Multi-energy field coupled reaction device for material preparation and mechanochemical reactions

Abstract

The present invention belongs to the technical field of nano material preparation and mechanochemical reaction, and specifically relates to a multi-energy field coupling reaction device for material preparation and mechanochemical reaction. The device includes a base, a magnetic field generating electromechanical device, a mechanochemical reaction tank and a magnetic grinding body; the magnetic grinding body is a composite of a permanent magnet and a wear-resistant material, and the permanent magnet is coated with a wear-resistant material. The device can be used to strengthen and improve the existing solvent-free green chemical synthesis routes of mechanical alloying, inorganic material preparation, organic chemical reaction, and polymer chemical reaction. It can also use mechanical energy, magnetic field energy and one or more energy fields of ultrasound, microwave, light energy, high-voltage arc plasma field, and induction electric energy to synergistically couple to design a chemical reaction system that is conducive to reducing activation energy and accelerating reaction speed. The device can be used to study the mechanism of chemical reactions under multi-energy field conditions and is suitable for single-phase, two-phase or multi-phase reaction systems in solid, liquid, and gas phases.

Description

Technical Field

[0001] The invention belongs to the technical field of nano material preparation and mechanochemical reaction, and in particular relates to a multi-energy field coupling reaction device for material preparation and mechanochemical reaction. Background Art

[0002] "Mechanochemical reaction" is also called "mechanical chemical reaction". The development history of mechanochemistry originated in the primitive Stone Age. For example, wheat was ground into powder, house building materials were manufactured, and pottery was made. Throughout human history, the mortar and pestle have always been able to embody ancient alchemy and modern mechanochemical technology. With the development of industrial civilization, various types of ball mills began to be used on the basis of the use of pestles and mortars in ancient times. The principle is to use the movement of the roller-driven grinding balls to apply interfacial mechanical forces to the reagents, which are used for mechanical alloying of metals, synthesis of nanopowders or mechanochemical reactions.

[0003] Any chemical reaction is conditional. During a chemical reaction, the reactant molecules need to overcome energy barriers to be converted into products. The energy required for this process is usually provided by heat, light, pressure or electric potential, which works by changing the distribution of reactants on their ground state potential energy surface or by moving them to the excited state potential energy surface, and crosses the energy barrier to initiate or accelerate the chemical reaction. For example: in the presence of vinegar, cinnabar will replace metallic mercury when ground with a copper mortar and pestle; the conditions for the reaction of halogen elements with hydrogen vary with the elements; calcium carbonate is heated and decomposed into calcium oxide and carbon dioxide; electrolysis of water can produce hydrogen and oxygen; synthesis of ammonia requires pressure, temperature and catalysts; double decomposition reactions require the presence of solvents. Mechanochemical reactions are chemical reactions caused by the direct absorption of mechanical energy by reactants. In a sense, mechanochemical reactions are non-equilibrium reactions that occur when reactants transfer energy through mechanical forces on the surface or boundary of a solid to excite and activate molecules. Compared with the traditional chemical reaction, which requires thermal excitation of molecules or atoms by flames and high temperatures, electron collision excitation in plasma, light excitation of photon-molecule interactions, chemical energy excitation in exothermic chemical reactions, and ion beam excitation in accelerators, chemical reactions stimulated by mechanical energy are an expansion of the above chemical reaction conditions. At present, the scientific community still knows very little about the research on the mechanism of mechanical energy conversion and excitation of molecules or atoms in mechanochemical reactions, which is far from enough.

[0004] Since W. Ostwald (1909 Nobel Prize winner in Chemistry) from the University of Leipzig in Germany, in his German book Handbuchder allgemeinen Chemie Band 1: Die chemische Literatur und die Organisation der Wissenschaft published in 1919, put mechanochemistry on a par with thermochemistry and electrochemistry, and first proposed the term mechanochemistry and added it to the types of reactions triggered by mechanical energy, the development of mechanochemistry has been stagnant until the mid-20th century, with only a few research groups in the world engaged in related work. This was largely due to the fact that the branches of chemistry at that time - organic chemistry, physical chemistry, and polymer chemistry - were in a period of extremely rapid development and expansion, and chemists had no time to pay attention to the less prominent field of mechanochemistry. After the mid-20th century, the situation has improved significantly. In 1984, the International Mechanochemistry Association (IMA) was established; in 1993, the first International Conference on Mechanochemistry and Mechanical Alloying (INCOME) was held in Slovakia.

[0005] Mechanochemistry is an interdisciplinary subject that involves inorganic chemistry, organic chemistry, solid chemistry, mechanomechanics, structural chemistry, physical chemistry, quantum mechanics, and other disciplines. It mainly studies the chemical reactions of solids caused by mechanical forces. These solids can be specifically divided into inorganic compounds, organic small molecules, metals, polymers, and non-metallic elements according to their chemical composition. Compared with conventional chemistry, mechanochemistry has different characteristics: (1) Mechanical forces can induce some chemical reactions that are difficult or impossible to carry out using thermal energy; (2) The mechanochemical reactions of some substances have different reaction mechanisms and speeds from thermochemical reactions; (3) Compared with thermochemistry, mechanochemistry is much less affected by the surrounding environment and is a non-equilibrium reaction; (4) Because mechanical activation changes the thermodynamic properties of some reactants, some mechanochemical reactions can proceed in directions that are thermodynamically impossible under conventional conditions. Mechanochemistry has overturned the traditional concept of chemical reactions in the scientific community and also provided opportunities for exploring new chemical reactions.

