JP2005238204A - Organic or inorganic compound synthesizing apparatus and method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus and a method suitable for conducting plasma reaction in large amount by making molecules of an organic solvent plasmatic. <P>SOLUTION: This organic or inorganic compound synthesizing method employs a gas phase - liquid phase mixing unit made up by comprising a potential difference generating unit for providing a potential difference between the electrodes set up in a reaction vessel with an empty space between them, a unit connected to the above empty space, for charging a liquid organic medium of insulating properties and a minute material, and a unit for discharging the liquid organic medium remaining in a state that the minute material is mixed in above empty space, reaction products, the organic medium and the minute material. By providing a potential difference between the electrodes using the potential difference generating unit, an electron flow is formed via the minute material from the minus electrode to the plus electrode and also, based on the potential difference, the plasma of the organic medium is induced on the surface of the minute material causing ions and free radicals to be produced to cause a plasma reaction to occur, and the reaction products formed by the plasma reaction are taken out of the reaction vessel. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a gas-liquid layer mixing apparatus and a mixing method for generating a gas-liquid layer mixture by generating plasma between electrodes, and an organic or inorganic compound apparatus and method using these apparatuses.

In the conventional plasma polymerization reaction, a potential difference is applied to parallel electrodes, a gas is supplied to a gap between the electrodes, and a polymerization reaction by gas-gas (gas phase-liquid phase) is caused.
Conventionally, the ammonia fixing method is the only industrial means for fixing nitrogen.

  Patent Document 1 describes a method for producing a synthesis gas using a modifying agent for an organic compound, wherein the reforming reaction is performed under low-frequency plasma.

  In Patent Document 2, a substrate holder, an excitation electrode, and an organic reactive substance supply unit are provided in a vacuum chamber, and an excitation electrode surrounding a deposition portion surface of a deposition target substrate held by the substrate holder is disclosed. A plasma polymerization reaction apparatus for generating a polymerized film of an organic reactive material in which a coiled high-frequency electrode and a shield surrounding the coiled high-frequency electrode, or a curved electrode surrounding the surface of the deposition portion of the deposition substrate is provided. Has been.

  Patent Document 3 discloses a method of generating hydrogen gas from a raw material gas containing an organic compound containing hydrogen atoms, a discharge gap is formed by arranging a pair of electrodes facing each other, and at least of these electrodes One is a reduced-diameter electrode whose end facing the discharge gap has a reduced diameter, and the source gas is supplied to the discharge gap so that the gas flow is concentrated in the discharge gap. A hydrogen generation method is described in which a voltage is applied to cause a gas discharge in the discharge gap, the raw material gas is subjected to a discharge treatment, and converted to a hydrogen-containing gas containing hydrogen gas.

In U.S. Patent No. 6,057,049, a plasma fuel converter includes an electrically conductive structure for forming a first electrode, and the second electrode creates a gap with respect to the first electrode in the reaction chamber. Disposed, a fuel-air mixture is introduced into the gap, and a power source is electrode connected to the first and second electrodes, with a voltage in the range of approximately 100 volts to 40 kilovolts and approximately 10 milliamps to 1 amp. Providing a current in the range to generate a glow discharge to regenerate the fuel.
Patent Document 5 describes a method for producing hydrogen by decomposing a nitrogen-free hydrogen-containing compound with low-temperature plasma.

Patent Document 6 consists of subjecting an organic pigment powder having a specific surface area of ^{2 to} 250 m ² / g to inert gas plasma irradiation, and then contacting the irradiated organic pigment powder with a monomer solution to perform graft polymerization. A method for producing an organic pigment having excellent dispersion stability in a solvent in which graft polymerization is carried out in the solvent at a pigment concentration of 0.1 to 13% by weight and a monomer concentration of 0.05 to 20% by weight is described.

JP 2003-137503 A Japanese Patent No. 2911127 JP 2003-212502 A Special table 2003-507321 gazette JP 2002-338203 A JP-A-8-302228

  The present invention uses a liquid organic solvent to dissociate chemical bonds of the organic solvent by plasma, and enables supply of the organic solvent and formation of plasma to be easily performed in a large amount and efficiently. It is an object of the present invention to provide an organic or inorganic compound apparatus and method capable of forming a gas phase-liquid phase mixture at a molecular level.

  The present invention relates to a reaction vessel, a positive electrode and a negative electrode arranged with a space in the reaction vessel, a potential difference generator for applying a potential difference between these electrodes, and an insulating liquid connected to the space A gas phase configured to include a device for introducing a minute substance containing a medium and a reaction gas, a liquid medium that stays in a state where the minute substance is mixed in the space, and a device for deriving the reaction product, the medium, and the minute substance. -Consisting of a liquid phase mixing device, and by applying a potential difference between the electrodes by the potential difference generating device, an electron flow from the minus electrode to the plus electrode is formed through the minute substance, and based on the potential difference Plasma of the solvent and reactive gas is induced on the surface of the minute substance to generate ions and radicals to generate a plasma reaction, which is generated by the plasma reaction. Providing an organic or inorganic compound synthesis apparatus and method for extracting reactant from said derivation device to vessel outside of the reaction vessel.

Further, in the present invention, the medium is an organic medium, and the minute substance is a single bubble of a reactive gas or a bubble containing a minute dielectric, semiconductor, and conductor, and an organic compound synthesis apparatus and method I will provide a.
Further, the present invention provides the organic compound synthesis, wherein the medium is an organic medium, and the minute substance is a single bubble of a reaction gas or a substance containing a minute dielectric, semiconductor, or conductor. Apparatus and methods are provided.

  The present invention also provides a reaction vessel, a plus electrode and a minus electrode arranged with a space in the reaction vessel, a potential difference generator for applying a potential difference between these electrodes, and a mist connected to the space. And the medium is a device for introducing a fine substance containing a reactive gas having good conductivity, a mist-like solvent that stays in a mixed state of a mist-like fine substance in the space, and a reaction product, a solvent, and A gas phase-liquid phase mixing device configured to include a minute substance deriving device, and by applying a potential difference between the electrodes by the potential difference generating device, an electron flow from the minus electrode to the plus electrode is caused to occur in the minute substance. And forming a plasma reaction by inducing plasma of the solvent and reactive gas on the surface of the minute substance based on the potential difference to generate ions and radicals, Providing an organic or inorganic compound synthesis apparatus and method for extracting reactants generated by plasma reaction from said derivation device to vessel outside of the reaction vessel.

