JP2010023023A - Gas-liquid reaction apparatus and gas-liquid reaction method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To keep the consumption of a reactive gas to the minimum. <P>SOLUTION: A gas-liquid reaction apparatus is provided with: a reaction vessel 10 having a reaction space 11; a liquid material supply unit 20 for supplying a liquid material, containing a reactive substrate, to the reaction space; a gas supply unit 30 for supplying the reactive gas to the reaction space; a liquid pool part 41 which is connected to the reaction space and has a liquid pool space 45 for accumulating a production liquid produced by reacting the reactive substrate with the reactive gas; and a discharge unit 40 for discharging the production liquid in the liquid pool part while keeping the reaction space and the liquid pool space in hermetically-sealed states. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a gas-liquid reaction apparatus and a gas-liquid reaction method.

  As a gas-liquid reaction apparatus that mixes liquid raw material and reaction gas and obtains a predetermined product by chemical reaction and its reaction method, the raw material liquid and reaction gas are put into a reaction vessel, and the reaction gas is sealed and heated. Is known which uses a batch type process in which a solution is dissolved in a raw material liquid and the inside of the container is stirred for a predetermined time. However, when the batch process described above is used, a reaction vessel with a relatively large capacity is used to increase the production volume, so uniform mixing and temperature adjustment in the vessel is difficult, and the reaction with high selectivity. It is not easy to control.

  Therefore, in recent years, a gas-liquid reactor of a flow process that causes various chemical reactions while flowing a raw material solution and a reactive gas in a flow path having a relatively small cross-sectional area has attracted attention. In this type of gas-liquid reaction apparatus, a chemical reaction region part that performs mixing, heating, reaction, and the like, and a flow path that communicates these are provided. By supplying a raw material liquid and a reaction gas, a predetermined reaction time is provided. A chemical reaction is configured to be performed. Thus, when a flow-type gas-liquid reactor is used, a highly pure product can be obtained by performing highly selective reaction control. In addition, since the flow-type gas-liquid reactor generally has a smaller reaction area than the batch type, precise control of chemical reaction conditions such as temperature is possible, and dangers represented by carbon monoxide, fluorine, and hydrogen. Even when a highly reactive gas species is used as a reaction gas under high pressure, the risk of explosion and the like can be reduced.

For example, Patent Document 1 discloses a method of directly fluorinating by using a flow-type gas-liquid reactor and circulating a reaction substrate solution and a reaction gas containing fluorine in a microchannel. With this technology, chemical reactions can be performed efficiently and high heat removal efficiency can be achieved. Therefore, the synthesis reaction involving exothermic reactions can be performed safely, the yield can be expected to improve, and the handling is easy. Has been.
Patent Document 2 discloses a technique for efficiently performing a reaction in a gas-liquid mixed phase flow by using a gas-liquid reaction apparatus having a plurality of reaction gas introduction portions into a microchannel.

JP-T-2001-521816 JP 2007-105668 A

However, the following problems exist in the conventional technology as described above.
In the above technique, an excessive amount of reaction gas, which is several times or more in molar ratio, is caused to flow into the reaction tube with respect to the amount of gas necessary for a chemical reaction to obtain a product from a raw material liquid. The problem of wasting arises.
For example, in the technique described in Patent Document 1, after a raw material liquid and a reaction gas are flown into a reaction tube in a flow system and chemically synthesized, an unreacted gas (gas phase gas and dissolved in the liquid phase is dissolved together with the product solution. Gas) flows out of the reaction tube, and a large amount of reaction gas is wasted.
Moreover, in the technique described in Patent Document 2, the product liquid and the reaction gas are separated by using a gas-liquid separator after the chemical reaction, and the product liquid is recovered, but the gas-liquid separator stores the liquid. At the same time, since the reaction gas is discharged as needed, it does not contribute to the suppression of the reaction gas consumption.

  The present invention has been made in consideration of the above points, and an object of the present invention is to provide a gas-liquid reaction apparatus and a gas-liquid reaction method capable of minimizing reaction gas consumption. .

In order to achieve the above object, the present invention employs the following configuration.
The gas-liquid reaction device of the present invention includes a reaction vessel having a reaction space, a liquid material supply device that supplies a liquid material containing a reaction substrate to the reaction space, a gas supply device that supplies a reaction gas to the reaction space, A gas-liquid reaction apparatus having a liquid storage section connected to the reaction space and having a liquid storage space for storing a product liquid generated by a reaction between the reaction substrate and the reaction gas, the reaction space and the liquid storage It has a discharge device for discharging the generated liquid from the liquid reservoir while keeping the space sealed.

The discharge device is provided with a reaction gas control device that controls the supply amount of the reaction gas according to the pressure of the reaction gas in the reaction space, and provided in the liquid storage portion with an opening in the liquid storage space. A configuration having a discharge hole and a discharge control device that controls the discharge amount of the product liquid from the discharge hole in accordance with the liquid level of the product liquid in the liquid reservoir can be suitably employed.
Thus, in the present invention, in order to set the pressure of the reaction gas in the reaction vessel to a desired value, the supply amount of the reaction gas is controlled by the reaction gas control device according to the pressure of the reaction gas in the reaction space, After the gas pressure reaches the desired value, the supply of the reaction gas is stopped. Also, when the pressure of the reaction gas decreases due to the reaction with the reaction substrate, similarly, the reaction gas is supplied by the reaction gas control device according to the pressure of the reaction gas in the reaction space, so that the pressure of the reaction gas is desired. It becomes possible to maintain the value.
In the present invention, when the liquid level of the product liquid in the liquid reservoir is sufficiently higher than the discharge hole, and the reaction space and the liquid storage space are maintained in a sealed state, a predetermined amount from the discharge hole. (For example, the amount of product liquid generated by the reaction between the reaction substrate and the reaction gas) is discharged, and the liquid level of the product liquid may be lower than the discharge hole. When there is a possibility that the sealed state is released, it is possible to prevent the liquid level from being lowered by suppressing the discharge amount of the generated liquid from the discharge hole.

Moreover, in this invention, the structure which has the preliminary reaction apparatus which pre-reacts the said liquid material and the said reaction gas supplied toward the said reaction container can be employ | adopted suitably.
Accordingly, in the present invention, since the liquid material and the reaction gas are preliminarily reacted, the reaction substrate and the reaction gas supplied to the reaction container can be set to conditions suitable for the reaction in the reaction container.

As the preliminary reaction apparatus, a configuration in which a preliminary reaction is performed under reaction conditions different from the reaction conditions in the reaction vessel can be suitably employed depending on the reaction characteristics between the reaction substrate and the reaction gas.
Accordingly, in the present invention, it is possible to cope with the case where the reaction conditions suitable for the preliminary reaction are different from the reaction conditions in the reaction vessel, and the reaction substrate and the reaction gas that have been pre-reacted under the optimal preliminary reaction conditions. Can be supplied to the reaction vessel.

Moreover, in this invention, the structure which has a suction device which discharges the said production | generation liquid of the said liquid reservoir part by negative-pressure suction can be employ | adopted suitably.
Thereby, in the present invention, the product liquid accumulated in the liquid reservoir can be forcibly sucked and efficiently discharged.

Further, as the liquid material supply device in the gas-liquid reaction device, the liquid material is supplied from one end side of the reaction vessel, and the gas supply device supplies the reaction gas from the other end side of the reaction vessel. It is possible to suitably adopt the configuration.
As a result, in the present invention, the liquid material enters the reaction gas from the reaction gas supply hole in the reverse direction as in the case where the liquid material and the reaction gas are supplied from the same side of the reaction vessel, or the reaction gas flows into the liquid material supply hole. Therefore, the liquid material can be prevented from flowing back and entering, and a stable liquid material supply and reaction gas supply can be realized.

In addition, as the liquid reservoir in the gas-liquid reaction apparatus, a configuration provided in a part of the reaction vessel can be suitably employed.
As a result, in the present invention, it is not necessary to separately provide a liquid reservoir independently of the reaction vessel, and the apparatus can be reduced in size and price.