[0006] The basic characteristic of mechanochemical phenomena is the coupling between the inertial motion from microscale to macroscale and the instantaneous accumulation and relaxation of macroscopic energy to molecular van der Waals force strain, which leads to the breaking of old chemical bonds and the formation of new chemical bonds. Mechanical force can make the local area reach a plasma-like state in a very short time (on the order of 100 nanoseconds). This high-energy excited state will cause the solid lattice to dissociate, produce defects, and activate to promote the occurrence of chemical reactions. For organic molecules, mechanical force changes the bond angle of covalent bonds in the molecule. This geometric deformation leads to a decrease in the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital, and then chemical reactions occur. In general, the mechanism of action of mechanochemistry has both thermal effects and unique non-thermal effects caused by mechanical forces. Mechanochemical technology provides a general, easy-to-optimize, and scalable method to prepare molecules and materials, and has good applications in the preparation of nanomaterials, intermetallic compounds, cement, and ceramic materials. The method of synthesizing advanced materials by mechanochemical means is usually called "mechanical alloying" (MA mechanicalalloying) or "reaction milling" (RM reaction milling). Now it seems that this description is not very accurate and cannot summarize all the fields involved in mechanochemical reactions. This dynamic energy coupling from macro to micro, across length scales and time scales has also greatly expanded the application and research fields of mechanochemistry. In the field of organic chemistry, mechanochemistry can be used for the synthesis of organic molecules, biomolecules and organometallic compounds; in material chemistry, it can be used for the synthesis and preparation of inorganic materials, metal-organic framework compounds, nanomaterials and various alloys or metal compounds; especially in inorganic chemistry, no solvent is used, chemical reactions can occur only by grinding, milling and stirring, making it the best choice for solvent-free green chemical synthesis. The advantages of mechanochemical methods are environmental friendliness, finer product particle size, higher purity, faster and more thorough reactions. It can be used for solid-solid, solid-liquid, solid-gas and multiphase chemical reactions.

[0007] At present, the equipment for realizing mechanochemical reactions is mainly divided into two categories, one is ball mills, such as planetary mills, stirred mills, and vibrating mills; the other is magnetic grinding devices. Planetary mills, stirred mills, and vibrating mills generate both shear force and impact force. Among them, planetary mills are the most widely used in laboratories. This device is to install two or more self-rotating cylindrical containers on a rotatable disc. During operation, the grinding balls and the samples to be ground are placed in the container, and then the disc and the container rotate in opposite directions. At high speeds, the grinding balls in the container will produce mechanical impact and good friction effects on the samples. The planetary mill was first invented by the German family business Fritsch in 1961. Today, this old company founded in 1920 has been passed down to the fourth generation of the family and is still committed to the development of such instruments. In addition to planetary mills, vibrating mills are also relatively common. This form of mechanical mill was also produced by the German RETSCH company in the 1930s. Its working principle is to put grinding balls and samples in parallel containers, and vibrate the container back and forth in the horizontal direction. Mechanical energy is transmitted through the impact and friction of the grinding balls on the samples. The SPEX series of vibration mills have been selling well for more than 80 years.

[0008] Chinese patent CN102701193A discloses a method for preparing graphene or graphene oxide, which belongs to the technical field of nanomaterial preparation. The preparation method includes wet preparation and dry preparation. The wet preparation is to put carbon material, magnetic steel needle grinding body and solvent into a grinding container, which is sealed; the container is placed in a space with a conversion magnetic field, and peeled off, and a mixture of graphite nano-microsheets and graphene is obtained after peeling; the nano-graphite microsheets-graphene and the steel needle are separated, and a transparent suspension of graphene is obtained after sedimentation and centrifugal separation. The dry preparation is to put carbon material and magnetic steel needle grinding body into a grinding container, which is sealed; the container is placed in a space with a conversion magnetic field, and peeled off, and a mixture of graphite nano-microsheets-graphene dry powder is obtained after peeling. The present invention has the characteristics of high collision frequency, high grinding efficiency and short preparation time.

[0009] Chinese patent CN109825738A discloses a method for preparing a copper-based Cu / C / Ni / TiB2 composite material, which comprises grinding a mixture of copper powder and flake graphite to obtain a Cu / C composite powder; grinding Ni powder to obtain ground Ni powder; preparing TiB2 nanopowder by sol-gel method; mixing the Cu / C composite powder, ground Ni powder and TiB2 nanopowder, adding anhydrous ethanol to obtain a composite solution; pouring the composite solution into a suction filtration funnel, setting two U-shaped permanent magnets with opposite magnetic properties on the outer side of the lower part of the funnel so that the composite solution naturally settles under the action of the magnetic field, and then performing suction filtration and drying to obtain a composite powder; placing the composite powder into a hot pressure furnace mold, and hot pressing and sintering to obtain the composite material. The composite material prepared by the present invention has excellent mechanical properties, wear resistance and electrical conductivity.

[0010] The forces generated by the planetary mill, stirring mill, and vibration mill are mainly mechanical forces such as shear, impact, and friction; Chinese patents CN102701193A and CN109825738A are all stainless steel grinding bodies, with high frequency and high collision efficiency, but are limited to the peeling preparation of sheet materials such as graphite and molybdenum sulfide and the composite preparation of metal powder and graphite. Due to the characteristics of stainless steel grinding bodies, such as low hardness, easy wear, and small collision force, for inorganic materials with a hardness greater than that of the grinding body material, the grinding body is very easy to wear during grinding, introducing impurities to contaminate the sample, and no chemical reaction is involved, so its application range is greatly limited. Summary of the invention

[0011] The purpose of the present invention is to provide a multi-energy field coupling reaction device for material preparation and mechanochemical reaction induced by magnetic field and multi-energy field synergistic coupling. The device can be used to strengthen and improve the existing solvent-free green chemical synthesis routes of mechanical alloying, inorganic material preparation, organic chemical reaction, and polymer chemical reaction. It can also use mechanical energy, magnetic field energy and one or more energy fields of ultrasound, microwave, light energy, high-voltage arc plasma field, and induction electric energy to synergistically couple to design a chemical reaction system that is conducive to reducing activation energy and accelerating reaction speed. The device can be used to study the mechanism of chemical reactions under multi-energy field conditions and is suitable for single-phase, two-phase or multi-phase reaction systems in solid, liquid, and gas phases.

[0012] The device of the present invention mainly comprises the following parts:

[0013] (1) Electromechanical devices for generating magnetic fields;

[0014] (2) Mechanochemical reaction tank;

[0015] (3) Magnetic grinding body;

[0016] (iv) device control panel;

[0017] (I) Electromechanical device for generating magnetic field

[0018] The magnetic field generating electromechanical device is an electromagnet similar to the stator of a motor. The magnetic field strength is controlled by adjusting the magnitude of the current. The distribution of the electromagnets is similar to the distribution of the stator of the motor, N-S-N-S... an even number of them are surrounded in sequence, and the space surrounded by the magnets is the space where the mechanochemical reaction tank is placed. The rotating magnetic field is generated by the NS pole transformation of the electromagnets distributed around. The number of coil turns, the magnitude and direction of the current control the magnetic field strength and polarity transformation, and a rotating magnetic field in a clockwise or counterclockwise direction is formed in sequence. The magnitude of the magnetic field strength on the surface of the electromagnet is designed to be within the range of 0 to 10T.

