed on the outer surface. E 相界面 It is the electric field in the "double electric layer at the interface", that is, Figure 1 The " E 相界面 = E 外According to the physical electrical principle, the electric field strength is mainly determined by the charge density on the inner surface of the electrode plate, that is, E 相界面 = E 外 = σ 内表面 / ε 0 (where ε 0 is the dielectric constant of vacuum, about 8.85×10 -12 C 2 ‧N -1 ‧m -2 ). At the same time, the charge density on the inner surface of the electrode plate can be adjusted by the voltage Δ U 电极板 It can be regulated and has good controllability. Since the electric field strength of chemical bonds can usually reach 10 10 At the V / m level, we can usually choose the electric field strength at the electrode interface E 相界面 is 10 10 The study was conducted in the range of 1% to 10% V / m. That is, the electric field strength at the electrode interface was selected. E 相界面 In 10 8 ~10 9 If the electric field strength is within the range of 10 V / m, then this range of electric field strength is sufficient to induce chemical bonds in most microparticles and generate ionic chemical bonds, thereby activating the microparticles adsorbed on the outer surface of the electrode. According to classical transition state theory, these activated microparticles will more easily cross the transition state energy barrier and transform into thermodynamically more stable products. Consequently, the microparticles that are capable of participating in the chemical reaction will react more rapidly on the outer surface of the electrode to produce thermodynamically more stable product ions, polarized molecules, or other microparticles, thereby achieving the chemical reaction rate catalyzed by the microparticles involved. Of course, for a specific chemical reaction, the actual interfacial electric field strength range required for electric field activation of the reactant microparticles on the outer surface of the electrode needs to be adjusted according to the actual target of the electric field catalysis and ultimately determined through actual experiments. However, it is important to note that if the interfacial electric field strength is too high, it can easily lead to electrolysis in the solution system or electrochemical corrosion of the electrode plate. Conversely, if the interfacial electric field strength is too low, the electric field catalysis effect may be poor for many chemical reactions.

[0034] The inventor's research shows that according to the basic principles of physical electricity, if we want to obtain the electric field strength at the electrode interface E 相界面 In 10 8 ~10 9 V / m range, surface charge density on the electrode σ内表面 About 0.001~0.01 C / m 2 , equivalent to about 6×10 15 ~6×10 16 Unit charge / m 2 If the charged particles of unit charge are arranged in parallel on a plane, it can be estimated that the diameter of the charged particles of unit charge cannot be greater than about 4 to 12 nm. Obviously, the diameter of all metal atoms is smaller than this value. For example, the diameter of an iron atom is about 0.25 nm. Even if each iron atom provides a net electron, it can still meet the internal surface charge density of 0.01 C / m 2 Moreover, according to the metal bond valence band theory, the average number of net electrons that can be added to the conduction band of the metal inner surface by one metal atom is far greater than one, which means that the charge density of the metal inner surface can actually be calculated in terms of electrons. Obviously, for most conductive materials, especially for any metal electrode plate, the charge density that can be achieved on its inner surface is far greater than 0.01 C / m 2 At the same time, according to the literature (Huang Ziqing. Introduction to Electrolyte Solution Theory (Revised Edition) [M]. Beijing: Science Press, 2010.), for aqueous electrolyte systems, the radius of various hydrated ions is generally less than 0.5 nm. Therefore, the thickness of the double layer at the electrode interface is usually very thin, usually not more than 0.5 nm. According to the basic principles of physical electricity, it can be calculated that the electric field strength at the electrode interface is required to be E 相界面 In 10 8 ~10 9 V / m range, that is, the surface charge density inside the electrode σ 内表面 In the range of 0.001~0.01 C / m 2 range, the actual voltage Δ applied to the double layer at the electrode interface U 双电层 It should be no greater than 0.05~0.5 V. Accordingly, the actual voltage applied to the positive and negative electrode plates Δ U 电极板It should be less than 0.1~1 V. Obviously, this voltage range has little effect on many electrolyte aqueous solution systems. For example, the theoretical electrolysis voltage of water is 1.23 V, not to mention that the actual electrolysis voltage will be much larger due to the existence of overpotential. Therefore, in many cases, the interfacial electric field of the double electric layer at the electrode interface is used to carry out electric field catalysis of chemical reactions in the electrolyte solution system. The voltage applied to the positive and negative electrode plates generally does not lead to obvious electrolysis reactions in the electrolyte solution system. At the same time, the use of inert precious metals as electrode materials can also effectively avoid the occurrence of electrochemical corrosion of electrodes. In short, the use of various interfacial double electric layers as capacitor devices has been commercialized, and their capacitance can usually reach above the faraday level, and can even reach thousands of faradays. Here, we employ this interfacial double-layer technology to regulate the charge density on the inner surface of the electrode plates by controlling the voltage applied to the positive and negative electrode plates. Ultimately, we can achieve, under macroscopically controllable conditions, an interfacial electric field of sufficient strength similar to that achieved in a microscopic environment. This field can activate microscopic particles such as ions, polarized molecules, or molecules adsorbed on the outer surface of the electrode, and is applicable to electric-field catalysis in many solution-based chemical reactions. Typically, interfacial double-layer technology is used as a method for manufacturing capacitors. Here, we transform this method into a method for achieving, under macroscopically controllable conditions, an interfacial electric field of sufficient strength similar to that achieved in a microscopic environment for electric-field catalysis.

[0035] The inventor's research shows that for the relative dielectric constant ε r For relatively small non-electrolyte solution systems, it is often difficult to directly obtain an electrode interface electric field of sufficient strength through the above method. For example, if the relative dielectric constant of the solution system is ε r Less than 100, the distance between the positive and negative electrode plates is 0.01 m, and the electric field strength at the electrode interface is required to be E 相界面 In 10 8 ~10 9 V / m range, that is, the surface charge density inside the electrode σ 内表面 In the range of 0.001~0.01 C / m 2 range, then the electric field strength in the bulk phase of the solution will be greater than 10 6 ~10 7 V / m range, the voltage Δ applied to the positive and negative electrode plates with a distance of 0.01 m U 电极板 It will also require more than 10 4 ~10 5V range. Under normal circumstances, these conditions are difficult to achieve. Therefore, we can use the following technology to solve this problem: add a small molecular weight inert electrolyte that can dissociate into anions and cations in the solution and does not participate in chemical reactions to the non-electrolyte solution system that requires electric field catalysis, so that the original non-electrolyte solution system becomes an electrolyte solution system. In this way, the relative dielectric constant of the entire system is ε r From relatively small to infinite; or, adding a small molecular weight inert electrolyte that does not participate in the chemical reaction to the non-electrolyte solution system that requires electric field catalysis, and adding a co-solvent that can help these inert electrolytes dissociate into anions and cations in the solution, so that the original non-electrolyte solution system becomes an electrolyte solution system, so that the relative dielectric constant of the entire system ε r From relatively small to infinite. Small molecular weight inert electrolytes dissociate into anions and cations with very small ionic radius in the solution system. When a certain voltage Δ is applied to the positive and negative electrode plates, U 电极板 When the cations and anions with very small ionic radius are electrically adsorbed on the outer surface of the positive and negative electrode plates, they form a double electric layer at the electrode interface with the charges on the inner surface of the electrodes. E 相界面 In 10 8 ~10 9 V / m range, that is, the surface charge density inside the electrode σ 内表面 In the range of 0.001~0.01 C / m 2 range, correspondingly, the charge surface density of the electrode outer surface is σ 极化 Also between 0.001 and 0.01 C / m 2 Assuming that these anions and cations are single-charged ions, the surface density of anions or cations adsorbed on the outer surface of the positive or negative electrode is approximately 6×10 15 ~6×10 16 pcs / m 2 According to the literature (Huang Ziqing. Introduction to Electrolyte Solution Theory (Revised Edition) [M]. Beijing: Science Press, 2010.), for aqueous electrolyte systems, the radius of various hydrated ions is generally less than 0.5 nm, far less than the range of 4 to 12 nm. According to the hydrated ion radius of 0.5 nm, even if these hydrated ions are ions of unit charge and are electrically adsorbed on the outer surface of the electrode in a monolayer parallel distribution, the surface density is about 6×10 15 ~6×10 16 pcs / m 2 The actual occupied area ratio of hydrated ions is about 6×10 -3~6×10 -2 m 2 / m 2 This shows that when the surface charge density of the electrode is σ 极化 0.001~0.01 C / m 2 In the range of , these anions and cations are far from being able to cover the entire outer surface of the electrode, but only occupy a small part of the outer surface area of ​​the electrode. That is to say, in addition to a small area of ​​the outer surface of the electrode where these anions and cations are electrically adsorbed, most of the outer surface of the electrode between these electrically adsorbed anions and cations is also adsorbed with various other polarizable molecules, molecules and other microscopic particles of the solution system, and all ions, polarizable molecules or molecules and other microscopic particles adsorbed on the outer surface of the electrode will be in the electrode interface electric field (for example E 相界面 In 10 8 ~10 9 V / m range), these molecules and other microparticles involved in the chemical reaction in the original non-electrolyte solution system are activated. These activated molecules and other microparticles then react more rapidly on the electrode's outer surface to produce product molecules and other microparticles. By adding a low-molecular-weight inert electrolyte to a non-electrolyte solution system, transforming it into an electrolyte solution, we have solved the problem of how to electric-field catalyze various chemical reactions occurring in non-electrolyte solution systems with relatively low relative dielectric constants.

[0036] The inventor's research shows that the above measures alone cannot guarantee that the electric field catalysis method can be effectively applied to chemical reactions in solution systems. Because only the ions, polarized molecules, molecules and other microscopic particles adsorbed on the inner and outer surfaces of the electrode plates are activated by the electric field at the electrode interface, these adsorbed ions, polarized molecules, molecules and other microscopic particles are still a very small part relative to the entire solution system, and most of the ions or molecules and other microscopic particles that have not been activated are still present in the bulk phase of the solution. At the same time, it is difficult for the ions or polarized molecules and other microscopic particles adsorbed on the inner and outer surfaces of the electrode plates due to the action of the electric field to automatically break away from the electrode interface and return to the bulk phase. That is to say, under normal circumstances, due to the influence of factors such as the electric field force, the mutual mass transfer process between the bulk phase of the solution and the outer surface of the electrode of the ions or molecules and other microscopic particles involved in the chemical reaction is not very effective, especially for ions or polarized molecules and other microscopic particles. In this case, even if the chemical reactions of microscopic particles such as ions, polarized molecules, and molecules activated on the outer surface of the electrode are faster, their impact on the entire solution system is still very limited, ultimately resulting in the ineffective electric field catalysis of the chemical reactions of the entire solution system. In particular, the electric field catalysis of the chemical reactions of ions in the electrolyte solution system is even more difficult to carry out effectively. To this end, based on the basic principles of physical electricity and electrochemistry, we will use the following technology to solve this problem: on the positive and negative electrode plates in contact with the solution system, a voltage with controllable magnitude and direction, alternating between zero voltage and a constant voltage, is applied periodically, so that the voltage changes periodically between zero voltage and a constant voltage in a certain manner. In this way, under a certain voltage, the ions, polarized molecules, molecules and other microparticles adsorbed on the inner and outer surfaces of the electrodes are activated by the electric field. According to classical transition state theory, these activated ions, polarized molecules, molecules and other microparticles will more easily cross the transition state energy barrier and transform into thermodynamically more stable products. In this way, the ions, polarized molecules, molecules and other microparticles that can participate in chemical reactions will react more quickly on the outer surface of the electrode to generate thermodynamically more stable product ions, polarized molecules, molecules and other microparticles. In the absence of voltage, these product ions, polarized molecules, molecules and other microparticles adsorbed on the inner and outer surfaces of the electrode plates will more easily desorb and return to the bulk phase of the solution. With the periodic change of voltage, new ions or molecules and other microparticles participating in the chemical reaction in the bulk phase of the solution system are constantly adsorbed on the outer surface of the electrode plates and activated by the electrode phase interface electric field. They cross the transition state energy barrier more quickly on the outer surface of the electrode and transform into thermodynamically more stable product ions or molecules and other microparticles, and then return to the bulk phase. The specific form of the periodic voltage change is determined by the actual requirements of the adsorption and desorption of microscopic particles such as ions or molecules on the outer surface of the electrode plates during the electric field catalysis process. In this way, the microscopic particles such as ions or molecules involved in the chemical reaction in the solution system are continuously catalyzed by the electric field at the electrode interface, and are converted into products more quickly.Obviously, the technology of periodically changing voltage not only solves the problem of how to quickly activate most of the microscopic particles in the bulk phase of the solution by the electric field at the phase interface and ensure the effective implementation of the electric field catalysis process, but also solves the difficulties encountered by the current electric field catalysis method in applying it to the electrolyte solution system. Of course, the period of this periodic voltage change cannot be too short to ensure that the microscopic particles such as ions or molecules involved in the chemical reaction have enough time to adsorb on the outer surface of the electrode plate and be activated by the electric field and undergo chemical reactions, and at the same time have enough time to desorb and return to the bulk phase of the solution. At the same time, it also avoids the generation of alternating current in the electrolyte solution system and reduces the catalytic effect of the electric field at the electrode phase interface. Normally, periodically changing voltage is a technology used to generate alternating current. Here, we transform it into a technology that can ensure the effective implementation of the electric field catalysis process by adopting a low-frequency periodic voltage change method.

[0037] The inventor's research shows that in order to more effectively catalyze the chemical reaction process, it is necessary to accelerate the adsorption and desorption process of microscopic particles such as ions or molecules participating in the chemical reaction in the solution system on the outer surface of the electrode plate, and ensure that as many microscopic particles such as ions or molecules participating in the chemical reaction as possible are activated through the electric field at the electrode interface. To this end, we can use the following technology, in which the voltage applied to the positive and negative electrode plates alternates between zero voltage and a certain voltage, and changes periodically in the following manner: start with zero voltage and maintain it for a period of time, then slowly increase the voltage in the forward direction until it reaches the maximum forward voltage and maintains it for a period of time; then instantly drop to zero voltage and maintain it for a period of time, then slowly increase the voltage in the reverse direction until it reaches the maximum reverse voltage and maintains it for a period of time; finally, instantly drop to zero voltage again, and then repeat the next cycle. "Maintaining zero pressure for a period of time" ensures that ions, polarized molecules, molecules, and other microscopic particles originally adsorbed on the outer surface of the electrode plate have sufficient time to desorb from the outer surface of the electrode plate and return to the bulk phase of the solution without the influence of the electric field force; "slowly increasing pressure" can prevent the rapid adsorption of a large number of solvent molecules in the solution system on the outer surface of the electrode plate, which would affect the adsorption process of ions or molecules and other microscopic particles participating in the chemical reaction on the outer surface of the electrode plate, ensuring that ions or molecules and other microscopic particles participating in the chemical reaction can be effectively adsorbed on the outer surface of the electrode plate; "maintaining maximum voltage for a period of time" ensures that the electrode phase interface electric field fully activates ions or molecules and other microscopic particles adsorbed on the outer surface of the electrode and participating in the chemical reaction, and these activated ions or molecules and other microscopic particles participating in the chemical reaction have sufficient time to transform into product ions or molecules and other microscopic particles through the transition potential barrier on the outer surface of the electrode. The specific parameters such as the zero pressure maintenance time, the voltage increase time, and the maximum voltage maintenance time are ultimately determined by the actual effect of the electrocatalytic catalysis of the chemical reaction in the solution system. Typically, a periodically varying voltage is a technique used to generate a specific alternating current. Here, we transform this into a technique that accelerates the adsorption and desorption of microscopic particles such as ions or molecules involved in chemical reactions in a solution system on the outer surface of the electrode plate by adopting a specific voltage variation method.

[0038] The inventor's research shows that in order to more effectively catalyze the chemical reaction process by electric field, it is necessary to further accelerate the adsorption and desorption process of microscopic particles such as ions or molecules in the solution system that participate in the chemical reaction on the outer surface of the electrode plate, and ensure that as many microscopic particles such as ions or molecules that participate in the chemical reaction as possible are activated by the electric field at the electrode interface. To this end, we can also use the following technology to process the face-to-face positive and negative electrode plates into face-to-face agitator blades and install them on the agitator of the solution system. In this way, in the process of applying a periodically changing voltage that alternates between zero voltage and a certain voltage on the positive and negative electrode plates, due to the stirring action of the agitator, the mutual mass transfer process of microscopic particles such as ions or molecules in the solution system between the bulk phase of the solution and the outer surface of the positive and negative electrode plates can be effectively accelerated, and the adsorption process of microscopic particles such as ions or molecules on the outer surface of the electrode plate and the process of desorption and returning to the bulk phase of the solution can be effectively accelerated. Typically, a stirrer is a technology used to accelerate the mass transfer process in the bulk phase of a solution. Here, we transform it into a technology that can accelerate the adsorption and desorption process of microscopic particles such as ions or molecules in the solution system (including microscopic particles such as ions or molecules participating in chemical reactions and microscopic particles such as product ions or molecules) on the outer surface of the electrode plate by combining it with periodic voltage changes.

[0039] The inventor's research shows that in order to obtain the interfacial electric field under macroscopically controllable conditions by adopting this interfacial double-layer technology, it is necessary to avoid the occurrence of continuous electrolysis reaction in the catalyzed solution system or continuous electrochemical corrosion of the anode electrode plate due to the large voltage applied to the positive and negative electrode plates during the electric field catalysis process. In order to solve this problem, according to the physical electrical principles and relevant electrochemical theories, we use a capacitor in series in the circuit that applies voltage to the positive and negative electrode plates as a "control capacitor", or other electrical devices equivalent to a capacitor as a "control capacitor". Through this series "control capacitor", it is possible to prevent the generation of continuous direct current on the positive and negative electrode plates in the same series circuit, effectively preventing the occurrence of continuous electrolysis reaction in the solution system or preventing the occurrence of continuous electrochemical corrosion of the anode electrode. Normally, a capacitor is used as a device for storing charge in a circuit. Here, we convert it into a technology that prevents the occurrence of continuous electrolysis reaction in the solution system or continuous electrochemical corrosion of the anode electrode during the electric field catalysis process by blocking the direct current of the circuit.

[0040] The inventor's research shows that if the chemical reaction system catalyzed by the electric field is an electrolyte solution system or a solution system with a large dielectric constant, then the capacitance of the double layer at the interface between the electrode plate and the solution system is C 双电层 According to the physical electrical principle, the voltage Δ applied to the positive and negative electrode plates is U 电极板A slight change in the charge density on the inner surface of the electrode plate will result in σ 内表面 The very large change finally leads to poor controllability of the charge density on the inner surface of the electrode. Therefore, it is often difficult to directly control the voltage Δ applied to the positive and negative electrode plates by electric field catalysis. U 电极板 To accurately control the interfacial electric field strength generated by the electrode plate E 相界面 To solve this problem, we can accurately measure the capacitance of the "control capacitor" in advance. C 控制电容 The size is then controlled by the voltage Δ applied to the "control capacitor" U 控制电容 To control the amount of charge it contains q 控制电容 ", thereby accurately controlling the charge on the inner surface of the positive and negative electrode plates in the same series circuit q 电极板 , thereby increasing the surface charge density of the electrode plate σ 内表面 The controllability ultimately ensures that the interfacial electric field strength generated by the positive and negative electrode plates at their inner sides in contact with the solution system can be accurately controlled. E 相界面 Usually, in a circuit, a capacitor is used as a device to store charge. Here, by connecting it in series in the circuit, the voltage Δ U 电极板 Converted into the voltage Δ that needs to be controlled on the "control capacitor" U 控制电容 , so that the voltage Δ applied to the "control capacitor" is controlled U 控制电容 Converted into a method for controlling the electric field strength of the interface generated by the electrode plate in electric field catalysis E 相界面 method.