In addition, as the bottom of the liquid reservoir in the gas-liquid reaction apparatus, a configuration in which the diameter is gradually reduced as it goes downward can be suitably employed.
Thereby, in this invention, the cross-sectional area in a front-end | tip part (bottom edge part) can be made small by forming the bottom part of a liquid reservoir part in cone shape, for example. Therefore, in the present invention, it is possible to more reliably fill the bottom of the liquid reservoir with the product liquid even when the amount of the product liquid is small. As a result, by disposing the discharge hole for the product liquid at the bottom end, it is possible to more reliably prevent the reaction gas from flowing out of the discharge hole and maintain the sealed state of the reaction space and the liquid storage space.

Moreover, as said reaction container in said gas-liquid reaction apparatus, the structure formed in the tubular shape and wound around the outer periphery of the heating apparatus which heats the said reaction container can be employ | adopted suitably.
Thereby, in this invention, the contact area of reaction container and a heating apparatus becomes large, and can heat a reaction container efficiently. Moreover, in this invention, it becomes possible to ensure the length of the reaction space of a reaction container largely with respect to a fixed installation space. Therefore, in the present invention, it is possible to ensure a long reaction space and improve productivity.

Moreover, as an inner surface bottom portion facing the reaction space in the reaction vessel, a configuration having a planar shape can be suitably employed.
Thereby, in the present invention, the thickness of the liquid material (raw material liquid) in the reaction vessel can be made thinner than the case where the inner surface bottom is an arcuate surface, such as a circular tube, for the same amount of liquid material. It is possible to efficiently dissolve the reaction gas in the liquid material.
In this case, it is preferable that the inner surface bottom is substantially horizontal.
Moreover, as the inner surface bottom portion, a configuration in which a cross section in the width direction is formed in a substantially V shape gradually going downward as it goes toward the central portion can be suitably employed.

Moreover, as an inner surface bottom portion facing the reaction space in the reaction vessel, a configuration in which the extending direction is inclined with respect to the horizontal direction can be suitably employed.
By inclining the inner bottom facing the reaction space in the reaction vessel with respect to the horizontal direction, the flow rate of the liquid material can be easily adjusted.

  In this case, for example, the reaction vessel is configured to be rotatable around the horizontal axis on one end side, and by raising and lowering the other end side, the inclination angle can be adjusted to an arbitrary value, and the gas-liquid reaction characteristics ( The optimum tilt angle can be selected according to the type of liquid material and reaction gas.

The inclination angle of the extending direction with respect to the horizontal direction is preferably 5 ° or more and 45 ° or less.
When the inclination angle is less than 5 °, the difference in the flow rate of the liquid material is small compared to the horizontal case, and the effect of adjusting the flow rate of the liquid material by the inclination is less likely to occur. If it exceeds 45 °, the flow rate between the liquid material and the reaction gas increases, so that the contact time in the reaction space is shortened, making it unsuitable for reactions that require a long time. These disadvantages can be avoided by setting the angle to 45 ° or less.

As the inner surface bottom portion in the gas-liquid reaction apparatus, a configuration in which the downstream side is positioned higher than the upstream side can be suitably employed.
Thereby, in this invention, the flow velocity of a liquid material and reaction gas will become slow by gravity, and it becomes possible to lengthen the contact time in reaction space.

  On the other hand, the gas-liquid reaction method of the present invention includes a step of supplying a liquid material containing a reaction substrate and a reaction gas to a reaction space in a reaction vessel, and a step of reacting the liquid material and the reaction gas to generate a product liquid. And a step of storing the product liquid in a liquid reservoir portion having a liquid storage space connected to the reaction space, the liquid reservoir while sealing the reaction space and the liquid storage space. A step of discharging a part of the product liquid.

Further, in the gas-liquid reaction method, according to the step of controlling the supply amount of the reaction gas according to the pressure of the reaction gas in the reaction space, and according to the liquid level of the product liquid in the liquid reservoir, A procedure including a step of controlling the discharge amount of the product liquid from a discharge hole provided to open in the liquid storage space can also be suitably employed.
Thus, in the present invention, in order to set the pressure of the reaction gas in the reaction vessel to a desired value, the supply amount of the reaction gas is controlled according to the pressure of the reaction gas in the reaction space, and the pressure of the reaction gas is desired. After reaching the value, supply of the reaction gas is stopped. When the pressure of the reaction gas decreases due to the reaction with the reaction substrate, the reaction gas is similarly supplied (supplemented) according to the pressure of the reaction gas in the reaction space, so that the pressure of the reaction gas is set to a desired value. It becomes possible to maintain.
In the present invention, when the liquid level of the product liquid in the liquid reservoir is sufficiently higher than the discharge hole, and the reaction space and the liquid storage space are maintained in a sealed state, a predetermined amount from the discharge hole. (For example, the amount of product liquid generated by the reaction between the reaction substrate and the reaction gas) is discharged, and the liquid level of the product liquid may be lower than the discharge hole. When there is a possibility that the sealed state is released, it is possible to prevent the liquid level from being lowered by suppressing the discharge amount of the generated liquid from the discharge hole.

In the gas-liquid reaction method described above, a procedure including a preliminary reaction step in which the liquid material supplied toward the reaction vessel and the reaction gas are preliminarily reacted can be suitably employed.
Accordingly, in the present invention, since the liquid material and the reaction gas are preliminarily reacted, the reaction substrate and the reaction gas supplied to the reaction container can be set to conditions suitable for the reaction in the reaction container.

In the gas-liquid reaction method described above, a procedure in which a preliminary reaction is performed under reaction conditions different from the reaction conditions in the reaction vessel can be suitably employed according to the reaction characteristics between the reaction substrate and the reaction gas.
Accordingly, in the present invention, it is possible to cope with the case where the reaction conditions suitable for the preliminary reaction are different from the reaction conditions in the reaction vessel, and the reaction substrate and the reaction gas that have been pre-reacted under the optimal preliminary reaction conditions. Can be supplied to the reaction vessel.

Moreover, in said gas-liquid reaction method, the procedure which has the process of making the negative pressure suction and discharge | emit the said production | generation liquid of the said liquid reservoir part can also be employ | adopted suitably.
Thereby, in the present invention, the product liquid accumulated in the liquid reservoir can be forcibly sucked and efficiently discharged.

In the gas-liquid reaction method, a configuration in which the liquid material is supplied from one end side of the reaction vessel and the reaction gas is supplied from the other end side of the reaction vessel can be suitably employed.
As a result, in the present invention, the liquid material enters the reaction gas from the reaction gas supply hole in the reverse direction as in the case where the liquid material and the reaction gas are supplied from the same side of the reaction vessel, or the reaction gas flows into the liquid material supply hole. Therefore, the liquid material can be prevented from flowing back and entering, and a stable liquid material supply and reaction gas supply can be realized.

Moreover, in said gas-liquid reaction method, the structure which provides the said liquid reservoir part in a part of said reaction container can also be employ | adopted suitably.
As a result, in the present invention, it is not necessary to separately provide a liquid reservoir independently of the reaction vessel, and the apparatus can be reduced in size and price.

In addition, in the gas-liquid reaction method described above, a configuration in which the bottom of the liquid reservoir is gradually reduced in diameter as it goes downward can be suitably employed.
Thereby, in this invention, the cross-sectional area in a front-end | tip part (bottom edge part) can be made small by forming the bottom part of a liquid reservoir part in cone shape, for example. Therefore, in the present invention, it is possible to more reliably fill the bottom of the liquid reservoir with the product liquid even when the amount of the product liquid is small. As a result, by disposing the discharge hole for the product liquid at the bottom end, it is possible to more reliably prevent the reaction gas from flowing out of the discharge hole and maintain the sealed state of the reaction space and the liquid storage space.

