JP2007209973A - Gas-liquid reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microreactor which effectively performs a gas-liquid reaction. <P>SOLUTION: This gas-liquid reactor has a reaction vessel 10 filled with fine particles 12 with a diameter of 1 μm to 1 mm, a liquid lead-in port 18 for leading-in a liquid to the reaction vessel 10, a gas lead-in port 20 for leading-in a gas to the reaction vessel 10, and a gas lead-out port 16 for leading-out a reaction product. This constitution forms a fine and curved channel in a clearance between fine particles 12 to accelerate dissolution of gas into liquid. As a result, with the combination with a microchip, or the like, a continuous reactor including gas-liquid reaction comes into practical use. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a gas-liquid reaction apparatus that mixes a fluid and a gas in a minute space and performs an organic synthesis reaction in a continuous flow field.

  There is a batch process in which raw materials are charged into a container and mixed by a stirring member for a predetermined time as a method of mixing a plurality of raw materials to perform a chemical reaction, which allows many industrial organic reactions to be performed. Has been. However, in a batch type process, a relatively large container must be used, and time is required until uniform mixing and temperature adjustment, and it is difficult to perform reaction control with high selectivity. Accordingly, there is a problem of reduction in product purity and yield due to the formation of by-products, particularly for reactions that require such control strictly. In addition, it is necessary to take excessive safety measures for reactions that are difficult to control and have a risk of explosion.

For example, the catalytic hydrogenation reaction is performed by suspending activated carbon particles carrying Pd catalyst in the reaction liquid in the reaction kettle. There is a risk of causing Therefore, a hook structure that keeps the inner wall wet at all times is required. At the time of liquid removal cleaning after the completion of the reaction, the same problem of drying activated carbon particles occurs at the bottom of the kettle and there is a risk of explosion, so it is necessary to carefully clean it so that it does not dry. In addition, since hydrogen has low solubility in the liquid, there are cases where the pressure in the kettle is increased to about 2 to 3 MPa, which not only increases the initial cost, but the gas component emitted from the liquid by the pressurization causes the explosion. Sometimes it is made.
In addition, in the ozone reaction utilizing the oxidizing property of ozone, an intermediate called ozonide has explosive properties, so that a large reaction kettle is more dangerous.

  On the other hand, in recent years, a microchannel chip that causes various chemical reactions while flowing a solution or a gas using a channel (microchannel) having a minute channel cross-sectional area has been attracting attention. A microchannel chip is provided with a region for mixing, heating, reaction, and the like on one chip and a flow path for communicating them, and a specific reaction is performed if a material (raw material) is supplied to this. It is comprised so that. The mixed region is usually formed by joining a plurality of flow paths.

  By using such a microchannel chip, a highly selective product can be controlled and a product with high purity can be produced. In addition, it is easy to control an explosive reaction by performing precise temperature control. Although the yield per hour is not large, mass production is possible by using a continuous process.

  However, in the microchannel chip, the mixing reaction between the liquids can be performed satisfactorily, but the gas-liquid reaction may cause partial blockage because the gas does not flow well. In addition, regarding the gas-liquid reaction, the gas mixing ratio tends to be locally unbalanced due to the low solubility of the gas and the size of the bubbles. In order to prevent this, the mixing ratio of each part is made uniform by devising a mechanical stirring method to reduce the size of the foam, but it requires a complicated equipment configuration and avoids an increase in cost. Absent.

  In addition, since there is no microreactor that efficiently performs a gas-liquid reaction in this way, for example, a manufacturing process that includes a gas-liquid reaction in the reaction process (for example, a peptide synthesis process) is continued using a microchannel chip. In some cases, the gas-liquid reaction process becomes a bottleneck, and there is a problem that it is difficult to perform continuation and automation.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a microreactor that efficiently performs a gas-liquid reaction.

  In order to achieve the object, the gas-liquid reaction apparatus according to claim 1 includes a reaction vessel filled with fine particles having a diameter of 1 μm to 1 mm, a liquid inlet for introducing a liquid into the reaction vessel, and the reaction. It has a gas inlet for introducing gas into the container and an outlet for deriving a reaction product.