[0041] The inventor's research shows that in order to improve the automatic control performance of the electric field catalysis process, a circuit can be added to measure the actual voltage of the "control capacitor" Δ U 控制电容 The "pressure control device" can set a certain voltage change form, and according to the "set voltage Δ U 设定 ” and its actual voltage of “control capacitor” U 控制电容 The size relationship between them outputs a "voltage control signal" to the power supply device of the entire circuit, causing the power supply device to change the output voltage ΔU 电源 Size. When Δ U 控制电容 <Δ U 设定 When the “pressure control device” outputs an “increase” control signal to the power supply, the power supply then increases the output voltage Δ U 电源 Until the Δ of the "control capacitor" U 控制电容 Equal to Δ U 设定 ; When Δ U 控制电容 =Δ U 设定 When the "pressure control device" outputs a "hold" control signal to the power supply, the power supply then maintains the output voltage Δ U 电源 unchanged; when Δ U 控制电容 >Δ U 设定 When the “pressure control device” outputs a “decrease” control signal to the power supply, the power supply then reduces the output voltage Δ U 电源 Until the Δ of the "control capacitor" U 控制电容 Equal to Δ U 设定 Therefore, the actual voltage of the “control capacitor” is guaranteed to be U 控制电容 According to the voltage Δ set by the "pressure control device" U 设定 The capacitance of the "control capacitor" C 控制电容 Under the condition of no change, the charge of the "control capacitor" q 控制电容 Also with its set voltage Δ U 设定 At the same time, the amount of charge on the positive and negative electrodes in the same series circuit changes. q 电极板 Also related to the charge of the "control capacitor" q 控制电容 Therefore, the voltage Δ of the "control capacitor" can be controlled by the "pressure control device". U 控制电容 Precisely control the surface charge density of the positive and negative electrode plates by changing the method σ 内表面 The change of the electric field strength at the electrode interface E 相界面 The way of change.

[0042] The inventor's research shows that due to the capacitance of the double electric layer at the interface between the electrode plate and the solution system C 双电层 The size is closely related to the state change of the chemical reaction system and may change during the electric field catalysis process. If you want to maintain the electric field strength at the electrode interface during the electric field catalysis process, E 相界面 unchanged, that is, the surface charge density of the electrode plate σ 内表面 remains unchanged, then the voltage Δ applied to the positive and negative electrode plates U 电极板 It should change with the change of the solution system state. However, due to the actual capacitance of the double layer at the interface between the electrode plate and the solution system C 双电层 The size is often not fixed, and it is often difficult to directly control the voltage Δ applied to the positive and negative electrode plates. U 电极板 The surface charge density of the electrode plate can be effectively controlled by σ 内表面 However, by adding a “control capacitor” in the circuit, the actual voltage Δ U 控制电容 By using the "pressure control device", we can effectively maintain the surface charge density of the electrode plate during the entire electric field catalysis process. σ 内表面 When the state of the solution system changes, the capacitance of the double electric layer at the interface between the electrode plate and the solution system C 双电层 At this time, due to the initial charge density on the positive and negative electrode plates, the surface charge density σ 内表面 If the original value is maintained, then the voltage on the positive and negative electrode plates Δ U 电极板 will change. At this time, the power supply output voltage Δ U 电源 is the original voltage Δ U 电极板 Maintaining balance, when Δ U 电极板 After the change, Δ U 电源 will no longer be affected by the voltage Δ U 电极板 Maintain balance, so the charges on the positive and negative electrodes q 电极板 Correspondingly, the charge on the "control capacitor" in series relationship q 控制电容 will also change synchronously, and accordingly, its voltage Δ U控制电容 will also change accordingly. U 控制电容 <Δ U 设定 When the “pressure control device” outputs an “increase” control signal to the power supply, the power supply then increases the output voltage Δ U 电源 Until the Δ of the "control capacitor" U 控制电容 Re-equal to Δ U 设定 ; When Δ U 控制电容 =Δ U 设定 When the "pressure control device" outputs a "hold" control signal to the power supply, the power supply then maintains the output voltage Δ U 电源 unchanged; when Δ U 控制电容 >Δ U 设定 When the “pressure control device” outputs a “decrease” control signal to the power supply, the power supply then reduces the output voltage Δ U 电源 Until the Δ of the "control capacitor" U 控制电容 Re-equal to Δ U 设定 In other words, the "pressure control device" can automatically maintain the actual voltage of the "control capacitor" Δ U 控制电容 Stable at the set voltage Δ U 设定 Accordingly, the charge on the "control capacitor" can be stabilized. q 控制电容 At the same time, the charge on the positive and negative electrode plates in series is stabilized synchronously q 电极板 , and its internal surface charge density σ 内表面 Therefore, the charge of the "control capacitor" is maintained by the "pressure control device". q 控制电容 Stable way to precisely control the surface charge density of positive and negative electrode plates σ 内表面 Remains unchanged when the state of the solution system changes, that is, maintains the electric field strength at the electrode interface when the state of the solution system changes E 相界面 constant.

[0043] Based on the above research, the inventors proposed a practical method for electric field catalysis of chemical reactions in various solution systems, such as Figure 2As shown, this method has the following characteristics: First, in the solution system that needs to be catalyzed by electric field ( Figure 2 Place the positive and negative electrode plates facing each other in (2) Figure 2 In (6), the electrode plate material is selected according to the actual required electric field catalysis requirements such as inner surface charge density, corrosion resistance, and mechanical properties; and an external voltage Δ is applied to the positive and negative electrode plates. U 电极板 The voltage is determined by the electric field strength at the electrode interface required for electric field catalysis. E 相界面 The magnitude of the electric field at the electrode interface is determined by E 相界面 The surface charge density of the electrode plate σ 内表面 Secondly, the positive and negative electrode plates facing each other are processed into the form of facing stirrer blades and installed on the stirrer of the solution system (such as Figure 2 Third, a specific power supply is used in the entire circuit ( Figure 2 (11)), the power supply can output a periodically changing voltage Δ with controllable magnitude and direction, alternating between zero voltage and a certain voltage. U 电源 , and can be controlled according to the external input "voltage control signal" ( Figure 2 (10)) to adjust the power supply output voltage Δ U 电源 The power supply output voltage Δ U 电源 The specific form is determined by the "voltage control signal", and its maximum value is determined by the actual situation. Fourth, a capacitor is connected in series in the circuit that applies voltage to the positive and negative electrode plates. C 控制电容 A precisely sized capacitor is used as the "control capacitor" ( Figure 2 (8)), or other electrical devices equivalent to a capacitor as a "control capacitor". Fifth, the capacitance of the "control capacitor" C 控制电容 The size is determined by the maximum charge and maximum voltage that the entire series circuit needs to control during the electric field catalysis process, and the maximum charge that the entire series circuit needs to control is determined by the surface charge density of the positive and negative electrode plates. σ 内表面 Maximum value and surface area of ​​electrode plate A 电极板 The maximum voltage is determined by the actual output voltage of the power supply Δ U 电源 Sixth, there is a "pressure control device" on the "control capacitor" to measure its actual voltage ( Figure 2(9)), and the "pressure control device" can set a certain voltage change form, and according to the set voltage Δ U 设定 Instead of measuring the actual voltage of the "control capacitor" Δ U 控制电容 The relationship between the output "voltage control signal" ( Figure 2 (10)) to the power supply device of the entire circuit, so that the power supply device changes the output voltage Δ U 电源 Size, to ensure the actual voltage of the "control capacitor" Δ U 控制电容 Set the voltage Δ according to the "pressure control device" U 设定 Seventh, the "pressure control device" sets the voltage Δ U 设定 The variation is as follows: first, maintain zero voltage for a period of time, then slowly increase the voltage in the forward direction until the maximum forward voltage is maintained for a period of time; then drop to zero voltage instantaneously and maintain it for a period of time, then slowly increase the voltage in the reverse direction until the maximum reverse voltage is maintained for a period of time; finally, drop to zero voltage instantaneously again, and then repeat the next cycle. The specific parameters such as zero voltage maintenance time, voltage increase time and maximum voltage maintenance time are ultimately determined by the actual effect of electrolytic catalysis of the chemical reaction in the solution system. Eighth, connect a resistor (such as Figure 2 (7)). Considering that the current of the entire circuit cannot be overloaded during the voltage mutation process, a resistor must be connected in series with the entire circuit. The resistance value is determined by the maximum voltage output by the power supply and the peak current that the circuit needs to control. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 Schematic diagram of the principle of using the electric field at the electrode interface to activate ions, polarized molecules or molecules adsorbed on the outer surface of the electrode.

[0045] Figure 2 A practical method for electric field catalysis of chemical reactions in various solution systems.

[0046] In the figure: (1) is the reaction tank; (2) is the solution system; (3) is the conductive outer shell of the stirrer straight rod; (4) is the conductive inner rod of the stirrer straight rod; (5) is the insulating layer between the outer shell and the inner rod of the stirrer straight rod; (6) is the face-to-face positive and negative electrode plates (processed into the shape of face-to-face stirrer blades and installed on the conductive outer shell and the conductive inner rod of the stirrer straight rod respectively. The single-sided surface area is A 电极板 , the internal surface charge q 电极板 , the surface charge density of the electrode σ内表面 , the voltage applied to the positive and negative electrode plates Δ U 电极板 ); (7) is the resistance of the entire circuit (corresponding voltage Δ U 电压 ); (8) is the "control capacitance" (voltage Δ U 控制电容 ,capacitance C 控制电容 , charge q 控制电容 ); (9) is a "pressure control device" (which can set a "set voltage Δ U 设定 ", and compare the set voltage Δ U 设定 The relationship between the actual voltage of other devices is measured, and a "voltage control signal" is output according to the comparison result); (10) is the "voltage control signal"; (11) is the power supply (which can output a periodically changing voltage Δ with controllable size and direction, alternating between zero voltage and a certain voltage) U 电源 , and can accept "voltage control signal"); (12) is a circuit. DETAILED DESCRIPTION

[0047] The present invention is described in detail below with reference to the embodiments and drawings. It should be understood that these embodiments are only used to specifically illustrate the implementation of the present invention in certain circumstances, and the various parameters listed in each embodiment are also only used to specifically illustrate the application of the embodiment under specific conditions. All these specific descriptions are not intended to limit the scope of application of the present invention. After reading the present invention, various modifications and improvements to the embodiments made by those skilled in the art, or the implementation and application of the present invention in other circumstances, as long as they do not depart from the characteristics of the claims attached to the present invention, all fall within the scope defined by the claims attached to the present invention and belong to the scope of protection of the present invention.

[0048] Example 1

[0049] This embodiment specifically describes how to construct an electric field catalytic system suitable for the seed decomposition process of sodium aluminate solution in the aluminum industry according to the invention content.

[0050] Sodium aluminate solution is an electrolyte solution system, the main chemical components of which are sodium hydroxide NaOH, sodium aluminate NaAl(OH)4, and solvent water H2O. Both NaOH and NaAl(OH)4 are strong electrolytes, that is, the cations present in the solution system are mainly Na + ‧4H2O hydrated ions, anions are mainly OH - ions and Al(OH)4 -‧4H2O hydrated ions. The decomposition of sodium aluminate solution seed crystals is one of the key steps in the Bayer process for producing alumina. Its main chemical reactions are as follows: NaAl(OH)4(aq) = NaOH(aq) + Al(OH)3(cr) Because the decomposition process is slow, generally taking 30 to 70 hours, and the decomposition rate is low, usually 45% to 52%, it remains a "bottleneck" in the alumina production process. The literature (Li Jie. Research on the structure and decomposition mechanism of supersaturated sodium aluminate solution [D]. Changsha: Central South University, 2001.) conducted a comprehensive and in-depth study on the decomposition mechanism of sodium aluminate solution. The study showed that the main reason for the slow decomposition of supersaturated sodium aluminate solution is that the main component in the solution, the tetracoordinate structure Al(OH)4 - ‧4H2O hydrated ions undergo dehydration and condensation to form various types of growth units with hexacoordinated Al-(OH)6 as the basic structural unit. This control step reacts slowly. The basic reaction form of the control step is as follows: Al(OH)4 - ‧4H2O = [Al(OH)4‧(OH2)2] - + 2H2O Among them, [Al(OH)4‧(OH2)2] - Therefore, by accelerating the chemical reaction rate of this control step through electric field catalysis, the speed of the entire seed decomposition process can be accelerated.

[0051] The process conditions for the decomposition of the sodium aluminate solution seed crystals in the embodiment are (expressed in the usual way of industrial production): total alkali concentration M (NaOH T ) is about 4.0 mol / L (including free NaOH in the solution and NaOH bound to NaAl(OH)4); the concentration of dissolved Al(OH)3 in the solution M (Al(OH)3) is about 2.5~0.75 mol / L (that is, the concentration of NaAl(OH)4); α K Caustic ratio M (NaOH T ) / M (Al(OH)3) is 1.6~5.33; the surface area of ​​the face-to-face agitator blade (that is, the surface area of ​​the face-to-face positive and negative electrode plates) A 电极板 Assume 1m 2 .

[0052] According to the contents and appended Figure 2, an electric field catalytic system suitable for the decomposition process of sodium aluminate solution seed crystals was constructed according to the following steps.

[0053] First, according to the present invention, the electrode plate material and the processing of the stirrer blades (such as Figure 2 According to the properties of sodium aluminate solution, the inner rod and outer shell of the stirrer straight rod can be made of stainless steel (such as Figure 2 (3) and (4) parts in the figure), which have good corrosion resistance and mechanical properties. At the same time, stainless steel with platinum electroplated on the surface can be used to process the positive and negative electrode plates facing each other, and processed into the shape of face-to-face stirrer blades (such as Figure 2 (6) components), respectively mounted on the conductive inner rod and the conductive outer shell of the stirrer straight rod (such as Figure 2 (6) in the figure). They not only have good electrochemical corrosion resistance and mechanical properties, but also, as metal materials, their inner surface charge density can meet the needs of electric field catalysis. The insulating layer between the inner rod and the outer shell of the stirrer straight rod (such as Figure 2 The (5) component) can be made of polytetrafluoroethylene material.

[0054] Second, determine the electric field strength at the electrode interface according to the present invention. E 相界面 and the surface charge density within the electrode σ 内表面 According to the form of the chemical reaction in the control step of the decomposition process of sodium aluminate solution seed crystals, the electric field strength required for electric field catalysis can be obtained by the four-coordinate structure Al(OH)4 - ‧Determination of the strength of the Al-O single bond in the 4H2O hydrated ion. According to the basic principles of physical electricity, under the electric field interaction of unit charge, there is the following relationship between the electric field strength and the electric field interaction energy. E = W 作用能 / ( r ‧ e ‧ N 0), where E represents the electric field strength, W 作用能 represents the electric field interaction energy, r represents the bond length, e The unit charge is approximately 1.602×10 -19 C, N 0 means Avogadro's constant is about 6.02×10 23 mol -1If the Al-O single bond is approximately equivalent to the electric field interaction between two cations and anions with unit charge at a distance of bond length, according to the basic principles of physical electricity, the electric field strength between the Al-O single bonds can be estimated based on their actual chemical bond energy and bond length. According to the data reported in authoritative references (Lange's Handbook of Chemistry, CRC Press Handbook of Chemistry and Physic), the Al-O single bond length is about 0.1618 nm and the bond energy is about 512 kJ / mol. It can be estimated that the electric field strength between the Al-O single bonds is about 3.3×10 10 V / m, which means that the actual electric field strength between Al-O single bonds should also be around 10 10 V / m level. According to the Al-O single bond energy of about 512 kJ / mol, it can be inferred that if the external electric field strength is 10 8 ~10 9 The V / m range is equivalent to affecting the chemical bond energy of Al-O single bond in the range of 1.6~16 kJ / mol, and the total bond energy of multiple chemical bonds can reach 10~60 kJ / mol. According to the current chemical reaction kinetics theory, the energy change in this range is enough to change the hydrated ion Al(OH)4 - ‧The speed of the 4H2O chemical reaction. Therefore, it is assumed that the electrode interface electric field strength required for the electric field catalytic decomposition of sodium aluminate solution seed crystals is E 相界面 is 10 9 V / m or so (of course, the actual required electric field strength at the electrode interface can be ultimately determined based on actual experiments of electric field catalysis). E 相界面 If the value is too large, it will easily lead to electrolysis reaction of sodium aluminate solution system or electrochemical corrosion of anode electrode plate. According to the physical electrical principle, the electric field strength of the electrode interface is E 相界面 Corresponding to the surface charge density of the electrode σ 内表面 = ε 0‧ E 相界面 ≈0.01 C / m 2 According to the process conditions of the decomposition of sodium aluminate solution seeds, the single-side area of ​​the face-to-face stirrer blades as positive and negative electrode plates is A 电极板 1 m 2 , the required surface charge density of the electrode can be obtained σ 内表面 The total charge required q 电极板 is 0.01 C.

[0055] Third, determine the actual voltage Δ applied to the positive and negative electrode plates according to the invention content. U 电极板 We know that the sodium aluminate solution system mainly contains cations Na + ‧4H2O hydrated ion, anion is OH - ions and Al(OH)4 - ‧4H2O hydrated ions. In the electric field catalysis process, OH - ions and Al(OH)4 - ‧4H2O hydrated ions are adsorbed on the outer surface of the positive electrode plate, forming a double electrical layer at the positive electrode interface; while Na + ‧4H2O hydrated ions are adsorbed on the outer surface of the negative electrode plate, also forming a double layer at the negative electrode interface. According to the data reported in authoritative references (Lange's Handbook of Chemistry, CRC Press Handbook of Chemistry and Physic), the Al-O single bond length is about 0.1618 nm, and the HO single bond length is about 0.096 nm. It can be estimated that Al(OH)4 - The ionic radius of 4H2O hydrate should be less than 0.5 nm. According to the literature (Huang Ziqing. Introduction to Electrolyte Solution Theory (Revised Edition) [M]. Beijing: Science Press, 2010.), the ionic radius of Na+ is 0.095 nm. So we can infer that Na + The hydrated ion radius of 4H2O is about 0.358 nm. We estimate that the maximum thickness of the double layer at the interface between the positive and negative electrodes is 0.5 nm. When the surface charge density of the control electrode is σ 内表面 About 0.01 C / m 2 , which is equivalent to the electric field strength at the electrode interface E 相界面 is 10 9 V / m, at this time, the actual voltage applied to the positive and negative electrode plates is Δ U 电极板 The maximum is about 1 V. If we consider the intrinsic capacitance of the electrode interface in the electric field catalysis during the decomposition of the sodium aluminate solution seed crystals, C 双电层 It may fluctuate as the decomposition of the sodium aluminate solution crystals proceeds, and the surface charge density of the electrode σ 内表面 Also between 0 and 0.01 C / m 2 The range is constantly changing, so the actual voltage applied to the positive and negative electrode plates Δ U 电极板It should vary in the range of 0 to 1 V.