Moreover, in said gas-liquid reaction method, the said reaction container is formed in a tubular shape, and the structure wound around the outer periphery of the heating apparatus which heats the said reaction container can also be employ | adopted suitably.
Thereby, in this invention, the contact area of reaction container and a heating apparatus becomes large, and can heat a reaction container efficiently. Moreover, in this invention, it becomes possible to ensure the length of the reaction space of a reaction container largely with respect to a fixed installation space. Therefore, in the present invention, it is possible to ensure a long reaction space and improve productivity.

  In the present invention, since the reaction space and the liquid storage space are sealed even when the product liquid in the liquid storage part is discharged, the reaction gas can be retained in the reaction space and the liquid storage space without flowing out of both the spaces. It becomes possible. Therefore, in the present invention, it is possible to suppress the consumption to the minimum necessary without wasting unreacted reaction gas.

In the gas-liquid reaction method described above, a configuration having a planar shape can be suitably employed as the inner bottom portion facing the reaction space in the reaction vessel.
Thereby, in the present invention, the thickness of the liquid material (raw material liquid) in the reaction vessel can be made thinner than the case where the inner surface bottom is an arcuate surface, such as a circular tube, for the same amount of liquid material. It is possible to efficiently dissolve the reaction gas in the liquid material.
In this case, it is preferable that the inner surface bottom is substantially horizontal.
Moreover, as the inner surface bottom portion, a configuration in which a cross section in the width direction is formed in a substantially V shape gradually going downward as it goes toward the central portion can be suitably employed.

In the gas-liquid reaction method described above, a configuration in which the extending direction is inclined with respect to the horizontal direction can be suitably employed as the inner bottom facing the reaction space in the reaction vessel.
By inclining the inner bottom facing the reaction space in the reaction vessel with respect to the horizontal direction, the flow rate of the liquid material can be easily adjusted.

In the gas-liquid reaction method, the inclination angle of the extending direction with respect to the horizontal direction is preferably 5 ° or more and 45 ° or less.
When the inclination angle is less than 5 °, the difference in the flow rate of the liquid material is small compared to the horizontal case, and the effect of adjusting the flow rate of the liquid material by the inclination is less likely to occur. If it exceeds 45 °, the flow rate between the liquid material and the reaction gas increases, so that the contact time in the reaction space is shortened, making it unsuitable for reactions that require a long time. These disadvantages can be avoided by setting the angle to 45 ° or less.

As the inner surface bottom in the gas-liquid reaction method, a configuration in which the downstream side is provided above the upstream side can be suitably employed.
Thereby, in this invention, the flow velocity of a liquid material and reaction gas will become slow by gravity, and it becomes possible to lengthen the contact time in reaction space.

It is a figure which shows embodiment of this invention, Comprising: It is a schematic block diagram of a gas-liquid reaction apparatus. It is a flowchart figure which produces | generates a product. It is a schematic block diagram of the gas-liquid reaction apparatus which concerns on 2nd Embodiment. It is a flowchart figure which produces | generates a product in 2nd Embodiment. It is a schematic block diagram of the gas-liquid reaction apparatus which concerns on 3rd Embodiment. It is a schematic block diagram of the gas-liquid reaction apparatus which concerns on 4th Embodiment. It is a schematic block diagram of the gas-liquid reaction apparatus which concerns on 5th Embodiment. It is a schematic block diagram of the gas-liquid reaction apparatus which concerns on 6th Embodiment. It is a schematic block diagram of the gas-liquid reaction apparatus of another form. It is a schematic block diagram of the gas-liquid reaction apparatus of another form. It is a schematic block diagram of the gas-liquid reaction apparatus of another form. It is a schematic block diagram of the gas-liquid reaction apparatus which concerns on 7th Embodiment. It is sectional drawing of the width direction of a reaction tube. It is a top sectional view of a reaction tube. It is a BB line sectional view in Drawing 12. It is a figure which shows another form of reaction space. It is a figure which shows another form of reaction space. It is a figure which shows another form of reaction space. It is a figure which shows another form of reaction space. It is a schematic block diagram of the gas-liquid reaction apparatus which concerns on 8th Embodiment. It is a schematic block diagram which shows the modification of a gas-liquid reaction apparatus. It is a schematic block diagram which shows the modification of heater installation.

Hereinafter, embodiments of the gas-liquid reaction apparatus and gas-liquid reaction method of the present invention will be described with reference to FIGS.
In each drawing used for the following description, the scale of each member is appropriately changed to make each member a recognizable size.

(First embodiment)
FIG. 1 is a schematic configuration diagram of a gas-liquid reaction apparatus according to the present invention.
The gas-liquid reaction apparatus 1 shown in this figure includes a reaction tube (reaction vessel) 10 having a reaction space 11 therein, a raw material supply apparatus (liquid material supply apparatus) 20, a gas supply apparatus (gas supply apparatus) 30, and product discharge. The apparatus (discharge device) 40 and the storage tank 50 are mainly configured.

  The reaction tube 10 is arranged along the horizontal direction and is made of a material selected from stainless steel, brass, fluorine-based material, glass, vinyl chloride, polycarbonate, etc., based on the corrosion resistance and pressure resistance against the reagents used in the reaction, the reaction substrate, etc. Stainless steel and brass are preferably used in consideration of the robustness. The size (inner diameter) of the reaction tube 10 is not particularly limited, but those within the range of 0.005 to 1000 mm are preferably used. Similarly, the capacity of the reaction tube 10 is not particularly limited, but is preferably in the range of 0.001 to 1 L, and more preferably in the range of 0.01 to 0.2 L. The outer wall of the reaction tube 10 is provided with a thermocouple for temperature measurement, a heater for heating, and a heat insulating material (all not shown). The temperature of the reaction tube 10 is increased based on the measurement result of the thermocouple. It is controlled by a controller (not shown) that controls the operation of the temperature heater.

  The raw material supply device 20 supplies a liquid material containing a reaction substrate as a raw material to the reaction space 11 of the reaction tube 10, and includes a raw material storage tank 21, a liquid feeding device 22, and a check valve 23. ing. The liquid material (raw material) stored in the raw material storage tank 21 is supplied via a liquid supply pipe 24 connected to one end side (left side in FIG. 1) of the reaction tube 10 by a liquid supply device 22 constituted by a pump or the like. It is supplied to the reaction space 11 of the reaction tube 10. A valve may be provided between the liquid feeding device 22 and the check valve 23.

  The gas supply device 30 supplies a reaction gas (reaction gas) to the reaction space 11 of the reaction tube 10, and includes a gas cylinder 31, a flow rate control device 32, a check valve 33, a pressure gauge 34, a relief valve. 35. The reaction gas stored in the gas cylinder 31 is connected to the check valve 33, pressure gauge 34, relief valve 35, and one end side of the reaction tube 10 (left side in FIG. 1) after the flow rate is controlled by the flow rate control device 32. It is supplied to the reaction space 11 of the reaction tube 10 through the introduction tube 36. The arrangement order of the pressure gauge 34 and the relief valve 35 may be reversed.

  The product discharge device 40 has a liquid reservoir 41, a valve 42, and a resistor 43. The liquid reservoir 41 has a liquid reservoir space 45 inside, and is connected to the reaction tube 10 by a discharge tube 44. The product generated by the reaction between the raw material and the reaction gas in the reaction tube 10 is stored in the liquid storage space 45 through the discharge tube 44. A discharge pipe 47 is connected to the bottom of the liquid reservoir 41. The inside of the discharge pipe 47 communicates with the liquid storage space 45 through a discharge hole 46 provided in the bottom of the liquid storage portion 41 so as to open to the liquid storage space 45. The discharge pipe 47 is provided with the valve 42 and the resistor 43 in order, and the product stored in the liquid reservoir 41 corresponds to the flow resistance in the resistor 43 when the valve 42 is open. It is discharged and stored in the storage tank 50 from the discharge hole 46 through the discharge pipe 47 at a speed.

  The reaction space 11 of the reaction tube 10 and the liquid storage space 45 of the liquid storage portion 41 that communicates with the reaction space 11 via the inside of the discharge tube 44 are arranged inside the discharge tube 44 by closing the valve 42. And the sealed state is maintained.

