JP2017213519A - Gas-liquid reaction device having micronanobubble generator and gas-liquid reaction method using the gas-liquid reaction device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas-liquid reaction device and a gas-liquid reaction method using the gas-liquid reaction device capable of conducting a gas-liquid reaction in industrial large scale and effectively, and further conducting settlement, operation and maintenance of the device economically and effectively.SOLUTION: The gas-liquid reaction device and the gas-liquid reaction method using the gas-liquid reaction device has a micronanobubble generator in a reaction tank of the gas-liquid reaction device and generates micronanobubble of a reaction gas existing in a gas phase of the reaction tank to a reaction material-containing liquid existing in a liquid phase of the reaction tank by the micronanobubble generator for solving the above described problem. The above described problem is further solved by using a liquid flow method as the micronanobubble generator, supplying the reaction material-containing liquid existing in the liquid phase of the reaction tank with pressure and aspirating the reaction gas from the reaction tank with a negative pressure aspiration.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas-liquid reaction device for reacting a liquid containing a reactant and a gas containing a reaction gas in a reaction tank, and a gas-liquid reaction method using the gas-liquid reaction device.

  A liquid containing a reactant (hereinafter also referred to as “reactant-containing liquid”) and a gas containing a reactant gas (hereinafter also referred to as “reactant gas”) are mixed to perform gas-liquid reaction with high efficiency. In order to do this, it is important to increase the contact area between the two.

  In order to satisfy this requirement, as described in Patent Document 1, a reactant-containing liquid and a reaction gas are introduced into a reaction tank, and the mixture is heated in a sealed manner, and the contact area between the two is increased by stirring to increase the gas-liquid reaction. A batch or continuous process method, in which a large number of disks are mounted close to the rotation axis, and the gas is acted on the thin film of the solution formed on the disk surface by rotating in a state where it partially infiltrates the reactant-containing liquid. For example, a disk method for causing a reaction gas to jet and a jet flow of a reactant-containing liquid to cause a contact reaction, and the like are employed.

The batch-type or continuous-type process method is advantageous as a method for carrying out gas-liquid reaction in a large scale and efficiently on an industrial scale. However, in order to increase the efficiency of gas-liquid reaction, the liquid phase is used in a reaction gas atmosphere. In order to increase the contact area between the gas and the gas phase, it is necessary to vigorously stir. Furthermore, in order to increase the efficiency of the gas-liquid reaction, it is also necessary to perform the gas-liquid reaction at a high temperature and a high pressure.
As a technique for efficiently performing a gas-liquid reaction, Patent Document 2 discloses, in a gas-liquid reaction in which benzene is cyclohexane, as shown in FIG. A gas-liquid reaction apparatus is disclosed in which a liquid is extracted and supplied to a high shear device 140, and hydrogen gas bubbles having an average bubble diameter of 100 μm are contained in the liquid by the high shear device 140 and refluxed to the reactor 110. In Patent Document 3, as shown in FIG. 8, in a gas-liquid reaction in which an aromatic nitro compound is converted to an aromatic amine compound, the aromatic nitro compound solution 208 is extracted from the vial 209 through the filter 207, and hydrogen gas is extracted. A gas-liquid reaction apparatus is disclosed which is introduced to contain hydrogen microbubbles, introduced into a catalyst fixing officer and allowed to proceed with a hydrogenation reaction, and then refluxed to the vial 209.

  However, in the gas-liquid reaction apparatus as in Patent Document 2, in order to perform the gas-liquid reaction with high efficiency, it is necessary to set the pressure in the reactor 110 to a high pressure of usually 5 MPa to 20 MPa. It is difficult to operate while maintaining the circulation path of the liquid containing benzene containing 140 at such a high pressure, and it is difficult to install, operate and maintain the apparatus economically and efficiently.

  In addition, the gas-liquid reaction apparatus such as Patent Document 3 described above is difficult to process in large quantities because the aromatic nitro compound solution 208 containing hydrogen microbubbles undergoes a gas-liquid reaction through a catalyst fixing agent. Since it is difficult to perform a liquid reaction under high temperature and high pressure, it is not suitable as an apparatus for performing a gas-liquid reaction efficiently on a large scale on an industrial scale.

  The inventors of the present invention can perform a gas-liquid reaction on an industrial scale in a large amount and efficiently, and can perform the installation, operation, and maintenance of the apparatus economically and efficiently, and the gas-liquid reaction apparatus. The present invention has been made by earnestly studying a gas-liquid reaction method using a liquid reactor.

International Publication No. 2007/100052 Japanese translation of PCT publication 2010-53882 JP 2014-005217 A

  The problem of the gas-liquid reaction apparatus of the present invention and the gas-liquid reaction method using the gas-liquid reaction apparatus is that a gas-liquid reaction can be carried out efficiently and in large quantities on an industrial scale, and the apparatus is installed, operated and maintained. Is to provide a gas-liquid reaction apparatus and a gas-liquid reaction method using the gas-liquid reaction apparatus.