[0019] The magnetic field generating electromechanical device may also be a permanent magnet, and any form of magnet is acceptable as long as it can form a rotating magnetic field.

[0020] (II) Mechanochemical Reactor

[0021] The mechanochemical reaction tank of the present invention consists of two parts: a sealing cover and a tank body.

[0022] The mechanochemical reaction tank of the present invention is placed in a space where a rotating magnetic field is formed. The magnetic grinding bodies in the mechanochemical reaction tank are acted upon by the attraction and repulsion of the rotating magnetic field, thus generating high-speed motion and high-frequency collisions with each other.

[0023] The opening of the grinding reaction tank can be arranged vertically, inclined or horizontally.

[0024] The grinding reaction tank can be equipped with one or more of a light source generating device, an ultrasonic generating device, a microwave generating device, a high-voltage arc plasma field generating device, an induced electromotive force generating device, an atmosphere control device or a heat exchange device. The multi-energy field includes one or more of mechanical energy, electromagnetic energy, high-voltage arc plasma, light energy, microwave or sound energy generated in a coordinated manner.

[0025] The sealing cover of the mechanochemical reaction tank is provided with a thermocouple sensor device, an atmosphere control device (gas pipe port and gas valve), a pressure gauge, and an anode part of a high-voltage electric arc plasma field.

[0026] The tank body of the mechanochemical reaction tank is provided with a light source generating device, an ultrasonic generating device, a microwave generating device, a cathode part of a high-voltage arc plasma field, and an induced electromotive force generating device can be placed inside the reaction tank.

[0027] The material of the mechanochemical reaction tank is consistent with the material of the magnetic grinding body as much as possible, and wear-resistant ceramic materials and polymer materials can be selected, such as hard wear-resistant ceramics such as aluminum oxide, zirconium oxide, silicon nitride, silicon carbide, and boron nitride, and polymer materials such as polytetrafluoroethylene, epoxy resin, polyurethane, nylon, and melamine wear-resistant materials. When the cathode part of the high-voltage arc plasma field is provided, the tank body must be made of metal material, such as stainless steel and wear-resistant hard alloy steel, which acts as the cathode for generating the high-voltage arc, and a high-voltage arc is generated between the anode and cathode to form a plasma field.

[0028] The bottom of the mechanochemical reaction tank is connected to the base, and a microwave generator and an ultrasonic generator are installed on the base; the reaction tank is surrounded by an electromagnet, and the silicon steel sheet and coil winding of the electromagnet part are wrapped with a steel plate sheath, and the mechanochemical reaction tank is placed in the steel plate sheath. The mechanochemical reaction tank can also be provided with a sealing cover and a heat exchange device, which can achieve sealing pressure resistance or heat exchange as needed.

[0029] The mechanochemical reaction tank can be provided with a light source generating device according to the needs of the reaction. During the mechanochemical reaction, light energy is coupled to excite the reactant molecules for photochemical reaction. The wavelength is selected in the range of visible light to ultraviolet light.

[0030] The mechanochemical reaction tank can be provided with an ultrasonic generator according to the needs of the reaction. During the mechanochemical reaction, the ultrasonic energy is coupled to excite the reactant molecules to accelerate the reaction speed or solve the problem of powder agglomeration in the preparation process of nanomaterials, thereby improving the preparation efficiency. The ultrasonic generator can be provided on a device base connected to the mechanochemical reaction tank.

[0031] The mechanochemical reaction tank can be provided with a microwave generator according to the needs of the reaction, and during the mechanochemical reaction, the microwave energy is coupled to excite the reactant molecules to accelerate the reaction speed. The microwave generator can be provided on a device base connected to the mechanochemical reaction tank.

[0032] The mechanochemical reaction tank can be provided with a high-voltage arc plasma field generating device according to the needs of the reaction, and an anode is provided on the sealing cover of the reaction tank, and the tank body itself is a cathode, and a plasma field occurs between the anode and cathode. When the material undergoing the mechanochemical reaction is in a plasma field formed by plasma generated by gas, the high-speed moving material is in the plasma field, and the material has a mechanical force with the grinding medium and can fully interact with the plasma to form a composite effect, and the reactant molecules are coupled and excited in the form of a plasma field to accelerate the reaction speed.

[0033] The mechanochemical reaction tank is provided with a movable induced electromotive force generating device inside the mechanochemical reaction tank according to the needs of the reaction to realize the generation of induced electromotive force. The induced electromotive force generating device is a squirrel cage-shaped grid, the length of the conductive metal strip of the grid is not greater than the length from the mouth of the grinding tank to the bottom, and the diameter of the grid is not greater than the inner diameter of the grinding tank. A plurality of conductive metal strips on the grid that are parallel to each other and perpendicular to the direction of the magnetic force lines cut the rotating magnetic force lines, causing electromagnetic induction phenomenon and generating instantaneous induced electromotive force. The magnitude of the instantaneous induced electromotive force is proportional to the rate of change of magnetic flux (E=BLVsinθ. Wherein, E is the induced electromotive force, B is the magnetic induction intensity, L is the conductor length, V is the speed of cutting the magnetic force lines, and θ is the angle between the V and B directions). The induced electromotive force at both ends of the conductive metal strip directly affects and induces changes in the binding force between the reactant molecules and atoms, or induces the deformation and polarization of the reactant molecules, which is easy to gain or lose electrons, and plays a catalytic effect of redox, which is used to facilitate the occurrence of redox reactions. The material of the metal strip includes but is not limited to copper, aluminum, iron, stainless steel, and high-strength wear-resistant steel. The shape can be cylindrical or in the form of a long strip. The upper and lower rings are made of insulating ceramics, polymers and other materials. There are through holes on the rings. The conductive metal strip is inserted into the hole to constrain it to form an open squirrel cage shape, and it is directly taken out after the mechanochemical reaction is completed.

