JP5936027B2 - Method for producing reaction product of substrate and hydrogen - Google Patents

Description

  The present invention relates to a method for producing a reaction product of a liquid phase substrate and hydrogen gas in the presence of a solid catalyst.

  As a method of reacting a liquid substrate or a substrate in a solution with hydrogen gas in the presence of a solid catalyst, a hydrogen reduction reaction of an organic compound having an unsaturated carbon bond or a hydrogenolysis reaction of a secondary or tertiary alcohol is known. It has been. In the hydrogen reduction reaction of the organic compound, the organic compound and hydrogen are adsorbed on a solid catalyst such as palladium carbon and Raney nickel and meet on the catalyst, and hydrogen is additionally bonded to an unsaturated carbon bond or an aldehyde group. It is a reaction. The alcohol hydrocracking reaction is a reaction in which the C—O bond in the alcohol is directly cleaved with hydrogen in the presence of a catalyst such as palladium carbon.

  All of these reactions are performed under high pressure conditions from the viewpoint of increasing the solubility of hydrogen gas in the substrate, and further under conditions that require high temperatures, and from the viewpoint of increasing the contact efficiency between the substrate and the solid catalyst. From under intense stirring. For this reason, in the production of compounds involving these reactions, it is necessary to carry out work in accordance with the High Pressure Gas Safety Law, and the first type pressure vessel that can withstand high temperature and high pressure conditions, and excellent stirring performance in this vessel A special device such as a stirring device is required.

  On the other hand, for example, microbubbles and nanobubbles are known as techniques for introducing minute bubbles into the liquid phase. For example, microbubbles usually have a bubble size of 50 μm or less, and have unique properties such as a slow rising rate of bubbles in the liquid phase, a self-pressurizing effect, and charging properties ( For example, see Patent Document 1.)

  As a technique using such properties of microbubbles, a crystallization method and a cleaning method using microbubbles are known (see, for example, Patent Documents 1 and 2). As a technique for using microbubbles in a synthesis method, a primary alcohol oxidation method in a liquid phase using oxygen microbubbles in the presence of a copper / TEMPO catalyst is known (see, for example, Non-Patent Document 1). . However, the use of microbubbles and nanobubbles for hydrogen reduction reactions that require gas-liquid-solid contact and hydrocracking reactions is not known.

JP 2009-131737 A JP 2004-121962 A

Mase, N.M. et al. Chem. Commun. 2011, 47 (7), 2086-2088.

  The present invention provides a new production method that does not require a reaction apparatus having a high stirring force for high temperature and high pressure in a gas-liquid-solid catalytic reaction in the presence of a solid catalyst between a liquid phase of a substrate and hydrogen gas.

  In the gas-liquid-solid contact reaction described above, the present inventors introduced the gas-liquid-solid contact reaction (hereinafter simply referred to as gas-liquid contact reaction) even at normal pressure by introducing hydrogen gas into the liquid phase with microbubbles. The present invention has been completed.

  That is, in the present invention, a reaction product generated by gas-liquid contact between a substrate and hydrogen in the presence of a solid catalyst by bringing the liquid phase containing the substrate into contact with hydrogen gas bubbles in the presence of the solid catalyst. In the manufacturing method, the substrate is any one of an organic compound having an unsaturated carbon bond, a secondary alcohol, a tertiary alcohol, and an aldehyde, and hydrogen gas bubbles introduced into the liquid phase are formed of hydrogen gas. Provided is a method for producing a reaction product of a substrate and hydrogen, which is a microbubble or a nanobubble.

  In the present invention, the substrate is an organic compound having an unsaturated carbon bond, and the solid catalyst is a catalyst for hydrogen reduction reaction of the organic compound, or the substrate is a secondary alcohol or a tertiary alcohol. There is provided the above method, wherein the solid catalyst is a catalyst for hydrocracking reaction of these alcohols, or the substrate is an aldehyde, and the solid catalyst is a catalyst for hydrogen reduction reaction of aldehyde. .

  Further, in the present invention, the organic compound having an unsaturated carbon bond is any one of an optionally substituted chain olefin and an optionally substituted cyclic olefin, and further, a monosubstituted olefin, The above process is provided which is any one of a disubstituted olefin, a trisubstituted olefin and a tetrasubstituted olefin.