[0056] Fourth, select the power supply device that provides voltage to the positive and negative electrode plates according to the invention content ( Figure 2 (11)), the power supply can output a periodically changing voltage Δ with controllable magnitude and direction, alternating between zero voltage and a certain voltage. U 电源 , and can be controlled according to the "voltage control signal" ( Figure 2 (10)) to adjust the output voltage Δ U 电源 Considering that the sodium aluminate solution system catalyzed by electric field is conductive and the conductive electrode is directly connected to the solution system, from the perspective of safety, the maximum output voltage of the power supply is selected to be 50 V, and the actual output voltage Δ U 电源 Around 0~40 V (within the 48 V safety voltage range).

[0057] Fifth, according to the invention, a capacitor must be connected in series in the circuit that applies voltage to the positive and negative electrode plates as a "control capacitor" ( Figure 2 (8)). Considering the actual output voltage Δ of the entire circuit power supply U 电源 The maximum value is around 40 V. At the same time, the amount of charge that needs to pass through the "control capacitor" q 控制电容 To precisely control the maximum charge of the positive and negative electrode plates in the series circuit q 电极板 is 0.01 C, that is, the surface charge density of the electrode as mentioned above σ 内表面 The maximum is 0.01 C / m2, so you can choose a capacitance C 控制电容 The capacitor element with a value of 0.01 C / 40 V = 0.25 mF is used as the "control capacitor". U 控制电容 When the range changes from 0 to 40 V, the amount of charge it contains is q 控制电容 The value of the positive and negative electrodes connected in series with the control capacitor will vary from 0 to 0.01 C. q 电极板 The surface charge density of the electrode will also vary in the range of 0~0.01 C. σ 内表面 Will be in the range of 0~0.01 C / m 2 Range changes, the electric field strength at the electrode interface E 相界面 Will be in 0~109 V / m range changes. That is, we can precisely control the voltage Δ of the "control capacitor" U 控制电容 To precisely control the electric field strength at the electrode interface E 相界面 .

[0058] Sixth, according to the appendix to the invention Figure 2 As shown, a resistor is connected in series with the entire circuit ( Figure 2 (7)). Considering that the current of the entire circuit cannot be overloaded during the voltage mutation process. The actual output voltage of the power supply of the entire circuit Δ U 电源 The maximum value is around 40 V. Assuming the maximum current does not exceed 0.1 A, the series resistance of the entire circuit is selected to be 400 Ω.

[0059] Seventh, according to the appendix to the invention Figure 2 As shown, assuming the actual voltage of the resistor is Δ U 电阻 , then the actual output voltage of the power supply Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 According to the eighth point below, the actual output voltage Δ U 电源 The size of the voltage control signal ( Figure 2 (10)) to adjust to ensure Δ U 控制电容 =Δ U 设定 .

[0060] Eighth, according to the invention, a "pressure control device" is added to the "control capacitor" to measure its actual voltage ( Figure 2 (9)), and the "pressure control device" can set a certain voltage change form, and according to the set voltage Δ U 设定 Instead of measuring the actual voltage of the "control capacitor" Δ U 控制电容 The relationship between the output "voltage control signal" ( Figure 2 (10)) to the power supply equipment of the entire circuit (such as Figure 2 As shown in (10), the power supply device changes the actual output voltage Δ U 电源 size to ensure the actual voltage of the "control capacitor" Δ U 控制电容According to the voltage Δ set by the "pressure control device" U 设定 The change mode changes. U 控制电容 <Δ U 设定 When the "voltage control signal" is "increase", the power supply increases the actual output voltage Δ U 电源 , until Δ U 控制电容 =Δ U 设定 ; When Δ U 控制电容 =Δ U 设定 When the “voltage control signal” is “hold”, the power supply is controlled to maintain the actual output voltage Δ U 电源 ; When Δ U 控制电容 >Δ U 设定 When the "voltage control signal" is "decrease", the power supply is controlled to reduce the actual output voltage Δ U 电源 , until Δ U 控制电容 =Δ U 设定 .

[0061] Ninth, according to the invention, "pressure control device" (such as Figure 2 (9) Set voltage Δ U 设定 The variation is as follows: first, the voltage is maintained at zero for a period of time, then the voltage is slowly increased in the forward direction to a maximum forward voltage of 40 V and maintained for a period of time; then the voltage is instantly dropped to zero and maintained at zero for a period of time, then the voltage is slowly increased in the reverse direction to a maximum reverse voltage of -40 V and maintained for a period of time; finally, the voltage is instantly dropped to zero again, and the cycle repeats. The specific parameters of the zero voltage maintenance time, the slow increase time, and the maximum voltage maintenance time are determined by actual experiments on the electrocatalytic decomposition process of sodium aluminate solution seed crystals.

[0062] Tenth, the reaction process of electric field catalysis during the decomposition of sodium aluminate solution seed crystals is described as follows.

[0063] (1) First, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The zero pressure is maintained for a period of time, and the zero pressure maintenance time is determined by the actual experiment of electrolytic catalysis during the decomposition of sodium aluminate solution crystals. At this time, due to the "control capacitance" (such as Figure 2(8) does not contain any charge, i.e. q 控制电容 =0, its voltage Δ U 控制电容 is also zero, that is, Δ U 控制电容 =Δ U 设定 The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "hold" signal, which controls the power supply (, Figure 2 (11)) maintains the actual output voltage Δ U 电源 =0, that is, the power supply has no output current. At this time, the "control capacitor" ( Figure 2 The amount of charge contained in (8) q 控制电容 Keep it at zero, correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on the inner surface of (6) q 电极板 Also remains zero, that is, the surface charge density inside the electrode σ 内表面 Also remains zero, the electrode interface electric field E 相界面 At this time, there are no ions or polarized molecules or other microscopic particles electrically adsorbed on the outer surfaces of the positive and negative electrode plates, and the sodium aluminate solution system is in a state of normal seed crystal decomposition process.

[0064] (2) Then, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is slowly increased in the forward direction. The time of slow voltage increase is determined by the actual experiment of electrolytic catalysis during the decomposition of sodium aluminate solution crystals. Figure 2 The voltage Δ in (8) U 控制电容 It is zero at the beginning, that is, there is Δ U 控制电容 <Δ U 设定 At this time, the "pressure control device" will output a "voltage control signal" ( Figure 2 (10) is the "increase" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Starting from zero, it increases positively until Δ U 控制电容 =Δ U 设定 So far, that is, the actual output voltage of the power supply Δ U电源 Start from zero and increase in a positive direction to ensure that the voltage of the "control capacitor" Δ U 控制电容 With the setting voltage Δ U 设定 Slowly increase the voltage in the forward direction. The voltage of the entire circuit has the following relationship: Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 . As the actual output voltage of the power supply Δ U 电源 Starting from zero and increasing in positive direction, the power supply starts to output positive current until the charge contained in the "control capacitor" is q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧Δ U 控制电容 Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The amount of charge on (6) q 电极板 Synchronous changes, that is, q 电极板 = q 控制电容 =0.25 mF‧Δ U 控制电容 , that is, the surface charge density of the electrode σ 内表面 = q 电极板 / A 电极板 =0.25mF‧Δ U 控制电容 / 1 m 2 , the electric field at the electrode interface E 相界面 = σ 内表面 / ε 0=0.25 mF‧Δ U 控制电容 / 1 m 2 / ε 0. At the same time, the outer surface of the positive electrode plate begins to electro-absorb the anion OH in the sodium aluminate solution system. - ions and Al(OH)4 - ‧4H2O hydrated ion, its charge surface density σ 极化 = σ内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the positive electrode interface; the negative electrode plate begins to electro-absorb the cation Na in the sodium aluminate solution system on the outer surface. + ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the negative electrode interface. In addition, due to the polarization electric field in the bulk phase of the sodium aluminate solution E 内极化 With external electric field E 外 The positive and negative electrode plates are processed into stirrer blades, and the solution system is constantly stirred during the entire sodium aluminate solution seed decomposition process. This technology greatly accelerates the OH in the solution phase. - ions, Al(OH)4 - ‧4H2O hydrated ions and Na + ‧The electrosorption process of 4H2O hydrated ions and other plasma from the bulk of the solution to the outer surface of the electrode.

[0065] (3) Until the “pressure control device” ( Figure 2 (9) Set voltage Δ U 设定 The voltage is boosted to a maximum forward voltage of 40 V and maintained for a period of time. The maximum voltage maintenance time is determined by the actual experiment of electrocatalysis during the decomposition of sodium aluminate solution crystals. Figure 2 (11)) Actual output voltage Δ U 电源 Also with Δ U 设定 The forward boost voltage continues to increase in the positive direction until the "control capacitor" ( Figure 2 The voltage Δ in (8) U 控制电容 Also boosted to a maximum voltage of 40 V, that is, Δ U 控制电容 =Δ U 设定 =40 V. At this time, the "voltage control device" outputs a "voltage control signal" ( Figure 2 (10) is the “hold” signal, which controls the actual output voltage of the power supply Δ U 电源Maintain Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 =40 V+Δ U 电极板 +Δ U 电阻 At the same time, the charge contained in the "control capacitor" remains q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧40 V=0.01 C. Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on (6) is also kept as q 电极板 = q 控制电容 =0.01 C, that is, the charge density on the inner surface of the electrode is kept at σ 内表面 = q 电极板 / A 电极板 =0.01 C / 1 m 2 =0.01 C / m 2 , the electric field at the electrode interface remains E 相界面 = σ 内表面 / ε 0=0.01 C / m 2 / 8.85×10 -12 C 2 ‧N -1 ‧m -2 ≈10 9 V / m. At the same time, the anion OH in the sodium aluminate solution system is electro-adsorbed on the outer surface of the positive electrode plate. - ions and Al(OH)4 - ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the positive electrode interface; the cation Na in the sodium aluminate solution system is electrically adsorbed on the outer surface of the negative electrode plate + ‧4H2O hydrated ion, its charge surface density σ 极化 = σ内表面 =0.01 C / m 2 , and form a double electric layer at the negative electrode interface. The Na2+ electrosorbed on the outer surface of the negative electrode plate + ‧4H2O hydrated ions will be in the electric field at the electrode interface E 相界面 ≈10 9 V / m is activated to form activated Na + ‧4H2O hydrated ions, using "[Na + ‧4H2O]*”. OH electrosorbed on the outer surface of the positive electrode plate - ions and Al(OH)4 - ‧4H2O hydrated ions will be in the electric field at the electrode interface E 相界面 ≈10 9 Activation occurs under the action of V / m to form activated OH - ions and Al(OH)4 - ‧4H2O hydrated ions, respectively "OH - *” and “[Al(OH)4 - ‧4H2O]*”. According to the transition state theory of chemical reaction kinetics, the activated [Al(OH)4 - ‧4H2O]* ions will be larger than the original Al(OH)4 - ‧4H2O ions more easily cross the transition energy barrier and transform into the thermodynamically more stable hexacoordinate structure [Al(OH)4‧(OH2)2] - . Due to the generated product [Al(OH)4‧(OH2)2] - It is also electrically adsorbed on the outer surface of the positive electrode and is under the action of the electrode interface electric field, so it is expressed as "[Al(OH)4‧(OH2)2] - *” means: the electric field at the electrode interface E 相界面 ≈10 9 Under the action of V / m, the following chemical reaction will occur on the outer surface of the positive electrode: [Al(OH)4 - ‧4H2O]* = [Al(OH)4‧(OH2)2] - * + 2H2O* At the same time, due to the polarization electric field inside the bulk phase of the sodium aluminate solution E 内极化 With external electric field E 外 The electric fields cancel each other out, and there is no net electric field in the bulk phase of the sodium aluminate solution. The bulk phase of the sodium aluminate solution system is still in the state of normal seed crystal decomposition process.

[0066] It should be noted that in the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is increased to the maximum forward voltage of 40 V and maintained for a period of time. During the decomposition of the sodium aluminate solution seed crystal, the capacitance of the double layer at the electrode plate interface is C 双电层 It is possible that the change in the solution state may cause the Δ U 电极板 If the capacitance of the double layer at the interface between the electrode plates C 双电层 becomes smaller, then Δ U 电极板 becomes larger, then Δ U 电源 <Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 , then, the positive and negative electrode plates ( Figure 2 The charge contained in (6) q 电极板 will be released and become less than 0.01 C, corresponding to the "control capacitance" ( Figure 2 The charge contained in (8) q 控制电容 will also be released synchronously and become less than 0.01 C. Then, the voltage of the “control capacitor” Δ U 控制电容 will also decrease, then Δ U 控制电容 <Δ U 设定 =40 V. At this time, the "voltage control device" will output a "voltage control signal" ( Figure 2 (10) is the "increase" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Increases positively until it reaches Δ U 控制电容 Re-equal to Δ U 设定 =40 V, and the charge on the "control capacitor" q 控制电容 The charge on the positive and negative electrodes will increase to 0.01 C. q 电极板 It will also increase and return to 0.01 C. If the capacitance of the double layer at the interface between the electrode plates C 双电层 becomes larger, then ΔU 电极板 becomes smaller, then Δ U 电源 >Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 , then the charge contained in the positive and negative electrode plates q 电极板 The increase becomes greater than 0.01 C, corresponding to the charge contained in the "control capacitor" q 控制电容 It will also increase synchronously to be greater than 0.01 C. Then, the voltage Δ U 控制电容 will also become larger, then Δ U 控制电容 >Δ U 设定 =40 V. At this time, the "voltage control device" will output the "voltage control signal" as a "decrease" signal, and the actual output voltage of the control power supply will be Δ U 电源 Decrease in positive direction until it reaches Δ U 控制电容 Re-equal to Δ U 设定 =40 V, and the charge on the "control capacitor" q 控制电容 It will also be reduced to 0.01 C, corresponding to the charge contained in the positive and negative electrode plates. q 电极板 It will also be reduced to 0.01 C. In other words, the "pressure control device" can automatically maintain the actual voltage of the "control capacitor" Δ U 控制电容 Stable at the set voltage Δ U 设定 = around 40 V. Accordingly, the charge of the "control capacitor" can be automatically maintained stable at around 0.01 C. At the same time, the charge on the positive and negative electrode plates in series is synchronously stabilized at 0.01 C, thereby accurately controlling the surface charge density of the positive and negative electrode plates when the state of the solution system changes. σ 内表面 Maintained at 0.01 C / m 2 Nearby, that is, when the state of the solution system changes, the electric field strength at the electrode interface is maintained E 相界面 is 10 9 V / m or so.

[0067] (4) Then the "pressure control device" ( Figure 2 (9) Set voltage ΔU 设定 The voltage drops to zero instantaneously and is maintained at zero for a period of time. The zero pressure maintenance time is determined by the actual experiment of electrolytic catalysis during the decomposition of sodium aluminate solution crystals. Figure 2 The voltage Δ in (8) U 控制电容 At the beginning, it is 40 V, that is, there is Δ U 控制电容 >Δ U 设定 =0. The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "decrease" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 From 40 V + Δ U 电极板 +Δ U 电阻 At this time, due to the voltage Δ U 控制电容 =40V greater than the power supply voltage Δ U 电源 =0, the charge on the "control capacitor" q 电极板 Rapidly discharge the charge from 0.01 C to the power supply until the charge is completely discharged q 控制电容 =0 and maintains for a period of time. The voltage of the “control capacitor” Δ U 控制电容 Also decreases to zero, that is, Δ U 控制电容 =Δ U 设定 =0. At this time, the "voltage control device" outputs the "voltage control signal" as the "hold" signal, and the actual output voltage of the control power supply is Δ U 电源 Keep output zero pressure Δ U 电源 =0 and maintain for a period of time. Correspondingly, when the "control capacitor" quickly releases the charge to the power supply until the charge is completely released, the charge on the positive and negative electrode plates q 电极板 Also released rapidly from 0.01 C until q 电极板 =0, positive and negative electrode plates ( Figure 2 (6)) Internal surface charge density σ 内表面 At the same time, from 0.01 C / m 2 Rapidly reduce to σ 内表面=0, electric field at the interface between positive and negative electrodes E 相界面 Also from 10 9 V / m quickly decreases to E 相界面 =0 and maintain for a period of time. At the same time, due to the loss of the electric field force, the activated OH groups originally electrically adsorbed on the outer surface of the positive electrode plate - *Ion and product ion [Al(OH)4‧(OH2)2] - * Will return to normal state from activated state OH - ions and [Al(OH)4‧(OH2)2] - ions. And, these normal state OH adsorbed on the outer surface of the positive electrode - ions and [Al(OH)4‧(OH2)2] - The ions will be more easily desorbed and return to the bulk phase of the solution without the action of the electric field. Similarly, due to the loss of the electric field force, the activated [Na + ‧4H2O]* ions will also return from the activated state to the normal state Na + ‧4H2O ions. And, these normal state Na adsorbed on the outer surface of the negative electrode + ‧4H2O ions will be more easily desorbed and returned to the bulk phase of the solution without the action of an electric field. At the same time, since the positive and negative electrode plates are processed into stirrer blades, the solution system is constantly stirred during the entire process of sodium aluminate solution seed decomposition. This technology further accelerates the desorption of OH ions originally electrosorbed on the outer surface of the positive and negative electrode plates. - ions, Al(OH)4 - ‧4H2O hydrated ions, Na + ‧4H2O hydrated ion and product [Al(OH)4‧(OH2)2] - The desorption process of ions from the outer surface of the electrode to the bulk phase of the solution. During a period of time when zero pressure is maintained, the charge density on the inner surface of the positive and negative electrode plates remains σ 内表面 =0, the electric field at the interface between positive and negative electrodes remains E 相界面 =0, all the ions originally adsorbed on the outer surfaces of the positive and negative electrode plates will be completely desorbed, and the sodium aluminate solution system is in the state of normal seed decomposition process.

[0068] (5) Then, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is slowly increased in the reverse direction (negative value), and the time of the slow increase is determined by the actual experiment of electrolytic catalysis during the decomposition of sodium aluminate solution crystals. Figure 2 The voltage Δ in (8) U 控制电容 It is zero at the beginning, that is, there is Δ U 控制电容 >Δ U 设定 The "pressure control device" will output a "voltage control signal" ( Figure 2 (10)) is the "decrease" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Start from zero and increase in the opposite direction (negative value) until it increases in the opposite direction to Δ U 控制电容 =Δ U 设定 So far, that is, the actual output voltage of the power supply Δ U 电源 Start from zero and increase in reverse to ensure that the voltage of the "control capacitor" Δ U 控制电容 With the setting voltage Δ U 设定 Slowly increase the voltage in the reverse direction. The voltage of the entire circuit has the following relationship: Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 . As the actual output voltage of the power supply Δ U 电源 Starting from zero, the power supply starts to output current in the reverse direction until the charge contained in the "control capacitor" is q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧Δ U 控制电容 Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The amount of charge on (6) q 电极板 = q 控制电容 =0.25 mF‧Δ U 控制电容 , that is, the surface charge density of the electrode σ 内表面 = q 电极板 / A 电极板 =0.25mF‧Δ U 控制电容 / 1 m2 , the electric field at the electrode interface E 相界面 = σ 内表面 / ε 0=0.25 mF‧Δ U 控制电容 / 1 m 2 / ε 0. At the same time, the outer surface of the positive electrode plate (the original negative electrode plate) begins to electro-absorb the anion OH in the sodium aluminate solution system. - ions and Al(OH)4 - ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the positive electrode interface; the outer surface of the negative electrode plate (the original positive electrode plate) begins to electro-absorb the cation Na in the sodium aluminate solution system + ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the negative electrode interface. In addition, due to the polarization electric field in the bulk phase of the sodium aluminate solution system E 内极化 With external electric field E 外 The positive and negative electrode plates are processed into stirrer blades, and the solution system is constantly stirred during the entire sodium aluminate solution seed decomposition process. This technology greatly accelerates the OH in the solution phase. - ions, Al(OH)4 - ‧4H2O hydrated ions and Na + ‧The electrosorption process of 4H2O hydrated ions and other plasma from the bulk of the solution to the outer surface of the electrode.