ADVANTAGE OF THE INVENTION According to this invention, the apparatus and method suitable for production of a large amount of reactant production by carrying out the plasma formation of a solvent, especially an organic solvent molecule efficiently and easily, and making a large amount of plasma can be provided.
In addition, it is possible to provide an apparatus and a method that can easily convert a reactive gas into a plasma and perform a plasma polymerization reaction efficiently and easily. Along with this, the organic solvent or the inorganic solvent can be easily modified.

  According to this example, a reaction vessel, a positive electrode and a negative electrode arranged with a space in the reaction vessel, a potential difference generating device for applying a potential difference between these electrodes, connected to the space An insulating liquid organic medium and a fine substance introduction device, a liquid organic medium that stays in a mixed state in the space, and a reaction product substance, an organic solvent, and a fine substance lead-out device. An organic compound synthesizing method comprising a phase-liquid phase mixing device, wherein an electron flow from the minus electrode to the plus electrode is formed through the minute substance by applying a potential difference between the electrodes by the potential difference generating device. In addition, plasma of an organic solvent is induced on the surface of the minute substance based on the potential difference to generate ions and radicals to cause a plasma reaction, and the plasma Organic compound synthesis method for extracting reactant produced by the reaction from the derivation device to vessel outside of the reaction vessel is constructed.

Further, a reaction vessel, a plus electrode and a minus electrode arranged with a space in the reaction vessel, a potential difference generator for applying a potential difference between these electrodes, a mist-like organic solvent connected to the space, and A gas phase comprising an introduction device for minute substances, a mist-like organic solvent that stays in a mixed state with mist-like minute substances in the space, and a reaction product substance, an organic solvent, and a derivation device for minute substances. -An organic compound synthesis method comprising a liquid phase mixing device, by forming a current flow from the negative electrode to the positive electrode through the minute substance by applying a potential difference between the electrodes by the potential difference generator; Based on the potential difference, plasma of an organic solvent is induced on the surface of the minute substance to generate ions and radicals to cause a plasma reaction, which is generated by the plasma reaction. Organic compound synthesis methods to retrieve the reaction material from said derivation device to vessel outside of the reaction vessel is constructed.
Here, the size of the minute substance is from nanometer (nm) to micrometer.

  Using a pulse potential difference, the chemical bond of nitrogen in the atmosphere is dissociated by colliding with the electron beam irradiated from the negative electrode and nitrogen in the atmosphere, and a plasma polymerization reaction is performed with the dissociated liquid molecules.

It is shielded by a sealing system, and it is possible to enclose an arbitrary gas and supply an arbitrary liquid other than alcohol to the positive electrode.
An ultrasonic device is provided, and a variable fine vibration can be applied to the device.
It is shielded by a heat insulating material and can be adjusted to an arbitrary temperature.

In order to form an electromagnetic force, it is possible to irradiate the apparatus with a laser or other electromagnetic waves having different wavelengths.
An electrostatic potential or magnetostatic potential can be applied to the device, and the potential can also be time dependent.

  Gas in the mixed material, for example, nitrogen and oxygen, liquid organic substances such as alcohol supplied to the positive electrode, for example, both the gas phase and the liquid phase by discharging or irradiating the alcohol liquid surface A liquid is formed by inducing plasma in molecules, causing nitrogen and oxygen in the gas phase to chemically react with liquid constituent molecules (for example, alcohol), and fixing nitrogen and oxygen into the liquid phase at the molecular level. A polymer polymerization reactor that generates atoms and molecules (for example, hydrogen in the case of alcohol) is provided.

A container sealed with air inside, a negative electrode and a positive electrode disposed in the container, and a mixture of an organic solvent and a fine substance is placed between the two electrodes, and the alcohol layer Equipped with an alcohol supply device for supplying alcohol as a source of the electron, emitting an electron beam from the negative electrode toward the positive electrode, and utilizing the conductivity of the minute substance to the electron flow from the negative electrode to the positive electrode There is provided a gas phase-liquid phase mixing device provided with a voltage application device for forming and colliding the electron beam with the alcohol and nitrogen in the atmosphere to destroy the structure of molecules of the alcohol and the atmosphere. In this case, the alcohol supplied to the end face is made dielectric and functions as a part of the plus electrode.
There are provided an ammonia production method and a hydrogen production method in which hydrogen gas and ammonia are produced simultaneously by the gas-liquid phase reactor method described above.

<Polymer production and use example>:
For example, when used as a fuel cell for an automobile or the like, a plastic having micropores of 50 (cm ³ ) in size (from a density of a grinding wheel to a density level of a loofah) is directly put into a reaction vessel, alcohol, etc. When a potential difference is applied between electrodes filled with an organic solvent having at least hydrogen (H), a surface electron stream is formed through the micropores (with the aid of the micropores). A polymer containing hydrogen is clinging to a microporous plastic as a skeleton. This can be directly used as a fuel cell for an automobile or the like. In order to extract hydrogen, it is possible to generate hydrogen contained in the polymer by applying an electrical signal (by passing a weak alternating current or direct current) or by applying thermal energy.

<Specific examples of organic solvent modification>
As a specific example of modifying the organic solvent, there is mixing at the molecular atom level that generates ions and radicals by mixing with an organic solvent containing at least H, such as sodium chloride and water, and contributes to the formation of an electron current.
In addition, a metal catalyst such as iron (including iron oxide) or copper is positively mixed into an organic solvent containing at least H such as alcohol to activate the electron flow and promote the decomposition of the organic solvent. The efficiency of hydrogen generation and nitrogen fixation can be increased.

  The present invention was made on the basis of the invention described in Japanese Patent Application No. 2003-379886, which was made by the present inventors and filed as a prior application. The contents of the examples described in the above are adopted as they are and are shown below. The contents described in the specification and drawings of the prior application are as follows. Therefore, the prior application examples here are examples described in the specification and drawings of the prior application, and Examples 1 and 2 are examples of the present invention.