In the first aspect of the present invention, a fine and curved flow path is formed in the gap between the fine particles having a diameter of 1 μm to 1 mm in the reaction vessel, and the gas to the liquid is diffused by diffusion in the turbulent flow. Dissolution is promoted.
If the particle size is too small, the pressure loss in the curved channel is increased and the flow of the fluid is hindered. On the other hand, if the particle size is too large, the channel cross-sectional dimension is increased and sufficient gas dispersion effect is obtained. Can't get.

A gas-liquid reaction apparatus according to a second aspect is characterized in that, in the invention according to the first aspect, the fine particles include at least one of porous silica, alumina, and SiC.
In the second aspect of the present invention, since the fine particles are porous, the specific surface area is increased, and turbulent flow is induced and reaction sites are increased.

A gas-liquid reaction apparatus according to a third aspect is the invention according to the first or second aspect, wherein the fine particles carry a catalyst.
In the invention according to claim 3, the catalyst supported on the fine particles accelerates the reaction. By supporting the catalyst on the surface of fine particles having a large specific surface area, high reaction efficiency can be obtained. If the particle size is too small, the pressure loss in the curved flow path becomes high and the flow of the fluid is inhibited. On the other hand, if the particle size is too large, the specific surface area becomes small and a sufficient gas catalytic effect can be obtained. Can not.

A gas-liquid reaction apparatus according to a fourth aspect is characterized in that, in the invention according to the third aspect, the catalyst contains any one of Pd, Ni, Co, Pt, and Cu.
The gas-liquid reaction apparatus according to claim 5 is characterized in that, in the invention according to any one of claims 2 to 4, the catalyst is supported by wet treatment.
In the invention according to claim 5, the catalyst can be supported up to the inside of the fine pores by supporting it by wet treatment.

The gas-liquid reactor according to claim 6 is the invention according to any one of claims 1 to 5, further comprising a dispersion plate for dispersing the gas injected into the liquid in the flow of the liquid. And
In the invention described in claim 6, even when the gas injected into the liquid is enlarged in the flow of the liquid, it is dispersed by the dispersion plate and refined to promote efficient mixing and reaction.

[7] The invention according to any one of [1] to [5], further comprising temperature adjusting means for adjusting the temperature of the reaction vessel.
In the invention according to claim 6, the fluid in the flow path is maintained at a temperature condition suitable for mixing and reaction, and the efficiency of the desired treatment is improved.

The gas-liquid reactor according to claim 8 divides the space in the reaction vessel with a porous membrane having a pore diameter of 0.5 μm or less, introduces gas into one space, introduces liquid into the other space, It is characterized by dissolving in a liquid by permeating the porous membrane.
In the invention according to claim 8, the gas permeates the porous membrane, so that the gas is finely dispersed in the liquid to promote dissolution.

The gas-liquid reactor according to claim 9 is characterized in that, in the invention according to claim 8, the porous membrane is made of PTFE (polytetrafluoroethylene) or PCTFE (polychlorotrifluoroethylene).
The gas-liquid reaction apparatus according to claim 10 has the gas-liquid reaction apparatus according to claim 8 or 9 disposed in the preceding stage, and the gas-liquid reaction apparatus according to any one of claims 1 to 7 disposed in the subsequent stage. It arrange | positions, and after making a gas-liquid reactor mix in a front | former stage gas-liquid reactor, reaction is accelerated | stimulated with a catalyst in a back | latter stage gas-liquid reactor.
In the invention according to the tenth aspect, the gas-liquid is mixed in the preceding gas-liquid reactor, so that the reaction is more efficiently promoted by the catalyst in the latter gas-liquid reactor.

  According to the gas-liquid reactor according to any one of claims 1 to 10, a gas-liquid reaction can be performed efficiently, whereby a continuous reactor including a gas-liquid reaction is combined with a microchip or the like. It can be put into practical use.

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an example of a gas-liquid reactor of the present invention.
This gas-liquid reaction apparatus is such that the reaction space in the cylindrical container 10 is filled with fine particles 12 made of a porous material or the like, and an introduction unit 14 for individually supplying liquid and gas to one end of the cylindrical container 10 includes: On the other hand, a lead-out part 16 for leading the gas-containing liquid after reaction is provided. The cylindrical container 10 is formed from a material having corrosion resistance, and has a sufficient length to ensure necessary mixing and reaction time.