[0069] (6) Until "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is reversed and boosted to a maximum voltage of -40 V and maintained for a period of time. The maximum voltage maintenance time is determined by the actual experiment of electrocatalysis during the decomposition of sodium aluminate solution crystals. Figure 2(11)) Actual output voltage Δ U 电源 Also with the voltage Δ U 设定 The reverse boost voltage continues to increase in the reverse direction until the "control capacitor" ( Figure 2 The voltage Δ in (8) U 控制电容 It is also reverse-boosted to a maximum voltage of -40 V, that is, there is Δ U 控制电容 =Δ U 设定 =-40 V. At this time, the "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "hold" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Maintain Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 =-40 V+Δ U 电极板 +Δ U 电阻 At the same time, the charge contained in the "control capacitor" remains q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧40 V=0.01 C. Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on (6) also remains q 电极板 = q 控制电容 =0.01 C, that is, the charge density on the inner surface of the electrode remains σ 内表面 = q 电极板 / A 电极板 =0.01 C / 1 m 2 =0.01 C / m 2 , the electric field at the electrode interface is maintained E 相界面 = σ 内表面 / ε 0=0.01 C / m 2 / 8.85×10 -12 C2 ‧N -1 ‧m -2 ≈10 9 V / m. At the same time, the outer surface of the positive electrode plate (the original negative electrode plate) electro-adsorbs the anion OH in the sodium aluminate solution system. - ions and Al(OH)4 - ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the positive electrode interface; the negative electrode plate (the original positive electrode plate) electrically adsorbs the cation Na in the sodium aluminate solution system on the outer surface + ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the negative electrode interface. The Na2+ electrosorbed on the outer surface of the negative electrode plate + ‧4H2O hydrated ions will be in the electric field at the electrode interface E 相界面 ≈10 9 V / m, activated to form activated [Na + ‧4H2O]* ions. OH electrosorbed on the outer surface of the positive electrode plate - ions and Al(OH)4 - ‧4H2O hydrated ions will also be in the electric field at the electrode interface E 相界面 ≈10 9 Activation occurs under the action of V / m to form activated OH - * ions and [Al(OH)4 - ‧4H2O]* ion. According to the transition state theory of chemical reaction kinetics, the activated [Al(OH)4 - ‧4H2O]* ions will be larger than the original Al(OH)4 - ‧4H2O ions more easily cross the transition energy barrier and transform into the thermodynamically more stable hexacoordinate structure [Al(OH)4‧(OH2)2] - ions. Due to the generated product [Al(OH)4‧(OH2)2] - It is also electrically adsorbed on the outer surface of the positive electrode and is under the action of the electrode interface electric field, so it is expressed as "[Al(OH)4‧(OH2)2] - *” means: the electric field at the electrode interface E 相界面 ≈109 Under the action of V / m, the following chemical reaction will occur on the outer surface of the positive electrode: [Al(OH)4 - ‧4H2O]* = [Al(OH)4‧(OH2)2] - * + 2H2O* At the same time, due to the polarization electric field inside the bulk phase of the sodium aluminate solution E 内极化 With external electric field E 外 The electric fields offset each other, and there is no net electric field in the bulk phase of the sodium aluminate solution. The bulk phase of the sodium aluminate solution system is still in the state of normal seed crystal decomposition process.

[0070] It should be noted that in the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The reverse voltage is boosted to the maximum voltage of -40 V and maintained for a period of time. During the decomposition of the sodium aluminate solution seed crystal, the capacitance of the double layer at the electrode plate interface is C 双电层 It is possible that the change in the solution state may cause the Δ U 电极板 Similar to the previous example, the “pressure control device” can automatically maintain the “control capacitance” ( Figure 2 (8) Actual voltage Δ U 控制电容 Stable at the set voltage Δ U 设定 = 40 V. Accordingly, the charge of the "control capacitor" can be maintained stable at around 0.01 C, while the positive and negative electrode plates ( Figure 2 The charge density on the inner surface of the positive and negative electrode plates is precisely controlled when the state of the solution system changes. σ 内表面 Maintained at 0.01 C / m 2 Nearby, that is, when the state of the solution system changes, the electric field strength at the electrode interface is maintained E 相界面 is 10 9 V / m or so.

[0071] (7) Then the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage drops to zero instantaneously and is maintained at zero for a period of time. The zero pressure maintenance time is determined by the actual experiment of electrolytic catalysis during the decomposition of sodium aluminate solution crystals. Figure 2The voltage Δ in (8) U 控制电容 At the beginning, it is -40 V, that is, there is Δ U 控制电容 <Δ U 设定 =0. The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "increase" signal, which controls the power supply (such as Figure 2 (11)) Actual output voltage Δ U 电源 From -40 V + Δ U 电极板 +Δ U 电阻 It starts to increase rapidly from negative value to zero. At this time, due to the voltage Δ U 控制电容 =-40 V less than the power supply voltage Δ U 电源 =0, the charge on the "control capacitor" q 电极板 Rapidly release the charge from 0.01 C to the power source in the reverse direction until the charge is completely released q 控制电容 =0 and maintains for a period of time. The voltage of the “control capacitor” Δ U 控制电容 Also increases from negative value to zero, that is, Δ U 控制电容 =Δ U 设定 =0. At this time, the "voltage control device" will output the "voltage control signal" as the "hold" signal, controlling the actual output voltage of the power supply Δ U 电源 Keep output zero pressure Δ U 电源 =0 and maintain for a period of time. Correspondingly, when the "control capacitor" quickly releases the charge to the power supply in the reverse direction until the charge is completely released, the positive and negative electrode plates ( Figure 2 The charge on the inner surface of (6) q 电极板 Also synchronously releases rapidly in the reverse direction from 0.01 C until q 电极板 =0, the surface charge density of the positive and negative electrodes σ 内表面 At the same time, from 0.01 C / m 2 Rapidly reduce to σ 内表面 =0, electric field at the interface between positive and negative electrodes E 相界面 Also from 10 9 V / m quickly decreases to E相界面 = 0 and maintain for a period of time. At the same time, due to the loss of the electric field force, the activated OH groups originally electrically adsorbed on the outer surface of the positive electrode plate (formerly the negative electrode plate) - *Ion and product ion [Al(OH)4‧(OH2)2] - * Will return to normal state from activated state OH - ions and [Al(OH)4‧(OH2)2] - ions. And, these normal state OH adsorbed on the outer surface of the positive electrode - ions and [Al(OH)4‧(OH2)2] - The ions will be more easily desorbed and return to the bulk phase of the solution without the action of the electric field. Similarly, due to the loss of the electric field force, the activated [Na + ‧4H2O]* ions will also return from the activated state to the normal state Na + ‧4H2O ions. And, these normal state Na adsorbed on the outer surface of the negative electrode + ‧4H2O ions will be more easily desorbed and returned to the bulk phase of the solution without the action of an electric field. At the same time, since the positive and negative electrode plates are processed into stirrer blades, the solution system is constantly stirred during the entire process of sodium aluminate solution seed decomposition. This technology further accelerates the desorption of OH ions originally electrosorbed on the outer surface of the positive and negative electrode plates. - ions, Al(OH)4 - ‧4H2O hydrated ions, Na + ‧4H2O hydrated ion and product [Al(OH)4‧(OH2)2] - The desorption process of ions from the outer surface of the electrode to the bulk phase of the solution. During a period of time when zero pressure is maintained, the charge density on the inner surface of the positive and negative electrode plates remains σ 内表面 =0, the electric field at the interface between positive and negative electrodes remains E 相界面 =0, all the ions originally adsorbed on the outer surfaces of the positive and negative electrode plates will be completely desorbed, and the sodium aluminate solution system is in the state of normal seed decomposition process.

[0072] (8) Subsequently, the “pressure control device” ( Figure 2 (9) Set voltage Δ U 设定 The voltage is slowly increased in the forward direction and the next cycle begins.

[0073] (9) Thus, as the voltage applied to the positive and negative electrode plates changes periodically, and the positive and negative electrode plates processed into agitator blades continuously stir in the solution system, the Al(OH)4- ‧4H2O hydrated ions are continuously activated by the electric field at the electrode interface to become [Al(OH)4 - ‧4H2O]* activated ions and more quickly transformed into the more stable hexacoordinated form of [Al(OH)4‧(OH2)2] on the outer surface of the electrode, crossing the transition state energy barrier. - , becoming a growth unit and eventually converted into aluminum hydroxide crystals Al(OH)3(cr) in the solution system.

[0074] Example 2

[0075] This embodiment specifically describes the construction of an electric field catalytic system suitable for the degradation of tetracycline-contaminated wastewater in an environmentally friendly industrial hydrogen peroxide aqueous solution system according to the invention.

[0076] Tetracycline (chemical formula is C 22 H 24 N2O8) is a widely used antibiotic. 22 H 24 Due to its naphthol ring structure, most N₂O₃ molecules cannot be fully metabolized by organisms, with over 85% being released into the environment. However, antibiotics that enter the environment are rarely completely degraded, instead producing a series of metabolic and degradation products. These products are often more toxic and can even cause more severe secondary pollution than the parent compound. Therefore, the complete degradation of tetracycline-contaminated wastewater in the environment is a pressing issue, and the use of aqueous hydrogen peroxide to oxidize tetracycline-contaminated wastewater is an alternative approach.

[0077] There are many types of tetracycline oxidation degradation products. The complete degradation products are mainly carbon dioxide and water. The nitrogen element produces different products according to different situations, and nitrogen dioxide is one of them. Assuming that hydrogen peroxide solution completely degrades tetracycline-contaminated wastewater, the overall chemical reaction is as follows: C 22 H 24 N2O8 + 52H2O2 = 22CO2 + 64H2O + 2NO2 Because the complete degradation of tetracycline is complex, direct oxidative degradation with hydrogen peroxide alone is difficult to achieve. Therefore, electric field catalysis can reduce the difficulty of each step in the degradation process, speeding up the entire degradation process and ensuring the complete degradation of tetracycline.

[0078] The process conditions for the degradation of tetracycline-contaminated wastewater by hydrogen peroxide solution in the embodiment are: hydrogen peroxide concentration M (H2O2) is about 0.1 mol / L; tetracycline concentration M (C 22 H 24N2O8) is 0.1 mmol / L; the surface area of ​​the face-to-face agitator blades (that is, the surface area of ​​the face-to-face positive and negative electrode plates) A 电极板 Assume 1m 2 Low-concentration hydrogen peroxide aqueous solution can be regarded as a non-electrolyte solution system, whose main chemical components are hydrogen peroxide H2O2 and solvent water H2O. Low-concentration hydrogen peroxide aqueous solution is used to degrade tetracycline-contaminated wastewater. The microscopic particles in the entire solution system are mainly H2O2 molecules, H2O molecules, and C 22 H 24 N2O8 molecule.

[0079] According to the contents and appended Figure 2 According to the following steps, an electric field catalytic system suitable for the degradation of tetracycline-contaminated wastewater in a hydrogen peroxide aqueous solution system was constructed.

[0080] First, according to the present invention, we have solved the problem of how to electric field catalyze various chemical reactions in non-electrolyte solution systems with relatively small relative dielectric constants by adding a small molecular weight inert electrolyte to a non-electrolyte solution system to convert it into an electrolyte solution system. Low-concentration hydrogen peroxide aqueous solution can be regarded as a non-electrolyte solution system with a relative dielectric constant of ε r About 80, less than 100. We can add a small amount of sodium chloride (NaCl) electrolyte to transform the low-concentration hydrogen peroxide aqueous solution into an electrolyte solution system containing 0.1 mol / L NaCl. In this way, the microscopic particles in the entire solution system exist in addition to H2O2 molecules, H2O molecules and C 22 H 24 In addition to N2O8 molecules, there are also cations Na + ‧4H2O hydrated ions and anions Cl - .

[0081] Second, according to the present invention, the electrode plate material and the processing of the stirrer blades (such as Figure 2 According to the properties of hydrogen peroxide aqueous solution, the inner rod and outer shell of the stirrer straight rod can be made of stainless steel (such as Figure 2 (3) and (4) parts in the figure), which have good corrosion resistance and mechanical properties. At the same time, stainless steel with platinum electroplated on the surface can be used to process the positive and negative electrode plates facing each other, and processed into the shape of face-to-face stirrer blades (such as Figure 2 (6) components), respectively mounted on the conductive inner rod and the conductive outer shell of the stirrer straight rod (such as Figure 2(6) in the figure). They not only have good electrochemical corrosion resistance and mechanical properties, but also, as metal materials, their inner surface charge density can meet the needs of electric field catalysis. The insulating layer between the inner rod and the outer shell of the stirrer straight rod (such as Figure 2 The (5) component) can be made of polytetrafluoroethylene material.

[0082] Third, determine the electric field strength at the electrode interface according to the present invention. E 相界面 and the surface charge density within the electrode σ 内表面 According to the chemical reaction form of the degradation process of tetracycline-contaminated wastewater by hydrogen peroxide aqueous solution system, the electric field strength required for electric field catalysis can be determined by the strength of various chemical bonds involved, including the OO single bond and HO single bond in H2O2, C 22 H 24 The CC single bond, C=C double bond, CH single bond, CO single bond, C=O double bond, CN single bond, HO single bond, and NH single bond in N2O8, etc. According to the basic principles of physical electricity, under the electric field interaction of unit charge, there is the following relationship between the electric field strength and the electric field interaction energy. E = W 作用能 / ( r ‧ e ‧ N 0), where E represents the electric field strength, W 作用能 represents the electric field interaction energy, r represents the bond length, e The unit charge is approximately 1.602×10 -19 C, N 0 means Avogadro's constant is about 6.02×10 23 mol -1If a double chemical bond is approximated as two equivalent single bonds, and each single bond is approximated as the electric field interaction between two anions and cations with unit charge, then according to the basic principles of physical electricity, the electric field strength between each chemical bond can be estimated based on the actual chemical bond energy and bond length of each chemical bond. According to authoritative references (Lange's Handbook of Chemistry, CRC Press Handbook of Chemistry and Physic), the bond lengths and bond energies are as follows: 0.148 nm, 498 kJ / mol for the OO single bond; 0.096 nm, 428 kJ / mol for the HO single bond; 0.154 nm, 368 kJ / mol for the CC single bond; 0.134 nm, 682 kJ / mol for the C=C double bond; 0.109 nm, 337 kJ / mol for the CH single bond; 0.143 nm, 389 kJ / mol for the CO single bond; 0.120 nm, 749 kJ / mol for the C=O double bond; 0.147 nm, 331 kJ / mol for the CN single bond; and 0.101 nm, 314 kJ / mol for the NH single bond. Based on the actual bond energies and bond lengths of the chemical bonds mentioned above, their electric field strengths are estimated to be approximately: 35×10 9 V / m; 46×10 9 V / m; 25×10 9 V / m; 26×10 9 ~52×10 9 V / m; 32×10 9 V / m; 28×10 9 V / m; 32×10 9 ~64×10 9 V / m; 23×10 9 V / m; 32×10 9 V / m. These calculations show that the actual electric field strength of these chemical bonds should also be around 10 10 V / m level. According to the actual bond energy of these chemical bonds, it can be inferred that if the external electric field strength is 10 8 ~10 9 The V / m range is equivalent to affecting the bond energy of these single chemical bonds by about 1~15 kJ / mol, and the total impact of multiple chemical bonds can reach nearly 10~100 kJ / mol. According to the current chemical reaction kinetics theory, energy changes in this range are sufficient to change the speed of chemical reactions involving molecules containing these chemical bonds. Therefore, it is assumed here that the electrode interface electric field strength required for the process of electric field catalytic hydrogen peroxide aqueous solution system to degrade tetracycline-contaminated wastewater is E 相界面 is 10 9V / m or so (of course, the actual required electric field strength at the electrode interface can be ultimately determined based on actual experiments of electric field catalysis). E 相界面 If the charge density is too high, it will cause electrolysis reaction in hydrogen peroxide aqueous solution system or electrochemical corrosion of anode electrode plate. σ 内表面 = ε 0 E 相界面 ≈0.01 C / m 2 According to the process conditions of the degradation of tetracycline-contaminated wastewater by hydrogen peroxide aqueous solution system, the single-side area of ​​the face-to-face agitator blades as positive and negative electrode plates is A 电极板 1 m 2 , then the required surface charge density of the electrode is formed σ 内表面 The total charge required q 电极板 is 0.01 C.

[0083] Fourth, determine the actual voltage Δ applied to the positive and negative electrode plates according to the invention content. U 电极板 We know that the solution system mainly contains cations Na + ‧4H2O hydrated ion, anion is Cl - ions. In the electric field catalysis process, Cl - Ions are adsorbed on the outer surface of the positive electrode plate to form a double electrical layer at the positive electrode interface; + ‧4H2O hydrated ions are adsorbed on the outer surface of the negative electrode plate, also forming a double layer at the negative electrode interface. According to the data reported in authoritative references (Lange's Handbook of Chemistry, CRC Press Handbook of Chemistry and Physic), Na + The ionic radius is about 0.099 nm, Cl - The ionic radius is about 0.181 nm. According to the literature (Huang Ziqing. Introduction to Electrolyte Solution Theory (Revised Edition) [M]. Beijing: Science Press, 2010.) + The ionic radius of Na is 0.095 nm, so it can be inferred that + The ion radius of 4H2O hydrate is about 0.358 nm. We estimate that the maximum thickness of the double layer at the interface between the positive and negative electrodes is 0.5 nm. When the surface charge density of the control electrode is σ 内表面 About 0.01 C / m 2, which is equivalent to the electric field strength at the electrode interface E 相界面 is 10 9 V / m, at this time, the actual voltage applied to the positive and negative electrode plates is Δ U 电极板 The maximum is about 1 V. If we consider the intrinsic capacitance of the electrode interface in the process of electric field catalysis in the degradation of tetracycline-contaminated wastewater in a hydrogen peroxide aqueous solution system, C 双电层 The surface charge density of the electrode may fluctuate as the degradation of tetracycline-contaminated wastewater by the hydrogen peroxide aqueous solution system proceeds. σ 内表面 Also between 0 and 0.01 C / m 2 The range is constantly changing, so the actual voltage applied to the positive and negative electrode plates Δ U 电极板 It should vary in the range of 0 to 1 V.

[0084] Fifth, select the power supply device that provides voltage to the positive and negative electrode plates according to the invention content ( Figure 2 (11)), the power supply can output a periodically changing voltage Δ with controllable magnitude and direction, alternating between zero voltage and a certain voltage. U 电源 , and can be controlled according to the "voltage control signal" ( Figure 2 (10)) to adjust the output voltage Δ U 电源 Considering that the hydrogen peroxide aqueous solution system catalyzed by electric field is conductive and the conductive electrode is directly connected to the solution system, from the perspective of safety, the maximum output voltage of the power supply is selected to be 50 V, and the actual output voltage Δ U 电源 Around 0~40 V (within the 48 V safety voltage range).