  In order to solve the above problems, a gas-liquid reaction apparatus of the present invention and a gas-liquid reaction method using the gas-liquid reaction apparatus are provided with a micro-nano bubble generator in a reaction tank of the gas-liquid reaction apparatus. The reactant containing liquid present in the liquid phase of the reaction tank and the reaction gas present in the gas phase of the reaction tank are supplied to the generator, and the reactant containing liquid containing the micro-nano bubbles of the reaction gas is supplied to the liquid phase. It is characterized by this.

  Further, as the micro / nano bubble generating device, a liquid flow type device capable of economically generating a large amount of micro / nano bubbles, which will be described later with an outline thereof shown in FIG. 6, is used. The above-mentioned problems can be further solved by supplying the reactant-containing liquid present in the liquid phase of the reaction tank under pressure and supplying the reaction gas from the gas phase of the reaction tank by the negative pressure generated thereby. Can do.

  The gas-liquid reaction apparatus of the present invention and the gas-liquid reaction method using this gas-liquid reaction apparatus have the following excellent effects.

  Adopting batch- or continuous-process gas-liquid reactions, and performing gas-liquid reactions at high temperatures and pressures in a hermetically sealed reaction tank, the gas-liquid reactions can be carried out on a large scale and efficiently on an industrial scale. It can be carried out.

  In addition, by using the micro / nano bubble generator to contain the reaction gas micro / nano bubbles in the reactant-containing liquid, the contact area between the liquid phase and the gas phase can be increased without vigorous stirring, which makes gas-liquid reaction more efficient. Can be done economically and economically.

  In addition, by supplying the reactant-containing liquid containing the reaction gas micro-nano bubbles to the liquid phase from the micro-nano bubble generator, the liquid phase can be stirred, and the gas-liquid reaction can be performed efficiently and economically. be able to.

  Further, by providing the micro / nano bubble generator in the reaction tank, the inside of the reaction tank can be stably maintained at a high pressure, and the installation, operation, and maintenance of the apparatus can be performed economically and efficiently. Furthermore, a liquid flow type apparatus is used as the micro / nano bubble generator, and the reactant-containing liquid present in the liquid phase of the reaction vessel is pressurized and supplied to the micro / nano bubble generator, and the negative pressure generated thereby causes the gas in the reaction vessel to flow. The reactant-containing liquid in the liquid phase can be stirred more efficiently and economically by sucking the reactant gas from the phase and supplying the reactant-containing liquid containing the reaction gas micro-nano bubbles to the liquid phase.

  Further, by using such a micro / nano bubble generator, the number average diameter and the total number of bubbles of the micro / nano bubbles can be determined not only by the pressure and flow rate of the reactant-containing liquid supplied to the micro / nano bubble generator, but also by the gas in the reaction tank. It can also be adjusted by the pressure of the reaction gas present in the phase.

It is a schematic diagram which shows 1st Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows 2nd Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows 3rd Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows 4th Embodiment of the gas-liquid reaction apparatus of this invention. It is a schematic diagram which shows 5th Embodiment of the gas-liquid reaction apparatus of this invention. It is sectional drawing which shows the outline | summary of the micro nano bubble generator which can be used suitably in the gas-liquid reaction apparatus of this invention. It is FIG. 1 of patent document 2 (Japanese translations of PCT publication No. 2010-53882) which is a prior art example. It is FIG. 1 of patent document 3 (Unexamined-Japanese-Patent No. 2014-005217) which is a prior art example.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, but the present invention is not limited thereto. In the following description, a gas-liquid reaction that performs a hydrogenation reaction of an organic compound, which is a representative example of a reduction reaction, will be mainly described. However, the gas-liquid reaction apparatus of the present invention and a gas-liquid reaction method using the gas-liquid reaction apparatus Can be used for gas-liquid reactions using organic chemicals or inorganic chemicals such as fats and oils, fatty acids and synthetic resins.

1. General Items of the Present Invention First, general items of the gas-liquid reaction device of the present invention and the gas-liquid reaction method using the gas-liquid reaction device (hereinafter also referred to as “device and method of the present invention”). explain.

  The apparatus and method of the present invention is a gas-liquid reaction of a batch type or continuous process method, in which a liquid containing a reactant (reactant-containing liquid) and a pressurized reaction are contained in a hermetically sealed reaction vessel. A gas (reaction gas) containing a gas is supplied to form a liquid phase and a gas phase to perform a gas-liquid reaction. In order to improve the reaction efficiency of the gas-liquid reaction, the gas-liquid reaction is preferably performed at a high temperature and a high pressure.