  In addition, there is provided the above method, wherein the organic compound having an unsaturated carbon bond is a chain alkyne which may be substituted, and further is any one of a mono-substituted alkyne and a di-substituted alkyne.

  The present invention uses an organic compound having an unsaturated carbon bond, a secondary alcohol, a tertiary alcohol, and an aldehyde as a substrate, and microbubbles or nanobubbles of hydrogen gas and the substrate in a liquid phase in the presence of a solid catalyst. In order to produce such a reaction product at normal pressure, the reaction product can be produced without the need for a reactor having a high stirring force for high temperature and pressure. Can be manufactured.

It is a figure which shows the outline of a structure of the reaction apparatus used in the Example of this invention. It is a figure which expands and shows a part of reactor of FIG.

  In the method for producing a reaction product of the present invention, a liquid phase containing a substrate and hydrogen gas bubbles are brought into contact with each other in the presence of a solid catalyst, and gas-liquid contact between the substrate and hydrogen in the presence of the solid catalyst is performed. In the method for producing a reaction product to be produced, hydrogen gas introduced into the liquid phase, wherein the substrate is any one of an organic compound having an unsaturated carbon bond, a secondary alcohol, a tertiary alcohol, and an aldehyde. These bubbles are hydrogen gas microbubbles or nanobubbles.

Examples of the reaction for producing such a reaction product include unsaturated carbonization, hydrogen reduction reaction for aldehyde groups, and hydrogenolysis reaction for hydroxyl groups of secondary or tertiary alcohols. For example, the hydrogen reduction reaction can be performed by using an organic compound or aldehyde having an unsaturated carbon bond as the substrate, and using a catalyst for hydrogen reduction reaction of the organic compound or aldehyde as the solid catalyst. The decomposition reaction can be performed by using a secondary alcohol or a tertiary alcohol as the substrate, and using the solid catalyst as a catalyst for hydrogenolysis of these alcohols.

  The organic compound having an unsaturated carbon bond in the substrate is not particularly limited as long as it is a compound capable of forming the liquid phase. Examples of the unsaturated carbon bond include a double bond or a triple bond between two carbon atoms. Examples of the organic compound having an unsaturated carbon bond include organic compounds that may contain heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, and halogen. Specifically, the organic compound may be substituted. Chain olefins that may be substituted, cyclic olefins that may be substituted, and chain alkynes that may be substituted may be mentioned. Among these, monosubstituted olefins, disubstituted olefins, trisubstituted olefins, and tetrasubstituted olefins may be mentioned. Examples of the optionally substituted chain alkyne include mono-substituted alkynes and di-substituted alkynes. Further, the carbon number of the organic compound is not particularly limited as long as the reaction can be performed in a solution and a slurry state.

  Examples of the olefin in the mono-substituted olefin, the di-substituted olefin, the tri-substituted olefin, and the tetra-substituted olefin include an unsaturated ring having 3 to 8 carbon atoms, and more specifically, an unsaturated ring having 4 to 6 carbon atoms. More specifically, an unsaturated ring having 6 carbon atoms can be mentioned. A heterocycle or the like indicates a partial ring with a reactive site. Moreover, as a substituent in monosubstituted olefin, disubstituted olefin, trisubstituted olefin, and tetrasubstituted olefin, monosubstituted alkyne and disubstituted alkyne, for example, C1-C20 alkyl which may be branched, C1 Examples include an optionally branched alkoxy having -20, an ether having 1-20 carbon atoms, a halogen such as F, Cl, Br, and I, a cyano group, and a nitro group. The number of carbon atoms in the alkyl, alkoxy, and ether as the substituent is more specifically 1-10, and more specifically 1-7.

  Examples of the chain olefin which may be substituted include propene, 2-methylpropene, hexa-1-ene, 4-methylhex-1-ene, 2-ethyl-4-methylhex-1-ene, 2,3- Examples include dimethyl-2-butene, styrene and cyclohexylethene. Examples of the optionally substituted cyclic olefin include cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene and indene. Examples of the chain alkyne that may be substituted include 1-octyne, 6-dodecine, ethynylbenzene, and 1-phenyl-1-nonine.