[Prior Application Example 1]
Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 shows a gas phase-liquid phase reactor 100 which is an embodiment of the present invention. This gas-liquid phase reactor includes the concept of a gas-liquid phase mixing device. Therefore, the gas phase-liquid phase reaction method described below also includes the concept of the gas phase-liquid phase mixing method.

  In FIG. 1, a gas phase-liquid phase reaction apparatus 100 includes a reaction vessel 1 sealed with an atmospheric gas containing at least nitrogen or argon (Ar) inside, and a negative electrode made of a metal probe inside the vessel. 2, a positive electrode 3 made of a conductor or a semiconductor disposed opposite to the negative electrode 2, and an organic solvent layer (a concept including an organic solvent film) which is liquid on the end face of the positive electrode 3 and is made dielectric. 4, an organic solvent supply device 5 for supplying an organic solvent that is a source of the organic solvent layer 4, and a potential difference applying device 6 that applies a potential difference between both the electrodes 2 and 3.

  Air, that is, the atmosphere, can be enclosed in the reaction vessel 1 as an atmospheric gas, and nitrogen alone, Ar alone, or a mixed gas of nitrogen and oxygen can be enclosed. These gases are sealed from the gas inlet 11 of the reaction gas conduit 22 also received in the reaction vessel 1.

  The negative electrode 2 is placed on the XYZ stage 7. The sealed reaction vessel 1 is also used for adjusting temperature, humidity, and gas humidity.

  The tip of the negative electrode 2 is a sharpened portion 12 and has a sharp needle shape (hereinafter, this sharpened portion may be referred to as a sharpened probe). In other words, the sharpened portion 42 has a reduced diameter toward the tip. In FIG. 1, there is one sharpened portion, but a plurality of these can be installed. A negative electrode having a plurality of sharpened portions 42 is formed. Moreover, it is good not only vertically but also horizontally.

  In the case of this example, the plus electrode 3 is constituted by a metal cylinder. The metal cylinder 12 has an organic solvent introduction hole 13 formed, and the organic solvent layer 4 is formed at the tip of the organic solvent introduction hole 13. The organic solvent layer 4 has a circular shape due to surface tension. Instead of the metal cylinder, the cylinder may be formed of a glass material or a ceramic material. In this case, a metal material or a semiconductor material is attached to the surface of the glass or ceramic cylinder.

  The metal cylinder 12 is held by the organic solvent supply device 5, and the organic solvent is supplied from the organic solvent supply device 5 to the organic solvent introduction hole 13 of the metal cylinder 12.

  The positive electrode 3 is held by the organic solvent supply device 5, is maintained in this holding state and is moved in the XYZ direction by the XYZ stage 14, thereby facing the positive electrode 2 and a small gap between the positive electrode 3. That is, the discharge gap 15 is formed.

  Thus, the metal cylinder 12 functions as the plus electrode 3 and also functions as an organic solvent guiding means. Thus, the organic solvent introduced in contact with the positive electrode 3 exhibits a liquid state and is given a dielectric property. Dielectricity may be imparted before introduction.

  As shown in FIG. 1, an ultrasonic generator 21 can be provided to apply variable fine vibration to the apparatus. The reaction vessel 1 can be adjusted to an arbitrary temperature by shielding it with a heat insulating material. A laser or other electromagnetic wave generator (not shown) having a different wavelength can be provided to irradiate the gap 15 with the electromagnetic wave. In addition, an electrostatic potential or an electrostatic potential can be applied between the gaps, and the potential can be time-dependent.

  When a potential difference is applied between the positive electrode 3 and the negative electrode by the voltage application device (potential difference application device) 6, a non-uniform electric field 44 (FIG. 2) is formed between the metal probe, the organic solvent, and the organic solvent inducing means. Is done. It is desirable to apply the potential difference on a pulse. Therefore, the plus electrode 3 can be said to be a non-uniform pulse electric field applying means. The intensity of the non-uniform electric field 44 is strongest at the sharp end of the metal probe.

  The phenomenon that occurs between the gaps 15 due to the formation of the non-uniform electric field 44 is shown in FIG. FIG. 2 is an explanatory diagram for ease of understanding. Due to the non-uniform electric field 44, the organic solvent having dielectric properties forms an upward flow 32 toward the sharp metal probe as shown in FIG. At that time, the electron beam (electron current) 31 from the sharp metal probe forming the negative electrode and the organic solvent moving to the metal probe as the upward flow 32 and the gas in the atmosphere (for example, nitrogen, argon, oxygen) are collided and dissociated. Can be made. Usually, since the bond energy between substance atoms is 10 eV or less, by applying a potential difference (by applying an electric field or magnetic field), it is possible to accelerate an electron or ion group to a kinetic energy higher than that energy. Then, the collision of these accelerated particles (waves in terms of quantum theory) with organic fluids and atmospheric gases dissociates the bonds of the substance molecules, and induces the subsequent plasma chemical reaction. In particular, collisions between accelerated electrons (accelerated ions), induced ascending fluid, and atmospheric gas cause an avalanche phenomenon, so that molecular dissociation occurs due to the chain equation of the mouse and the reaction can proceed with high efficiency. . The magnitude of this collision energy can be controlled by the magnitude of the applied potential difference, the material and sharpness of the metal probe, the type of organic solvent, the material of the organic solvent guiding means, and the like. As an example, a tungsten sharp probe (tip diameter, several n to several tens of μ) was set to minus, an organic solvent introducing device was set to plus, and electrons were accelerated by a pulse potential difference of 2400 V-15 KHz. Simultaneously, 1-butanol having a relative dielectric constant of 17.1 is electrically attracted to the negative electrode side by this potential difference, and an upward flow (molecular flow, nano flow, or micro flow) can be induced. As the organic solvent guiding means, a conductor, a semiconductor, an insulator, or a composite thereof can be used. In order to change the conductivity (the electron beam inductively irradiated from the minus tungsten electrode), an insulator is used. When a semiconductor is used, a conductor member is installed in the vicinity to secure a distribution circuit (an escape place) for irradiated electrons.