O Gas-liquid reaction There is no restriction | limiting in particular as a gas-liquid reaction which can apply the apparatus and method of this invention, Usually, it can apply to the known gas-liquid reaction performed under high temperature or high temperature and high pressure.
For example, radical carbonylation reaction, olefin hydroformylation reaction, direct fluorination reaction, oxygen oxidation reaction (reaction to obtain aldehyde from alcohol, reaction to obtain epoxy from alkene, photosinglet oxygen oxidation reaction, α-position oxidation reaction of ester, etc. ), Hydrogenation reaction (sugar alcohol production by hydrogenation of reducing sugar, hydrogenation reaction of olefin, hydrogenation reaction of carbonyl compound, hydrogenation reaction of cyano group, production of hydrogenated oil by hydrogenation of unsaturated glycerides of natural fats and oils , Reaction of hydrogenating unsaturated fatty acid with nickel catalyst, etc.), photohalogenation reaction of alkane, and Heck carbonylation reaction.

〇 Liquid containing reactive substance (Reactive substance-containing liquid)
The reactant-containing liquid used in the apparatus and method of the present invention may contain only the reactant, or may contain the reactant and solvent.

  As the solvent, one or more of water, an organic solvent, an ionic liquid (also referred to as an ionic liquid, an ionic fluid, or a room temperature molten salt), a liquid inorganic compound, or the like can be used. Examples of organic solvents include aliphatic hydrocarbons such as hexane, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone, diethyl ketone, and methyl ethyl ketone, aldehydes such as butyraldehyde, diethyl ether, dibutyl ether, Ethers such as diisobutyl ether, tetrahydrofuran and dioxane, esters such as ethyl acetate, butyl acetate and di-n-octyl phthalate, amines such as triethylamine, pyrrolidine and piperidine, amides such as dimethylformamide, sulfoxide such as dimethyl sulfoxide , Alcohols such as methanol, ethanol, propanol, isopropanol, diols such as ethylene glycol, propanediol, butanediol, nitriles such as acetonitrile, pyridine, etc. Heteroaromatic compounds, halogen solvents such as carbon tetrachloride, chloroform, dichloromethane, and dichloroethane, carboxylic acids such as acetic acid and formic acid, sulfonic acids, and fluorine-based inert liquids such as florinate (registered trademark), and these two types A mixed solvent having an arbitrary ratio as described above can also be used. Examples of the liquid inorganic compound include phosphoric acids such as sulfuric acid, phosphoric acid and phosphorous acid, nitric acid, hydrogen peroxide water and the like. Among these, an aqueous solvent and an organic solvent are preferable, and aromatic hydrocarbons, hydrocarbons, and alcohols are more preferable, and aromatic hydrocarbons are particularly preferable.

  When a solvent is used, the amount used is not limited, and the concentration of the reactant used is usually 0.001 mol or more, preferably 0.02 mol or more, more preferably 0.1 mol or more, per liter of the solvent. Therefore, it is preferable to use an amount of the solvent that is 20 mol or less, preferably 10 mol or less, more preferably 5 mol or less. When the amount of the solvent is larger than the above range, the productivity is lowered, and when the amount is smaller, it is disadvantageous in that the catalyst or the reactant is dissolved.

* Gas containing reaction gas (reaction gas)
Examples of the reaction gas include ozone, hydrogen, helium, fluorine, chlorine, carbon monoxide, carbon dioxide, sulfur dioxide, hydrogen chloride gas, ammonia gas, methane, ethane, propane, ethylene gas, and acetylene gas. Examples include singlet oxygen and triplet oxygen. Moreover, you may use these mixed gas or mixed gas of these reaction gas and other gas.

  The concentration of the reaction gas in the gas component is not particularly limited, but is selected from a range of 0.01 to 100% by volume, preferably 0.1% or more, more preferably 5% or more, particularly preferably. Is 10% or more. If the concentration of the reaction gas is lower than the above range, it is difficult to obtain sufficient reaction efficiency.

〇Catalyst In the apparatus and method of the present invention, a catalyst may or may not be used for the gas-liquid reaction, but in general, the use of the catalyst can perform the gas-liquid reaction more efficiently. preferable.

  As the catalyst, one containing at least one element (metal) selected from elements (metals) and lanthanoids of Groups 4 to 12 of the periodic table can be suitably used, and the catalyst is composed of silica, alumina, It can be used by being supported on the surface of a porous material such as silica alumina, zeolite, activated carbon or the like. For example, a Raney nickel catalyst or the like can be used when performing a hydrogenation reaction of a reducing sugar.

  When using a catalyst, it is preferable to use a homogeneous catalyst in a reactant-containing liquid present in the liquid phase in the reaction vessel. The amount of the catalyst used is not particularly limited, but it is preferably 0.1 ppm or more, particularly 1 ppm or more, 10% or less, particularly 1% or less as an active ingredient amount with respect to the reactant.

O Reaction conditions As described above, the apparatus and method of the present invention adopts a gas-liquid reaction of a batch type or a continuous process method, and is usually gas-liquid at high temperature and high pressure in a hermetically sealed reaction tank. Although the reaction is performed, the optimum range is appropriately set for conditions such as the temperature in the reaction vessel, the pressure in the reaction vessel, the reaction time, etc., depending on the type of gas-liquid reaction, reactant, reaction gas, etc. can do.