  The liquid reservoir 41 is provided with a liquid level gauge 48. The liquid level gauge 48 measures the liquid level position (liquid level) of the product stored in the liquid storage space 45 using light or ultrasonic waves, and when the liquid level position reaches a predetermined position. The ON signal is output to the discharge controller 49, and the OFF signal is output to the discharge controller 49 when the position of the liquid level is lower than the predetermined position. The discharge controller 49 controls the opening / closing of the valve 42 according to the output of the liquid level gauge 48.

There is no restriction | limiting in particular as synthesis reaction which can apply said gas-liquid reaction apparatus 1, It can use for known high-pressure gas-liquid synthesis reaction or atmospheric pressure gas-liquid synthesis reaction.
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 (olefin hydrogenation reaction, carbonyl compound hydrogenation reaction, cyano group hydrogenation reaction, etc.), alkane photohalogenation reaction, and Heck carbonylation reaction. Particularly, it is suitable for radical carbonylation reaction, olefin hydroformylation reaction, direct fluorination reaction and Heck carbonylation reaction, and is most suitable for Heck carbonylation reaction.

In this embodiment, when reacting the reaction substrate, a catalyst may or may not be used. In the case of using a catalyst, a homogeneous catalyst is preferably used, and in particular, one containing at least one element selected from elements (metals) of Groups 4 to 12 of the periodic table and lanthanoids (metal) is used. Further, the catalyst may contain at least one kind of metal other than the catalytic metal selected from the elements (metals) of Groups 4 to 12 of the periodic table and lanthanoids. Furthermore, the catalyst may contain a halogen.
These catalysts are usually contained in a liquid component containing a reaction substrate and supplied to the reaction tube 10. 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 the amount of the active ingredient relative to the reaction substrate.

In this embodiment, when reacting the reaction substrate, a solvent may be used, or the reaction substrate itself may be used in an amount equivalent to the solvent. When a solvent is used, the reaction substrate may be dissolved and supplied to the reaction tube 10, or may be supplied separately from the reaction substrate.
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 the organic solvent 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, pyridi Heteroaromatic compounds such as carbon tetrachloride, halogen solvents such as 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). Two or more kinds of mixed solvents in an arbitrary ratio 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 reaction substrate used is usually 0.001 mol or more, preferably 0.02 mol or more, more preferably 0.1 mol or more with respect to 1 liter of 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 small, it is disadvantageous in that the catalyst or the reaction substrate is dissolved.

Examples of the reaction gas (reaction gas) include oxygen, ozone, hydrogen, fluorine, chlorine, carbon monoxide, carbon dioxide, sulfur dioxide, hydrogen chloride gas, ammonia gas, methane, ethane, propane, ethylene gas, and acetylene gas. And oxygen includes 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 ratio, 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.

Next, the procedure for producing a product (synthetic product) using the gas-liquid reactor 1 will be described with reference to the flowchart of FIG.
When the reaction gas is supplied to the reaction space 11 of the reaction tube 10 with no product accumulated in the liquid reservoir 41, the reaction gas flows into the liquid storage space 45 from the discharge tube 44 and is discharged through the discharge hole 46. Since it flows out from the pipe 47, the valve 42 is first closed when producing the product (step S1). Here, the liquid feeding pipe 24 and the introduction pipe 36 are provided with check valves 23 and 33, respectively, to prevent the fluid in the reaction space 11 from flowing back through the liquid feeding pipe 24 and the introduction pipe 36. Since the discharge pipe 47 is also closed by the valve 42, the reaction space 11 and the liquid storage space 45 (and the inside of the discharge pipe 44) are sealed.

  Subsequently, the gas pressure in the reaction tube 10 is controlled to a desired value αMPa using the flow rate control device 32 (step S2). At this time, the gas pressure in the reaction space 11 in the reaction tube 10 is measured by the pressure gauge 34, and when the gas pressure in the reaction space 11 falls below αMPa, the gas pressure is adjusted using the flow rate control device 32. The reaction gas is supplemented so as to be α MPa. The filling interval can be performed over time or intermittently.

Then, after waiting for a predetermined time until the gas pressure in the reaction tube 10 is stabilized (step S3), it is determined whether or not the gas pressure is stabilized (step S4). When the gas pressure is stabilized, the liquid feeding device 22 is operated. Then, the raw material liquid is caused to flow from the raw material storage tank 21 into the reaction tube 10 through the liquid feeding tube 24 at a desired flow rate (VmL / min) (step S5).
When the raw material liquid is supplied to the reaction space 11, the reaction gas and the reaction substrate contained in the raw material liquid react to generate a product (product liquid) according to the supply amount of the raw material liquid (reaction substrate). Then, it is discharged to the liquid reservoir 41 through the discharge pipe 44.

  Whether the liquid level (position of the liquid level) of the product accumulated in the liquid reservoir 41 in the liquid reservoir 41 reaches a predetermined position and the product is sufficiently accumulated in the liquid reservoir 41, that is, generated from the discharge hole 46. The liquid level system 48 monitors whether or not the product has accumulated at the bottom of the liquid reservoir 41 to such an extent that no product flows out. When the liquid level has not reached the predetermined position, an OFF signal is output to the discharge controller 49. When the liquid level reaches the predetermined position, an ON signal is output to the discharge controller 49. The discharge controller 49 controls the opening and closing of the valve 42 according to the output of the liquid level system 48 (step S6). That is, the valve 42 is kept closed while the OFF signal is output, and the valve 42 is opened when the ON signal is output (step S7). As a result, the product accumulated in the liquid reservoir 41 is discharged from the discharge hole 46.

At this time, the discharge hole 46 is covered with the product, and the space where the reaction gas exists in the liquid storage space 45 is formed above the liquid level of the product, and the reaction gas does not flow out of the discharge hole 46. Sealed. Therefore, in the gas-liquid reactor 1, only the product is discharged while the reaction gas is sealed.
And the product discharged | emitted from the discharge hole 46 flows out into the storage tank 50 through the discharge pipe 47 with the flow volume according to the flow resistance by the resistor 43, and is stored.

  Here, according to the flow resistance by the resistor 43, the flow rate of the product flowing out from the liquid reservoir 41 and the amount of the product generated according to the supply amount of the raw material liquid (reaction substrate) by the operation of the liquid feeding device 22 When the production amount is balanced, the liquid level of the product in the liquid reservoir 41 is maintained substantially constant. On the other hand, when the flow rate of the product flowing out from the liquid reservoir 41 is larger than the amount of product produced, the liquid level of the product in the liquid reservoir 41 gradually decreases. When the discharge controller 49 detects that the liquid level of the product falls below a predetermined position and the level gauge 48 outputs an OFF signal (step S8), the discharge controller 49 closes the valve 42 (step S9). . As a result, the outflow of the product from the liquid reservoir 41 stops, the discharge hole 46 is exposed due to the decrease in the liquid level of the product, and the reaction gas is prevented from flowing out of the discharge hole 46.

  Thereafter, it is determined whether a necessary amount of product is stored in the storage tank 50 (step S10). If the necessary amount is not obtained, the above steps S5 to S9 are repeated to obtain the necessary amount. In some cases, product formation is complete.

  In addition, between the said step S5-step S9, the gas pressure in the reaction space 11 is monitored with the pressure gauge 34, and when gas pressure falls by consumption of the reaction gas accompanying reaction with a raw material liquid, it will fall. By supplying the reaction gas in an amount corresponding to the gas pressure into the reaction tube 10 continuously or intermittently by the gas supply device 30, the inside of the reaction tube 10 can be controlled to a desired gas pressure αMPa. The control range is preferably within α ± 20%, and more preferably within α ± 5%.

  As described above, in the present embodiment, the reaction space 11 of the reaction tube 10 and the liquid reservoir space 45 of the liquid reservoir 41 are maintained in a sealed state, and the product in the liquid reservoir 41 is discharged. A predetermined amount of product can be obtained while suppressing the consumption of gas to the minimum necessary. Therefore, in the present embodiment, waste of reaction gas can be greatly suppressed by applying the gas-liquid reaction apparatus 1 and the gas-liquid reaction method described above to an industrial process for obtaining a product by gas-liquid reaction. Thus, the cost of chemicals used for the reaction can be reduced.