[0034] The mechanochemical reaction tank can have gas inlet and outlet pipes under closed conditions according to the needs of the reaction, which are used for atmosphere control and pressure indication of the reaction system. The gas inlet and outlet pipes and the pressure gauge can be arranged on the sealing cover of the mechanochemical reaction tank.

[0035] The mechanochemical reaction tank may have a heat exchange device, namely a heat exchange jacket, according to the needs of the reaction, for temperature control of the reaction system. The heat exchange jacket may be arranged on the periphery of the mechanochemical reaction tank.

[0036] (III) Magnetic grinding body

[0037] The invention discloses a magnetic grinding body for material preparation and mechanochemical reaction, which is a composite of a permanent magnet and a wear-resistant material, wherein the permanent magnet is coated with the wear-resistant material.

[0038] The shape of the magnetic grinding body is spherical, rod-shaped or pebble-shaped.

[0039] The material of the permanent magnet is ferrite permanent magnet or rare earth permanent magnet.

[0040] The material of the wear-resistant material can be selected from existing wear-resistant ceramic materials and polymer materials, ceramic materials such as alumina, zirconia, silicon nitride, silicon carbide, boron nitride and other hard wear-resistant ceramics, polymer materials such as polytetrafluoroethylene, epoxy resin, polyurethane, nylon, melamine wear-resistant materials.

[0041] When the wear-resistant material is a split structure, the wear-resistant material is divided into two halves, and a hole is opened on each half of the wear-resistant material. After the two halves of the wear-resistant material are combined, the shape and size of the hole are adapted to the shape and size of the permanent magnet.

[0042] When the wear-resistant material is a split structure, the wear-resistant material is divided into two halves, a boss is arranged on one half of the wear-resistant material, a hole is opened on the boss, and a groove is arranged on the other half of the wear-resistant material, and a hole is also opened on the groove. After the two halves of the wear-resistant material are combined, the shape and size of the boss are adapted to the shape and size of the groove, and the shape and size of the hole are adapted to the shape and size of the permanent magnet.

[0043] When the wear-resistant material is an integrated structure, a hole is punched on the wear-resistant material blank and then the permanent magnet is placed in the hole; or a hole is punched on the wear-resistant material blank and then the permanent magnet is placed in the hole and then fired or thermally fused.

[0044] (IV) Device control panel

[0045] The control panel of the device of the present invention is the part that controls the functions of the device, and includes: a power control switch, a magnetic field conversion frequency, a magnetic field strength adjustment button, a microwave control switch, an ultrasonic control switch, a light source control switch, a time setting (run, stop, forward and reverse directions), a heat exchange control switch, a tank temperature display, a pressure display, and a high-voltage electric plasma field generation control switch.

[0046] The beneficial effects of the present invention are as follows:

[0047] The magnetic grinding body in the present invention is a composite of a permanent magnet and an outer layer of wear-resistant high-hardness ceramic material or polymer material. The advantage is that the repulsion and attraction between the magnetic grinding body and the external electromagnetic field are greater than those of ferromagnetic stainless steel materials, the jumping distance is farther, and the hardness of the magnetic grinding body is increased, which not only expands the preparation range of nanomaterials, but also increases the grinding space of the mechanochemical reaction tank, and can cover the preparation application range of various original ball mills.

[0048] The device of the present invention comprises a mechanochemical reaction tank, which is surrounded by an electromagnet, which is composed of an electromagnetic coil and an iron core. The three-phase electricity generates an alternating magnetic field. The electromagnet can be used to adjust the magnetic field strength and the magnetic field rotation frequency to meet the needs of chemical reactions. The magnetic grinding body is attracted and repelled by the changing magnetic field, and generates high-speed rotation and high-frequency collision shearing effects thousands of times per minute in the mechanochemical reaction tank. The energy of this strong high-frequency collision is transmitted to the reactant molecules to achieve an efficient grinding effect, which can be used for the rapid preparation of nanomaterials; in addition, the magnetic grinding body greatly increases the contact of the reactant molecules during the high-frequency collision process, and also weakens the binding force of the atoms in the reactant molecules, and also speeds up the progress of the reaction. According to the theory of quantum mechanics, whether a chemical reaction can occur depends on the spin state of the electrons outside the nucleus, and the magnetic field can affect the spin state of the electrons, thereby affecting the progress of the chemical reaction. Therefore, the energy field state is conducive to the occurrence of mechanochemical reactions. Since the outer layer is coated with wear-resistant ceramic materials or polymer materials, whether it is nanomaterial preparation or mechanochemical reaction, the pollution and influence caused by impurities generated by wear are greatly reduced, and solvent-free green chemical reactions are realized.

[0049] The purpose of the present invention is to provide a device for material preparation and mechanochemical reaction by magnetic field induction and multi-energy field synergistic coupling. The magnetic field is generated by a magnetic field generating electromechanical device (electromagnet) distributed around the reaction tank. The magnetic field strength is controlled by adjusting the magnitude of the current. The direction of the current changes the frequency. The magnitude of the magnetic field strength of the electromagnet is controlled at 0-10T, and a rotating magnetic field in a clockwise or counterclockwise direction is formed in turn. The mechanochemical reaction tank is placed in an effective space for forming a rotating magnetic field. The magnetic grinding body in the mechanochemical reaction tank senses the attraction and repulsion of the rotating magnetic field, driving the magnetic grinding body to perform high-frequency rotation and jumping and generate high-frequency collision, shearing, and friction with each other. While having the mechanical energy generated by a traditional ball mill, there is always magnetic field energy in the reaction tank, and the magnetic field energy exerts a force on any material placed therein. The essence of matter is electrical. Whether it is atoms or molecules, they are all negatively charged electrons moving in the positive Coulomb field of their nuclei. Therefore, from the perspective of microscopic mechanism, the magnetic field must have different degrees of influence on the charged microscopic particles (electrons, protons, various ions, etc.) placed in it. Its force is the Lorentz force. The Lorentz force can change the direction of movement of particles and may also induce the gain and loss of electrons and the polarization deformation of molecules. Chemical reaction is the process of breaking and forming chemical bonds accompanied by changes in the state of electron movement. The breaking of each old bond and the formation of a new bond are the results of the splitting and superposition of orbits. The state of the orbit and the change trend are directly related to the possibility of chemical bond exchange and the stability of the formed bonds. If the deformation occurs in the direction that is conducive to orbital superposition, it can enhance the delocalization effect that is crucial to the reaction system, reduce the activation energy and accelerate the chemical reaction. In addition to affecting the extension state of the front-line orbit, the magnetic field may also produce a polarization effect due to deformation, affecting the speed and difficulty of its dissociation, thereby affecting the speed of chemical reactions and making certain reactions that cannot occur under current conditions possible.