  For example, when performing a hydrogenation reaction of reducing sugar, the lower limit value of the temperature in the reaction vessel is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, more preferably 80 ° C. or higher, particularly preferably 110 ° C. or higher, The upper limit is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, further preferably 250 ° C. or lower, particularly preferably 200 ° C. or lower, and the lower limit of the hydrogen pressure is preferably 0.1 MPa or higher, more preferably 0.5 MPa. As described above, it is more preferably 1 MPa or more, particularly preferably 5 MPa or more, the upper limit value is preferably 30 MPa or less, more preferably 25 MPa or less, further preferably 20 MPa or less, and the reaction time is preferably 30 minutes or more and 9 hours or less.

2. First feature of the present invention The apparatus and method of the present invention performs the gas-liquid reaction of the batch type or continuous process method as described above. In this reaction, the micro / nano bubble generating device provided in the reaction vessel, The first feature is that the reactant-containing liquid present in the liquid phase of the reaction vessel contains micro-nano bubbles of the reaction gas present in the gas phase of the reaction vessel and is supplied to the liquid phase.

  As described above, the gas-liquid reaction of the batch type or the continuous type process method is adopted, and the gas-liquid reaction is performed by performing the gas-liquid reaction under a high pressure, preferably at a high temperature and a high pressure in an airtightly sealed reaction tank. It can be carried out in large quantities and efficiently on an industrial scale.

  In addition, by using the micro / nano bubble generator to contain the reaction gas micro / nano bubbles in the reactant-containing liquid, the contact area between the liquid phase and the gas phase can be increased without vigorous stirring, which makes gas-liquid reaction more efficient. Can be done economically and economically.

  In addition, by supplying the reactant-containing liquid containing the reaction gas micro-nano bubbles to the liquid phase from the micro-nano bubble generator, the liquid phase can be appropriately stirred without particularly installing a culture vessel agitator. It is possible to perform gas-liquid reaction efficiently and economically.

  In addition, by providing the micro / nano bubble generator inside the reaction tank, the inside of the reaction tank can be stably maintained at a high pressure, compared to the case where the micro / nano bubble generator is provided outside the reaction tank. It can be done economically and efficiently.

Reactive gas micro / nano bubbles In the present invention, the reactive substance-containing liquid contains reactive gas micro / nano bubbles. The “micro nano bubbles” of the present invention means “micro bubbles” and / or “nano bubbles”. While “normal bubbles” rapidly rise in water and burst and disappear on the surface, microbubbles with a diameter of 50 μm or less called “microbubbles” shrink in water and disappear. Together with free radicals, “nanobubbles”, which are ultrafine bubbles having a diameter of 100 nm or less, are generated, and these “nanobubbles” remain in water for a certain amount of time.

  In the present invention, bubbles having a number average diameter of 100 μm or less are referred to as “micro bubbles”, and bubbles having a number average diameter of 1 μm or less are referred to as “nano bubbles”. As a method for measuring bubbles such as micro-nano bubbles and nano bubbles, an electrical detection band method, a resonance mass measurement method, a particle locus analysis method, and the like are generally used.

  “Nano bubbles”, which are extremely fine bubbles, are also called “ultra fine bubbles”. Currently, in the ISO (International Organization for Standardization), the creation of an international standard for fine bubble technology is being considered, and once the international standard is created, the name of “nanobubble”, which is currently commonly used, There is a possibility that it will be unified into “Ultra Fine Bubble”.

  If the number-average diameter of the micro-nano bubbles is too large, the micro-nano bubbles expand due to a pressure drop in the micro-nano bubbles as the micro-nano bubbles rise in the liquid phase. As a result, the specific surface area of the micro-nano bubbles (surface area per unit weight) ) Increases, the effect of promoting the gas-liquid reaction is reduced.

Further, in order to increase the specific surface area of the micro / nano bubbles, the number of micro / nano bubbles per unit volume (hereinafter referred to as “total number of bubbles”) in the reactant-containing liquid to be brought into contact with the reactant is also important. The total number of bubbles per mL of the reactant-containing liquid is preferably 10 ⁵ or more, preferably 10 ⁶ to 10 ⁹ , more preferably 10 ⁷ to 10 ¹⁰ .

  The number average diameter and the total number of bubbles of these micro / nano bubbles can be appropriately set in an optimum range according to the gas-liquid reaction, the reactant, the type of reaction gas, etc. The structure of the micro / nano bubble generator described later It can be adjusted and set according to the generation conditions.