(Second Embodiment)
Then, 2nd Embodiment of the gas-liquid reaction apparatus 1 is described with reference to FIG.3 and FIG.4.
In these drawings, the same components as those of the first embodiment shown in FIGS. 1 and 2 are denoted by the same reference numerals, and the description thereof is omitted.
The second embodiment is different from the first embodiment in that a liquid delivery device is provided in the product discharge device 40, and the other configuration is the same as that of the first embodiment. Therefore, this point will be described below. .

As shown in FIG. 3, in the gas-liquid reaction device 1 in the second embodiment, a liquid feeding device 52 including a liquid feeding pump or the like is provided between the valve 42 of the discharge pipe 47 and the resistor 43. The driving of the liquid feeding device 52 is controlled by a discharge controller 49. The discharge controller 49 is configured to control opening / closing of the valve 42 and driving of the liquid feeding device 52 based on the measurement result of the liquid level gauge 48.
Other configurations are the same as those of the first embodiment.
The driving of the liquid feeding device 52 is not necessarily linked with the measurement result of the liquid level gauge 48.

In the gas-liquid reactor 1 configured as described above, when an ON signal is output from the level gauge 48 in step S6, the discharge controller 49 opens the valve 42 and the liquid feeding device 52 as shown in the flowchart of FIG. Is driven (step S17). As a result, the product stored in the liquid reservoir 41 flows out to the storage layer 50 through the discharge pipe 47 and is stored.
Thus, also in this embodiment, the same operation and effect as the first embodiment can be obtained.

In the second embodiment, the discharge controller 49 controls the driving of the liquid feeding device 52. However, the driving of the liquid feeding device 22 may be further controlled.
In this configuration, the liquid level of the product stored in the liquid reservoir 41 is discharged by discharging the amount of product corresponding to the amount of raw material supply in synchronization with the amount of raw material supplied by driving the liquid feeding device 22. Can be made constant at all times, and continuous product production can be easily realized.
Further, the discharge controller 49 is not an essential configuration, and the liquid feeding device 22 and the liquid feeding device 52 may be linked with each other.

(Third embodiment)
Then, 3rd Embodiment of the gas-liquid reaction apparatus 1 is described with reference to FIG.
In this figure, the same components as those of the first embodiment shown in FIGS. 1 and 2 are denoted by the same reference numerals, and the description thereof is omitted.
The third embodiment is different from the first embodiment in that a preliminary reaction tube for prereacting the raw material liquid and the reaction gas is provided, and the other configuration is the same as that of the first embodiment. The point will be described.

  As shown in FIG. 5, the gas-liquid reactor 1 in the third embodiment is provided with a preliminary reaction tube (preliminary reaction device) 15 on the upstream side of the reaction tube 10. The preliminary reaction tube 15 has the same configuration as the reaction tube 10 and can set reaction conditions such as pressure and temperature independently of the reaction tube 10. In the gas-liquid reaction device 1 of the present embodiment, the raw material liquid supplied from the raw material supply device 20 toward the reaction tube 10 and the reaction gas supplied from the gas supply device 30 toward the reaction tube 10 are reserved. The raw material liquid and reaction gas introduced into the reaction tube 15 and subjected to preliminary reaction (preliminary mixing) are supplied to the reaction tube 10.

  In the gas-liquid reactor 1 configured as described above, reaction conditions are set according to the reaction characteristics of the reaction substrate of the raw material liquid and the reaction gas. As this reaction condition, for example, when a lower reaction temperature is preferable, a cooling treatment is performed, and when a higher reaction temperature is preferable, a heat treatment is performed. Similarly, the gas pressure of the reaction gas is appropriately set according to the reaction characteristics.

  Thus, in this embodiment, in addition to obtaining the same operation and effect as the first embodiment, the raw material liquid and the reaction gas are pre-reacted under reaction conditions different from the reaction conditions in the reaction tube 10. Even when the pre-reaction conditions in the pre-reaction tube 15 are different from the reaction conditions in the reaction tube 10, the raw material liquid and the reaction gas can be pre-reacted under the optimum reaction conditions. The raw material liquid and the reaction gas can be supplied toward the reaction tube 10 in an optimum state, and a more efficient gas-liquid reaction can be realized.

(Fourth embodiment)
Then, 4th Embodiment of the gas-liquid reaction apparatus 1 is described with reference to FIG.
In FIG. 6, peripheral devices other than the reaction tube 10 are shown in a simplified manner. In this figure, the same components as those of the first embodiment shown in FIGS. 1 and 2 are denoted by the same reference numerals, and the description thereof is omitted.
In the above embodiment, the reaction tube 10 and the liquid reservoir 41 are separately provided. In the fourth embodiment, a case where the liquid reservoir 41 is provided in a part of the reaction tube 10 will be described.

As shown in FIG. 6, the reaction tube 10 is formed such that the end portion on the product discharge side is bent downward in the vertical direction. In the present embodiment, the bent portion serves as a liquid reservoir 41, and an internal liquid reservoir space 45 is provided in communication with the reaction space 11 in the reaction tube 10.
The bending angle of the bent portion is not particularly limited, but the inner angle can be selected from an angle greater than 0 degree and greater than 180 degrees, preferably in the range of 30 to 135 degrees, and preferably in the range of 75 to 105 degrees. The range is optimal.
Although not shown in FIG. 6, the liquid reservoir 41 is provided with a liquid level gauge or the like (the same applies to the following embodiments).

In the gas-liquid reactor 1 configured as described above, the products generated by the reaction in the reaction space 11 are sequentially accumulated in the liquid reservoir 41 and are discharged from the discharge pipe 47 according to the liquid level.
Therefore, in this embodiment, in addition to obtaining the same operation and effect as in the first embodiment, it is not necessary to provide the liquid reservoir 41 independently from the reaction tube 10, so that the apparatus can be reduced in size and weight. In addition, the price can be reduced.
The reaction tube 10 shown in the present embodiment does not necessarily have to be bent downward in the vertical direction, and is at an angle of 90 degrees or more with respect to the main body of the reaction tube 10 extending in the horizontal direction. It may be configured to bend at an angle having a component that is oriented toward the surface.

(Fifth embodiment)
Then, 5th Embodiment of the gas-liquid reaction apparatus 1 is described with reference to FIG.
In FIG. 7 as well, peripheral devices other than the reaction tube 10 are shown in a simplified manner. In this figure, the same components as those of the first embodiment shown in FIGS. 1 and 2 are denoted by the same reference numerals, and the description thereof is omitted.
In the above embodiment, both the raw material supply device 20 and the gas supply device 30 are configured to supply the raw material liquid and the reaction gas from one end side of the reaction tube 10 respectively, but in the fifth embodiment, the raw material supply device 20 and the gas supply device 30 are supplied from different sides. It is configured.

As shown in FIG. 7, in the raw material supply apparatus 20, the liquid feeding pipe 24 is connected to one end side (left side in FIG. 7) of the reaction tube 10, and in the gas supply apparatus 30, the introduction pipe 36 is the other end of the reaction tube 10. It is connected to the side (right side in FIG. 7), and the raw material liquid and the reaction gas are supplied from different sides.
Therefore, in this embodiment, in addition to obtaining the same operation and effect as the first embodiment, the raw material liquid is introduced as in the case where the raw material liquid and the reaction gas are supplied from the same side of the reaction tube 10. It is possible to prevent the liquid 36 from flowing back into the pipe 36 and to prevent the reaction gas from flowing back into the liquid feeding pipe 24 and to enter the liquid feed pipe 24, thereby realizing a stable raw material liquid supply and reaction gas supply.
In the present embodiment, the introduction pipe 36 of the gas supply device 30 is provided at the end on the other end side of the reaction tube 10. However, the present invention is not limited to this and does not face the liquid feeding pipe 24. If it is a range, it is good also as a structure provided in the approximate center part of the length direction of the reaction tube 10, for example.