  As shown in FIG. 1, an ultrasonic generator 21 can be provided to apply variable fine vibration to the apparatus. The reaction vessel 1 can be adjusted to an arbitrary temperature by shielding it with a heat insulating material. A laser or other electromagnetic wave generator (not shown) having a different wavelength can be provided to irradiate the gap 15 with the electromagnetic wave. You may make it irradiate an ion beam. An electrostatic potential can be applied between the gaps, and the potential can be time-dependent.

  As described above, a discharge phenomenon occurs between the electrodes 2 and 3. An electron beam (-e) is irradiated from the sharp end of the metal probe toward the organic solvent layer 4. Then, the organic solvent is attracted by the potential difference due to the non-uniform electric field 44 formed between the electrodes 2 and 3 or the electromagnetic force when the electromagnetic field is formed, and the upward flow 32 toward the sharp end of the metal probe, that is, the flow Become. At that time, a phenomenon occurs in which the electron beam 31 from the metal probe forming the negative electrode, the organic solvent moving to the metal probe as an upward flow, and a gas in the atmosphere, for example, nitrogen or oxygen collide.

  FIG. 3 is a photograph showing a state in which an upward flow of the organic solvent is formed toward the sharp end of the metal probe. FIG. 4 is a photograph showing a situation in which an upward flow is generated by changing the shape of the metal probe.

  FIG. 5 is a diagram corresponding to the contents of the photograph of FIG. 4 (a) corresponds to FIG. 3 (a), and FIG. 4 (b) corresponds to FIG. 3 (b). As shown in FIG. 4A, a small lift 32 is seen from the liquid 45 (corresponding to the organic solvent layer 4) at the stage of the upward flow generation. This gradually increases to form the upward flow 32 shown in FIG. 4B, and this upward flow 32 stays as a bulge 34 on the surface of the negative electrode 2 after the chemical bond is dissociated.

  Further, as shown in FIGS. 4A and 4B, the upward flow is formed in a granular form (b) or in a dew shape. And the produced | generated mixture or the reaction material is staying on the sharp probe. Therefore, the upward flow may be a granular flow, not a liquid flow, and is expressed as a flow here.

  In FIG. 1, a generated gas-liquid phase reaction mixture or a chemical substance generated as a result of a plasma polymerization reaction is passed through a reaction gas container 1 through an open passage of a generated gas suction pipe provided around a negative electrode 2. Can be taken out from. In addition, as shown in FIGS. 4A and 4B, the upward flow is formed in the atmospheric gas, so that it is generated in the atmospheric gas as a result of a gas phase-liquid phase mixture or a plasma polymerization reaction. Since a chemical substance is present, a take-out tube for taking out these substances may be attached to the reaction vessel 1. A gas inlet pipe 36 for atmospheric gas is attached to the reaction vessel 1.

  Thus, the organic solvent is directly supplied from the positive electrode 3 to the positive electrode 3 as an upward flow 32, and the electron beam 31 and the upward flow collide with each other very efficiently. Is often done.

  In this way, by applying a pulse potential difference, the rising liquid 32 of the liquid organic solvent supplied to the plus electrode 3 and the electron beam 31 irradiated from the minus electrode 2 collide with the rising liquid. A certain organic solvent dissociates a chemical bond, and nitrogen and oxygen in the atmospheric gas (atmosphere) collide with an electron beam irradiated from the negative electrode 2 to dissociate the chemical bond between nitrogen and oxygen. The dissociated organic solvent and dissociated gas atoms form a mixed state, and then the dissociated liquid molecules and gas atoms undergo a plasma polymerization reaction.

  That is, by using a gas phase-liquid phase mixing device, the atmospheric gas is made to collide with the positive ions accelerated by the negative electrode or the negative ions accelerated by the positive ions using the pulse potential difference. The chemical bonds can be dissociated and the plasma molecules can be reacted with the dissociated liquid molecules.

  As a non-uniform electrode pair, a potential difference is applied between the sharpened negative electrode and the positive electrode covered with liquid, and non-uniform plasma is induced by collision of the electron beam with the upward flow of the liquid and atmospheric gas. By dissociating molecules such as nitrogen and oxygen and liquids such as alcohols) and subsequent new chemical reactions, leaving them at low temperatures and pressures at low cost to liquids such as alcohols Generation (generation) of liquid constituent molecules (for example, hydrogen) is performed while fixing gas (for example, nitrogen).

  FIG. 6 shows how hydrogen is generated from the metal probe. The generated hydrogen was confirmed by SHIMAZUGC-I4BPTF as shown in FIG. FIG. 6A is a photograph showing before hydrogen generation, and FIG. 6B is a photograph showing that hydrogen is being generated.

Thus, the method of ammonia generation is the only industrially conventional method for nitrogen fixation, but it is placed in the atmosphere as in this example, and by discharge between the alcohol positive electrode and the sharp negative electrode, Hydrogen can be generated while fixing nitrogen in the atmosphere. That is, ammonia and hydrogen can be generated. That is, a reaction that reduces nitrogen gas to generate ammonia (NH ₃ ) can be caused.
As described above, the present embodiment is characterized in that a liquid electrode (plus electrode) is used and nitrogen fixation and hydrogen generation are performed by reaction in the atmosphere.

  When the liquid surface (+) supplied with alcohol and the sharp probe (-) which is the sharp part of the metal probe are opposed as both electrodes and a pulse potential difference is applied between them, an electron beam is emitted and simultaneously from the liquid surface Liquid forms an upward flow toward the sharp probe. At that time, the electron beam from the sharp probe (-) collides with the liquid molecules and the nitrogen and oxygen molecules in the atmosphere that thermally moves around the electron beam, thereby destroying the structures of the liquid molecules and the molecules in the atmosphere. In this process, hydrogen is generated from the vicinity of the pointed probe, and nitrogen is chemically bonded therein to cause a plasma polymerization reaction of alcohol.