  By making the reactant-containing liquid contain micro-nano bubbles of the reactant gas, the reactant gas can be left in the reactant-containing liquid for a long period of time, and the restriction of mass transfer in the gas-liquid reaction can be reduced. The reaction speed is not adversely affected even if the number average diameter of the micro / nano bubbles is small, but the saturation of the reactant-containing liquid in the reaction gas is limited, so it is economical if the number average diameter of the micro / nano bubbles is too small. Is inefficient. Further, the total number of bubbles can be generated under the setting conditions of the micro / nano bubble generator, and it is preferable that the number of bubbles is larger as long as the micro-vananoble can stably exist in the reaction with the reactant.

〇 Micro / nano bubble generation device As the micro / nano bubble generation device, a known or commercially available device can be used. For example, after a sufficient amount of gas is dissolved in water at a certain high pressure, the pressure is released. Turbulent flow generated by a liquid flow that stirs and mixes a mixed fluid consisting of liquid and gas as a loop flow by creating a supersaturated condition of the gas dissolved in For example, a “loop flow type bubble generating nozzle” using a phenomenon that bubbles are subdivided by the above can be used.

3. Second feature of the present invention The apparatus and method of the present invention uses a liquid flow type micro-nano bubble generator provided in a reaction vessel, and the micro-nano bubble generator contains a reactant present in the liquid phase of the reaction vessel. The second feature is that the liquid is pressurized and supplied, the reaction gas is sucked in from the gas phase of the reaction tank by the negative pressure generated thereby, and the reactant-containing liquid containing the reaction gas micro-nano bubbles is supplied to the liquid phase. It is what.

  By using such a micro-nano bubble generator, the reactant-containing liquid containing the reaction gas micro-nano bubbles can be efficiently and economically supplied to the liquid phase. Can be stirred more efficiently and economically.

  Furthermore, the number average diameter and the total number of bubbles of the micro / nano bubbles are adjusted not only by the pressure and flow rate of the reactant-containing liquid supplied to the micro / nano bubble generator, but also by the pressure of the reaction gas present in the gas phase of the reaction vessel. be able to.

This liquid flow type micro / nano bubble generator will be described with reference to FIG.
As the micro / nano bubble generating device 4, a liquid flow type, that is, a type of generating micro / nano bubbles by a liquid flow can be used. As a typical example of the liquid flow type micro / nano bubble generating device, a nozzle type is used. And a micro / nano bubble generator. This nozzle-type micro / nano bubble generator is as shown in FIG.

  In FIG. 6, a reactant-containing liquid E (hereinafter also referred to as “liquid E”) present in the liquid phase of the reaction tank is pressurized and supplied from the inlet 11 of the nozzle. The flow velocity is increased and turbulence is generated at the throat 12. The reaction gas F existing in the gas phase of the reaction tank is sucked from the gas inlet 14 due to the negative pressure generated by the flow of the liquid E, mixed with the liquid E in the suction portion 13, and micro-nano bubbles due to the turbulent flow in the throat portion 12. It becomes. The reactant-containing liquid G containing the reaction gas micro-nano bubbles thus formed is supplied from the outlet 15 to the liquid phase.

4). Embodiments of the Invention Next, referring to FIGS. 1 to 5, the first embodiment (FIG. 1), the second embodiment (FIG. 2), the third embodiment (FIG. 3), and the fourth embodiment of the invention. (FIG. 4) and 5th Embodiment (FIG. 5) are demonstrated.

  In the first to fifth embodiments, a nozzle-type device is used as the micro / nano bubble generation device 4. This micro / nano bubble generation device 4 is a gas phase of the reaction tank 1 in the first and fifth embodiments. D is provided in the liquid phase C of the reaction tank 1 in the second embodiment, and straddles the gas phase D and the liquid phase C of the reaction tank 1 in the third embodiment and the fourth embodiment. Is provided. When the micro / nano bubble generator 4 is provided in the gas phase D of the reaction tank 1 as in the first embodiment and the fifth embodiment, the micro / nano bubbles of the reaction gas B are included at the outlet of the micro / nano bubble generator 4. A pipe 8 is provided for guiding and supplying the reactant-containing liquid A into the liquid phase C.

  Moreover, in 4th Embodiment, as a pump for supplying the reactive substance containing liquid E which exists in the liquid phase C of the reaction tank 1 to the micro / nano bubble generating apparatus 4, the exterior of the reaction tank 1 is used as in other embodiments. The pump 5 provided in the reaction tank 1 is not used, but the pump provided in the reaction tank 1 is used. For example, an internal pump 6 in which a pump impeller (pump impeller) is disposed in the reaction tank 1 is provided. Used. In the fourth embodiment, the micro / nano bubble generating device 4 is provided across the gas phase D and the liquid phase C of the reaction tank 1. Of course, as in the first embodiment and the fifth embodiment, the reaction tank is used. 1 may be provided in the gas phase D, or may be provided in the liquid phase C of the reaction vessel 1 as in the second embodiment.

  In the fifth embodiment, the gas-liquid reactor of the first embodiment is provided with a reaction tank stirrer 7 for stirring the reactant-containing liquid A in the liquid phase C.