  FIG. 2A shows an embodiment relating to the introduction portion 14, which is composed of a plurality of nozzles 18 for introducing a liquid and a porous nozzle 20 for introducing a gas. The gas is introduced into the reaction space via the header space 22 in a state of being uniformly dispersed from the fine holes of the porous nozzle 20. Of course, the nozzles for ejecting the gas and the liquid may be appropriately distributed. If the reaction product contains gas, the derivation unit 16 may be provided with the same configuration as the introduction unit 14 as necessary, and the gas may be separated by gas-liquid separation.

  The cylindrical container 10 is provided with temperature adjusting means. For example, as shown in FIG. 2 (a), this is a temperature control jacket 24 through which a heating / cooling medium is circulated, and the diameter of the cylindrical container 10 is sufficient to heat or cool the internal fluid by the temperature control jacket 24. The dimensions are set to be Moreover, the cylindrical container 10 has thermal conductivity that allows such heating or cooling to be performed efficiently.

Since the surface of the fine particles 12 filled therein becomes a site that induces a reaction, it is preferable that the surface area be large. Therefore, the particle diameter of the fine particles 12 is preferably 1 μm to 1 mm. If the particle size is uniform, a smaller particle size can be selected. Further, as shown in FIG. 2B, the surface area ratio is remarkably improved by using the porous fine particles 12. For example, porous silica having an average particle size of 0.4 mm has a surface area of 1 m ² per gram.

  In the gas-liquid reaction apparatus having such a configuration, the liquid and the gas introduced from the respective introduction portions 14 flow between the fine particles 12 having a size of 1 μm to 1 mm filled in the container 10 at the respective speeds. Dissolves in the liquid according to its diffusion rate. Here, when the liquid flow is in a laminar flow state, it takes time to dissolve, but in the apparatus of this embodiment, the liquid flows in a state close to turbulent flow between the fine particles, so that mixing is promoted and the reaction is efficient. Get up. The liquid after the reaction is discharged from the outlet 16. With the gas-liquid reaction apparatus having such a configuration, the gas-liquid mixing reaction can be efficiently performed even in a continuous flow system.

  The reaction is further promoted by supporting the catalyst on the fine particles 12. The catalyst is selected from Pd, Pt, Cu, Zr, Nb, Co, Ni and the like, but Pd having a high hydrogen storage capacity is most preferable. In order to uniformly form Pd in the pores with respect to the porous fine particles 12 as shown in FIG. 2B, a wet treatment is preferable to a dry process such as sputtering. In the case of Pd, electroless plating with palladium chloride or reduction adsorption using a Pd complex salt is preferable. In the experiments by the inventors, a uniform film in the hole could not be obtained by vacuum deposition.

The conditions for the catalyst film formation treatment of the fine particles 12 are shown below.
(1) For electroless plating Liquid composition Palladium chloride 2.0 g / L
Ethylenediamine 4.6 g / L
Thiodiglycolic acid 50 mg / L
Trimethylamine borane 4.4 mg / L
pH adjusted to pH 7 with hydrochloric acid Temperature 50-60 ℃
(2) In case of Pd complex salt Liquid composition [Pd (NH ₄ ) ₄ ] Cl ₂ 0.1 Mol / L
Temperature Room temperature Time Leave for 12 hours In both cases of electroless plating and Pd complex salt, after film formation and drying, reduction treatment is performed at 300 ° C. for 4 hours in a hydrogen stream to store hydrogen.

  In the above, when the reaction is exothermic, a cooling medium is allowed to flow through the temperature control jacket 24. When the reaction is endothermic, the heating medium is allowed to flow so that the temperature of the fluid in the reaction space is increased. Maintain a suitable constant temperature. In the gas-liquid reaction apparatus of this embodiment, the reactor is small, the liquid is always filled in the entire reactor because it is a continuous flow, the entire reactor may be replaced at the time of maintenance, etc. The risk of explosion is greatly reduced. If it is a rapid exothermic reaction (explosive reaction), the explosion can be suppressed by increasing the flow rate of the cooling medium and adjusting the gas supply amount to be small.