[0050] The present invention is a device for material preparation and mechanochemical reaction by magnetic field induction and multi-energy field synergistic coupling, wherein a mechanochemical reaction tank is installed in a space where a rotating magnetic field is formed, and the magnetic grinding body in the mechanochemical reaction tank is subjected to the attraction and repulsion of the rotating magnetic field, generating high-speed motion, and under high-frequency collision conditions, due to the substantial increase in energy concentration, the reactants generate local instantaneous high temperature at the collision point, and even generate local micro-electric sparks, forming a local plasma state.

[0051] The device of the present invention comprises a mechanochemical reaction tank, in which a plurality of conductive metal strips parallel to each other and perpendicular to the direction of the magnetic field lines are placed in the mechanochemical reaction tank driven by a rotating magnetic field to form an induced electromotive force generating device, the conductive metal strips cut the magnetic field lines during the rotation of the magnetic field to generate an induced electromotive force, the two ends of the conductive metal strips and the metal grinding bodies that collide at high speed will also produce high-frequency collision contact and disconnection, and the tip discharges to generate a large number of electric sparks, and the positive and negative ends of the induced electromotive force synergistically induce the reactant molecules to gain or lose electrons, weaken the binding force between the reactant molecules and atoms, achieve the change of the reaction path, reduce the reaction conditions, catalyze and accelerate the redox reaction, and have a catalytic effect of redox. The grinding reaction space of the present invention has a high collision frequency between the grinding bodies, which is conducive to sufficient contact of the reactants, and at the same time, there are synergistic effects of energy forms such as magnetic field, mechanical energy, and induced electric energy, which easily generate tip discharge plasma at the moment of collision, which helps to improve the grinding efficiency of preparing nanomaterials, and is conducive to the chemical reactions that cannot occur under conventional conditions to occur in the form of mechanochemical reactions.

[0052] The device of the present invention includes a mechanochemical reaction tank. The magnetic grinding body in the reaction tank is attracted and repelled by the conversion magnetic field, and a high-frequency collision shearing effect is generated in the reaction tank. Under the action of electromagnetic field energy and mechanical energy field, a light source can be added to the mechanochemical reaction tank to generate light energy. The photon energy excites and activates molecules, and synergistically promotes the occurrence of related chemical reactions. While carrying out the mechanochemical reaction, the energy irradiation of different bands required for some photochemical reactions can be solved, and the occurrence of mechanochemical reactions can be synergistically promoted, so as to realize reactions that cannot be carried out under traditional conditions and design and explore new chemical reactions and their conditions.

[0053] The device of the present invention comprises a mechanochemical reaction tank, and the magnetic grinding body in the reaction tank is attracted and repelled by the conversion magnetic field, and a high-frequency collision shearing effect is generated in the reaction tank. Under the condition of having electromagnetic field energy and mechanical energy field, the mechanochemical reaction tank can also be equipped with an ultrasonic function, so that while the mechanochemical reaction is being carried out, the ultrasonic energy transfer required by some chemical reactions can be solved, and the occurrence of the mechanochemical reaction can be promoted by synergistic excitation. If solid matter participates in the reaction, ultrasonic energy can be used to solve the agglomeration problem of powders at the nanoscale, and the preparation quality of nano powders can be improved by synergistic action with mechanical energy and magnetic field energy, or the reactant molecules can be excited by the assistance of ultrasonic energy, so as to realize the reaction that cannot be carried out under traditional conditions and design and explore new chemical reaction mechanisms.

[0054] The device of the present invention includes a mechanochemical reaction tank. The magnetic grinding body in the reaction tank is attracted and repelled by the conversion magnetic field, and a high-frequency collision shearing effect is generated in the reaction tank. Under the conditions of having electromagnetic field energy and mechanical energy field, a microwave function can be added to the mechanochemical reaction tank to achieve the simultaneous transfer of energy to the reactant molecules through microwave energy transfer, mechanical energy, and magnetic field energy during the mechanochemical reaction, and synergistically excite and promote the occurrence of mechanochemical reactions, thereby achieving reactions that cannot be carried out under traditional conditions and designing and exploring new chemical reactions and their conditions.

[0055] The device of the present invention comprises a mechanochemical reaction tank, and the magnetic grinding body in the reaction tank is attracted and repelled by the conversion magnetic field, and a high-frequency collision shearing effect is generated in the reaction tank. Under the action of electromagnetic field energy and mechanical energy field, high-voltage arc plasma field energy can also be added in the mechanochemical reaction tank, and a plasma generator for generating a plasma field in the grinding tank space is provided, and the plasma generator comprises a plasma power supply, and the plasma field is located between the anode and the cathode of the plasma power supply. The synergistic effect of plasma and grinding mechanical energy makes it very easy for the powder to reach the nanometer scale under the mechanism of "melting-heat explosion-quenching"; at the same time, the high-voltage arc plasma can also cause the lattice of the powder particles to produce various defects such as dislocation, atomic vacancies and lattice distortion, and these defects greatly improve the activity of the powder. In the plasma field, the active material produces a synergistic coupling between mechanical energy, magnetic field energy and plasma, thereby greatly improving the efficiency of grinding, and through the assistance of high-voltage arc plasma energy, the reactant molecules are excited, and reactions that cannot be carried out under traditional conditions are realized, and new chemical reaction mechanisms are designed and explored. The above-mentioned additional induction electric energy, light energy, sound wave energy (microwave, ultrasound), high voltage arc plasma, etc. can add one or two or more of the above energy fields to the mechanical energy and magnetic field energy for synergistic coupling to promote the occurrence of chemical reactions. Due to the substantial increase in energy concentration, under high-frequency collision conditions, the synergistic coupling of multiple energy fields produces local instantaneous high temperatures, and the control of system temperature depends on the heat exchange mechanism of the equipment.