  The magnitude of this collision energy can be controlled by the magnitude of the applied potential difference, the material and sharpness of the metal probe, the type of organic solvent, the material of the organic solvent guiding means, and the like.

  FIG. 7 shows the transition of the FTIR (Fourier Transform Infrared Spectroscopy) signal when 1-butanol is used as the organic solvent. Clearly the molecular structure is destroyed. In particular, since the signal is broad as a whole, it is confirmed that 1-butanol is polymerized. This polymerization can also be confirmed from the fact that SEM images were obtained in vacuum. The formation of a peak near 1717 indicates that the alcohol was oxidized. Moreover, the possibility that a C═C bond was formed from the formation of a peak near 1650 is shown. In particular, since peaks near 1400, 1650, and 3300 are formed at the same time, it can be understood that the presence of nitrogen atoms is a major cause. FIG. 8 shows the measurement results of the material composition using EPMA (Electron Probe X-ray Microanalyzer). Thus, the nitrogen content was confirmed by constituent element measurement. It is clear that nitrogen was originally not in the 1-butanol molecule and was introduced from the surrounding atmosphere.

[Prior Application Example 2]
In the previous embodiment, the atmosphere gas was sealed in the reaction vessel 1. However, for the purpose of generating hydrogen, the reaction vessel 1 may be in a vacuum state. In this case, by using the previous device, the inside of the container is evacuated, a gap is formed between the negative electrode and the positive electrode arranged in the container, and a potential difference is applied, and the tip of the positive electrode A liquid is formed on the surface, an organic solvent containing hydrogen atoms is supplied to the structural formula from an organic solvent supply device that is made dielectric, and the organic solvent supplied to the tip surface of the plasma electrode is drawn to the negative electrode by a potential difference or electromagnetic force, In the meantime, a hydrogen generation method is configured in which hydrogen atoms of the organic solvent are dissociated from chemical bonds by colliding with an electron beam irradiated from the negative electrode to form hydrogen gas.

[Prior Application Example 3]
FIG. 9 is a diagram showing the configuration of another embodiment. The same components as those in the first embodiment are denoted by the same reference numerals and will not be described repeatedly. For the explanation, the explanation of the first embodiment is used.

  In FIG. 9, a gas phase-liquid phase reaction apparatus 100 includes a reaction vessel 1 sealed with an atmospheric gas containing at least nitrogen inside, and a minus made of a metal probe that is a sharp metal probe inside the reaction vessel. An electrode 2, an organic solvent 51 accommodated opposite to the negative electrode 2, a potential difference application device (voltage application device) 6, and a positive side of the potential difference application device 6 are connected to the reaction vessel 1. The plus electrode 43 is provided.

The reaction vessel 1 is a metallic vessel, but may be an insulator or a semiconductor. In this case, the plus electrode 43 is disposed near the level of the organic solvent.
In addition, a liquid phase supply device 52 and a gas phase supply device 46 that supply the organic solvent so as to communicate with the organic solvent 51 are provided in the reaction vessel 1, and a gas phase supply device 47 is provided in the upper space of the reaction vessel 1. It is provided.

  An insulating portion 48 is provided to insulate between the negative electrode 2 and the positive electrode 43, that is, the reaction vessel 1.

  A gas phase circulation device 49 is provided at the top of the gas phase-liquid phase reaction device 100. The gas-phase circulation device 49 is formed of a hollow pipe, and sucks a reaction product generated by the liquid level plasma reaction and injects and supplies nitrogen, air, and argon. The gas-phase supply device 46 provided at the bottom is provided with holes of nano, micro, or larger diameters to supply many fine bubbles, promote chemical reaction, and supply air, nitrogen, argon, etc. In addition, it works to efficiently promote nitrogen fixation or ammonia generation and hydrogen generation by liquid level plasma reaction.

  A minute gap 15 is formed between the negative electrode 2 and the organic solvent 51. Naturally, a gap is formed between the negative electrode 2 and the positive electrode 43 via the organic solvent 51.

  When the energy of the potential difference application device 6 is increased, the acceleration energy of electrons is increased, and the sharpness of the tip of the negative electrode 2 made of a metal probe is increased, the jelly-like substance can also be changed to the gas phase.

  Furthermore, the kinetic energy of the electrons can be reduced by reducing the power of the potential difference generator or reducing the sharpness of the metal probe, and by reacting incompletely instead of reacting completely in the gas phase, Nitrogen fixation to the particulate material can be performed. In this case, by partial (or incomplete) reaction, priority is given to jelly production, and reaction to the gas phase is suppressed.

  Then, the potential difference applying device 6 is used to connect the negative electrode 2 and the positive electrode to the reaction vessel 1 (or inside the reaction vessel made of the insulator or semiconductor described above and near the liquid surface. A dynamic (time-dependent such as pulse wave or sine wave) or static potential difference is applied between the electrode and the electrode. Then, electrons are irradiated from the negative electrode toward the liquid surface. The electrons travel along the liquid surface to form a circuit that moves to a positive electrode (in the case of a metallic reaction vessel, or an insulator or a semiconductor, a positive electrode provided inside the vessel and near the liquid surface). A liquid level rising portion 50 due to electromagnetic interaction is generated on the liquid surface of the organic solvent 51 facing the negative electrode 2, and plasma is generated by a discharge action by the negative electrode 2 on the liquid level rising portion 50. That is, the minus electrode 2 acts as a plasma generating electrode. At this time, the electrons have energy to dissociate the reaction gas provided from the organic solvent or the gas-phase supply device, so that these molecules are destroyed by a false chain reaction, and ammonia or Generate hydrogen. Further, nitrogen can be fixed in the organic solvent.

  During the liquid surface plasma reaction, the amount of liquid changes, but the distance between the plasma generation minus electrode and the liquid surface is determined by the driving means (not shown) or the liquid phase supply device 52 provided on the plasma generation minus electrode. Control to be constant by supplying liquid.