  FIG. 3A shows a case where a temperature control jacket 24 is also provided in the interior so that the reaction space filled with the fine particles 12 has a cylindrical shape. By doing in this way, the boundary area of reaction space and the temperature control jacket 24 is enlarged, and the temperature control effect is improved. Further, as shown in FIG. 2B, the reaction space may be flat and jackets may be installed on the front and back sides. The temperature control means is not limited to the one using a heat medium, and an appropriate one can be adopted. For example, in the case of heating, a coiled heater 24a can be used as shown in FIG. good.

  FIG. 5 shows another embodiment of the present invention, which is a membrane type gas-liquid reactor. In the gas-liquid reactor of this embodiment, a cylindrical porous film 26 is disposed in the cylindrical container 10a. The cylindrical container 10 a is provided with a liquid inlet 28, a gas inlet 30, and an outlet 32, and a temperature adjustment jacket 34 (temperature adjustment means) for circulating a heating / cooling medium is provided on the outer periphery.

  The gas flows into the space inside the porous membrane 26 from the gas inlet 30, and the liquid flows into the space outside the porous membrane 26 from the liquid inlet 28. The pore diameter of the porous membrane 26 is 0.5 μm or less, preferably 0.1 to 0.2 μm, which allows gas to pass but not liquid, and the material is preferably PTFE (polytetrafluoroethylene), PCTFE (polychlorotrifluoroethylene) or the like. Furthermore, as PTFE, Gore-Tex (trade name: Japan Gore-Tex Co., Ltd.) is preferable. The gas moves through the pores of the porous membrane 26, flows into the liquid through a path indicated by an arrow, and comes into contact therewith. When the fine gas comes into contact with the liquid and forcibly diffuses in the liquid, the gas temporarily exists in the liquid in excess of the allowable solubility, and the efficiency for the reaction increases. The liquid after the reaction is discharged from the outlet 32.

  As a suitable reaction performed by the apparatus of the embodiment shown in FIG. 5, there is an ozonolysis reaction using ozone as an oxidizing agent as shown in FIG. 6 (a). Ozone becomes oxygen and active oxygen on the assumption that it decomposes, and this active oxygen functions as a strong oxidizing agent. A liquid obtained by dissolving transstilbene in a solvent of dichloromethane and methanol is supplied from a liquid inlet, and ozone is injected from the gas inlet. In this case, quench with dimethyl sulfide to stop the reaction. The apparatus of this embodiment can also be used for dioxin oxidative decomposition as shown in FIG. Note that an ozonolysis catalyst may be used to increase the reaction efficiency. In this case, the apparatus of the first embodiment is suitable.

  Even in the apparatus of FIG. 5, there is no danger of explosion, such as the fact that the reactor is small, continuous liquid is always filled with liquid, and that the reactor must be replaced during maintenance. Decrease dramatically. In order to increase the contact area with the temperature control means, a modification as shown in FIG. 3 in the description of the previous embodiment is possible.

  FIG. 7 shows a gas-liquid reactor according to another embodiment of the present invention, in which the gas-liquid reactor according to the above-described two embodiments is arranged in series. Here, the film-type gas-liquid reactor of the second embodiment is disposed in the previous stage and used as a gas-liquid mixing means. The liquid containing the reagent pumped by the pump 36 and the gas pumped from the gas cylinder 38 are mixed in the front container 10a, and then enter the gas-liquid reactor at the rear stage, and the action of the catalyst supported on the fine particles 12 is obtained. Promotes the reaction. The liquid which is a reaction product is discharged from the outlet 32 and stored in the storage tank 40.