[0056] The mechanochemical reaction tank is equipped with an additional heat exchange function, and a thermocouple is set to monitor the reaction temperature in the reaction tank. While the mechanochemical reaction is in progress, the heat exchange required for part of the mechanochemical reaction that releases or absorbs heat can be solved, thereby increasing the reaction speed or improving the preparation efficiency.

[0057] The mechanochemical reaction tank is provided with a pressure indication function to realize that, while the mechanochemical reaction is being carried out, the need for gas to participate in some mechanochemical reactions can be solved, thereby increasing the reaction speed or improving the preparation efficiency.

[0058] In summary, the present invention also provides a grinding reaction device with rotating magnetic field control and multi-energy field synergistic coupling for material preparation and mechanochemical reaction. One way in which the mechanochemical method has obvious advantages over solution-based reactions is non-equilibrium reaction, which has fast reaction, high conversion rate, and is easy to achieve green chemical manufacturing without solvent participation. On the basis of existing reaction conditions such as heating, radiation, catalysis and electrochemistry, the device has the mechanical energy, heat exchanger and atmosphere pressure conditions of a high-energy ball mill. It can also apply one or two or more energy fields of ultrasound, microwave, light energy, induced electromotive force, and high-voltage arc plasma in the grinding space controlled by the corresponding magnetic field according to the needs of the reaction type. The synergistic coupling supplements the activation method that promotes the occurrence of chemical reactions. It can not only be used for mechanical alloying, nanopowder preparation and flaky metal powder preparation, but also can be widely used in inorganic material synthesis, organic compound synthesis, photochemical reaction, polymerization reaction and chemical reactions that cannot be completed under conventional conditions. Through the synergistic coupling of one or two or more energy fields including mechanical force / magnetic field / induced potential / light / microwave / ultrasound / heat exchange / plasma field, research and explore new chemical reaction mechanisms under the conditions of synergistic coupling of multiple energy fields, which is applicable to solid-solid, solid-liquid, solid-gas two-phase or multi-phase reaction systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 It is a schematic diagram of the structure of the magnetic grinding body of the present invention;

[0060] Figure 1 -a is a schematic diagram of the structure of a magnetic grinding body with a pebble-like split structure;

[0061] Figure 1 -b is a schematic diagram of a magnetic grinding body structure with a pebble-like split structure having bosses and grooves;

[0062] Figure 1 -c is a schematic diagram of the structure of a pebble-shaped magnetic grinding body;

[0063] Figure 1 -d is a schematic diagram of the structure of a spherical magnetic grinding body;

[0064] Figure 1 -e is a schematic diagram of the structure of a magnetic grinding body with a pebble-like integrated structure;

[0065] Figure 1 -f is a schematic diagram of the structure of a rod-shaped magnetic grinding body;

[0066] Figure 2 It is a schematic diagram of the structure of the device of the present invention;

[0067] Figure 3 is a schematic diagram of the structure of a device with a controller;

[0068] Figure 4It is a structural schematic diagram of the disc of the present invention;

[0069] Figure 5 It is a three-dimensional structural schematic diagram of the disc of the present invention;

[0070] Figure 6 It is a structural schematic diagram of the tank body of the mechanochemical reaction tank of the present invention;

[0071] Figure 7 It is a schematic diagram of the three-dimensional structure of the sealing cover of the mechanochemical reaction tank of the present invention;

[0072] Figure 8 It is a structural schematic diagram of the sealing cover of the mechanochemical reaction tank of the present invention;

[0073] Fig. 9 It is a structural schematic diagram of a sealing cover of a mechanochemical reaction tank with a high-voltage electrode mounting hole according to the present invention;

[0074] Fig.10 It is a structural schematic diagram of a mechanochemical reaction tank with a sealing cover of a high voltage electrode of the present invention;

[0075] Fig.11 It is a structural schematic diagram of the induced electromotive force generating device of the present invention;

[0076] Figure 1-11 In: 1. Wear-resistant material; 2. Permanent magnet; 3. Hole; 4. Boss; 5. Groove; 6. Thermocouple sensor device; 7. Atmosphere control device; 8. Pressure gauge; 9. Coil winding; 10. Silicon steel sheet; 11. Base; 12. Mechanochemical reaction tank; 13. Fan; 14. Window; 15. Steel plate sheath; 16. Mounting slot; 17. Device control panel; 18. Disc; 19. Microwave generator; 20. Ultrasonic generator; 21. Thread; 22. Heat exchange medium outlet; 23. Light source generator; 24. Heat exchange medium inlet; 25. Heat exchange device; 26. Light source generator mounting bolt; 27. Thermocouple sensor device mounting hole; 28. Atmosphere control device mounting hole; 29. ​​High-voltage electrode mounting hole; 30. High-voltage electrode; 31. Upper fixing ring; 32. Metal strip; 33. Lower fixing ring;

[0077] 121. tank body; 122. sealing cover;

[0078] 171. Light source switch; 172. Ultrasonic switch; 173. Microwave switch; 174. Magnetic field switch; 175. Power control switch; 176. High-voltage plasma field generation control switch; 177. Temperature and pressure display screen; 178. Fan switch; 179. Heat exchange switch. DETAILED DESCRIPTION

[0079] The present invention is further described below with reference to the embodiments.

[0080] like Figure 1-11 As shown, the multi-energy field coupling reaction device for material preparation and mechanochemical reaction includes a base 11, a magnetic field generating electromechanical device, a mechanochemical reaction tank 12 and a magnetic grinding body.

[0081] The magnetic grinding body used in the embodiment of the present invention is a composite of a permanent magnet 2 and a wear-resistant material 1 , and the permanent magnet 2 is coated by the wear-resistant material 1 .

[0082] The shape of magnetic grinding bodies is spherical, rod-shaped or pebble-shaped.

[0083] The material of the permanent magnet 2 is a ferrite permanent magnet or a rare earth permanent magnet.