(Sixth embodiment)
Then, 6th Embodiment of the gas-liquid reaction apparatus 1 is described with reference to FIG.
In FIG. 8 as well, peripheral devices other than the reaction tube 10 are shown in a simplified manner. In this figure, the same components as those of the first embodiment shown in FIGS. 1 and 2 are denoted by the same reference numerals, and the description thereof is omitted.
In the above embodiment, the reaction tube 10 is arranged along the horizontal direction, but in the sixth embodiment, the reaction tube 10 is arranged along the vertical direction.

  In the present embodiment, in addition to obtaining the same operations and effects as in the first embodiment, the installation area of the gas-liquid reactor 1 can be reduced as compared with the case where the reaction tube 10 is arranged horizontally. In other words, more gas-liquid reaction apparatuses 1 can be installed in the same installation area, and productivity can be improved.

In addition, when taking the structure which arrange | positions the reaction tube 10 along a perpendicular direction, as shown in FIG. 9, as shown in FIG. 9, the liquid reservoir 41 is provided in a part (lower end part) of the reaction tube 10. It is good also as a structure which provides. With this configuration, further downsizing can be realized.
Further, as a configuration in which the liquid reservoir 41 is provided in a part of the reaction tube 10, as shown in FIG. 10A, the lower end of the reaction tube 10 is bent in the horizontal direction, and the bent portion is used as the liquid reservoir 41. However, the same operation and effect can be obtained.

  In the gas-liquid reactor 1 described above, the product needs to be discharged in a state where the product sufficiently covers the discharge hole so that the reaction gas does not flow out of the discharge hole 46. In the case where the liquid reservoir 41 is provided in the part, there is an increased possibility that the reaction gas flows out particularly when the production rate of the product is relatively low. Therefore, as shown in FIG. 10B, the bottom of the liquid reservoir 41 is formed in a funnel shape (conical shape) that gradually decreases in diameter as it goes downward, and a discharge hole 46 is provided at the bottom end. As a result, even when the amount of product generated is small, the cross-sectional area at the tip (bottom end) is small, so that the product can easily accumulate and the discharge hole 46 can be covered, and the outflow of the reaction gas can be prevented more effectively. be able to.

  For example, the position of the liquid level for sealing the reaction space 11 is not limited to that in the liquid reservoir 41 but may be in the discharge pipe 47 or the resistor 43.

Further, for example, in the above-described embodiment, the configuration in which the heater for heating (heating device) is provided on the outer wall of the reaction tube 10 is described. However, the present invention is not limited to this. For example, as illustrated in FIG. The tubular reaction tube 10 may be wound around the outer periphery of the cylindrical heating device H.
In this configuration, the contact area between the reaction tube 10 and the heating device H is increased, and the reaction tube 10 can be efficiently heated. Also, with this configuration, it is possible to ensure a large reaction space length of the reaction tube 10 with respect to a certain installation space. Therefore, in the present invention, it becomes possible to secure a long reaction space, and the residence time becomes long, so that productivity can be improved.

(Seventh embodiment)
Subsequently, a seventh embodiment of the gas-liquid reactor 1 will be described with reference to FIGS. 12 to 19.
In these figures, peripheral devices other than the reaction tube 10 are also shown in a simplified manner. In this figure, the same components as those of the first embodiment shown in FIGS. 1 and 2 are denoted by the same reference numerals, and the description thereof is omitted.
In the above embodiment, the reaction tube 10 is, for example, a circular tube. In the seventh embodiment, an example using a rectangular tube having a rectangular cross section will be described.

As shown in FIG. 12, the reaction tube 10 in the present embodiment has a rectangular parallelepiped shape in appearance, and is shown in a cross-sectional view in the width direction of FIG. 13 (a cross-sectional view taken along line AA in FIG. 12). The inner bottom 10a facing the reaction space 11 is formed in a planar shape.
More specifically, the reaction tube 10 in the present embodiment forms a reaction space 11 having a rectangular cross section with a thin plate, and its bottom portion 10a is a flat surface (substantially horizontal surface) extending in the horizontal direction.

  14, the reaction space 11 is formed in a rectangular shape in plan view, and the liquid feeding pipe 24 (introduction pipe 36) and the discharge pipe 44 are composed of a raw material liquid and a reaction gas (product). , And hereinafter referred to as a fluid) with a gap in the flow direction (the vertical direction in FIG. 14). As shown in FIG. 15 as a cross-sectional view taken along line B-B, the reaction space 11 is also formed in a rectangular cross section in the fluid flow direction, and the bottom 10a of the reaction tube 10 is formed in a planar shape.

  There are no particular restrictions on the material of the reaction tube 10, and stainless steel, brass, fluorine-based resin material, glass, PVC, polycarbonate, etc. can be selected in consideration of the corrosion resistance and pressure resistance of the reagents used in the reaction. In consideration of the properties, it is preferable to use stainless steel or brass.

  Further, the size of the inside of the reaction tube 10 (reaction space 11) is not particularly limited, but the width and the depth are preferably in the range of 0.005 to 1000 mm, particularly in the range of 10 to 150 mm. If there is, it is more suitable. The ratio of the width and height of the reaction space 11 is not particularly limited, but is preferably in the range of 0.1 to 150,000, and more preferably in the range of 1 to 15000. This is because when the ratio is less than or equal to the above range, the dissolution rate of the reaction gas into the raw material liquid becomes slow, and the reaction does not proceed efficiently. Further, the capacity of the reaction tube 10 (volume of the reaction space 11) is not particularly limited, but is preferably within a range of 0.01 to 1.0 L. If it is 0.05-0.2L, it is more suitable. The capacity of the liquid reservoir 41 is not particularly limited, but is preferably in the range of 0.01 to 1.0 L.

In the reaction tube 10 having the above-described configuration, as shown in FIGS. 13 and 15, the raw material liquid G supplied to the reaction tube 10 has the same action as that of the above-described embodiment because the bottom 10 a has a planar shape. In addition to obtaining the effect, the thickness of the raw material liquid G in the reaction space 11 can be reduced compared to the case where the same amount of the raw material liquid is supplied to a circular tube having a circular arc bottom. It is possible to efficiently dissolve the reaction gas raw material solution.
Therefore, in this embodiment, it becomes possible to reduce the cost and man-hour for melt | dissolving a reactive gas in a raw material liquid.

  Note that the planar shape of the reaction tube 10 (reaction space 11) is not limited to the rectangle shown in FIG. 14, for example, a polygon (hexagon in the figure) as shown in FIG. 16 (a) or FIG. 16 (b). Further, it is also possible to make the corners of the rectangle arcuate as shown in FIG. When the triangular or polygonal shape is used, the reaction tube 10 can be easily manufactured by a cutting process using a cutting tool such as an end mill by providing an arc shape at the corner, and the manufacturing efficiency can be improved. In addition to the above-described cutting processing, various processing methods such as laser processing, wet etching, dry etching, and sand blasting can be used for the processing method.

  Further, the cross-sectional shape in the width direction of the reaction space 11 is not limited to the rectangular shape shown in FIG. 13, and if a planar shape (substantially horizontal plane) is formed on the bottom 10 a, for example, FIG. ) (A hexagon in the figure), or as shown in FIG. 17B, both ends of the rectangle may have an arc shape. Furthermore, as a form which has a planar shape but is not a horizontal surface, as shown in FIG.17 (c), you may form in the V shape which goes to the downward direction gradually as the cross section of a width direction goes to a center part. Even in this configuration, the thickness of the raw material liquid G in the reaction space 11 can be reduced compared to the case where the same amount of the raw material liquid is supplied to a circular tube having an arc shape at the bottom. It becomes possible to make dissolution proceed efficiently.

  Further, the cross-sectional shape in the flow direction of the fluid in the reaction space 11 is not limited to the rectangular shape extending in the horizontal direction shown in FIG. 15. For example, as shown in FIG. The shape may be inclined gradually downward or the reaction space 11 may have a certain width and gradually inclined downward toward the downstream side. In the case of having these shapes, the same actions and effects as those of the eighth embodiment described later can be obtained.