FIG. 8 shows a continuous flow type peptide synthesizer using the gas-liquid reactor of FIG. This peptide synthesizer is similar to n raw material liquid containers 2 (2-1, 2-2,..., 2-n) that contain a mixed solution in which an N-protected amino acid as a raw material is dissolved in an organic solvent. Premixing containers (premixing means) 3-1 and 3-2 for premixing and holding the raw material C-protected peptide and N-protected amino acid, a condensing agent container 4 for storing a condensing agent, and introducing these A microreactor 5 having a flow path for mixing and reacting, an oil / water separator 6 installed on the downstream side of the microreactor 5, and a gas-liquid reaction device 7 for mixing hydrogen gas into the separated fluid and performing a hydrogenation reaction with a catalyst. And is configured. The gas-liquid reaction device 7 includes a gas-liquid reaction device (gas-liquid mixer) 8 according to the first embodiment of the present invention and a gas-liquid reaction device (catalyst reactor) 9 according to the second embodiment. It is configured.
The outlet of the raw material liquid container 2 and the catalytic reactor 9 are connected to the premixing containers 3-1 and 3-2 via pipe lines having the on-off valve V and the pump P, respectively.

The N-protected amino acid is an amino acid inactivated by binding a protective group to an amino group, and the C-protected peptide is a peptide (k) inactivated by binding a protective group to a carboxyl group. Here, the (k) peptide means a peptide having k amino acid residues used in the k-th treatment. In other words, in the k-th reaction,
The reaction of (k) peptide + amino acid → (k + 1) peptide occurs, and the generated peptide becomes the raw material for the next reaction.

  Examples of the N-protected amino acid include carbobenzoxyl amino acid (k), and examples of the C-protected peptide include (k) peptide-t-butyl ester. These also mean amino acids or peptides used for the k-th reaction (k = 1 to n).

  The condensing agent is an agent that dehydrates and condenses a carboxyl group and an amino group of an N-protected amino acid and a C-protected peptide, and uses an appropriate one depending on the reaction. In order to facilitate separation, a condensing agent having water solubility as well as solubility in an organic solvent is preferable. In particular, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) and diisopropylpropylcarbodiimide (DIPCDI) are preferable because the by-produced urea derivative is water-soluble.

  The microreactor (mixing reaction means) 5 is configured as a substrate unit including a mixing channel that joins microchannels having a channel width (a diffusion movement distance of molecules perpendicular to the flow direction) of 500 μm or less. Dimensions and shapes are designed for the reaction to be performed. In this example, a simple Y-shaped channel is used, but a type in which a plurality of channels are alternately joined may be used. Preliminary mixing containers (preliminary mixing means) 3-1 and 3-2 are connected to one introduction flow path, and a condensing agent container 4 is connected to the other flow path via a pipe line having a pump P, respectively. . It is preferable that the microreactor 5 is provided with a heating / warming means according to the reaction, and a pressure gauge, an analysis means, etc. are installed to monitor the reaction.

  In this example, the oil / water separator 6 has a double tube structure in which a filter tube 52 made of a porous membrane having water repellency is disposed inside a cylindrical container 50. By flowing the reaction product fluid under pressure, only the water-soluble component is discharged and separated from the pores of the filter tube 52. As the material of the porous film having water repellency, PTFE (polytetrafluoroethylene), PCTFE (polychlorotrifluoroethylene), etc. are preferably used, and the average pore diameter is 1 μm or less, preferably 0.1 to 0.5 μm, more preferably 0.1 to 0.2 μm. is there. Furthermore, as PTFE, Gore-Tex (trade name: Japan Gore-Tex Co., Ltd.) is preferable. As a method of forming the porous membrane, a method of sintering, a method of forming a honeycomb structure, or various methods of manufacturing other filtration membranes can be appropriately employed.

  In this peptide synthesizer, the gas-liquid reactor 7 performs a deprotection reaction by catalytic hydrogenation of a protecting group (carbobenzoxy group, benzyl group, etc.) at the amino group side terminal of the peptide produced in the preceding stage. For example, FIG. 9A shows a reaction in which hydrogen acts on oxyphenylalanine to remove the protecting group (carbobenzoxy group), and FIG. 9B shows a reaction in which hydrogen acts on benzoylphenylalanine to protect the protecting group (benzyl). This is a reaction in which the group is removed. In this way, the de-C protection reaction is performed to prepare for the next peptide binding reaction.