[0084] The wear-resistant material 1 is made of wear-resistant ceramic material or polymer material. The wear-resistant ceramic material is aluminum oxide, zirconium oxide, silicon nitride, silicon carbide or boron nitride, etc. The polymer material is polytetrafluoroethylene, epoxy resin, polyurethane, nylon or melamine wear-resistant material, etc.

[0085] The wear-resistant material 1 may be an integrated structure, such as Figure 1 -e, Figure 1 -f. The wear-resistant material 1 can also be a split structure, such as Figure 1 -a, Figure 1 -b, Figure 1 -c, Figure 1 -d; a hole 3 for placing the permanent magnet 2 is opened inside the wear-resistant material 1, and the shape and size of the hole 3 are adapted to the shape and size of the permanent magnet 2.

[0086] When the wear-resistant ceramic 1 is a split structure, the wear-resistant material 1 is divided into two halves, and a hole 3 is opened on each half of the wear-resistant material 1. Figure 1 -a, Figure 1 -c, Figure 1 -d. After the two halves of the wear-resistant material 1 are combined, the shape and size of the hole 3 are adapted to the shape and size of the permanent magnet 2 .

[0087] When the wear-resistant material 1 is a split structure, Figure 1 -b, the wear-resistant material 1 is divided into two halves, a boss 4 is arranged on one half of the wear-resistant material 1, and a hole 3 is opened on the boss 4, and a groove 5 is arranged on the other half of the wear-resistant material 1, and a hole 3 is also opened on the groove 5. After the two halves of the wear-resistant material 1 are combined, the shape and size of the boss 4 are adapted to the shape and size of the groove 5, and the shape and size of the hole 3 are adapted to the shape and size of the permanent magnet 2.

[0088] When the wear-resistant material 1 is an integrated structure, Figure 1 -e, Figure 1-f, after drilling a hole 3 on the wear-resistant material 1 blank and firing it, the permanent magnet 2 is placed in the hole; or after drilling a hole 3 on the wear-resistant material 1 blank, the permanent magnet 2 is placed in the hole 3 and then fired or thermally fused.

[0089] The mechanochemical reaction tank is provided with one or more of a light source generating device 23 , an ultrasonic generating device 20 , a microwave generating device 19 , a high-voltage arc plasma field generating device, an induced electromotive force generating device, an atmosphere control device 7 or a heat exchange device 25 .

[0090] A concave space is opened at the top of the base 11, and a magnetic field generating electromechanical device is installed in the concave space; the magnetic field generating electromechanical device includes a silicon steel sheet 10 and a coil winding 9 wound on the silicon steel sheet, and the silicon steel sheet 10 is vertically and evenly distributed in the concave space; a steel plate sheath 15 is installed at the center position of the magnetic field generating electromechanical device, and a mechanochemical reaction tank 12 is placed in the steel plate sheath 15, and the bottom of the mechanochemical reaction tank 12 is connected to the bottom of the concave space, and the base 11 is also connected to the device control panel 17.

[0091] The device control panel 17 is provided with a light source switch 171; an ultrasonic switch 172; a microwave switch 173; a magnetic field switch 174; a power control switch 175; a high-voltage electric plasma field generation control switch 176; a temperature and pressure display screen 177; a fan switch 178; and a heat exchange switch 179. The device control panel 17 is connected to the corresponding components controlled by it through a circuit. The light source switch 171 is provided with a button for adjusting the wavelength of the light source; the ultrasonic switch 172 is provided with a frequency increase, decrease and ultrasonic time control button; the microwave switch 173 is provided with a wavelength increase, decrease and microwave time control button; the magnetic field switch 174 is provided with a magnetic field conversion frequency, a magnetic field strength adjustment button and a grinding time button; the grinding time setting includes functions such as running, stopping, forward and reverse directions; the heat exchange switch 179 includes a heat exchange medium flow rate increase, decrease and heat exchange time control button.

[0092] A window 14 is provided in the middle of the base 11, and a fan 13 is installed at the bottom of the window 14 for heat dissipation of the magnetic field generating electromechanical device; an inwardly recessed mounting groove 16 is provided at the top of the window 14, a disc 18 is provided in the mounting groove 16, an ultrasonic generating device 20 and a microwave generating device 19 are provided on the disc 18, and the disc 18 is connected to the mounting groove 16 at the top of the window through a thread 21.

[0093] The mechanochemical reaction tank 12 includes a sealing cover 122 and a tank body 121 arranged on the top. A heat exchange device 25 is arranged around the tank body 121. A heat exchange medium outlet 22 is arranged on the upper part of the heat exchange device 25; a heat exchange medium inlet 24 is arranged on the lower part; a light source generating device 23 is arranged at the bottom of the tank body 121; the light source generating device 23 arranged at the bottom of the tank body 121 is installed at the bottom of the tank body 121 through the light source generating device mounting bolts 26.

[0094] The top of the sealing cover 122 is connected to the thermocouple sensor device 6 and the atmosphere control device 7. The pressure gauge 8 is installed on the atmosphere control device 7. The atmosphere control device 7 is a gas pipe port and a gas valve, which can be connected to an external gas cylinder to adjust the pressure. The sealing cover 122 is provided with a thermocouple sensor device mounting hole 27 and an atmosphere control device mounting hole 28; or the sealing cover 122 is provided with a high-voltage electrode 30, and the sealing cover 122 is provided with a high-voltage electrode mounting hole 29, a thermocouple sensor device mounting hole 27 and an atmosphere control device mounting hole 28. The high-voltage electrode 30 and the tank body 121 form a high-voltage arc plasma field generating device.

[0095] The induced electromotive force generating device includes a conductive metal strip 32, an upper fixing ring 31 and a lower fixing ring 33. The conductive metal strip 32 is fixed by the upper fixing ring 31 at the top and the lower fixing ring 33 at the bottom. The upper fixing ring 31 and the lower fixing ring 33 are both provided with through holes for the conductive metal strip 32 to pass through, so as to fix the conductive metal strip 32. The conductive metal strip 32 is cylindrical or long in shape. The upper fixing ring 31 and the lower fixing ring 33 have the same structure, and are made of insulating ceramic or polymer materials.