[0085] Sixth, according to the invention, a capacitor must be connected in series in the circuit that applies voltage to the positive and negative electrode plates as a "control capacitor" ( Figure 2 (8)). Considering the actual output voltage Δ of the entire circuit power supply U 电源 The maximum value is around 40 V. At the same time, the amount of charge that needs to pass through the "control capacitor" q 控制电容 To precisely control the maximum charge of the positive and negative electrode plates in the series circuit q 电极板 is 0.01 C, that is, the surface charge density of the electrode as mentioned above σ 内表面 Maximum 0.01 C / m 2 , then, you can choose a capacitance C控制电容 The capacitor element with a value of 0.01 C / 40 V = 0.25 mF is used as the "control capacitor". U 控制电容 When the range changes from 0 to 40 V, the amount of charge it contains is q 控制电容 The value of the positive and negative electrodes connected in series with the control capacitor will vary from 0 to 0.01 C. q 电极板 The surface charge density of the electrode will also vary in the range of 0~0.01 C. σ 内表面 Will be in the range of 0~0.01 C / m 2 Range changes, the electric field strength at the electrode interface E 相界面 Will be in 0~10 9 V / m range changes. That is, we can precisely control the voltage Δ of the "control capacitor" U 控制电容 To precisely control the electric field strength at the electrode interface E 相界面 .

[0086] Seventh, according to the appendix to the invention Figure 2 As shown, a resistor is connected in series with the entire circuit ( Figure 2 (7)). Considering that the current of the entire circuit cannot be overloaded during the voltage mutation process. The actual output voltage of the power supply of the entire circuit Δ U 电源 The maximum value is around 40 V. Assuming the maximum current does not exceed 0.1 A, the series resistance of the entire circuit is selected to be 400 Ω.

[0087] Eighth, according to the appendix to the invention Figure 2 As shown, assuming the actual voltage of the resistor is Δ U 电阻 , then the actual output voltage of the power supply Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 According to the ninth point below, the actual output voltage Δ U 电源 The size of the voltage control signal ( Figure 2 (10)) to adjust to ensure Δ U 控制电容 =Δ U 设定 .

[0088] Ninth, according to the invention, a "pressure control device" is added to the "control capacitor" to measure its actual voltage ( Figure 2 (9)), and the "pressure control device" can set a certain voltage change form, and according to the set voltage Δ U 设定 Instead of measuring the actual voltage of the "control capacitor" Δ U 控制电容 The relationship between the output "voltage control signal" ( Figure 2 (10)) to the power supply equipment of the entire circuit (such as Figure 2 As shown in (10), the power supply device changes the actual output voltage Δ U 电源 size to ensure the actual voltage of the "control capacitor" Δ U 控制电容 According to the voltage Δ set by the "pressure control device" U 设定 The change mode changes. U 控制电容 <Δ U 设定 When the "voltage control signal" is "increase", the power supply increases the actual output voltage Δ U 电源 , until Δ U 控制电容 =Δ U 设定 ; When Δ U 控制电容 =Δ U 设定 When the “voltage control signal” is “hold”, the power supply is controlled to maintain the actual output voltage Δ U 电源 ; When Δ U 控制电容 >Δ U 设定 When the "voltage control signal" is "decrease", the power supply is controlled to reduce the actual output voltage Δ U 电源 , until Δ U 控制电容 =Δ U 设定 .

[0089] Tenth, according to the invention, "pressure control device" (such as Figure 2 (9) Set voltage Δ U 设定The variation is as follows: First, the voltage is maintained at zero for a period of time, then the voltage is slowly increased in the forward direction to a maximum forward voltage of 40 V and maintained for a period of time; then the voltage is instantly dropped to zero and maintained at zero for a period of time, then the voltage is slowly increased in the reverse direction to a maximum reverse voltage of -40 V and maintained for a period of time; finally, the voltage is instantly dropped to zero again, and the cycle repeats. The specific parameters of the zero-voltage maintenance time, the slow voltage increase time, and the maximum voltage maintenance time were determined by actual experiments on the electrocatalytic degradation of tetracycline-contaminated wastewater in a hydrogen peroxide aqueous solution system.

[0090] Eleventh, the electric field catalytic reaction process of degrading tetracycline-contaminated wastewater in a hydrogen peroxide aqueous solution system is described as follows.

[0091] (1) First, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The zero pressure is maintained for a period of time, and the zero pressure maintenance time is determined by the actual experiment of electrocatalysis in the process of degrading tetracycline-contaminated wastewater by hydrogen peroxide aqueous solution system. At this time, due to the "control capacitance" (such as Figure 2 (8) does not contain any charge, i.e. q 控制电容 =0, its voltage Δ U 控制电容 is also zero, that is, Δ U 控制电容 =Δ U 设定 The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "hold" signal, which controls the power supply (, Figure 2 (11)) maintains the actual output voltage Δ U 电源 =0, that is, the power supply has no output current. At this time, the "control capacitor" ( Figure 2 The amount of charge contained in (8) q 控制电容 Keep it at zero, correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on the inner surface of (6) q 电极板 Also remains zero, that is, the surface charge density inside the electrode σ 内表面 Also remains zero, the electrode interface electric field E 相界面 At this time, there are no ions or polarized molecules or other microscopic particles electrically adsorbed on the outer surfaces of the positive and negative electrode plates, and the hydrogen peroxide aqueous solution system is in a normal state of degrading tetracycline-contaminated wastewater.

[0092] (2) Then, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The slow pressure increase is in the positive direction, and the slow pressure increase time is determined by the actual experiment of electrocatalysis in the process of degrading tetracycline-contaminated wastewater by hydrogen peroxide aqueous solution system. Figure 2 The voltage Δ in (8) U 控制电容 It is zero at the beginning, that is, there is Δ U 控制电容 <Δ U 设定 At this time, the "pressure control device" will output a "voltage control signal" ( Figure 2 (10) is the "increase" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Starting from zero, it increases positively until Δ U 控制电容 =Δ U 设定 So far, that is, the actual output voltage of the power supply Δ U 电源 Start from zero and increase in a positive direction to ensure that the voltage of the "control capacitor" Δ U 控制电容 With the setting voltage Δ U 设定 Slowly increase the voltage in the forward direction. The voltage of the entire circuit has the following relationship: Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 . As the actual output voltage of the power supply Δ U 电源 Starting from zero and increasing in positive direction, the power supply starts to output positive current until the charge contained in the "control capacitor" is q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧Δ U 控制电容 Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The amount of charge on (6) q 电极板 Synchronous changes, that is, q 电极板 = q 控制电容 =0.25 mF‧Δ U 控制电容, that is, the surface charge density of the electrode σ 内表面 = q 电极板 / A 电极板 =0.25 mF‧Δ U 控制电容 / 1 m 2 , the electric field at the electrode interface E 相界面 = σ 内表面 / ε 0=0.25 mF‧Δ U 控制电容 / 1 m 2 / ε 0. At the same time, the outer surface of the positive electrode plate begins to electro-absorb the anion Cl in the hydrogen peroxide aqueous solution system containing 0.1 mol / L NaCl. - ions, whose surface charge density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the positive electrode interface; the negative electrode plate begins to electro-adsorb the cation Na in the hydrogen peroxide aqueous solution system containing 0.1 mol / L NaCl. + Hydrated ions, whose surface charge density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the negative electrode interface. In addition, due to the polarization electric field in the bulk phase of the hydrogen peroxide aqueous solution containing 0.1 mol / L NaCl E 内极化 With external electric field E 外 The positive and negative electrode plates are processed into agitator blades, and the solution system is constantly stirred during the entire process of degrading tetracycline-contaminated wastewater with hydrogen peroxide solution. This technology greatly accelerates the Cl in the solution phase. - ions and Na + The electrosorption process of hydrated ions and other plasmas from the bulk phase of the solution to the outer surface of the electrode also greatly accelerates the mass transfer process of various other molecules in the solution system between the outer surfaces of the positive and negative electrodes and the bulk phase of the solution.

[0093] (3) Until the “pressure control device” ( Figure 2 (9) Set voltage Δ U 设定 The voltage is boosted to a maximum forward voltage of 40 V and maintained for a period of time. The maximum voltage maintenance time is determined by the actual experiment of electrocatalytic degradation of tetracycline-contaminated wastewater by hydrogen peroxide aqueous solution system. Figure 2 (11)) Actual output voltage Δ U 电源 Also with Δ U 设定 The forward boost voltage continues to increase in the positive direction until the "control capacitor" ( Figure 2 The voltage Δ in (8) U 控制电容 Also boosted to a maximum voltage of 40 V, that is, Δ U 控制电容 =Δ U 设定 =40 V. At this time, the "voltage control device" outputs a "voltage control signal" ( Figure 2 (10) is the “hold” signal, which controls the actual output voltage of the power supply Δ U 电源 Maintain Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 =40 V+Δ U 电极板 +Δ U 电阻 At the same time, the charge contained in the "control capacitor" remains q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧40 V=0.01C. Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on (6) is also kept as q 电极板 = q 控制电容 =0.01 C, that is, the charge density on the inner surface of the electrode is kept at σ 内表面 = q 电极板 / A 电极板 =0.01 C / 1 m 2 =0.01 C / m2 , the electric field at the electrode interface remains E 相界面 = σ 内表面 / ε 0=0.01 C / m 2 / 8.85×10 -12 C 2 ‧N -1 ‧m -2 ≈10 9 V / m. At the same time, the anion Cl in the solution system is electro-adsorbed on the outer surface of the positive electrode plate. - ions, whose surface charge density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the positive electrode interface; the cation Na in the solution system is electrically adsorbed on the outer surface of the negative electrode plate + ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the negative electrode interface.

[0094] According to the data reported in authoritative references (Lange's Handbook of Chemistry, CRC Press Handbook of Chemistry and Physic), Na + The ionic radius is about 0.099 nm, Cl - The ionic radius is about 0.181nm. According to the literature (Huang Ziqing. Introduction to Electrolyte Solution Theory (Revised Edition) [M]. Beijing: Science Press, 2010.) + The ionic radius of Na is 0.095 nm, so it can be inferred that + The hydrated ion radius of 4H2O is approximately 0.358 nm. The charge density on the electrode surface is 0.01 C / m 2 , which is equivalent to the Cl on the outer surface of the positive and negative electrodes - ions and Na + ‧The surface density of 4H2O hydrated ions is 6×10 16 pcs / m 2 From this we can calculate that even if Cl is electrosorbed on the outer surface of the positive and negative electrodes, - ions and Na + ‧4H2O hydrated ions are arranged in parallel in a single layer with a surface density of about 6×10 16 pcs / m2 Cl - ions and Na + ‧The actual area occupied by 4H2O hydrated ions is about 8×10 -3 m 2 / m 2 and 3×10 -2 m 2 / m 2 This shows that when the surface charge density of the electrode is σ 极化 0.01 C / m 2 When Cl - ions and Na + ‧4H2O hydrated ions are far from covering the entire outer surface of the electrode, but only occupy a small part of the outer surface area of ​​the electrode. In other words, in addition to the small area of ​​the outer surface of the positive and negative electrodes where these anions and cations are electrically adsorbed, the outer surface of the electrode between these electrically adsorbed anions and cations also adsorbs various other polarized molecules or molecules of the hydrogen peroxide aqueous solution system, including H2O2 molecules, H2O molecules and C 22 H 24 N2O8 molecules. It should be noted that these H2O2 molecules, H2O molecules and C 22 H 24 N2O8 molecules will not only be adsorbed on the outer surface of the positive electrode, but also on the outer surface of the negative electrode. And all ions, polarized molecules or molecules adsorbed on the outer surface of the positive and negative electrodes will be in the electrode interface electric field ( E 相界面 ≈10 9 V / m), which includes H2O2 molecules and C 22 H 24 N2O8 molecules. These activated H2O2 molecules and C 22 H 24 N2O8 molecules are represented by "H2O2*" and "C 22 H 24 N2O8*”. According to the transition state theory of chemical reaction kinetics, the activated H2O2* and C 22 H 24 N2O8* molecules will more easily cross the transition state energy barrier than the original unactivated molecules to undergo a complete degradation chemical reaction and generate product molecules such as CO2, H2O and NO2. Since the generated products are also adsorbed on the outer surface of the positive and negative electrodes and are under the influence of the electrode interface electric field, they are represented by "CO2*", "H2O*" and "NO2*" respectively. That is: at the electrode interface electric field E 相界面 ≈109 Under the action of V / m, the following complete degradation chemical reaction will occur on the outer surface of the positive and negative electrodes: C 22 H 24 N2O8* + 52H2O2* = 22CO2* + 64H2O* + 2NO2* At the same time, due to the polarization electric field inside the bulk phase of the solution E 内极化 With external electric field E 外 The electric fields cancel each other out, and there is no net electric field in the bulk phase of the hydrogen peroxide aqueous solution system, and the bulk phase is still in the normal state of tetracycline degradation process.

[0095] It should be noted that in the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is boosted to the maximum forward voltage of 40 V and maintained for a period of time. During the degradation of tetracycline-contaminated wastewater by hydrogen peroxide aqueous solution system, the capacitance of the double electric layer at the electrode plate interface is C 双电层 It is possible that the change in the solution state may cause the Δ U 电极板 If the capacitance of the double layer at the interface between the electrode plates C 双电层 becomes smaller, then Δ U 电极板 becomes larger, then Δ U 电源 <Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 , then, the positive and negative electrode plates ( Figure 2 The charge contained in (6) q 电极板 will be released and become less than 0.01 C, corresponding to the "control capacitance" ( Figure 2 The charge contained in (8) q 控制电容 will also be released synchronously and become less than 0.01 C. Then, the voltage of the “control capacitor” Δ U 控制电容 will also decrease, then Δ U 控制电容 <Δ U 设定 =40 V. At this time, the "voltage control device" will output a "voltage control signal" ( Figure 2 (10) is the "increase" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Increases positively until it reaches Δ U 控制电容 Re-equal to Δ U 设定 =40 V, and the charge on the "control capacitor" q 控制电容 The charge on the positive and negative electrodes will increase to 0.01 C. q 电极板 It will also increase and return to 0.01 C. If the capacitance of the double layer at the interface between the electrode plates C 双电层 becomes larger, then Δ U 电极板 becomes smaller, then Δ U 电源 >Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 , then the charge contained in the positive and negative electrode plates q 电极板 The increase becomes greater than 0.01 C, corresponding to the charge contained in the "control capacitor" q 控制电容 It will also increase synchronously to be greater than 0.01 C. Then, the voltage Δ U 控制电容 will also become larger, then Δ U 控制电容 >Δ U 设定 =40 V. At this time, the "voltage control device" will output the "voltage control signal" as a "decrease" signal, and the actual output voltage of the control power supply will be Δ U 电源 Decrease in positive direction until it reaches Δ U 控制电容 Re-equal to Δ U 设定 =40 V, and the charge on the "control capacitor" q 控制电容 It will also be reduced to 0.01 C, corresponding to the charge contained in the positive and negative electrode plates. q 电极板 It will also be reduced to 0.01 C. In other words, the "pressure control device" can automatically maintain the actual voltage of the "control capacitor" Δ U 控制电容 Stable at the set voltage Δ U 设定= around 40 V. Accordingly, the charge of the "control capacitor" can be automatically maintained stable at around 0.01 C. At the same time, the charge on the positive and negative electrode plates in series is synchronously stabilized at 0.01 C, thereby accurately controlling the surface charge density of the positive and negative electrode plates when the state of the solution system changes. σ 内表面 Maintained at 0.01 C / m 2 Nearby, that is, when the state of the solution system changes, the electric field strength at the electrode interface is maintained E 相界面 is 10 9 V / m or so.

[0096] (4) Then the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage drops to zero instantaneously and is maintained at zero for a period of time. The zero pressure maintenance time is determined by the actual experiment of electrocatalysis in the process of degrading tetracycline-contaminated wastewater with hydrogen peroxide aqueous solution. Figure 2 The voltage Δ in (8) U 控制电容 At the beginning, it is 40 V, that is, there is Δ U 控制电容 >Δ U 设定 =0. The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "decrease" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 From 40 V + Δ U 电极板 +Δ U 电阻 At this time, due to the voltage Δ U 控制电容 =40 V greater than the supply voltage Δ U 电源 =0, the charge on the "control capacitor" q 电极板 Rapidly discharge the charge from 0.01 C to the power supply until the charge is completely discharged q 控制电容 =0 and maintains for a period of time. The voltage of the “control capacitor” Δ U 控制电容 Also decreases to zero, that is, Δ U 控制电容 =Δ U 设定 =0. At this time, the "voltage control device" outputs the "voltage control signal" as the "hold" signal, and the actual output voltage of the control power supply is ΔU 电源 Keep output zero pressure Δ U 电源 =0 and maintain for a period of time. Correspondingly, when the "control capacitor" quickly releases the charge to the power supply until the charge is completely released, the charge on the positive and negative electrode plates q 电极板 Also released rapidly from 0.01 C until q 电极板 =0, positive and negative electrode plates ( Figure 2 (6)) Internal surface charge density σ 内表面 At the same time, it also increases from 0.01C / m 2 Rapidly reduce to σ 内表面 =0, electric field at the interface between positive and negative electrodes E 相界面 Also from 10 9 V / m quickly decreases to E 相界面 = 0 and maintain for a period of time. At the same time, due to the loss of the electric field force, the various activated ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates will return from the activated state to the normal state, and these normal ions, polarized molecules and molecules adsorbed on the outer surface of the positive and negative electrodes will be more easily desorbed and returned to the solution phase without the action of the electric field. There is Cl on the outer surface of the positive electrode plate. - ions, H2O2 molecules, H2O molecules and C 22 H 24 N2O8 molecules, as well as CO2, H2O and NO2 molecules generated after degradation reaction; there is Na on the outer surface of the negative electrode plate. + ‧4H2O hydrated ion, H2O2 molecule, H2O molecule and C 22 H 24 N2O8 molecules, as well as CO2, H2O and NO2 molecules generated after the degradation reaction. At the same time, since the positive and negative electrode plates are processed into agitator blades, the solution system is constantly stirred during the entire process of degrading tetracycline-contaminated wastewater with a hydrogen peroxide aqueous solution system. This technology further accelerates the desorption process of various ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates from the outer surface of the electrode to the bulk phase of the solution. During a period of time when zero pressure is maintained, the charge density on the inner surface of the positive and negative electrode plates remains σ 内表面 =0, the electric field at the interface between positive and negative electrodes remains E 相界面 =0, all the ions, polarized molecules and molecules originally adsorbed on the outer surfaces of the positive and negative electrode plates will be completely desorbed, and the hydrogen peroxide aqueous solution system is in the state of normal degradation of tetracycline-contaminated wastewater.