First, a first embodiment of the present invention will be described with reference to FIG.
In the first embodiment, a gas-liquid reaction between a liquid (reactive substance-containing liquid) A containing a reactive substance and a gas (reactive gas) B containing a reactive gas is performed as follows.
1) A liquid (reactant containing liquid) A containing a reactant is supplied from a liquid supply device 2 to a hermetically sealed reaction tank 1, and a pressurized reaction gas is supplied from a pressurized gas supply device 3. The contained gas (reaction gas) B is supplied to form a liquid phase C and a gas phase D of the reaction tank.
2) The temperature in the reaction vessel is raised to a predetermined temperature by a heating means (not shown) such as a heater, and the pressure in the reaction vessel is raised to a predetermined pressure by the pressurized gas supply device 3 to react. The gas-liquid reaction is started with the inside of the tank at a high temperature and high pressure.
3) The reactant-containing liquid A is extracted from the liquid phase C of the reaction tank 1 by the pump 5 and pressurized.
It is supplied to a nozzle-type micro / nano bubble generator 4 provided in the gas phase D of the reaction tank 1.
4) The reaction gas A is sucked into the micro / nano bubble generating device 4 from the gas phase D of the reaction tank 1 by the negative pressure generated by the flow of the reactant-containing liquid A.
5) In this way, the reactant-containing liquid A containing the micro-nano bubbles of the reaction gas B is guided and supplied into the liquid phase C through the pipe 8 provided at the outlet of the micro-nano bubble generator 4. .

  In the first embodiment, the gas-liquid reaction of the batch type process method is adopted, and the gas-liquid reaction is carried out on an industrial scale by performing the gas-liquid reaction at high temperature and high pressure in the airtightly sealed reaction tank 1. And can be performed efficiently.

  In addition, by using the micro-nano bubble generating device 4 and containing the reaction gas B micro-vananoble in the reactant-containing liquid A, the contact area between the liquid phase C and the gas phase D can be increased without vigorous stirring. The gas-liquid reaction can be performed efficiently and economically.

In addition, the liquid phase C can be stirred by introducing the reactant-containing liquid A containing the micro-nano bubbles of the reaction gas B from the micro-nano bubble generator 4 into the liquid phase C, and the gas-liquid reaction Can be carried out efficiently and economically.
Further, by providing the micro / nano bubble generator 4 in the reaction tank 1, the inside of the reaction tank 1 can be stably maintained at a high pressure, and the installation, operation and maintenance of the apparatus can be performed economically and efficiently. Can do.

Further, a liquid flow type device is used as the micro / nano bubble generation device 4, and the reactant-containing liquid A present in the liquid phase C of the reaction vessel 1 is pressurized and supplied to the micro / nano bubble generation device. The reactant gas B is sucked from the gas phase D of the reaction tank 1 and the reactant A-containing liquid A containing the micro-nano bubbles of the reactant gas B is introduced into the liquid phase C to be supplied. Liquid A can be stirred more efficiently and economically.
In addition, by using such a micro / nano bubble generating device 4, the number average diameter and the total number of bubbles of the micro / nano bubbles are determined not only by the pressure and flow rate of the reactant-containing liquid A supplied to the micro / nano bubble generating device 4 but also by the reaction. It can also be adjusted by the pressure of the reaction gas B present in the gas phase D of the tank 1.

  In particular, as in the first embodiment, the reactant-containing liquid A is extracted from the lower part of the reaction tank 1 in the vertical direction, and the micro / nano bubbles of the reaction gas B are removed from the micro / nano bubble generator 4 provided at the upper part of the reaction tank 1 in the vertical direction. By introducing and supplying the contained reactant A liquid A into the liquid phase C, the reactant A-containing liquid A in the liquid phase C can be sufficiently stirred in the vertical and vertical directions.

  In order to stir the reactant A-containing liquid A in the liquid phase C, the reaction tank 1 for performing the gas-liquid reaction is usually provided with a reaction tank agitator 7 as in the fifth embodiment of the present invention shown in FIG. However, in the first embodiment, since the reactant-containing liquid A in the liquid phase C can be stirred by the circulation of the reactant-containing liquid A, it is not necessary to install the reaction tank agitator 7 or even if it is installed. Since the energy required for driving the reaction vessel agitator 7 can be reduced, installation, operation and maintenance of the apparatus can be performed economically and efficiently.

  The stirring state of the reactant-containing liquid A in the liquid phase C varies depending on the capacity of the reaction tank 1, the shape of the reaction tank 1, the depth of the liquid phase C, and the like. In order to perform well, it is possible to adjust / design the installation position, inclination, the number of installations, etc. of the vertical and vertical directions of the micro / nano bubble generating device 4.

  As for the vertical vertical position of the micro-nano bubble generator 4, it can be provided in the gas phase D of the reaction tank 1 as in the first and fifth embodiments, or as in the second embodiment. It can also be provided in the liquid phase C of the reaction vessel 1, or can be provided across the gas phase D and the liquid phase C of the reaction vessel 1 as in the third and fourth embodiments.