FIG. 10 shows an example of a reaction product expected to be generated by a plasma polymerization reaction of an organic solvent with nitrogen and oxygen by liquid level plasma. As shown in this example, nitrogen is fixed to the dissociated organic solvent. That is, according to this method, an atmosphere gas containing at least nitrogen is sealed in a container, a gap is formed between the negative electrode and the positive electrode disposed in the container, a potential difference is applied, and the positive electrode is contacted. The organic solvent is supplied from an organic solvent supply device that is liquid and made dielectric, and the supplied organic solvent is attracted to the negative electrode by a potential difference or electromagnetic force, and in the meantime, it collides with an electron beam irradiated from the negative electrode. A nitrogen fixing reaction method and apparatus for dissociating a chemical bond of an organic solvent, dissociating nitrogen atoms from gas molecules of an atmospheric gas, and performing nitrogen reaction for chemically reacting the dissociated nitrogen atoms with the dissociated organic solvent are configured. .
And according to this reaction method, nitrogen can be fixed to alcohol at room temperature and normal pressure to produce ammonia.

Next, examples of the present invention will be described.
The contents of Example 1 are shown in FIG. In the case of this embodiment, the organic or inorganic compound synthesizing apparatus 200 includes a space portion 62 inside a cylindrical reaction vessel 61, two sides disposed on both sides of the space portion 62 and at the end of the reaction vessel 61. Electrode, that is, negative electrode 63 and positive electrode 64, potential difference generating device 65 for applying a potential difference between these two electrodes 63, 64, an organic solvent connected to the space 62, and a fine substance introduction tube containing a reactive gas 66, an introduction device (means) 67 including an organic solvent 70 in the space 62 in which the fine substance 71 is mixed and stays in a mixed state and presents an insulative liquid, the reaction product substance, the organic solvent and the fine substance are discharged. A gas-liquid-phase mixing device including a lead-out device (means) 73 including the discharge pipe 72 and a temperature control device 74 for controlling the temperature of the organic solvent 70 in the space 62 is provided. As an example of an organic or inorganic compound synthesizer, an organic compound synthesizer will be mainly described as an example. Therefore, the contents of the examples are applied to an inorganic compound synthesizer.

  Each of the electrodes 63 and 64 has an outlet function for an organic solvent and a minute substance, and an outlet function for an reactant, an organic solvent, and the minute substance.

  A potential difference is applied between the two electrodes 63 and 64 by the potential difference generating device 65 to form a flow from the minus electrode 63 to the plus electrode to the electron beam, that is, an electron current. In this case, the organic solvent is a material having poor insulation or conductivity (hereinafter, described as insulation. In short, it is used in the sense that it is poorer than the conductivity of a minute substance and is insulative). However, due to the presence of a large number of minute substances, an electron flow circuit due to the short circuit phenomenon of the electron current is formed through the minute substances.

The minute substance can be formed by a single bubble of a reactive gas or a bubble including a minute dielectric, semiconductor, or conductor.
In addition, the minute substance can be formed by mixing a single bubble of a reactive gas or a bubble containing a minute dielectric, semiconductor, or conductor and an inorganic, for example, minute glassy spherical substance.

  Due to the potential difference generated by the potential difference generating device 65, plasma is induced on the surface of the minute substance 71 on which the electron current is formed, alone or together with the reaction gas, to generate ions and radicals. By reaction of ions, radicals, etc., that is, a plasma reaction occurs to generate a reactant. The produced reactant is taken out of the reaction vessel 61 through the discharge pipe 72 together with the flowing organic solvent and fine substance by the outlet device.

  The two electrodes can be configured as metal electrodes, and the metal electrodes are provided with a large number of small holes, and are used for introducing and discharging the solvent and the minute substance to and from the reaction vessel 61.

  As described above, in this example, a minute reaction gas is mixed as a minute substance in the insulating organic solvent 70 which is in a liquid state. The reactive gas is made of, for example, nitrogen, argon, hydrogen, etc., and the reactive gas can be mixed with a dielectric such as glass, or a minute substance such as metal or semiconductor as described above. By mixing them, when an electric potential difference is applied, that is, when an electric potential is applied, an electron flow on the surface (including the interface and creepage) of the minute substance can easily flow. This electron flow activates organic solvent molecules on the surface of the minute substance that is a bubble, and plasma is generated. In this way, a plasma reaction occurs between the organic solvents decomposed along with the plasma generation or the reaction gas converted into a plasma, and a reactive substance is generated.

  In a liquid organic solvent, bubbles consisting of a single reactant gas, or minute derivatives, minute semiconductors, and minute metals are mixed in the bubbles. A potential difference is applied in such a state, and it is easy to flow an electron flow by using the surface of a minute substance bubble, further a minute derivative, a minute semiconductor, and a minute metal, and a large amount of plasma reaction can be performed. .

  When two electrodes 63 and 64 are provided facing each other in the reaction vessel 61, an organic solvent (pre-reaction substance) such as alcohol is sealed in the space 62, and a potential difference is applied to the electrodes 63 and 64, both electrodes 63 , 64 depends on the electrical resistance between the electrodes. In the case of an organic solvent (liquid) as an insulator, a high potential difference is required to cause a plasma organic reaction. In order to obtain high efficiency, an electron current is generated with a low potential difference to cause a plasma organic reaction. For this reason, a large number of fine gas bubbles having good conductivity due to the reaction gas are mixed in the organic solvent 70. If the minute gas bubbles are mixed in one or a combination of glass, semiconductor, metal, etc., a better result can be obtained. You may mix minute substances, such as glass, a semiconductor, and a metal, in the form which is independent from minute gas bubbles, or does not throw in a reactive gas.

  When the minute substance 71 is mixed in the organic solvent 70 in this way, an electron flow easily flows between the two electrodes via the minute substance 71. That is, the electrical conductivity (or electrical resistivity) of the organic solvent 70 that is an insulator can be controlled. The electric conductivity can be adjusted by a reaction gas, a dielectric, a semiconductor, a conductor, or a combination thereof (including a mixing ratio) as a substance to be mixed. In this way, the electron flow in the organic solvent travels from the negative electrode 63 to the positive electrode 64 through the reaction gas, derivative, semiconductor, and conductor surface.