  Next, a step of synthesizing a peptide having (n + 1) amino residues (= (n + 1) peptide) using the peptide synthesizer configured as described above will be described. In the first premixing container 3-1, an organic solvent solution of an amino acid whose N-terminal is activated in advance, for example, amino acid-t-butyl ester, is prepared. In the first synthesis, an N-protected amino acid such as carbobenzoxyl amino acid (1) is introduced into the premixing vessel 3-1, and mixed with an appropriate means such as a stirring blade installed in the vessel. The organic solvent liquid containing this amino acid-t-butyl ester and carbobenzoxyl amino acid (1) is pumped by the pump P and introduced into the inlet on one side of the microreactor 5. An aqueous carbodiimide solution that is a water-soluble condensing agent is pumped by a pump P and introduced from another inlet of the microreactor 5.

  In the microreactor 5, the two liquids are mixed at an equivalent amount of 1: 1, and a dehydration condensation reaction with high selectivity and high yield is performed to produce a dipeptide having two amino acid residues. The effluent from the microreactor 5 is a two-phase mixed solution containing an organic solvent containing the produced peptide, an unreacted amino acid derivative, a carbodiimide reagent, and a by-product water-soluble urea.

  This two-phase mixed liquid is introduced into the continuous oil-water separator 6 and separated into an organic phase (oil component) and an aqueous component. The separated aqueous component is discharged into the discharge container 54 and discharged out of the system, and the dipeptide in the organic phase is further introduced into the gas-liquid mixer 8 and hydrogen is introduced. The dipeptide solution in which hydrogen is dissolved is introduced into the catalytic reactor 9, and a catalytic hydrogenation reaction is performed by the effect of the Pd catalyst. This removes the carbobenzoxyl group and produces dipeptide-t-butyl ester. This is stored in the premix container 3-2 together with the organic solvent. This is the first peptide synthesis reaction.

  In the second synthesis reaction, the carbobenzoxyl amino acid (2) is introduced and mixed into the dipeptide-t-butyl ester stored in the premixing vessel 3-2. This mixed liquid is introduced into the inlet on one side of the microreactor 5 by the pump P, mixed and reacted with the water-soluble carbodiimide aqueous solution in the same way as the first time, and after the same process as the first time, tri (3) peptide-t-butyl Esters are produced. The produced solution is already emptied and stored in the cleaned premixing container 3-1. The premixing containers 3-1 and 3-2 are used alternately for each repeated synthesis. Of course, three or more premixing containers may be used. After repeating the same reaction operation n times, the (n + 1) peptide is obtained by removing the t-butyl ester with trifluoroacetic acid (TFA).

  With the continuous synthesizer of this embodiment, liquid phase synthesis of peptides can be continuously performed using the microreactor 5. Moreover, since the amount of carbobenzoxyl amino acid can be equalized using the microreactor 5 and column chromatography purification is possible at any stage as required, the peptide solid phase synthesis method, the conventional liquid phase synthesis method Compared to, the target peptide with high purity can be obtained more easily and economically.

  In addition, since the process from the microreactor 5 to the catalytic reactor 9 is a continuous flow system, there is no stagnation, and the residence time required for the reaction and the time required for separation and mixing can all be controlled uniformly. It became possible to manufacture.

  10 and 11 show a gas-liquid reaction apparatus according to another embodiment of the present invention, in which a dispersion plate 60 is arranged so as to intersect with a flow path formed by the fine particles 12. As shown in FIGS. 11B and 11C, the dispersion plate 60 is formed with fine openings 62a and 62b made of circular holes or radial slits, and the density of these openings 62a and 62b is the fine particle 12. Is set to be smaller than the density of the gap formed. Therefore, when the gas collects and enlarges in the continuous flow path formed by the fine particles 12, it has the effect of atomizing it again and dispersing it in the liquid.

  In this embodiment, the container for storing the fine particles 12 is a unit container 66 composed of a cylindrical side plate 64 and a dispersion plate 60 covering both ends thereof, as shown in FIG. Then, as shown in FIG. 10, a suitable number of unit containers 66 are accommodated in series in a longer cylindrical container body 68 to form a flow path by the fine particles 12 in which the dispersion plates 60 are evenly arranged. Yes. As shown in FIG. 11 (d), the dispersion plate 60 is disposed inside the end of the side plate 64 of each unit container 66, and the adjacent dispersion plates 60 are not in direct contact with each other, and the minute space 70 is interposed therebetween. Is supposed to form. This prevents the dispersion plate 60 from closing the fine openings 62a and 62b.