  As for the inclination of the micro / nano bubble generating device 4, for example, the reactant containing liquid A containing the micro bubbles of the reaction gas B is supplied vertically downward of the reaction tank 1. With such setting, stirring can be performed mainly so as to convection in the vertical direction, and the reactant-containing liquid A containing the micro-nano bubbles of the reaction gas B is supplied in the tangential direction of the side wall of the reaction tank 1. If it sets so, it can stir so that it may descend | fall spirally.

  The number of the micro / nano bubble generators 4 installed in the vertical vertical direction is, for example, by installing a plurality of micro / nano bubble generators 4 at equal intervals along the side wall of the reaction tank 1. The reactant A-containing liquid A can be stirred uniformly.

  As the gas-liquid reaction progresses, the pressure of the gas phase D in the reaction tank 1 decreases. Therefore, in order to keep the pressure of the gas phase D constant and perform the gas-liquid reaction homogeneously and uniformly, the reaction tank 1 It is preferable to provide a supply control device that measures the pressure of the gas phase D with a sensor and controls the supply amount of the reaction gas B from the pressurized gas supply device 3 based on the measured value.

  Further, in the first embodiment, the gas-liquid reaction apparatus of the batch type process method is shown, but the discharge for discharging the liquid phase C liquid in the reaction tank 1 while keeping the reaction tank 1 in an airtightly sealed state. By providing the apparatus, a gas-liquid reaction apparatus of a continuous process method can be obtained. In this case, from the liquid supply device 2 and the pressurized gas supply device 3, while the liquid phase C liquid in the reaction tank 1 containing the reaction product of the reactant and the reaction gas is continuously discharged by the discharge device. , Respectively, a liquid (reactant-containing liquid) A containing a reactant and a gas (reactant gas) B containing a pressurized reaction gas are continuously supplied.

  In order to keep the liquid level of the liquid phase C in the reaction tank 1 constant and perform the gas-liquid reaction uniformly and uniformly, the discharge device includes a liquid supply device according to the liquid level of the liquid phase C in the reaction tank 1 It is preferable to provide a discharge control device for controlling the supply amount of the reactant A-containing liquid A from 2 and / or the discharge amount of the liquid C in the reaction tank 1.

  Furthermore, as means for pressurizing and supplying the reactant-containing liquid E present in the liquid phase C of the reaction tank 1 to the micro / nano bubble generating device 4, the first to third embodiments and the fifth embodiment are provided. As described above, the pump 5 provided outside the reaction tank 1 may be used, or as in the fourth embodiment, the internal pump 6 having a pump impeller (pump impeller) inside the reaction tank 1 is used. May be. The internal pump 6 generally includes a pump shaft having a pump impeller fixed at one end and an electric motor connected to the pump shaft and rotationally driven. The pump impeller, the pump shaft, and the electric motor are all included. Can be arranged inside the reaction tank 1, a pump shaft is provided so as to penetrate the wall of the reaction tank 1, a pump impeller is arranged inside the reaction tank 1, and an electric motor is arranged outside the reaction tank 1. You can also Further, the pump impeller provided by applying electromagnetic force, magnetic force or the like from the outside of the reaction tank 1 does not depend on a member that is rotated and connected to a pump impeller such as a pump shaft. Can also be directly rotated.

As described above, the gas-liquid reaction apparatus of the present invention and the gas-liquid reaction method using the gas-liquid reaction apparatus exhibit the following excellent effects by including the first feature.
O Adopting batch-type or continuous process-type gas-liquid reaction, and performing gas-liquid reaction at high temperature and high pressure in an airtightly sealed reaction tank, the gas-liquid reaction is mass and efficient on an industrial scale. Can be done.
〇 By using the micro / nano bubble generator to contain reactive gas micro / nano bubbles in the reactant-containing liquid, the contact area between the liquid phase and the gas phase can be increased without vigorous stirring, and gas-liquid reactions can be carried out efficiently.・ Can be done economically.
〇 By supplying the reactant-containing liquid containing the reaction gas micro / nano bubbles to the liquid phase from the micro / nano bubble generator, the liquid phase can be agitated and the gas-liquid reaction can be carried out efficiently and economically. Can do.
O By providing the micro / nano bubble generator in the reaction tank, the inside of the reaction tank can be stably maintained at a high pressure, and the apparatus can be installed, operated and maintained economically and efficiently. (Specifically, since the internal / external pressure difference of the micro / nano bubble generator can be reduced, the wall thickness of the micro / nano bubble generator can be reduced, and the existing micro / nano bubble generator can be used without changing to a pressure resistant structure. (In addition, since the type and number of components such as equipment and piping provided outside the reaction vessel can be minimized, facilities and labor to prevent liquid leakage due to high pressure can be minimized.) Further, by minimizing the distance from the micro / nano bubble generating device to the point where the reactant containing liquid containing micro bubbles is supplied, it is possible to prevent the efficiency from decreasing due to the coalescence of the micro / nano bubbles in the pipe.