  Further, the connection position of the liquid feeding pipe 24 (introducing pipe 36) and the discharge pipe 44 to the reaction pipe 10 is shown in FIG. 19A in addition to the arrangement arranged in the fluid flow direction shown in FIG. Thus, it is good also as a structure arrange | positioned on a diagonal line. In this configuration, the flow length of the raw material liquid can be increased, and the reaction gas can be efficiently dissolved. In the case of using a plurality of types of raw material liquids and reaction gases, those previously mixed may be introduced into the reaction space 11 or, for example, as shown in FIGS. When a reaction gas is used, an introduction port may be provided for each type.

(Eighth embodiment)
Next, an eighth embodiment of the gas-liquid reactor 1 will be described with reference to FIG.
In this figure as well, peripheral devices other than the reaction tube 10 are shown in a simplified manner. In this figure, the same reference numerals are given to the same elements as those of the first embodiment shown in FIG. 1, and the description thereof is omitted.
In the first embodiment, the reaction tube 10 is arranged to extend in the horizontal direction, but in the eighth embodiment, the reaction tube 10 is inclined with respect to the horizontal direction.

That is, as shown in FIG. 20, the reaction tube 10 in the present embodiment is disposed so as to be inclined at an angle θ with respect to the horizontal direction so as to gradually go downward as it goes downstream of the fluid. The angle θ is preferably 5 ° or more and 45 ° or more.
Other configurations are the same as those of the first embodiment.

  In the case of the horizontal arrangement of the reaction tube 10 shown in the first embodiment, it may be difficult to form a stable phase state between the reaction gas and the raw material liquid. In this case, the reaction efficiency is reduced or stabilized. Product manufacture can be difficult. On the other hand, in the case of the vertical arrangement (vertical arrangement) of the reaction tubes 10 shown in FIGS. 8 to 10, although a stable gas-liquid two-layer flow is formed, the moving speed of the raw material liquid increases due to the action of gravity. Therefore, it is difficult to make the reaction gas and the raw material liquid contact for a long time, and it is assumed that the reaction gas is not suitable for a synthesis reaction that requires a long time reaction.

  Therefore, in the gas-liquid reactor 1 having the above configuration, since the reaction tube 10 is inclined with respect to the horizontal direction, the raw material liquid moves at a constant speed, so that a stable two-layer flow can be formed. become. Moreover, in this embodiment, since the moving speed of the raw material liquid does not increase as the reaction tube 10 is arranged in the vertical direction, the raw material liquid and the reaction gas can be synthesized and reacted in a predetermined time.

  When the inclination angle θ is less than 5 °, the difference between the horizontal flow rate and the horizontal flow rate is small, and when it exceeds 45 °, the moving speed of the raw material liquid increases and the contact between the raw material liquid and the reaction gas occurs. Since time may be shortened, it is preferably 5 ° or more and 45 ° or less.

  Further, as a method for adjusting the inclination angle θ, for example, the reaction tube 10 is rotatably supported around an axis in a direction perpendicular to the paper surface in FIG. 20, and reaction is performed using a linear motion mechanism such as a hydraulic actuator or an electric actuator. By raising and lowering one end of the tube 10, the reaction tube 10 can be arranged at an arbitrary inclination angle, and an optimum inclination angle (that is, the movement speed of the raw material liquid) according to the reaction characteristics of the reaction gas and the raw material liquid. Can be set easily.

In the reaction tube 10 shown in FIG. 20, both the raw material supply device 20 and the gas supply device 30 are configured to supply the raw material liquid and the reaction gas from one end side of the reaction tube 10, respectively, as shown in FIG. In the same manner as in the fifth embodiment (see FIG. 7), the liquid feeding pipe 24 is connected to one end side (left side in FIG. 21) of the reaction tube 10, and the gas supply device 30 has the introduction pipe 36 in the reaction tube 10. It is good also as a structure connected to the other end side (right side in FIG. 21), and supplying a raw material liquid and a reactive gas from a mutually different side.
In this configuration, as in the case where the raw material liquid and the reaction gas are supplied from the same side of the reaction tube 10, the raw material liquid flows back into the introduction pipe 36 or the reaction gas flows back into the liquid feeding pipe 24 and enters. Therefore, stable raw material liquid supply and reaction gas supply can be realized.

Further, in the present embodiment, the configuration in which the reaction tube 10 is arranged to be inclined with respect to the horizontal direction so as to gradually move downward as it goes to the downstream side of the fluid has been exemplified. It is good also as a structure which inclines with respect to a horizontal direction and arrange | positions so that it may go gradually upwards as it goes to the side.
In this configuration, the moving speed gradually decreases due to the action of gravity, so that the contact time between the reaction gas and the raw material liquid in the reaction space 11 can be increased.

  As described above, the preferred embodiments according to the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the examples. Various shapes, combinations, and the like of the constituent members shown in the above-described examples are examples, and various modifications can be made based on design requirements and the like without departing from the gist of the present invention.

  For example, in the above embodiment, as a method for heating the reaction tube 10, a configuration in which a heater (heating device) is provided on the outer wall of the reaction tube 10, or a long tubular reaction tube 10 is arranged on the outer periphery of a cylindrical heating device H. In addition to these configurations, the heater H may be inserted (embedded) in a ninety-nine fold shape inside the reaction tube 10 as shown in FIG.

Moreover, in the said embodiment, although it was set as the structure which sends a raw material liquid after filling the reaction gas in the inside of the reaction tube 10, it is not limited to this, A reaction gas is supplied after feeding a fixed amount of raw material liquid. It is good also as a structure to enclose. In addition, before introducing at least one of the reaction gas and the raw material liquid into the reaction tube 10, only the solvent used for the raw material liquid or the raw material liquid is first introduced into the reaction tube 10 and the liquid reservoir 41. May be stored. In this case, for example, a product may be generated in the same procedure as in the first embodiment based on the following steps.
(1) Open the valve for controlling the flow rate of the raw material liquid or solvent, and introduce only the solvent used for the raw material liquid or the raw material liquid.
(2) To stop the introduction of the solvent or the raw material liquid, the valves for controlling these flow rates are closed.
(3) On the other hand, the gas flow control valve is opened to introduce the gas.
(4) Close the valve to stop gas introduction.

  Although the storage tank 50 mentioned above is normally set to atmospheric pressure, it is good also as a structure which pressurizes the inside of the storage tank 50 and suppresses the gaseous-phase remigration of dissolved gas. It is also possible to adopt a configuration in which the storage tank 50 is set to β lower than the gas pressure α in the reaction tube 10 and the unreacted gas is recovered by moving the dissolved gas back to the gas phase by the differential pressure. .

  Moreover, as the resistor 43 described above, a desired back pressure may be applied to the reaction tube 10 (reaction space 11) and the liquid reservoir 41 (liquid reservoir space 45), and the structure of the resistor 43 is particularly limited. For example, a back pressure valve, a hollow pipe with a small inner diameter (made by SUS, made by PEEK, etc.), a particle-filled pipe, a diaphragm, an inorganic or organic integrated structure (so-called monolithic structure) built inside Etc. can be used. In practical use, it is effective to use a back pressure valve, a particle-filled pipe, or a hollow pipe.

Further, the above-described liquid level gauge, relief valve, and check valve may be used as necessary, and may be omitted individually.
The gas pressure in the reaction tube 10 is usually controlled at a constant value α, but the α value may be varied during the gas-liquid reaction according to the chemical characteristics of the gas-liquid reaction to be performed.

  In addition, a switching valve connected to the reaction tube 10 or the liquid reservoir 41 is installed for the purpose of collecting the reaction gas sealed in the reaction tube 10 after the gas-liquid reaction, and the reaction is performed via the switching valve after the gas-liquid reaction. It is good also as a structure which collect | recovers the unreacted gas which stays in the pipe | tube 10.