  The secondary alcohol and tertiary alcohol in the substrate are not particularly limited as long as they are compounds capable of forming the liquid phase. Examples of the secondary alcohol include 2-propanol, 2-butanol, 2-octanol, and cyclohexanol. Examples of the tertiary alcohol include 2-methyl-2-propanol and 1-methylcyclohexanol.

  The aldehyde in the substrate is not particularly limited as long as it is a compound that can form the liquid phase. Examples of the aldehyde include aromatic aldehydes such as benzaldehyde, aliphatic aldehydes such as cyclohexanecarbaldehyde, and saturated and unsaturated linear or branched aliphatic aldehydes.

The liquid phase is a phase in which the substrate exists as a liquid. Examples of such a liquid phase include liquid substrates, substrate solutions, and suspensions of liquid substrates and substrate solutions. A known solvent can be used as a solvent or a suspension dispersion medium when the liquid phase is a substrate solution. One type or two or more types of solvents may be used. Examples of such solvents include benzene, toluene, xylene, hexane, heptane, octane, cyclohexane, methanol, ethanol, propanol, acetic acid, ethyl acetate, water, and mixed solvents thereof. A secondary alcohol such as 2-propanol is not preferred.

  The solid catalyst is not particularly limited as long as it is a solid catalyst used for hydrogen reduction reaction or hydrocracking reaction by gas-liquid contact between a liquid phase substrate and hydrogen gas. As the solid catalyst, a solid catalyst usually used in a hydrogen reduction reaction or a hydrocracking reaction under a high pressure condition can be used. One or more solid catalysts may be used. Examples of such a solid catalyst for hydrogen reduction reaction include palladium carbon, Raney nickel, and rhodium catalyst. Examples of the solid catalyst for hydrocracking reaction include palladium on carbon.

  The form of the solid catalyst is not particularly limited as long as it is a form used for hydrogen reduction reaction or hydrocracking reaction by gas-liquid contact between a liquid phase substrate and hydrogen gas. For example, the form of particles dispersed in the liquid phase Or a packed bed of particles arranged in a pipe through which the liquid phase passes. The solid catalyst in the form of particles is composed of, for example, particles of a catalyst component, a particulate carrier, and a catalyst component supported thereon.

  Microbubbles usually have (1) a low ascending speed, (2) a friction reducing effect, (3) a large surface area per unit volume, (4) a self-pressurizing effect, (5) abrupt dissolution And (6) the surface potential characteristics are manifested, (7) crushing by ultrasonic irradiation, and (8) the biological activity against living organisms. The bubbles are 50 μm or less. In the present invention, such normal microbubbles can be used.

  Microbubbles can be generated by a commonly used method. As such a method, for example, as a method of utilizing supersaturation, a sufficient amount of solute gas is dissolved in a sealed container containing a solvent to dissolve a sufficient amount, and then the solvent in which the solute gas is dissolved by pressurization is decompressed, A method of generating solute gas microbubbles in the solvent can be mentioned. The gas-liquid shearing method is a method in which a solute gas is supplied to a vortex of a solvent and the solute gas is sheared in the solvent to generate microbubbles of the solute gas in the solvent. The microbubbles in the present invention can be generated using a device that generates microbubbles by any of these methods. Examples of such microbubble generators include MA-2 type and AS-K3 type manufactured by Asp.

  The diameter of the bubbles of the microbubbles is obtained, for example, by photographing the liquid phase supplied with the microbubbles through a stereomicroscope and randomly measuring the diameter of an appropriate number of bubbles displayed in the obtained image. be able to. The diameter of the bubble of the nanobubble can be measured using a known measuring device, and examples of such a measuring device include a particle sensor PS100 manufactured by Hokuto Electronics Co., Ltd. Moreover, as a measuring apparatus which can measure the diameter of both the bubble of a micro bubble and a nano bubble, Shimadzu Corporation Corporation Shimadzu nanoparticle diameter distribution measuring apparatus SALD-7100 is mentioned, for example.