  The plasma reaction is induced by the energy (kinetic energy, electromagnetic energy) of the electron flow through the minute substance, the organic solvent molecules are destroyed (decomposed), the reaction gas molecules are destroyed, ions and radicals are induced, and the plasma A reaction is induced. This plasma reaction is used to create reactive organisms that adhere to and deposit on the surface of minute substances. It will also float in the surrounding organic solvent.

  In FIG. 11, organic solvent molecules and air (examples when used as one of the reaction gases) are induced as plasma containing ions and radicals by an electron flow formed by utilizing a minute substance between two electrodes. Is done. Ions and radicals generated by plasma induction bind to surrounding ions and radicals, and are deposited and deposited on the surface of a minute substance while repeating the binding.

  As the solvent, C (carbon), O (oxygen), H (hydrogen), N (nitrogen), S (sulfur), Na (sodium), Mg (magnesium), Al (aluminum), Ca (calcium), P An insulating organic solvent or inorganic solvent containing (phosphorus) as a constituent element is used. As described above, alcohol is used as an example of the organic solvent. Furthermore, as described above, as the organic minute substance, as described above, a simple bubble by a reaction gas (air, nitrogen, oxygen, argon, helium, hydrogen or a mixed gas thereof), or a dielectric, a semiconductor, a conductor, or a combination of these bubbles. It contains a fine substance composed of a mixture and a composite, and further includes a single bubble and a dielectric, semiconductor, conductor, or a mixture or composite of these bubbles. In the derivative, semiconductor, conductor, or a mixture or composite thereof, the reaction efficiency can be increased by forming a lot of minute pores such as zeolite.

<Examples of inorganic solvent>:
As an example of an inorganic solvent, sodium chloride, calcium, etc. are mixed in water, mixed with an organic solvent containing at least H, and ions and radicals are generated, which are mixed at the molecular atom level contributing to the formation of electron current. It is done.
As the potential difference to be applied, a static application, a pulse shape, or an application method of changing with time is adopted.

  Organic solvent molecules, such as monomer molecules, undergo fragmentation by electron bombardment and the molecular chain is cut into plasma to produce mono- or radicals. These radicals recombine and a molecular chain grows. Furthermore, molecular chain scission and recombination are repeated, and finally a polymer is formed.

  The solvent and the minute substance from which the reactants are separated are circulated again by the introduction device 67 and guided to the space 62.

  FIG. 2 shows a second embodiment. The same number is attached | subjected about the structure same as Example 1, and the description about Example 1 is used in order to avoid duplication of description. A description will be given centering on characteristic portions different from the first embodiment.

  In the first embodiment, a liquid solvent, for example, an organic solvent is sealed in the space 62. In this embodiment, a reaction organic substance such as alcohol atomized in a mist is used as the organic solvent 70A. The

  The minute substance 71 </ b> A is also atomized, stays in the space 62 in a mixed state with the atomized organic solvent, and is discharged by the derivation device 73. Accordingly, as in the first embodiment, the mist-like organic solvent 70A and the mist-like minute substance 71A flow in the space 62. The minute substance 71A is configured to have better conductivity than the solvent.

  Due to the potential difference applied by the potential difference generating device 65, an electron flow is generated from the minus electrode 63, and electrons flow toward the plus electrode 64. In this case, the electron flow is short-circuited between the minute substances 71A with sufficient kinetic energy and electromagnetic energy by the action of the minute substance 71A that stays and flows in the space 62, and flows along the surface of the minute substance 71A. By this electron flow, an organic solvent gas containing molecules of the atomized organic solvent 70A and a reactive gas such as nitrogen are induced as plasma containing ions and radicals. Only mist-like organic solvent gas and fine substances can be introduced. Ions and radicals generated by plasma induction become mist-like polymers and fine substances, for example, polymers deposited on the surface of glass while repeating bonding between surrounding ions and radicals.

  In the above two embodiments, the cylindrical reaction vessel 61 is used, but it is not limited to this shape. The reaction vessel 61 may have a conical shape with a narrow upper portion and a wide lower portion, or may have a rectangular parallelepiped shape. The introduction pipe 66 and the discharge pipe 72 may be directly attached to the reaction vessel 61 instead of via the electrodes 63 and 64. Further, the temperature in the reaction vessel 61 is adjusted by a temperature adjusting device 74.

  The above is summarized as shown in FIG. In FIG. 13, measure 1 is to measure the plasma of a solvent, particularly organic solvent molecules, measure 2 is to perform a plasma polymerization reaction with organic solvent molecules using a reaction gas, and measure 3 is a large amount of plasma. And plasma reaction, making it suitable for mass production and improving efficiency.

  As a countermeasure, when a minute substance with good conductivity is mixed in the solvent, an electron flow is generated through the minute substance, and the organic solvent molecules on the minute substance surface are turned into plasma, and the reaction gas is also used. First, the reaction gas is also converted into plasma on the surface of the minute substance. A plasma polymerization reaction is caused by plasmatized organic solvent molecules and plasmatized reaction gas.

  More specifically, an organic solvent or an inorganic solvent is used as the solvent, and in the case of the organic solvent, a liquid organic solvent or a mist (gaseous) organic solvent is used. Mix minute substances in liquid organic solvent. The minute substance is caused by the potential difference by the bubbles by the reaction gas itself, by the bubbles by other reaction gas itself, by mixing other minute substances in the bubbles, or by mixing other minute substances independently. Make the flow of electron flow easier. Similarly, fine substances are mixed in the mist-like organic solvent.

  By doing so, the organic solvent is modified by repeating decomposition and bonding, or a polymer is easily formed. In addition, a reaction product can be easily generated by a plasma polymerization reaction using an organic solvent and a reaction gas. Naturally, the contents of the invention of the prior application can be implemented by the apparatus of the method shown in the first and second embodiments.