  At the end of the container main body 68, gas and liquid introduction paths 72 and 74 are provided so as to merge in the introduction space 76, and a lead-out path 78 is provided on the other side. A temperature adjusting device 80 is provided so as to cover the outer periphery of the container body 68. The temperature adjusting device 80 can employ appropriate means such as an electric heating element or a heat medium flow path for temperature adjustment.

  In the gas-liquid reactor of this embodiment, the gas and liquid introduced into the introduction space 76 from the introduction paths 72 and 74 are first dispersed in the state of being dispersed via the fine openings 62a and 62b of the dispersion plate 60. When entering the unit container 66, contact mixing of the liquid and gas is promoted in the fine flow path formed by the fine particles 12, and when the catalyst is supported on the surface of the fine particles 12, the reaction proceeds by the action of the catalyst.

  This mixed fluid further passes through the fine openings 62a and 62b of the dispersion plate 60 at the other end of the unit container 66, the minute space 70, and the fine openings 62a and 62b of the dispersion plate 60 of the next unit container 66, and the next unit. It is introduced into a fine channel formed by the fine particles 12 in the container 66, and further mixing and reaction are performed. Thereafter, this process is repeated for each unit container 66 and finally derived from the outlet path 78. In this process, the gas enlarged in the fine particle flow path is refined and dispersed in the liquid every time it passes through the dispersion plate 60, so that a reduction in reaction efficiency due to gas enlargement is prevented.

  Further, in this embodiment, a reduction in reaction efficiency due to gas enlargement is prevented by the dispersion plate 60 arranged at appropriate intervals, so that the fine flow path by the fine particles 12 can be set long. Further, the entire flow path can be configured with simple operations by sequentially arranging the unit containers 66 in the container main body 68, and the length can be easily changed, maintained, and replaced.

(Example)
A hydrogenation reaction using a Pd catalyst was performed using the apparatus shown in FIG. The volume of the unit container 66 in FIG. 10 filled with particles has an inner diameter of 5 mm and a length of 10 mm. Nine unit containers 66 are arranged in series, and the length of the particle filling portion is 90 mm. The pressure loss and catalytic effect when Pd is supported on the surface of the Lica particles having different particle diameters and placed in the unit container 66 and the hydrogen mixed liquid of solvent ethanol is introduced into the container body 68 from the introduction path at a flow rate of 100 ml / h. It was measured. The result was as shown in FIG. The catalytic effect represents a reaction rate expressed as 1 in the case of a batch processing apparatus.

  In the case where Pd was supported on the surface of silica particles having a particle diameter of 300 nm to 1 μm (Comparative Example 1), no liquid movement occurred even when the maximum operating pressure of the used pump exceeded 1 MPa. Next, when the particle size was adjusted to 10 to 50 μm, the passage of the liquid was observed, but the pressure loss reached around 0.5 MPa. When the particle size was 300 to 500 μm, the pressure became 0.1 MPa or less, and the catalytic effect was 300 times faster than the conventional batch process. Further, in the case where the particle diameter was increased to 3 to 5 mm (Comparative Example 2), the pressure loss was almost eliminated, but the catalytic effect was reduced.

  From this result, it is understood that when the viscosity is based on a solvent having an ethanol level, a particle diameter of about 400 μm is preferable. On the other hand, when the viscosity is at the water level, a particle size of around 600 μm is considered preferable. The optimum particle size varies depending on the viscosity of the liquid and the water and poor water solubility. The particle size with low pressure loss and catalytic effect is 1 μm to 1 mm, most preferably 100 μm to 1 mm.