[0097] (5) Then, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The reverse slow pressure rise (negative value) is determined by the actual experiment of electrocatalysis in the process of degrading tetracycline-contaminated wastewater with hydrogen peroxide aqueous solution. Figure 2 The voltage Δ in (8) U 控制电容 It is zero at the beginning, that is, there is Δ U 控制电容 >Δ U 设定 The "pressure control device" will output a "voltage control signal" ( Figure 2 (10)) is the "decrease" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Start from zero and increase in the opposite direction (negative value) until it increases in the opposite direction to Δ U 控制电容 =Δ U 设定 So far, that is, the actual output voltage of the power supply Δ U 电源 Start from zero and increase in reverse to ensure that the voltage of the "control capacitor" Δ U 控制电容 With the setting voltage Δ U 设定 Slowly increase the voltage in the reverse direction. The voltage of the entire circuit has the following relationship: Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 . As the actual output voltage of the power supply Δ U 电源 Starting from zero, the power supply starts to output current in the reverse direction until the charge contained in the "control capacitor" is q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧Δ U 控制电容 Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The amount of charge on (6) q 电极板 = q 控制电容 =0.25 mF‧ΔU 控制电容 , that is, the surface charge density of the electrode σ 内表面 = q 电极板 / A 电极板 =0.25 mF‧Δ U 控制电容 / 1 m 2 , the electric field at the electrode interface E 相界面 = σ 内表面 / ε 0=0.25 mF‧Δ U 控制电容 / 1m 2 / ε 0. At the same time, the outer surface of the positive electrode plate (the original negative electrode plate) began to electro-adsorb the anion Cl in the hydrogen peroxide aqueous solution system containing 0.1 mol / LNaCl. - ions, whose surface charge density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the positive electrode interface; the outer surface of the negative electrode plate (the original positive electrode plate) begins to electro-adsorb the cation Na in the hydrogen peroxide aqueous solution system containing 0.1 mol / L NaCl. + Hydrated ions, whose surface charge density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the negative electrode interface. In addition, due to the polarization electric field in the bulk phase of the hydrogen peroxide aqueous solution containing 0.1 mol / LNaCl E 内极化 With external electric field E 外 The positive and negative electrode plates are processed into agitator blades, and the solution system is constantly stirred during the entire process of degrading tetracycline-contaminated wastewater with hydrogen peroxide solution. This technology greatly accelerates the Cl in the solution phase. - ions and Na +The electrosorption process of hydrated ions and other plasmas from the bulk phase of the solution to the outer surface of the electrode also greatly accelerates the mass transfer process of various other molecules in the solution system between the outer surfaces of the positive and negative electrodes and the bulk phase of the solution.

[0098] (6) Until "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The reverse voltage is boosted to a maximum voltage of -40 V and maintained for a period of time. The maximum voltage maintenance time is determined by the actual experiment of electrocatalysis in the process of degrading tetracycline-contaminated wastewater with hydrogen peroxide aqueous solution. Figure 2 (11)) Actual output voltage Δ U 电源 Also with the voltage Δ U 设定 The reverse boost voltage continues to increase in the reverse direction until the "control capacitor" ( Figure 2 The voltage Δ in (8) U 控制电容 It is also reverse-boosted to a maximum voltage of -40V, that is, there is Δ U 控制电容 =Δ U 设定 =-40 V. At this time, the "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "hold" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Maintain Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 =-40 V+Δ U 电极板 +Δ U 电阻 At the same time, the charge contained in the "control capacitor" remains q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧40 V=0.01 C. Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on (6) also remains q 电极板 = q 控制电容 =0.01 C, that is, the charge density on the inner surface of the electrode remains σ内表面 = q 电极板 / A 电极板 =0.01 C / 1 m 2 =0.01 C / m 2 , the electric field at the electrode interface is maintained E 相界面 = σ 内表面 / ε 0=0.01 C / m 2 / 8.85×10 -12 C 2 ‧N -1 ‧m -2 ≈10 9 V / m. At the same time, the anion Cl in the solution system is electro-adsorbed on the outer surface of the positive electrode plate (the original negative electrode plate). - ions, whose surface charge density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the positive electrode interface; the negative electrode plate (the original positive electrode plate) electrically adsorbs the cation Na in the solution system on the outer surface + ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the negative electrode interface.

[0099] As mentioned above, when the surface charge density of the electrode is σ 极化 0.01 C / m 2 When Cl - ions and Na + ‧4H2O hydrated ions are far from covering the entire outer surface of the electrode, but only occupy a small part of the outer surface area of ​​the electrode. In other words, in addition to the small area of ​​the outer surface of the positive and negative electrodes where these anions and cations are electrically adsorbed, the outer surface of the electrode between these electrically adsorbed anions and cations also adsorbs various other polarized molecules or molecules of the hydrogen peroxide aqueous solution system, including H2O2 molecules, H2O molecules and C 22 H 24 N2O8 molecules. It should be noted that these H2O2 molecules, H2O molecules and C 22 H 24N2O8 molecules will not only be adsorbed on the outer surface of the positive electrode, but also on the outer surface of the negative electrode. And all ions, polarized molecules or molecules adsorbed on the outer surface of the positive and negative electrodes will be in the electrode interface electric field ( E 相界面 ≈10 9 V / m), which includes H2O2 molecules and C 22 H 24 N2O8 molecules. According to the transition state theory of chemical reaction kinetics, the activated H2O2* and C 22 H 24 N2O8* molecules will more easily cross the transition energy barrier than the original unactivated molecules to undergo a complete degradation chemical reaction and generate product molecules such as CO2*, H2O* and NO2*. The generated products are also adsorbed on the outer surface of the positive and negative electrodes. That is: at the electrode interface electric field E 相界面 ≈10 9 Under the action of V / m, the following complete degradation chemical reaction will occur on the outer surface of the positive and negative electrodes: C 22 H 24 N2O8* + 52H2O2* = 22CO2* + 64H2O* + 2NO2* At the same time, due to the polarization electric field inside the bulk phase of the solution E 内极化 With external electric field E 外 The electric fields cancel each other out, and there is no net electric field in the bulk phase of the hydrogen peroxide aqueous solution system, and the bulk phase is still in the normal state of tetracycline degradation process.

[0100] It should be noted that in the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The reverse voltage is boosted to the maximum voltage of -40 V and maintained for a period of time. During the degradation of tetracycline-contaminated wastewater by hydrogen peroxide aqueous solution system, the capacitance of the double electric layer at the electrode plate interface is C 双电层 It is possible that the change in the solution state may cause the Δ U 电极板 Similar to the previous example, the “pressure control device” can automatically maintain the “control capacitance” ( Figure 2 (8) Actual voltage Δ U 控制电容 Stable at the set voltage Δ U 设定= 40 V. Accordingly, the charge of the "control capacitor" can be maintained stable at 0.01 C, while the positive and negative electrode plates ( Figure 2 The charge density on the inner surface of the positive and negative electrode plates is precisely controlled when the state of the solution system changes. σ 内表面 Maintained at 0.01 C / m 2 Nearby, that is, when the state of the solution system changes, the electric field strength at the electrode interface is maintained E 相界面 is 10 9 V / m or so.

[0101] (7) Then the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage drops to zero instantaneously and is maintained at zero for a period of time. The zero pressure maintenance time is determined by the actual experiment of electrocatalysis in the process of degrading tetracycline-contaminated wastewater with hydrogen peroxide aqueous solution. Figure 2 The voltage Δ in (8) U 控制电容 At the beginning, it is -40 V, that is, there is Δ U 控制电容 <Δ U 设定 =0. The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "increase" signal, which controls the power supply (such as Figure 2 (11)) Actual output voltage Δ U 电源 From -40 V + Δ U 电极板 +Δ U 电阻 It starts to increase rapidly from negative value to zero. At this time, due to the voltage Δ U 控制电容 =-40 V less than the power supply voltage Δ U 电源 =0, the charge on the "control capacitor" q 电极板 Rapidly release the charge from 0.01C to the power supply in the reverse direction until the charge is completely released q 控制电容 =0 and maintains for a period of time. The voltage of the “control capacitor” Δ U 控制电容 Also increases from negative value to zero, that is, Δ U 控制电容 =Δ U 设定=0. At this time, the "voltage control device" will output the "voltage control signal" as the "hold" signal, controlling the actual output voltage of the power supply Δ U 电源 Keep output zero pressure Δ U 电源 =0 and maintain for a period of time. Correspondingly, when the "control capacitor" quickly releases the charge to the power supply in the reverse direction until the charge is completely released, the positive and negative electrode plates ( Figure 2 The charge on the inner surface of (6) q 电极板 Also synchronously releases rapidly in the reverse direction from 0.01 C until q 电极板 =0, the surface charge density of the positive and negative electrodes σ 内表面 At the same time, from 0.01 C / m 2 Rapidly reduce to σ 内表面 =0, electric field at the interface between positive and negative electrodes E 相界面 Also from 10 9 V / m quickly decreases to E 相界面 = 0 and maintain for a period of time. At the same time, due to the loss of the electric field force, the various activated ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates will return from the activated state to the normal state, and these normal ions, polarized molecules and molecules adsorbed on the outer surface of the positive and negative electrodes will be more easily desorbed and returned to the solution phase without the action of the electric field. There is Cl on the outer surface of the positive electrode plate. - ions, H2O2 molecules, H2O molecules and C 22 H 24 N2O8 molecules, as well as CO2, H2O and NO2 molecules generated after degradation reaction; there is Na on the outer surface of the negative electrode plate. + ‧4H2O hydrated ion, H2O2 molecule, H2O molecule and C 22 H 24 N2O8 molecules, as well as CO2, H2O and NO2 molecules generated after the degradation reaction. At the same time, since the positive and negative electrode plates are processed into agitator blades, the solution system is constantly stirred during the entire process of degrading tetracycline-contaminated wastewater with a hydrogen peroxide aqueous solution system. This technology further accelerates the desorption process of various ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates from the outer surface of the electrode to the bulk phase of the solution. During a period of time when zero pressure is maintained, the charge density on the inner surface of the positive and negative electrode plates remains σ 内表面 =0, the electric field at the interface between positive and negative electrodes remains E 相界面=0, all the ions, polarized molecules and molecules originally adsorbed on the outer surfaces of the positive and negative electrode plates will be completely desorbed, and the hydrogen peroxide aqueous solution system is in the state of normal degradation of tetracycline-contaminated wastewater.

[0102] (8) Subsequently, the “pressure control device” ( Figure 2 (9) Set voltage Δ U 设定 The voltage is slowly increased in the forward direction and the next cycle begins.

[0103] (9) Thus, as the voltage applied to the positive and negative electrode plates changes periodically, and the positive and negative electrode plates processed into the stirrer blades continuously stir in the solution system, the H2O2 molecules and C 22 H 24 N2O8 molecules are continuously activated by the electric field at the electrode interface to become H2O2* molecules and C 22 H 24 N2O8* molecules and complete degradation chemical reactions occur faster on the outer surface of the electrode.

[0104] Example 3

[0105] This embodiment specifically describes the construction of an electric field catalytic system suitable for the chemical industry for synthesizing ammonia in a liquid ammonia solution system containing dissolved nitrogen and hydrogen, based on the content of the invention.

[0106] In the modern chemical industry, ammonia is the main raw material for the fertilizer industry and basic organic chemicals. Synthetic ammonia refers to ammonia directly synthesized from nitrogen and hydrogen under high temperature, high pressure and the presence of a catalyst. It is a basic inorganic chemical process with the following reaction: N2 + 3H2 = 2NH3 However, the current high-temperature, high-pressure process conditions for ammonia synthesis are relatively demanding. Furthermore, thermodynamic calculations show that low temperature and high pressure are more favorable to the equilibrium of the ammonia synthesis reaction. Therefore, converting nitrogen into nitrogen-containing compounds under relatively mild, low-temperature conditions is a hot topic in chemical research. One alternative method is to generate ammonia by chemically reacting nitrogen and hydrogen molecules in a solution under the influence of an electric field. We know that the solubility of nitrogen and hydrogen in water is very low, but their solubility in liquid ammonia solvent is relatively high. For example, at 298 K and 50 atmospheres, the solubility of nitrogen and hydrogen in liquid ammonia is 5.73 l / kg and 4.471 l / kg respectively; at 298 K and 200 atmospheres, the solubility of nitrogen and hydrogen in liquid ammonia is 22.48 l / kg and 20.077 l / kg respectively (Wiebe, R.; Tremearne, TH Solubility of Nitrogen in Liquid Ammonia at 25°from 25 to 1000 Atmospheres. Journal of American Chemical Society, 1933, 55(3): 975–978. Wiebe, R.; Tremearne, TH The Solubility of Hydrogen inLiquid Ammonia at 25, 50, 75 and 100° and at Pressures to 1000 Atmospheres. Journal of American Chemical Society, 1934, 56(11): 2357–2360.). Therefore, here, we use a liquid ammonia solution containing dissolved nitrogen and hydrogen as an example to illustrate the electric field catalysis process when nitrogen molecules and hydrogen molecules react chemically in the solution. Of course, we can also choose other solvents with higher nitrogen and hydrogen solubility and that do not participate in the chemical reaction, depending on the actual experimental conditions. This will be more beneficial for the electric field catalysis of the ammonia synthesis reaction in the solution system.

[0107] The process conditions for the ammonia synthesis reaction in the liquid ammonia solution system targeted by the embodiment are: a temperature of 298 K and a total pressure of 400 atmospheres, a saturated solution of nitrogen and hydrogen in a ratio of 1:3 in the liquid ammonia solution, with a volume concentration of N2 molecules and H2 molecules of approximately 0.54 mol / kg and 1.3 mol / kg, respectively; the single-side area of ​​the face-to-face agitator blades (that is, the single-side surface area of ​​the face-to-face positive and negative electrode plates) A 电极板 Assume 1m 2The liquid ammonia solution containing dissolved nitrogen and hydrogen is a non-electrolyte solution system, and the microscopic particles in the solution system are mainly NH3 molecules, N2 molecules and H2 molecules.

[0108] According to the contents and appended Figure 2 , an electric field catalytic system suitable for the ammonia synthesis reaction in a liquid ammonia solution system containing dissolved nitrogen and hydrogen is constructed according to the following steps.

[0109] First, according to the present invention, we have solved the problem of how to electric field catalyze various chemical reactions in non-electrolyte solution systems with relatively small relative dielectric constants by adding a small molecular weight inert electrolyte to a non-electrolyte solution system to convert it into an electrolyte solution system. A liquid ammonia solution containing dissolved nitrogen and hydrogen is a non-electrolyte solution system with a relative dielectric constant of ε r About 17, much less than 100. We can add a small amount of sodium chloride (NaCl) electrolyte to transform the liquid ammonia solution containing dissolved nitrogen and hydrogen into an electrolyte solution system containing 0.1 mol / kg NaCl (the most suitable concentration condition can be adjusted according to the actual experimental conditions). At the same time, considering that the dielectric constant of the liquid ammonia solvent is relatively small, we can add water with a relatively large dielectric constant as a co-solvent to the solution system, such as adding 20% ​​water (the most suitable addition amount can be adjusted according to the actual experimental conditions) to help sodium chloride (NaCl) better exist in the solution system in the form of ions. In this way, in addition to NH3 molecules, N2 molecules and H2 molecules, the microscopic particles in the entire solution system also contain H2O molecules, cations Na + ‧4H2O hydrated ions and anions Cl - ion.

[0110] Second, according to the present invention, the electrode plate material and the processing of the stirrer blades (such as Figure 2 (6) parts in the figure). According to the properties of the liquid ammonia solution, the inner rod and outer shell of the agitator straight rod can be made of stainless steel (such as Figure 2 (3) and (4) parts in the figure), which have good corrosion resistance and mechanical properties. At the same time, stainless steel with platinum electroplated on the surface can be used to process the positive and negative electrode plates facing each other, and processed into the shape of face-to-face stirrer blades (such as Figure 2 (6) components), respectively mounted on the conductive inner rod and the conductive outer shell of the stirrer straight rod (such as Figure 2 (6) in the figure). They not only have good electrochemical corrosion resistance and mechanical properties, but also, as metal materials, their inner surface charge density can meet the needs of electric field catalysis. The insulating layer between the inner rod and the outer shell of the stirrer straight rod (such as Figure 2 The (5) component) can be made of polytetrafluoroethylene material.

[0111] Third, determine the electric field strength at the electrode interface according to the present invention. E 相界面 and the surface charge density within the electrode σ 内表面 According to the form of the ammonia synthesis reaction in a liquid ammonia solution system containing dissolved nitrogen and hydrogen, the electric field strength required for electric field catalysis can be determined by the strength of the N≡N triple bond and the HH single bond involved. According to the basic principles of physical electricity, under the electric field interaction of unit charge, there is the following relationship between the electric field strength and the electric field interaction energy E = W 作用能 / ( r ‧ e ‧ N 0), where E represents the electric field strength, W 作用能 represents the electric field interaction energy, r represents the bond length, e The unit charge is approximately 1.602×10 -19 C, N 0 means Avogadro's constant is about 6.02×10 23 mol -1 If we approximate the triple chemical bond as three equivalent single bonds, and approximate each single bond as the electric field interaction between two anions and a cation with unit charge, based on the basic principles of physical electricity, we can estimate the electric field strength between each chemical bond based on the actual chemical bond energy and bond length of each chemical bond. According to the relevant textbooks on inorganic chemistry, the bond length and bond energy data of the N≡N triple bond and the HH single bond are as follows: N≡N triple bond 0.1098 nm, 946 kJ / mol; HH single bond 0.074 nm, 436 kJ / mol, and their electric field strengths are estimated to be approximately: 30×10 9 ~90×10 9 V / m; 60×10 9 V / m. These calculations show that the actual electric field strength of these chemical bonds should also be around 10 10 V / m level. According to the actual bond energy of these chemical bonds, it can be inferred that if the external electric field strength is 10 8 ~10 9The V / m range is equivalent to affecting the bond energy of these single chemical bonds by about 0.7~30 kJ / mol, and the total impact of multiple chemical bonds can reach nearly 4~100 kJ / mol. According to the current theory of chemical reaction kinetics, energy changes in this range are sufficient to change the speed of chemical reactions involving molecules containing these chemical bonds. Therefore, it is assumed here that the electrode phase interface electric field strength required for the electric field catalysis reaction of synthesizing ammonia in a liquid ammonia solution system containing dissolved nitrogen and hydrogen is E 相界面 is 10 9 V / m or so (of course, the actual required electric field strength at the electrode interface can be ultimately determined based on actual experiments of electric field catalysis). E 相界面 If the value is too large, it will easily lead to electrolysis reaction of liquid ammonia solution system or electrochemical corrosion of anode electrode plate. According to the physical electrical principle, the surface charge density of electrode is σ 内表面 = ε 0‧ E 相界面 ≈0.01 C / m 2 According to the process conditions of the ammonia synthesis reaction in a liquid ammonia solution system containing nitrogen and hydrogen, the single-side area of ​​the face-to-face stirrer blades as the positive and negative electrode plates is A 电极板 1 m 2 , then the required surface charge density of the electrode is formed σ 内表面 The total charge required q 电极板 is 0.01 C.

[0112] Fourth, determine the actual voltage Δ applied to the positive and negative electrode plates according to the invention content. U 电极板 We know that the solution system mainly contains cations Na + ‧4H2O hydrated ion, anion is Cl - ions. In the electric field catalysis process, Cl - Ions are adsorbed on the outer surface of the positive electrode plate to form a double electrical layer at the positive electrode interface; + ‧4H2O hydrated ions are adsorbed on the outer surface of the negative electrode plate, also forming a double layer at the negative electrode interface. According to the data reported in authoritative references (Lange's Handbook of Chemistry, CRC Press Handbook of Chemistry and Physic), Na + The ionic radius is about 0.099 nm, Cl -The ionic radius is about 0.181 nm. According to the literature (Huang Ziqing. Introduction to Electrolyte Solution Theory (Revised Edition) [M]. Beijing: Science Press, 2010.) + The ionic radius of Na+‧4H2O is 0.095 nm, so we can infer that the hydrated ionic radius of Na+‧4H2O is about 0.358 nm. We estimate it based on the maximum thickness of the double layer at the interface between the positive and negative electrodes of 0.5 nm. When the surface charge density of the control electrode is σ 内表面 About 0.01 C / m 2 , which is equivalent to the electric field strength E of the electrode interface being 10 9 V / m, at this time, the actual voltage applied to the positive and negative electrode plates is Δ U 电极板 The maximum is about 1 V. If we consider the intrinsic capacitance of the electrode interface during the electric field catalysis of the ammonia synthesis reaction in a liquid ammonia solution system containing dissolved nitrogen and hydrogen, C 双电层 It may fluctuate as the ammonia synthesis reaction of the liquid ammonia solution system proceeds, and the surface charge density of the electrode σ 内表面 Also between 0 and 0.01 C / m 2 The range is constantly changing, so the actual voltage applied to the positive and negative electrode plates Δ U 电极板 It should vary in the range of 0 to 1 V.