In addition, the gas-liquid reaction apparatus of the present invention and the gas-liquid reaction method using the gas-liquid reaction apparatus exhibit the following excellent effects by including the second feature.
O Liquid-phase reactant-containing liquid can be stirred more efficiently and economically.
〇 Adjust the number average diameter and total number of micro-nano bubbles not only by the pressure and flow rate of the reactant-containing liquid supplied to the micro-nano bubble generator, but also by the pressure of the reaction gas present in the gas phase of the reaction tank. Can do.

DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Liquid supply apparatus 3 Pressurized gas supply apparatus 4 Micro nano bubble generator 5 Pump (provided outside the reaction tank) 6 Internal pump (provided inside the reaction tank) 7 Reaction tank agitator 8 Reaction gas For supplying the reactant-containing liquid containing micro-nano bubbles in the liquid phase and supplying it A Liquid containing reactant (reactant-containing liquid)
B Gas containing reaction gas (reaction gas)
C Liquid phase of reaction tank D Gas phase of reaction tank E Reactant-containing liquid present in liquid phase of reaction tank F Reactant gas present in gas phase of reaction tank G Reactant-containing liquid containing micro-nano bubbles of reaction gas 11 Inlet part 12 Throat part 13 Suction part 14 Gas inlet 15 Outlet part 105 Pump 110 Reactor 140 High shear device 207 Filter 208 Aromatic nitro compound solution 209 Vial

Claims (14)

An airtightly sealed reaction vessel, a liquid supply device for supplying a liquid containing a reactant to the reaction vessel, and a pressurized gas supply device for supplying a gas containing a pressurized reaction gas to the reaction vessel; A gas-liquid reactor comprising:
A micro-nano bubble generator is provided in the reaction vessel,
A gas-liquid reactor characterized in that the gas micro-nano bubbles are generated in the liquid phase of the reaction vessel by the micro-nano bubble generator.   The micro-nano bubble generator is supplied with the liquid present in the liquid phase of the reaction tank and the gas present in the gas phase of the reaction tank, and the liquid containing the micro-nano bubbles of the gas is liquid-phased. The gas-liquid reaction apparatus according to claim 1, wherein the gas-liquid reaction apparatus is supplied to the apparatus.   The gas-liquid reaction apparatus according to claim 1 or 2, wherein the micro / nano bubble generation apparatus is of a system driven using a liquid flow.   The liquid present in the liquid phase of the reaction vessel is pressurized and supplied to the micro / nano bubble generator, and the gas is sucked from the gas phase of the reaction vessel by the negative pressure generated thereby, so that the micro / nano bubbles are introduced into the liquid. The gas-liquid reaction apparatus according to any one of claims 1 to 3, wherein the gas-liquid reaction apparatus is contained.   The gas-liquid reactor according to any one of claims 1 to 4, wherein the micro / nano bubble generator is provided in a gas phase of the reaction vessel.   The gas-liquid reactor according to any one of claims 1 to 4, wherein the micro / nano bubble generator is provided in a liquid phase of the reaction vessel.   The gas-liquid reactor according to any one of claims 1 to 4, wherein the micro / nano bubble generator is provided across the gas phase and the liquid phase of the reaction vessel.   The gas-liquid reaction apparatus according to any one of claims 2 to 7, wherein a pump installed outside a reaction tank is used as means for pressurizing and supplying the liquid to the micro / nano bubble generation apparatus.   The gas-liquid reaction apparatus according to any one of claims 2 to 7, wherein a pump installed inside a reaction tank is used as means for pressurizing and supplying the liquid to the micro / nano bubble generation apparatus.   As means for pressurizing and supplying the liquid to the micro / nano bubble generator, a pump impeller provided inside a reaction tank is rotationally driven by applying electromagnetic force, magnetic force, etc. from the outside of the reaction tank. The gas-liquid reaction apparatus in any one of Claims 2-7.   The said pressurized gas supply apparatus is provided with the supply control apparatus which controls the supply_amount | feed_rate of the said gas according to the pressure of the said gas in the gaseous phase of the said reaction tank, The one of Claims 1-10 characterized by the above-mentioned. The gas-liquid reactor described in 1.   The gas-liquid according to any one of claims 1 to 11, further comprising a discharge device that discharges the liquid in a liquid phase of the reaction tank while maintaining the reaction tank in a hermetically sealed state. Reactor.   The gas-liquid reaction device according to claim 12, wherein the discharge device includes a discharge control device that controls a discharge amount of the liquid in accordance with a liquid level of the liquid phase in the reaction tank.   A gas-liquid reaction method, wherein a reaction between a liquid containing a reactant and a reaction gas is performed by the gas-liquid reaction apparatus according to any one of claims 1 to 13.

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