Moreover, about the product liquid collect | recovered after gas-liquid reaction, it is good also as a structure which reuses a solvent after isolate | separating a product.
The reaction gas used in the gas-liquid reaction in the above embodiment may be in a supercritical state (supercritical fluid) by controlling pressure and temperature.

The gas-liquid phase state inside the reaction tube suitable for the gas-liquid reaction apparatus of the present invention includes reaction tube diameter, reaction tube length, reaction gas species, reaction gas concentration, reaction gas pressure, material solvent species, material solvent flow rate, etc. (I) stratified flow (stratified flow), (ii) plug flow in which gas plug and liquid plug alternately flow, (iii) gas plug and liquid slug alternately Flowing slug flow, (iv) bubbly flow, (v) churn flow, (vi) annular flow, (vii) annular-sidpersed flow (Viii) plug flow.
In the gas-liquid reactor of the present invention, a stratified flow or a slag flow is preferable, and a stratified flow is most preferable in consideration of reaction efficiency.

  DESCRIPTION OF SYMBOLS 1 ... Gas-liquid reaction device, 10 ... Reaction tube (reaction vessel), 11 ... Reaction space, 15 ... Preliminary reaction tube (preliminary reaction device), 20 ... Raw material supply device (liquid material supply device), 30 ... Gas supply device ( Gas supply device), 40 ... product discharge device (discharge device), 41 ... liquid reservoir, H ... heating device

Claims (30)

A reaction vessel having a reaction space; a liquid material supply device for supplying a liquid material containing a reaction substrate to the reaction space; a gas supply device for supplying a reaction gas to the reaction space; and the reaction substrate connected to the reaction space; A gas-liquid reaction device having a liquid storage part having a liquid storage space for storing a product liquid generated by reaction with the reaction gas,
A gas-liquid reaction apparatus comprising: a discharge device that discharges the product liquid in the liquid storage section while sealing the reaction space and the liquid storage space. The gas-liquid reactor according to claim 1,
The exhaust device is a reaction gas control device that controls a supply amount of the reaction gas according to a pressure of the reaction gas in the reaction space;
A discharge hole provided in the liquid reservoir portion so as to open to the liquid reservoir space;
A gas-liquid reaction apparatus comprising: a discharge control device that controls a discharge amount of the product liquid from the discharge hole in accordance with a liquid level of the product liquid in the liquid reservoir. The gas-liquid reactor according to claim 1 or 2,
A gas-liquid reaction apparatus comprising: a pre-reaction apparatus that pre-reacts the liquid material and the reaction gas supplied toward the reaction container. The gas-liquid reactor according to claim 3,
The pre-reaction apparatus performs a pre-reaction under reaction conditions different from the reaction conditions in the reaction vessel in accordance with reaction characteristics between the reaction substrate and the reaction gas. In the gas-liquid reaction device according to any one of claims 1 to 4,
A gas-liquid reaction device comprising a suction device that sucks and discharges the product liquid in the liquid reservoir by negative pressure. In the gas-liquid reactor according to any one of claims 1 to 5,
The liquid material supply device supplies the liquid material from one end side of the reaction vessel,
The gas supply device supplies the reaction gas from the other end of the reaction vessel. In the gas-liquid reaction device according to any one of claims 1 to 6,
The gas-liquid reaction apparatus, wherein the liquid reservoir is provided in a part of the reaction vessel. In the gas-liquid reactor according to any one of claims 1 to 7,
The gas-liquid reactor is characterized in that the bottom of the liquid reservoir is formed with a diameter that gradually decreases in the downward direction. In the gas-liquid reaction device according to any one of claims 1 to 8,
The gas-liquid reaction apparatus is characterized in that the reaction container is formed in a tubular shape and is wound around an outer periphery of a heating apparatus for heating the reaction container. In the gas-liquid reaction device according to any one of claims 1 to 9,
The gas-liquid reaction apparatus characterized in that an inner bottom portion facing the reaction space in the reaction vessel has a planar shape. The gas-liquid reactor according to claim 10,
The gas-liquid reaction apparatus characterized in that the inner bottom is a substantially horizontal plane. The gas-liquid reactor according to claim 10,
The gas-liquid reactor is characterized in that the bottom surface of the inner surface is formed in a V-shape that gradually goes downward as the cross section in the width direction goes to the center. In the gas-liquid reaction device according to any one of claims 1 to 12,
The gas-liquid reaction apparatus characterized in that the inner surface bottom portion facing the reaction space in the reaction vessel is arranged such that the extending direction is inclined with respect to the horizontal direction. The gas-liquid reactor according to claim 13,
The gas-liquid reaction apparatus, wherein an inclination angle of the extending direction with respect to the horizontal direction is not less than 5 ° and not more than 45 °. The gas-liquid reactor according to claim 13 or 14,
The gas-liquid reaction apparatus is characterized in that the bottom surface of the inner surface is provided such that the downstream side is positioned higher than the upstream side. A step of supplying a liquid material containing a reaction substrate and a reaction gas to a reaction space in the reaction vessel; a step of reacting the liquid material and the reaction gas to generate a product liquid; and a liquid storage space connected to the reaction space. A gas-liquid reaction method comprising a step of storing the product liquid in a liquid reservoir part,
A gas-liquid reaction method comprising a step of discharging the product liquid in the liquid reservoir while keeping the reaction space and the liquid reservoir space in a sealed state. The gas-liquid reaction method according to claim 16,
Controlling the supply amount of the reaction gas according to the pressure of the reaction gas in the reaction space;
And a step of controlling a discharge amount of the product liquid from a discharge hole provided in the liquid storage space in accordance with a liquid level of the product liquid in the liquid reservoir. Reaction method. The gas-liquid reaction method according to claim 16 or 17,
A gas-liquid reaction method comprising a pre-reaction step of pre-reacting the liquid material and the reaction gas supplied toward the reaction vessel. The gas-liquid reaction method according to claim 18,
A gas-liquid reaction method, wherein a pre-reaction is performed under reaction conditions different from the reaction conditions in the reaction vessel in accordance with reaction characteristics between the reaction substrate and the reaction gas. In the gas-liquid reaction method according to any one of claims 16 to 19,
A gas-liquid reaction method comprising a step of sucking and discharging the product liquid in the liquid reservoir by negative pressure. In the gas-liquid reaction method according to any one of claims 16 to 20,
A gas-liquid reaction method, wherein the liquid material is supplied from one end side of the reaction vessel, and the reaction gas is supplied from the other end side of the reaction vessel. The gas-liquid reaction method according to any one of claims 16 to 21,
A gas-liquid reaction method, wherein the liquid reservoir is provided in a part of the reaction vessel. The gas-liquid reaction method according to any one of claims 16 to 22,
The gas-liquid reaction method, wherein the bottom of the liquid reservoir is formed with a gradually reduced diameter as it goes downward. The gas-liquid reaction method according to any one of claims 16 to 23,
The gas-liquid reaction method, wherein the reaction vessel is formed in a tubular shape and is wound around an outer periphery of a heating device for heating the reaction vessel. In the gas-liquid reaction method according to any one of claims 16 to 24,
The gas-liquid reaction method, wherein an inner bottom portion facing the reaction space in the reaction vessel has a planar shape. The gas-liquid reaction method according to claim 25,
The gas-liquid reaction method, wherein the inner bottom is a substantially horizontal plane. The gas-liquid reaction method according to claim 25,
The gas-liquid reaction method, wherein the inner bottom portion is formed in a V shape that gradually goes downward as the cross section in the width direction goes to the central portion. In the gas-liquid reaction method according to any one of claims 16 to 27,
A gas-liquid reaction method, wherein an extending direction of the inner bottom facing the reaction space in the reaction vessel is inclined with respect to a horizontal direction. The gas-liquid reaction method according to claim 28, wherein
The gas-liquid reaction method, wherein an inclination angle of the extending direction with respect to the horizontal direction is 5 ° or more and 45 ° or less. The gas-liquid reaction method according to claim 28 or 29,
The gas-liquid reaction method, wherein the inner surface bottom portion is provided such that the downstream side is positioned higher than the upstream side.

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