[0113] Fifth, select the power supply device that provides voltage to the positive and negative electrode plates according to the invention content ( Figure 2 (11)), the power supply can output a periodically changing voltage Δ with controllable magnitude and direction, alternating between zero voltage and a certain voltage. U 电源 , and can be controlled according to the "voltage control signal" ( Figure 2 (10)) to adjust the output voltage Δ U 电源 Considering that the liquid ammonia solution system catalyzed by electric field is conductive and the conductive electrode is directly connected to the solution system, from the perspective of safety, the maximum output voltage of the power supply is selected to be 50 V, and the actual output voltage Δ U 电源 Around 0~40 V (within the 48 V safety voltage range).

[0114] Sixth, according to the invention, a capacitor must be connected in series in the circuit that applies voltage to the positive and negative electrode plates as a "control capacitor" ( Figure 2 (8)). Considering the actual output voltage Δ of the entire circuit power supply U 电源The maximum value is around 40 V. At the same time, the amount of charge that needs to pass through the "control capacitor" q 控制电容 To precisely control the maximum charge of the positive and negative electrode plates in the series circuit q 电极板 is 0.01 C, that is, the surface charge density of the electrode as mentioned above σ 内表面 Maximum 0.01 C / m 2 , then, you can choose a capacitance C 控制电容 The capacitor element with a value of 0.01 C / 40 V = 0.25 mF is used as the "control capacitor". U 控制电容 When the range changes from 0 to 40 V, the amount of charge it contains is q 控制电容 The value of the positive and negative electrodes connected in series with the control capacitor will vary from 0 to 0.01 C. q 电极板 The surface charge density of the electrode will also vary in the range of 0~0.01 C. σ 内表面 Will be in the range of 0~0.01 C / m 2 Range changes, the electric field strength at the electrode interface E 相界面 Will be in 0~10 9 V / m range changes. That is, we can precisely control the voltage Δ of the "control capacitor" U 控制电容 To precisely control the electric field strength at the electrode interface E 相界面 .

[0115] Seventh, according to the appendix to the invention Figure 2 As shown, a resistor is connected in series with the entire circuit ( Figure 2 (7)). Considering that the current of the entire circuit cannot be overloaded during the voltage mutation process. The actual output voltage of the power supply of the entire circuit Δ U 电源 The maximum value is around 40 V. Assuming the maximum current does not exceed 0.1 A, the series resistance of the entire circuit is selected to be 400 Ω.

[0116] Eighth, according to the appendix to the invention Figure 2 As shown, assuming the actual voltage of the resistor is Δ U 电阻 , then the actual output voltage of the power supply Δ U 电源 =Δ U 控制电容+Δ U 电极板 +Δ U 电阻 According to the ninth point below, the actual output voltage Δ U 电源 The size of the voltage control signal ( Figure 2 (10)) to adjust to ensure Δ U 控制电容 =Δ U 设定 .

[0117] Ninth, according to the invention, a "pressure control device" is added to the "control capacitor" to measure its actual voltage ( Figure 2 (9)), and the "pressure control device" can set a certain voltage change form, and according to the set voltage Δ U 设定 Instead of measuring the actual voltage of the "control capacitor" Δ U 控制电容 The relationship between the output "voltage control signal" ( Figure 2 (10)) to the power supply equipment of the entire circuit (such as Figure 2 As shown in (10), the power supply device changes the actual output voltage Δ U 电源 size to ensure the actual voltage of the "control capacitor" Δ U 控制电容 According to the voltage Δ set by the "pressure control device" U 设定 The change mode changes. U 控制电容 <Δ U 设定 When the "voltage control signal" is "increase", the power supply increases the actual output voltage Δ U 电源 , until Δ U 控制电容 =Δ U 设定 ; When Δ U 控制电容 =Δ U 设定 When the “voltage control signal” is “hold”, the power supply is controlled to maintain the actual output voltage Δ U 电源 ; When Δ U 控制电容 >Δ U 设定 When the "voltage control signal" is "decrease", the power supply is controlled to reduce the actual output voltage Δ U 电源 , until Δ U控制电容 =Δ U 设定 .

[0118] Tenth, according to the invention, "pressure control device" (such as Figure 2 (9) Set voltage Δ U 设定 The variation is as follows: first, the voltage is maintained at zero for a period of time, then the voltage is slowly increased in the forward direction to a maximum forward voltage of 40 V and maintained for a period of time; then the voltage is instantly dropped to zero and maintained at zero for a period of time, then the voltage is slowly increased in the reverse direction to a maximum reverse voltage of -40 V and maintained for a period of time; finally, the voltage is instantly dropped to zero again, and the cycle repeats. The specific parameters of the zero-voltage maintenance time, the slow voltage increase time, and the maximum voltage maintenance time are determined by actual experiments on the electrocatalytic synthesis of ammonia in a liquid ammonia solution system containing dissolved nitrogen and hydrogen.

[0119] Eleventh, the reaction process of ammonia synthesis in a liquid ammonia solution system containing dissolved nitrogen and hydrogen by electric field catalysis is described as follows.

[0120] (1) First, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The zero pressure is maintained for a period of time. The zero pressure maintenance time is determined by the actual experiment of electrocatalytic synthesis of ammonia in a liquid ammonia solution system containing nitrogen and hydrogen. At this time, due to the "control capacitance" (such as Figure 2 (8) does not contain any charge, i.e. q 控制电容 =0, its voltage Δ U 控制电容 is also zero, that is, Δ U 控制电容 =Δ U 设定 The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "hold" signal, which controls the power supply (, Figure 2 (11)) maintains the actual output voltage Δ U 电源 =0, that is, the power supply has no output current. At this time, the "control capacitor" ( Figure 2 The amount of charge contained in (8) q 控制电容 Keep it at zero, correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on the inner surface of (6) q 电极板 Also remains zero, that is, the surface charge density inside the electrode σ 内表面Also remains zero, the electrode interface electric field E 相界面 At this time, there are no ions or polarized molecules or other microscopic particles electrically adsorbed on the outer surfaces of the positive and negative electrode plates, and the liquid ammonia solution system is in the state of a normal ammonia synthesis reaction process.

[0121] (2) Then, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The slow pressure increase is in the forward direction, and the slow pressure increase time is determined by the actual experiment of electrocatalysis of ammonia synthesis reaction in a liquid ammonia solution system containing nitrogen and hydrogen. Figure 2 The voltage Δ in (8) U 控制电容 It is zero at the beginning, that is, there is Δ U 控制电容 <Δ U 设定 At this time, the "pressure control device" will output a "voltage control signal" ( Figure 2 (10) is the "increase" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Starting from zero, it increases positively until Δ U 控制电容 =Δ U 设定 So far, that is, the actual output voltage of the power supply Δ U 电源 Start from zero and increase in a positive direction to ensure that the voltage of the "control capacitor" Δ U 控制电容 With the setting voltage Δ U 设定 Slowly increase the voltage in the forward direction. The voltage of the entire circuit has the following relationship: Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 . As the actual output voltage of the power supply Δ U 电源 Starting from zero and increasing in positive direction, the power supply starts to output positive current until the charge contained in the "control capacitor" is q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧Δ U 控制电容Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The amount of charge on (6) q 电极板 Synchronous changes, that is, q 电极板 = q 控制电容 =0.25 mF‧Δ U 控制电容 , that is, the surface charge density of the electrode σ 内表面 = q 电极板 / A 电极板 =0.25 mF‧Δ U 控制电容 / 1 m 2 , the electric field at the electrode interface E 相界面 = σ 内表面 / ε 0=0.25 mF‧Δ U 控制电容 / 1 m 2 / ε 0. At the same time, the outer surface of the positive electrode plate begins to electro-absorb the anion Cl in the liquid ammonia solution system containing 0.1 mol / kg NaCl and 20% water. - ions, whose surface charge density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the positive electrode interface; the cation Na in the liquid ammonia solution containing 0.1 mol / kg NaCl and 20% water begins to be electrically adsorbed on the outer surface of the negative electrode plate. + Hydrated ions, whose surface charge density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the negative electrode interface. In addition, due to the polarization electric field in the bulk phase of the liquid ammonia solution containing 0.1 mol / kg NaCl and 20% water E 内极化 With external electric field E 外The positive and negative electrode plates are processed into stirrer blades, and the solution system is constantly stirred during the entire process of ammonia synthesis reaction in the liquid ammonia solution system containing dissolved nitrogen and hydrogen. This technology greatly accelerates the Cl in the solution phase. - ions and Na + The electrosorption process of hydrated ions and other plasmas from the bulk phase of the solution to the outer surface of the electrode also greatly accelerates the mass transfer process of various other molecules in the solution system between the outer surfaces of the positive and negative electrodes and the bulk phase of the solution.

[0122] (3) Until the “pressure control device” ( Figure 2 (9) Set voltage Δ U 设定 The voltage is boosted to a maximum forward voltage of 40 V and maintained for a period of time. The maximum voltage maintenance time is determined by actual experiments on the electrocatalytic synthesis of ammonia in a liquid ammonia solution system containing dissolved nitrogen and hydrogen. Figure 2 (11)) Actual output voltage Δ U 电源 Also with Δ U 设定 The forward boost voltage continues to increase in the positive direction until the "control capacitor" ( Figure 2 The voltage Δ in (8) U 控制电容 Also boosted to a maximum voltage of 40 V, that is, Δ U 控制电容 =Δ U 设定 =40 V. At this time, the "voltage control device" outputs a "voltage control signal" ( Figure 2 (10) is the “hold” signal, which controls the actual output voltage of the power supply Δ U 电源 Maintain Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 =40 V+Δ U 电极板 +Δ U 电阻 At the same time, the charge contained in the "control capacitor" remains q 控制电容 = C 控制电容 ‧Δ U 控制电容=0.25 mF‧40 V=0.01 C. Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on (6) is also kept as q 电极板 = q 控制电容 =0.01 C, that is, the charge density on the inner surface of the electrode is kept at σ 内表面 = q 电极板 / A 电极板 =0.01 C / 1 m 2 =0.01 C / m 2 , the electric field at the electrode interface remains E 相界面 = σ 内表面 / ε 0=0.01 C / m 2 / 8.85×10 -12 C 2 ‧N -1 ‧m -2 ≈10 9 V / m. At the same time, the anion Cl in the solution system is electro-adsorbed on the outer surface of the positive electrode plate. - ions, whose surface charge density σ 极化 = σ 内表面 =0.01C / m 2 , and form a double electric layer at the positive electrode interface; the cation Na in the solution system is electrically adsorbed on the outer surface of the negative electrode plate + ‧4H2O hydrated ion, its charge surface density σ 极化 = σ 内表面 =0.01 C / m 2 , and form a double electric layer at the negative electrode interface.

[0123] According to the data reported in authoritative references (Lange's Handbook of Chemistry, CRC Press Handbook of Chemistry and Physic), Na + The ionic radius is about 0.099 nm, Cl - The ionic radius is about 0.181nm. According to the literature (Huang Ziqing. Introduction to Electrolyte Solution Theory (Revised Edition) [M]. Beijing: Science Press, 2010.) + The ionic radius of Na is 0.095 nm, so it can be inferred that+ The hydrated ion radius of 4H2O is approximately 0.358 nm. The charge density on the electrode surface is 0.01 C / m 2 , which is equivalent to the Cl on the outer surface of the positive and negative electrodes - ions and Na + ‧The surface density of 4H2O hydrated ions is 6×10 16 pcs / m 2 From this we can calculate that even if Cl is electrosorbed on the outer surface of the positive and negative electrodes, - ions and Na + ‧4H2O hydrated ions are arranged in parallel in a single layer with a surface density of about 6×10 16 pcs / m 2 Cl - ions and Na + ‧The actual area occupied by 4H2O hydrated ions is about 8×10 -3 m 2 / m 2 and 3×10 -2 m 2 / m 2 This shows that when the surface charge density of the electrode is σ 极化 0.01 C / m 2 When Cl - ions and Na + ‧4H2O hydrated ions are far from covering the entire outer surface of the electrode, but only occupy a small part of the outer surface area of ​​the electrode. In other words, in addition to a small area of ​​the outer surface of the positive and negative electrodes where these anions and cations are electrically adsorbed, most of the outer surface of the electrode between these electrically adsorbed anions and cations are also adsorbed with various other polarized molecules or molecules of the liquid ammonia solution system, including NH3 molecules, N2 molecules, H2 molecules and H2O molecules. It should be noted that these NH3 molecules, N2 molecules, H2 molecules and H2O molecules will not only be adsorbed on the outer surface of the positive electrode, but also on the outer surface of the negative electrode. And all ions, polarized molecules or molecules adsorbed on the outer surface of the positive and negative electrodes will be in the electrode interface electric field ( E 相界面 ≈10 9V / m), which includes N2 molecules and H2 molecules that participate in the chemical reaction of synthesizing ammonia. These activated N2 molecules and H2 molecules are represented by "N2*" and "H2*", respectively. According to the transition state theory of chemical reaction kinetics, the activated N2* and H2* molecules that participate in the chemical reaction will more easily cross the transition state energy barrier than the original unactivated molecules to undergo a complete chemical reaction of synthesizing ammonia and generate NH3 molecules. Since the generated products are also adsorbed on the outer surface of the positive and negative electrodes and are under the action of the electrode interface electric field, they are represented by "NH3*". That is: at the electrode interface electric field E 相界面 ≈10 9 Under the action of V / m, the following chemical reaction for synthesizing ammonia will occur on the outer surface of the positive and negative electrodes: N2* + 3H2* = 2NH3* At the same time, due to the polarization electric field inside the bulk phase of the solution E 内极化 With external electric field E 外 The electric fields in the liquid ammonia solution cancel each other out, and there is no net electric field in the bulk phase, which is still in the normal state of the ammonia synthesis reaction process.

[0124] It should be noted that in the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is boosted to a maximum forward voltage of 40 V and maintained for a period of time. During the ammonia synthesis reaction in a liquid ammonia solution system containing nitrogen and hydrogen, the capacitance of the double layer at the electrode plate interface is increased. C 双电层 It is possible that the change in the solution state may cause the Δ U 电极板 If the capacitance of the double layer at the interface between the electrode plates C 双电层 becomes smaller, then Δ U 电极板 becomes larger, then Δ U 电源 <Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 , then, the positive and negative electrode plates ( Figure 2 The charge contained in (6) q 电极板 will be released and become less than 0.01 C, corresponding to the "control capacitance" ( Figure 2 The charge contained in (8) q 控制电容will also be released synchronously and become less than 0.01 C. Then, the voltage of the “control capacitor” Δ U 控制电容 will also decrease, then Δ U 控制电容 <Δ U 设定 =40 V. At this time, the "voltage control device" will output a "voltage control signal" ( Figure 2 (10) is the "increase" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Increases positively until it reaches Δ U 控制电容 Re-equal to Δ U 设定 =40 V, and the charge on the "control capacitor" q 控制电容 The charge on the positive and negative electrodes will increase to 0.01 C. q 电极板 It will also increase and return to 0.01 C. If the capacitance of the double layer at the interface between the electrode plates C 双电层 becomes larger, then Δ U 电极板 becomes smaller, then Δ U 电源 >Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 , then the charge contained in the positive and negative electrode plates q 电极板 The increase becomes greater than 0.01 C, corresponding to the charge contained in the "control capacitor" q 控制电容 It will also increase synchronously to be greater than 0.01 C. Then, the voltage Δ U 控制电容 will also become larger, then Δ U 控制电容 >Δ U 设定 =40 V. At this time, the "voltage control device" will output the "voltage control signal" as a "decrease" signal, and the actual output voltage of the control power supply will be Δ U 电源 Decrease in positive direction until it reaches Δ U 控制电容 Re-equal to Δ U 设定 =40 V, and the charge on the "control capacitor" q控制电容 It will also be reduced to 0.01 C, corresponding to the charge contained in the positive and negative electrode plates. q 电极板 It will also be reduced to 0.01 C. In other words, the "pressure control device" can automatically maintain the actual voltage of the "control capacitor" Δ U 控制电容 Stable at the set voltage Δ U 设定 = around 40 V. Accordingly, the charge of the "control capacitor" can be automatically maintained stable at around 0.01 C. At the same time, the charge on the positive and negative electrode plates in series is synchronously stabilized at 0.01 C, thereby accurately controlling the surface charge density of the positive and negative electrode plates when the state of the solution system changes. σ 内表面 Maintained at 0.01 C / m 2 Nearby, that is, when the state of the solution system changes, the electric field strength at the electrode interface is maintained E 相界面 is 10 9 V / m or so.

[0125] (4) Then the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The pressure drops to zero instantaneously and is maintained at zero for a period of time. The zero pressure maintenance time is determined by the actual experiment of electrocatalytic synthesis of ammonia in a liquid ammonia solution system containing nitrogen and hydrogen. Figure 2 The voltage Δ in (8) U 控制电容 At the beginning, it is 40 V, that is, there is Δ U 控制电容 >Δ U 设定 =0. The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "decrease" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 From 40 V + Δ U 电极板 +Δ U 电阻 At this time, due to the voltage Δ U 控制电容 =40 V greater than the supply voltage Δ U 电源 =0, the charge on the "control capacitor" q 电极板 Rapidly release the charge to the power supply from 0.01C until the charge is completely releasedq 控制电容 =0 and maintains for a period of time. The voltage of the “control capacitor” Δ U 控制电容 Also decreases to zero, that is, Δ U 控制电容 =Δ U 设定 =0. At this time, the "voltage control device" outputs the "voltage control signal" as the "hold" signal, and the actual output voltage of the control power supply is Δ U 电源 Keep output zero pressure Δ U 电源 =0 and maintain for a period of time. Correspondingly, when the "control capacitor" quickly releases the charge to the power supply until the charge is completely released, the charge on the positive and negative electrode plates q 电极板 Also released rapidly from 0.01 C until q 电极板 =0, positive and negative electrode plates ( Figure 2 (6)) Internal surface charge density σ 内表面 At the same time, from 0.01 C / m 2 Rapidly reduce to σ 内表面 =0, electric field at the interface between positive and negative electrodes E 相界面 Also from 10 9 V / m quickly decreases to E 相界面 = 0 and maintain for a period of time. At the same time, due to the loss of the electric field force, the various activated ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates will return from the activated state to the normal state, and these normal ions, polarized molecules and molecules adsorbed on the outer surface of the positive and negative electrodes will be more easily desorbed and returned to the solution phase without the action of the electric field. There is Cl on the outer surface of the positive electrode plate. - ions, NH3 molecules, N2 molecules, H2 molecules and H2O molecules, as well as NH3 molecules generated by the synthesis of ammonia; there is Na on the outer surface of the negative electrode plate. + ‧4H2O hydrated ions, NH3 molecules, N2 molecules, H2 molecules and H2O molecules, as well as NH3 molecules generated by the ammonia synthesis reaction. At the same time, since the positive and negative electrode plates are processed into stirrer blades, the solution system is constantly stirred during the entire process of the ammonia synthesis reaction in the liquid ammonia solution system dissolved with nitrogen and hydrogen. This technology further accelerates the desorption process of various ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates from the outer surface of the electrode to the bulk phase of the solution. During a period of time when zero pressure is maintained, the charge density on the inner surface of the positive and negative electrode plates remains σ 内表面=0, the electric field at the interface between positive and negative electrodes remains E 相界面 =0, all the ions, polarized molecules and molecules originally adsorbed on the outer surfaces of the positive and negative electrode plates will be completely desorbed, and the liquid ammonia solution system is in the state of normal ammonia synthesis reaction process.