  FIG. 13 shows a gas-liquid reactor according to another embodiment of the present invention, in which fine particles 12 are filled in a cylindrical container 80 formed of a porous body. A gas flow path 84 for supplying gas is formed between the cylindrical container 80 and the outer container 82. Cylindrical container 80 formed of a porous body Since the cylindrical container 80 forms the gas flow path 84 in the longitudinal direction, it has the effect of atomizing the gas and dispersing it in the liquid between the fine particles. The end portion of the apparatus is a sealed cylinder 86, and the gas flow path 84 does not extend to the end. This is because the reaction time becomes insufficient. In this embodiment, the cylindrical container 80 is formed on the outer side, but may be formed on the inner side or on both the inner and outer sides.

It is (a) sectional drawing and (b) perspective view which show the gas-liquid reaction device of one embodiment of this invention. (A) is a figure which expands and shows the principal part of embodiment of FIG. 1, (b) is a figure which expands and shows the microparticles | fine-particles 1212. (A) is a figure which expands and shows the principal part of other embodiment, (b) is a perspective view which shows other embodiment. It is sectional drawing which shows the gas-liquid reaction apparatus of further another embodiment of this invention. It is sectional drawing which shows the gas-liquid reaction apparatus of further another embodiment of this invention. 6 is a chemical reaction formula showing an example of a reaction performed in the apparatus of the embodiment shown in FIG. It is a figure which shows the gas-liquid reaction apparatus of further another embodiment of this invention. It is sectional drawing which shows embodiment of the peptide synthesizer using the gas-liquid reaction apparatus of embodiment of FIG. It is a chemical reaction formula which shows an example of the reaction performed with the apparatus of embodiment shown in FIG. It is sectional drawing which shows the gas-liquid reaction apparatus of further another embodiment of this invention. (A) is a figure which shows the principal part of the apparatus of embodiment shown in FIG. 10, (b) is the top view, (c) is a top view of a modification. It is a graph which shows the effect | action of the gas-liquid reaction apparatus of FIG. It is sectional drawing which shows the gas-liquid reaction apparatus of further another embodiment of this invention.

Explanation of symbols

10, 10a, container 12 fine particle 12
DESCRIPTION OF SYMBOLS 14 Introduction part 16 Derivation part 24 Temperature control jacket 26 Porous membrane 28 Liquid introduction port 30 Gas introduction port 32 Outlet port 34 Temperature control jacket 60 Dispersion plate 66 Unit container 68 Container main body 72,74 Introduction path 76 Derivation path

Claims (10)

A reaction vessel filled with fine particles having a diameter of 1 μm to 1 mm;
A liquid inlet for introducing liquid into the reaction vessel;
A gas inlet for introducing gas into the reaction vessel;
A gas-liquid reactor characterized by having an outlet for deriving a reaction product.   The gas-liquid reactor according to claim 1, wherein the fine particles are made of porous silica, alumina, or SiC.   The gas-liquid reaction apparatus according to claim 1 or 2, wherein the fine particles carry a catalyst.   The gas-liquid reactor according to claim 3, wherein the catalyst contains any one of Pd, Ni, Co, Pt, and Cu.   The gas-liquid reaction apparatus according to any one of claims 2 to 4, wherein the catalyst is supported by wet treatment.   6. The gas-liquid reaction apparatus according to claim 1, further comprising a dispersion plate that disperses the gas injected into the liquid in the flow of the liquid.   The gas-liquid reaction apparatus according to any one of claims 1 to 6, further comprising heating means for heating the reaction vessel.   A space in the reaction vessel is partitioned by a porous membrane having a pore size of 0.5 μm or less, a gas is introduced into one space, a liquid is introduced into the other space, and the gas is allowed to permeate the porous membrane. A gas-liquid reactor characterized by being dissolved in   The gas-liquid reactor according to claim 6, wherein the porous membrane is made of PTFE (polytetrafluoroethylene) or PCTFE (polychlorotrifluoroethylene).   The gas-liquid reaction apparatus according to claim 8 or 9 is disposed in the front stage, the gas-liquid reaction apparatus according to any one of claims 1 to 7 is disposed in the rear stage, and the gas-liquid reaction apparatus in the front-stage gas-liquid reaction apparatus A gas-liquid reactor characterized in that the reaction is promoted by a catalyst in the latter gas-liquid reactor after mixing.

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