[0096] Although the present invention has been described in detail by referring to the accompanying drawings and in combination with the preferred embodiments, the present invention is not limited thereto. Without departing from the spirit and essence of the present invention, a person of ordinary skill in the art may make various equivalent modifications or substitutions to the embodiments of the present invention, and these modifications or substitutions shall be within the scope of the present invention. Any person of ordinary skill in the art who is familiar with the present invention may easily think of changes or substitutions within the technical scope disclosed by the present invention, and all of these shall be within the scope of protection of the present invention.

Claims

1. A multi-energy field coupling reaction device for material preparation and mechanochemical reaction, comprising a base (11), characterized in that: It also includes a magnetic field generating electromechanical device, a mechanochemical reaction tank (12) and a magnetic grinding body; the magnetic grinding body is a composite of a permanent magnet (2) and a wear-resistant material (1), and the permanent magnet (2) is coated by the wear-resistant material (1); it is suitable for single-phase, two-phase or multi-phase reaction systems in solid, liquid and gas phases; The magnetic field generating device can form a rotating magnetic field, and the mechanochemical reaction tank (12) is placed in a space where the rotating magnetic field is formed; The mechanochemical reaction tank (12) is also provided with an induced electromotive force generating device, which comprises a plurality of conductive metal strips (32), an upper fixing ring (31) and a lower fixing ring (33). The conductive metal strips (32) are fixed by the upper fixing ring (31) at the top and the lower fixing ring (33) at the bottom. The upper fixing ring (31) and the lower fixing ring (33) are both provided with through holes through which the conductive metal strips (32) can pass, so as to fix the conductive metal strips (32). The conductive metal strips (32) are in the shape of a cylinder or a long sheet. The upper fixing ring (31) and the lower fixing ring (33) have the same structure. The material of the upper fixing ring (31) and the lower fixing ring (33) is insulating ceramic or polymer material. The conductive metal strips (32) are perpendicular to the direction of the magnetic field lines of the rotating magnetic field. During the rotation of the rotating magnetic field, the conductive metal strips (32) cut the magnetic field lines of the rotating magnetic field to generate induced electromotive force.

2. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 1, characterized in that: The shape of the magnetic grinding body is spherical, rod-shaped or pebble-shaped; the material of the permanent magnet (2) is a ferrite permanent magnet or a rare earth permanent magnet; the material of the wear-resistant material (1) is a wear-resistant ceramic material or a polymer material, and the wear-resistant ceramic material is aluminum oxide, zirconium oxide, silicon nitride, silicon carbide or boron nitride; the polymer material is polytetrafluoroethylene, epoxy resin, polyurethane, nylon or melamine wear-resistant material.

3. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 1, characterized in that: The wear-resistant material (1) is of an integrated structure or a split structure; a hole (3) for placing the permanent magnet (2) is provided inside the wear-resistant material (1); the shape and size of the hole (3) are adapted to the shape and size of the permanent magnet (2).

4. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 3, characterized in that: When the wear-resistant material (1) is a split structure, the wear-resistant material (1) is divided into two halves, and a hole (3) is provided on each half of the wear-resistant material (1). After the two halves of the wear-resistant material (1) are combined, the shape and size of the hole (3) are adapted to the shape and size of the permanent magnet (2); or when the wear-resistant material (1) is a split structure, the wear-resistant material (1) is divided into two halves, a boss (4) is provided on one half of the wear-resistant material (1), and the hole (3) is provided on the boss (4), and a groove (5) is provided on the other half of the wear-resistant material (1), and the hole (3) is also provided on the groove (5). After the two halves of the wear-resistant material (1) are combined, the shape and size of the boss (4) are adapted to the shape and size of the groove (5), and the shape and size of the hole (3) are adapted to the shape and size of the permanent magnet (2).

5. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 1, characterized in that: The mechanochemical reaction tank is provided with one or more of a light source generating device (23), an ultrasonic generating device (20), a microwave generating device (19), a high-voltage arc plasma field generating device, an atmosphere controlling device (7) or a heat exchanging device (25).

6. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 1, characterized in that: A concave space is provided at the top of the base (11), and a magnetic field generating electromechanical device is installed in the concave space; the magnetic field generating electromechanical device comprises a silicon steel sheet (10) and a coil winding (9) wound on the silicon steel sheet, and the silicon steel sheet (10) is vertically and evenly arranged in the concave space; a steel plate sheath (15) is installed at the center of the magnetic field generating electromechanical device, a mechanochemical reaction tank (12) is placed in the steel plate sheath (15), and the bottom of the mechanochemical reaction tank (12) is connected to the bottom of the concave space, and the base (11) is also connected to a device control panel (17).

7. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 1 or 6, characterized in that: A window (14) is provided in the middle of the base (11), and a fan (13) is installed at the bottom of the window (14) for dissipating heat from the magnetic field generating electromechanical device; an inwardly recessed mounting groove (16) is provided at the top of the window (14), a disc (18) is provided in the mounting groove (16), an ultrasonic generating device (20) and a microwave generating device (19) are provided on the disc (18), and the disc (18) is connected to the mounting groove (16) at the top of the window via a thread (21).

8. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 1, characterized in that: The mechanochemical reaction tank (12) comprises a sealing cover (122) arranged on the top and a tank body (121); a heat exchange device (25) is arranged around the tank body (121); a heat exchange medium outlet (22) is arranged on the top of the heat exchange device (25); and a heat exchange medium inlet (24) is arranged on the bottom; a light source generating device (23) is arranged at the bottom of the tank body (121); a thermocouple sensor device (6) and an atmosphere control device (7) are connected to the top of the sealing cover (122); and a pressure gauge (8) is installed on the atmosphere control device (7).

9. The multi-energy field coupling reaction device for material preparation and mechanochemical reaction according to claim 8, characterized in that: A thermocouple sensor device mounting hole (27) and an atmosphere control device mounting hole (28) are provided on the sealing cover (122); or a high-voltage electrode (30) is provided on the sealing cover (122), and a high-voltage electrode mounting hole (29), a thermocouple sensor device mounting hole (27) and an atmosphere control device mounting hole (28) are provided on the sealing cover (122), and the high-voltage electrode (30) and the tank body (121) form a high-voltage arc plasma field generating device.

Images