[0126] (5) Then, the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is slowly increased in the reverse direction (negative value). The time of the slow increase is determined by the actual experiment of electrocatalysis of ammonia synthesis reaction in a liquid ammonia solution system containing nitrogen and hydrogen. Figure 2 The voltage Δ in (8) U 控制电容 It is zero at the beginning, that is, there is Δ U 控制电容 >Δ U 设定 The "pressure control device" will output a "voltage control signal" ( Figure 2 (10)) is the "decrease" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Start from zero and increase in the opposite direction (negative value) until it increases in the opposite direction to Δ U 控制电容 =Δ U 设定 So far, that is, the actual output voltage of the power supply Δ U 电源 Start from zero and increase in reverse to ensure that the voltage of the "control capacitor" Δ U 控制电容 With the setting voltage Δ U 设定 Slowly increase the voltage in the reverse direction. The voltage of the entire circuit has the following relationship: Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 . As the actual output voltage of the power supply Δ U 电源 Starting from zero, the power supply starts to output current in the reverse direction until the charge contained in the "control capacitor" is q 控制电容 = C 控制电容 ‧Δ U 控制电容 =0.25 mF‧Δ U 控制电容Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The amount of charge on (6) q 电极板 = q 控制电容 =0.25 mF‧Δ U 控制电容 , that is, the surface charge density of the electrode σ 内表面 = q 电极板 / A 电极板 =0.25 mF‧Δ U 控制电容 / 1 m 2 , the electric field at the electrode interface E 相界面 = σ 内表面 / ε 0=0.25 mF‧Δ U 控制电容 / 1 m 2 / ε 0. At the same time, the outer surface of the positive electrode plate (the original negative electrode plate) begins to electro-absorb the anion Cl in the liquid ammonia solution system containing 0.1 mol / kg NaCl and 20% water. - ions, whose surface charge density σ 极化 = σ 内表面 =0.25mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the positive electrode interface; the outer surface of the negative electrode plate (the original positive electrode plate) begins to electro-adsorb the cation Na in the liquid ammonia solution system containing 0.1 mol / kg NaCl and 20% water. + Hydrated ions, whose surface charge density σ 极化 = σ 内表面 =0.25 mF‧Δ U 控制电容 / 1 m 2 , and form a double electric layer at the negative electrode interface. In addition, due to the polarization electric field in the bulk phase of the liquid ammonia solution containing 0.1 mol / kg NaCl and 20% water E 内极化 With external electric field E 外The positive and negative electrode plates are processed into stirrer blades, and the solution system is constantly stirred during the entire process of ammonia synthesis reaction in the liquid ammonia solution system containing dissolved nitrogen and hydrogen. This technology greatly accelerates the Cl in the solution phase. - ions and Na + The electrosorption process of hydrated ions and other plasmas from the bulk phase of the solution to the outer surface of the electrode also greatly accelerates the mass transfer process of various other molecules in the solution system between the outer surfaces of the positive and negative electrodes and the bulk phase of the solution.

[0127] (6) Until "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The voltage is reversed and boosted to a maximum voltage of -40 V and maintained for a period of time. The maximum voltage maintenance time is determined by the actual experiment of electrocatalysis of ammonia synthesis reaction in a liquid ammonia solution system containing dissolved nitrogen and hydrogen. Figure 2 (11)) Actual output voltage Δ U 电源 Also with the voltage Δ U 设定 The reverse boost voltage continues to increase in the reverse direction until the "control capacitor" ( Figure 2 The voltage Δ in (8) U 控制电容 It is also reverse-boosted to a maximum voltage of -40 V, that is, there is Δ U 控制电容 =Δ U 设定 =-40 V. At this time, the "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "hold" signal, which controls the power supply ( Figure 2 (11)) Actual output voltage Δ U 电源 Maintain Δ U 电源 =Δ U 控制电容 +Δ U 电极板 +Δ U 电阻 =-40 V+Δ U 电极板 +Δ U 电阻 At the same time, the charge contained in the "control capacitor" remains q 控制电容 = C 控制电容 ‧Δ U 控制电容=0.25 mF‧40 V=0.01 C. Correspondingly, the positive and negative electrode plates in the series circuit ( Figure 2 The charge on (6) also remains q 电极板 = q 控制电容 =0.01 C, that is, the charge density on the inner surface of the electrode remains s 内表面 = q 电极板 / A 电极板 =0.01 C / 1 m 2 =0.01 C / m 2 , the electric field at the electrode interface is maintained E 相界面 = s 内表面 / e 0=0.01 C / m 2 / 8.85×10 -12 C 2 ‧N -1 ‧m -2 ≈10 9 V / m. At the same time, the anion Cl in the solution system is electro-adsorbed on the outer surface of the positive electrode plate (the original negative electrode plate). - ions, whose surface charge density s 极化 = s 内表面 =0.01 C / m 2 , and form a double electric layer at the positive electrode interface; the negative electrode plate (the original positive electrode plate) electrically adsorbs the cation Na in the solution system on the outer surface + ‧4H2O hydrated ion, its charge surface density s 极化 = s 内表面 =0.01 C / m 2 , and form a double electric layer at the negative electrode interface.

[0128] As mentioned above, when the surface charge density of the electrode is s 极化 0.01 C / m 2 When Cl - ions and Na +‧4H2O hydrated ions are far from covering the entire outer surface of the electrode, but only occupy a small part of the outer surface area of ​​the electrode. In other words, in addition to a small area of ​​the outer surface of the positive and negative electrodes where these anions and cations are electrically adsorbed, most of the outer surface of the electrode between these electrically adsorbed anions and cations are also adsorbed with various other polarized molecules or molecules of the hydrogen peroxide aqueous solution system, including NH3 molecules, N2 molecules, H2 molecules and H2O molecules. It should be noted that these NH3 molecules, N2 molecules, H2 molecules and H2O molecules will not only be adsorbed on the outer surface of the positive electrode, but also on the outer surface of the negative electrode. And all ions, polarized molecules or molecules adsorbed on the outer surface of the positive and negative electrodes will be in the electrode interface electric field ( E 相界面 ≈10 9 V / m) are activated, including N2 molecules and H2 molecules involved in the ammonia synthesis reaction. According to the transition state theory of chemical reaction kinetics, the activated N2* and H2* molecules involved in the chemical reaction will more easily cross the transition state energy barrier than the original unactivated molecules to undergo a complete degradation chemical reaction and generate product molecules such as NH3*. The generated products are also adsorbed on the outer surface of the positive and negative electrodes. That is: at the electrode interface electric field E 相界面 ≈10 9 Under the action of V / m, the following chemical reaction for synthesizing ammonia will occur on the outer surface of the positive and negative electrodes: N2* + 3H2* = 2NH3* At the same time, due to the polarization electric field inside the bulk phase of the solution E 内极化 With external electric field E 外 The electric fields in the liquid ammonia solution cancel each other out, and there is no net electric field in the bulk phase, which is still in the normal state of the ammonia synthesis reaction process.

[0129] It should be noted that in the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The reverse voltage is boosted to the maximum voltage of -40 V and maintained for a period of time. During the ammonia synthesis reaction in a liquid ammonia solution system containing nitrogen and hydrogen, the capacitance of the double layer at the electrode plate interface is C 双电层 It is possible that the change in the solution state may cause the Δ U 电极板 Similar to the previous example, the “pressure control device” can automatically maintain the “control capacitance” ( Figure 2 (8) Actual voltage Δ U 控制电容 Stable at the set voltage Δ U设定 = 40 V. Accordingly, the charge of the "control capacitor" can be maintained stable at around 0.01 C, while the positive and negative electrode plates ( Figure 2 The charge density on the inner surface of the positive and negative electrode plates is precisely controlled when the state of the solution system changes. s 内表面 Maintained at 0.01 C / m 2 Nearby, that is, when the state of the solution system changes, the electric field strength at the electrode interface is maintained E 相界面 is 10 9 V / m or so.

[0130] (7) Then the "pressure control device" ( Figure 2 (9) Set voltage Δ U 设定 The pressure drops to zero instantaneously and is maintained at zero for a period of time. The zero pressure maintenance time is determined by the actual experiment of electrocatalytic synthesis of ammonia in a liquid ammonia solution system containing nitrogen and hydrogen. Figure 2 The voltage Δ in (8) U 控制电容 At the beginning, it is -40 V, that is, there is Δ U 控制电容 <Δ U 设定 =0. The "pressure control device" outputs the "voltage control signal" ( Figure 2 (10)) is the "increase" signal, which controls the power supply (such as Figure 2 (11)) Actual output voltage Δ U 电源 From -40 V + Δ U 电极板 +Δ U 电阻 It starts to increase rapidly from negative value to zero. At this time, due to the voltage Δ U 控制电容 =-40 V less than the power supply voltage Δ U 电源 =0, the charge on the "control capacitor" q 电极板 Rapidly release the charge from 0.01 C to the power source in the reverse direction until the charge is completely released q 控制电容 =0 and maintains for a period of time. The voltage of the “control capacitor” Δ U 控制电容 Also increases from negative value to zero, that is, Δ U 控制电容 =Δ U 设定=0. At this time, the "voltage control device" will output the "voltage control signal" as the "hold" signal, controlling the actual output voltage of the power supply Δ U 电源 Keep output zero pressure Δ U 电源 =0 and maintain for a period of time. Correspondingly, when the "control capacitor" quickly releases the charge to the power supply in the reverse direction until the charge is completely released, the positive and negative electrode plates ( Figure 2 The charge on the inner surface of (6) q 电极板 Also synchronously releases rapidly in the reverse direction from 0.01 C until q 电极板 =0, the surface charge density of the positive and negative electrodes s 内表面 At the same time, from 0.01 C / m 2 Rapidly reduce to s 内表面 =0, electric field at the interface between positive and negative electrodes E 相界面 Also from 10 9 V / m quickly decreases to E 相界面 = 0 and maintain for a period of time. At the same time, due to the loss of the electric field force, the various activated ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates will return from the activated state to the normal state, and these normal ions, polarized molecules and molecules adsorbed on the outer surface of the positive and negative electrodes will be more easily desorbed and returned to the solution phase without the action of the electric field. There is Cl on the outer surface of the positive electrode plate. - ions, NH3 molecules, N2 molecules, H2 molecules and H2O molecules, as well as NH3 molecules generated by the synthesis of ammonia; there is Na on the outer surface of the negative electrode plate. + ‧4H2O hydrated ions, NH3 molecules, N2 molecules, H2 molecules and H2O molecules, as well as NH3 molecules generated by the ammonia synthesis reaction. At the same time, since the positive and negative electrode plates are processed into stirrer blades, the solution system is constantly stirred during the entire process of the ammonia synthesis reaction in the liquid ammonia solution system dissolved with nitrogen and hydrogen. This technology further accelerates the desorption process of various ions, polarized molecules and molecules originally adsorbed on the outer surface of the positive and negative electrode plates from the outer surface of the electrode to the bulk phase of the solution. During a period of time when zero pressure is maintained, the charge density on the inner surface of the positive and negative electrode plates remains s 内表面 =0, the electric field at the interface between positive and negative electrodes remains E 相界面 =0, all the ions, polarized molecules and molecules originally adsorbed on the outer surfaces of the positive and negative electrode plates will be completely desorbed, and the liquid ammonia solution system is in the state of normal ammonia synthesis reaction process.

[0131] (8) Subsequently, the “pressure control device” ( Figure 2 (9) Set voltage Δ U 设定 The voltage is slowly increased in the forward direction and the next cycle begins.

[0132] (9) In this way, as the voltage applied to the positive and negative electrode plates changes periodically, and the positive and negative electrode plates processed into agitator blades continuously stir in the solution system, the N2 molecules and H2 molecules in the solution system are continuously activated by the electric field at the electrode interface to become N2* molecules and H2* molecules, and the chemical reaction of synthesizing ammonia occurs faster on the outer surface of the electrode.

Claims

1. A method for electric field catalysis of chemical reactions in electrolyte solution systems, characterized by: Positive and negative electrode plates are placed face to face in the solution system, and voltage is applied to the positive and negative electrode plates. The positive and negative charge layers on the inner surfaces of the positive and negative electrode plates respectively form a positive and negative electrode interface double layer with the anions and cations in the solution electrically adsorbed on the outer surface, and an electrode interface electric field is formed in the interface double layer. The electrode interface electric field is used to activate ions, polarized molecules, molecules and other microscopic particles adsorbed on the outer surface of the electrode.

2. A method for electric field catalysis of chemical reactions in non-electrolyte solution systems, characterized by: By adding an inert electrolyte that can dissociate into anions and cations in the solution and does not participate in chemical reactions to a non-electrolyte solution system, the solution system is converted into an electrolyte solution system. Then, positive and negative electrode plates facing each other are placed in the solution system, and voltage is applied to the positive and negative electrode plates. The positive and negative charge layers on the inner surfaces of the positive and negative electrode plates respectively form a positive and negative electrode interface double layer with the anions and cations in the solution electrically adsorbed on the outer surface, and an electrode interface electric field is formed in the interface double layer. The electrode interface electric field is used to activate ions, polarized molecules, molecules and other microscopic particles adsorbed on the outer surface of the electrode.

3. A method for electric field catalysis of chemical reactions in non-electrolyte solution systems, characterized by: By adding an inert electrolyte that does not participate in chemical reactions and a co-solvent that can help the electrolyte dissociate into anions and cations in the solution to a non-electrolyte solution system, the solution system is converted into an electrolyte solution system. Then, positive and negative electrode plates facing each other are placed in the solution system, and voltage is applied to the positive and negative electrode plates. The positive and negative charge layers on the inner surfaces of the positive and negative electrode plates respectively form a positive and negative electrode interface double layer with the anions and cations in the solution electrically adsorbed on the outer surface, and an electrode interface electric field is formed in the interface double layer. The electrode interface electric field is used to activate ions, polarized molecules, molecules and other microscopic particles adsorbed on the outer surface of the electrode.

4. The method according to claim 1, claim 2, or claim 3, which is applicable to electric field catalysis of chemical reactions in various solution systems, characterized in that: The facing positive and negative electrode plates are processed into facing agitator blades and installed on the agitator of the solution system.

5. The method of electric field catalysis applicable to chemical reactions in various solution systems according to claim 1, claim 2, or claim 3, characterized in that: A periodically changing voltage is applied to the positive and negative electrode plates, alternating between zero voltage and a certain voltage.

6. The method of electric field catalysis for chemical reactions in various solution systems according to claim 5, characterized in that: The periodic voltage change applied to the positive and negative electrode plates is as follows: it starts with zero voltage and is maintained for a period of time, then slowly increases in the forward direction until it reaches the maximum forward voltage and is maintained for a period of time; then it drops to zero voltage instantaneously and is maintained at zero voltage for a period of time, then slowly increases in the reverse direction until it reaches the maximum reverse voltage and is maintained for a period of time; finally, it drops to zero voltage instantaneously again, and then the next cycle is repeated.

7. The method of electric field catalysis for chemical reactions in various solution systems according to claim 1, claim 2, or claim 3, characterized in that: In the circuit that applies voltage to the positive and negative electrode plates, a capacitor is connected in series as a "control capacitor", or other electrical devices equivalent to a capacitor are used as "control capacitors". This "control capacitor" not only prevents the generation of continuous DC current on the positive and negative electrode plates in the same series circuit, thereby preventing continuous electrolysis reactions in the solution system and preventing continuous electrochemical corrosion of the anode electrode; but also controls the "charge amount" contained in the "control capacitor" by controlling the voltage applied to it, thereby controlling the charge amount on the inner surface of the positive and negative electrode plates in the same series circuit, and then controlling the charge density on the inner surface of the electrode plates, and ultimately controlling the electric field strength at the electrode interface generated by the positive and negative electrode plates.

8. The method of electric field catalysis for chemical reactions in various solution systems according to claim 7, characterized in that: There is a circuit to measure the actual voltage of the "control capacitor" Δ U 控制电容 The "pressure control device" can set the voltage change form and can adjust the voltage according to the "set voltage Δ U 设定 "It is to measure the actual voltage of the "control capacitor" Δ U 控制电容 The magnitude relationship between them outputs a "voltage control signal" to the power supply device of the entire circuit, causing the power supply device to change the output voltage Δ U 电源 Size, that is: when Δ U 控制电容 <Δ U 设定 When the "pressure control device" outputs an "increase" control signal to the power supply, the power supply then increases the output voltage Δ U 电源 Until the Δ of "control capacitance" U 控制电容 Equal to Δ U 设定 ; When Δ U 控制电容 =Δ U 设定 When the "pressure control device" outputs a "hold" control signal to the power supply, the power supply then maintains the output voltage Δ U 电源 unchanged; when Δ U 控制电容 >Δ U 设定 When the "pressure control device" outputs a "decrease" control signal to the power supply, the power supply then reduces the output voltage Δ U 电源 Until the Δ of "control capacitance" U 控制电容 Equal to Δ U 设定 .

9. A method for electric field catalysis of chemical reactions in various solution systems according to claim 8, characterized in that "Pressure control device" set voltage Δ U 设定 The variation is as follows: the voltage is maintained at zero for a period of time, then the voltage is slowly increased in the forward direction until it reaches the maximum forward voltage and maintained for a period of time; then the voltage is dropped to zero instantaneously and maintained at zero for a period of time, then the voltage is slowly increased in the reverse direction until it reaches the maximum reverse voltage and maintained for a period of time; finally, the voltage is dropped to zero instantaneously again, and then the next cycle is repeated.

10. The method of electric field catalysis for chemical reactions in various solution systems according to claim 1, claim 2, or claim 3, characterized in that: The facing positive and negative electrode plates are processed into the form of facing stirring blades and installed on the stirrer of the solution system; the power supply that applies voltage to the positive and negative electrode plates can output a voltage with controllable size and direction, alternating between zero voltage and a certain voltage, and periodically changing, and can adjust the size of the power supply output voltage according to the external input "voltage control signal"; a capacitor is connected in series in the circuit that applies voltage to the positive and negative electrode plates as a "control capacitor", or other electrical devices equivalent to a capacitor are used as "control capacitors"; there is a "pressure measuring control device" on the "control capacitor" to measure its actual voltage, and the "pressure measuring control device" can set the voltage change form and adjust the voltage according to the voltage control signal. The relationship between the set voltage and the actual voltage of the "control capacitor" measured by it outputs a "voltage control signal" to the power supply equipment of the entire circuit, so that the power supply equipment changes the output voltage to ensure that the actual voltage of the "control capacitor" changes in accordance with the change method of the voltage set by the "pressure measuring control device"; the voltage change form of the "pressure measuring control device" is: first maintain at zero voltage for a period of time, then start to slowly increase in the forward direction until the maximum forward voltage is maintained for a period of time; then drop to zero voltage instantaneously, and maintain at zero voltage for a period of time, then start to slowly increase in the reverse direction until the maximum reverse voltage is maintained for a period of time; finally drop to zero voltage instantaneously again, and then the next cycle is repeated.

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