The figure which shows the structure of the Example of prior invention. The figure which shows the phenomenon formed between the gaps 15 explanatoryly. A photograph showing the situation where an upward flow is formed. Other pictures showing the situation where upward flow is formed. The figure comprised corresponding to the photograph shown in FIG. The figure which shows the hydrogen generation condition. The figure which shows the FTIR signal before and behind irradiating an electron beam to 1-butanol. The substance composition measurement result using EPMA is shown. The figure which shows the structure of the other Example of prior invention. The figure which shows the example of the reaction product anticipated. The figure which shows the structure of the Example of this invention. The figure which shows the structure of the other Example of this invention. The block diagram explaining the content of a present Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 61 ... Reaction container, 62 ... Space part, 63 ... Negative electrode, 64 ... Positive electrode, 65 ... Potential difference generator, 66 ... Introduction pipe, 67 ... Introduction device (means), 70, 70A ... Organic solvent, 71, 71A ... Fine substance, 72 ... discharge pipe, 73 ... lead-out device (means), 74 ... temperature control device, 200 ... organic and inorganic compound synthesis device.

Claims (8)

Reaction vessel, plus and minus electrodes arranged with a space in the reaction vessel, potential difference generator for applying a potential difference between these electrodes, insulating liquid medium and reaction gas connected to the space Vapor-liquid phase mixing comprising a micro-substance introducing device containing liquid, a liquid medium that stays in a mixed state with the micro-substance, and a reaction product, medium, and micro-substance deriving device Consisting of equipment
By applying a potential difference between the electrodes by the potential difference generator, an electron flow from the minus electrode to the plus electrode is formed through the minute substance, and the solvent is formed on the surface of the minute substance based on the potential difference. And plasma of reaction gas is induced to generate ions and radicals to generate a plasma reaction, and a reactant generated by the plasma reaction is taken out of the reaction vessel from the derivation device. Inorganic compound synthesizer.   2. The organic compound synthesizer according to claim 1, wherein the medium is an organic medium, and the minute substance is a single bubble of a reactive gas or a bubble including a minute dielectric, semiconductor, and conductor.   2. The organic compound synthesizer according to claim 1, wherein the medium is an organic medium, and the minute substance includes a single bubble of a reaction gas or a substance including a minute dielectric, semiconductor, and conductor. . A reaction vessel, a positive electrode and a negative electrode arranged with a space in the reaction vessel, a potential difference generating device for applying a potential difference between these electrodes, a mist solvent connected to the space, and the medium, A device for introducing a fine substance containing a reactive gas having good conductivity, a mist-like solvent that stays in a mixed state with a mist-like fine substance in the space, and a device for deriving a reaction product, a solvent and a fine substance. Consisting of a gas-liquid phase mixing device comprised of,
By applying a potential difference between the electrodes by the potential difference generating device, an electron flow from the minus electrode to the plus electrode is formed through the minute substance, and on the surface of the minute substance with the solvent based on the potential difference. An organic or inorganic material characterized by inducing plasma of a reactive gas to generate ions and radicals to generate a plasma reaction, and taking out a reactant generated by the plasma reaction from the derivation device to the outside of the reaction vessel Compound synthesizer. Reaction vessel, plus and minus electrodes arranged with a space in the reaction vessel, potential difference generator for applying a potential difference between these electrodes, insulating liquid medium and reaction gas connected to the space Vapor-liquid phase mixing comprising a micro-substance introduction device containing a liquid, a liquid medium that stays in a mixed state in the space, and a reaction product substance, a solvent, and a micro-substance deriving device An organic or inorganic compound synthesis method comprising an apparatus,
By applying a potential difference between the electrodes by the potential difference generator, an electron flow from the minus electrode to the plus electrode is formed through the minute substance, and the solvent is formed on the surface of the minute substance based on the potential difference. And plasma of reaction gas is induced to generate ions and radicals to generate a plasma reaction, and a reactant generated by the plasma reaction is taken out of the reaction vessel from the derivation device. Inorganic compound synthesis method. A reaction vessel, a positive electrode and a negative electrode arranged with a space in the reaction vessel, a potential difference generating device for applying a potential difference between these electrodes, a mist solvent connected to the space, and the medium, A device for introducing a fine substance containing a reactive gas having good conductivity, a mist-like solvent that stays in a mixed state with a mist-like fine substance in the space, and a device for deriving a reaction product, a solvent and a fine substance. An organic or inorganic compound synthesizing method comprising a gas phase-liquid phase mixing device configured to include,
By applying a potential difference between the electrodes by the potential difference generating device, an electron flow from the minus electrode to the plus electrode is formed through the minute substance, and plasma is induced on the surface of the minute substance based on the potential difference. An organic or inorganic compound synthesizing method characterized in that ions and radicals are generated to cause a plasma reaction, and a reactant generated by the plasma reaction is taken out of the reaction vessel from the derivation device. A reaction vessel, a positive electrode and a negative electrode arranged with a space in the reaction vessel, a potential difference generating device for applying a potential difference between these electrodes, an insulating liquid organic medium connected to the space, and a minute From a gas phase-liquid phase mixing apparatus comprising a substance introduction apparatus, a liquid organic medium that stays in a mixed state with a minute substance in the space, and a reaction product substance, an organic solvent, and a minute substance lead-out apparatus An organic or inorganic compound synthesis method,
By applying a potential difference between the electrodes by the potential difference generator, an electron flow from the minus electrode to the plus electrode is formed through the minute substance, and an organic solvent is formed on the surface of the minute substance based on the potential difference. An organic compound synthesizing method characterized by inducing plasma and generating ions and radicals to cause a plasma reaction, and taking out a reactant generated by the plasma reaction from the derivation device to the outside of the reaction vessel. Reaction vessel, plus electrode and minus electrode arranged with a space in the reaction vessel, potential difference generator for applying a potential difference between these electrodes, mist organic solvent and minute substance connected to the space A gas phase-liquid comprising a mist-like organic solvent that stays in a state where a mist-like fine substance is mixed in the space, and a reaction product substance, an organic solvent, and a derivation device for the fine substance. An organic or inorganic compound synthesis method comprising a phase mixing device,
By applying a potential difference between the electrodes by the potential difference generating device, an electron flow from the minus electrode to the plus electrode is formed through the minute substance, and an organic solvent is formed on the surface of the minute substance based on the potential difference. An organic compound synthesis method, characterized in that plasma is induced to generate ions and radicals to generate a plasma reaction, and a reactant generated by the plasma reaction is taken out of the reaction vessel from the derivation device.