  The nanobubble is a bubble having the same characteristics as the microbubble, and is generally a bubble having a diameter of 1 μm or less. In the present invention, such normal nanobubbles can be used. Nanobubbles can be generated by the same method as microbubbles, can also be generated by self-contraction of microbubbles, and can also be generated by a method of generating microbubbles by crushing.

The form of the gas-liquid contact reaction between the hydrogen gas and the substrate in the presence of the solid catalyst in the present invention is not particularly limited as long as such a reaction proceeds. Examples of such a gas-liquid contact reaction include a method in which a predetermined amount of a substrate, a fixed catalyst, and hydrogen gas microbubbles are accommodated in the same reaction vessel and brought into gas-liquid contact, and a predetermined amount of liquid phase Examples include a form in which hydrogen gas microbubbles are continuously supplied to a reaction vessel containing a fixed catalyst, and a form in which a mixed fluid of hydrogen gas microbubbles or nanobubbles and a liquid phase is brought into contact with a solid catalyst. The solid catalyst may be dispersed in the liquid phase, stored in a predetermined container having liquid permeability, or fixed to a cylinder through which a mixed fluid of the liquid phase and hydrogen gas microbubbles flows. May be accommodated.

  The reaction temperature of the gas-liquid contact reaction is not particularly limited as long as this reaction proceeds, but can be determined from the viewpoint of the solubility of hydrogen gas in the liquid phase. For example, according to computer simulations, it is known that the solubility of hydrogen gas in ethanol is maximum at about 30 ° C., and that the solubility of hydrogen gas in toluene is maximum at about 60 ° C. Such a temperature having high properties can be set as the reaction temperature.

  The liquid phase may contain hydrogen gas bubbles larger than the microbubbles as long as the microbubbles or nanobubbles are included in the gas-liquid contact reaction. The liquid phase may further contain an additive such as a foam stabilizer as long as the gas-liquid contact reaction proceeds.

  According to the present invention, the hydrogen reduction reaction or hydrocracking reaction of a specific substrate, which has been performed under high pressure conditions using hydrogen gas and a solid catalyst, can be performed at normal pressure. According to such mild reaction conditions that can be employed in the present invention, it is not necessary to use a special apparatus that can withstand use at high temperature and high pressure. From the viewpoint of reducing the cost and workability of such equipment and its operation, the reaction pressure is preferably less than 1 MPa, more preferably less than 0.7 MPa, and even more preferably less than 0.5 MPa. The reaction temperature is preferably 10 to 100 ° C, more preferably 20 to 80 ° C, and further preferably 30 to 60 ° C. Of course, it is also possible to carry out the reaction under high pressure conditions of 1 MPa or more from the viewpoint of further promotion of the reaction.

  Examples of the present invention are shown below. The present invention is not limited to the following examples.

The apparatus used in this example is shown in FIG.
The apparatus of FIG. 1 includes a four-necked flask 1, a microbubble generator 2, a stirrer 3, and a hot plate 4. A stir bar 5 connected to the stirrer 3 and a stirring blade 6 disposed at the tip of the stirrer 3 are inserted in the middle tube of the four-necked flask 1, and the liquid phase in the flask 1 is inserted in the other side tube. Are connected to a drain pipe 7 for discharging the liquid, a supply pipe 8 for supplying a liquid phase into the flask 1, and a discharge pipe 9 for recycling excess hydrogen gas. As shown in FIG. 2, a cup 10 having liquid permeability is accommodated inside the four-necked flask 1, and a stirring rod 5 and a stirring blade 6 are disposed inside the cup 10. The distal end of the drainage pipe 7 is disposed at a position soaking in the liquid phase in the flask 1 outside the cup 10, and the distal end of the supply pipe 8 is disposed at a position for supplying the liquid phase inside the cup 10. The base end of the drainage pipe 7 is connected to the microbubble generator 2.

  On the other hand, a hydrogen gas cylinder (not shown) is connected to a trap 12 through a trap 11, and the trap 12 is connected to each of the surplus hydrogen gas recycling discharge pipe 9 and the microbubble generator 2. A hydrogen gas flow meter 14 is connected between the trap 12 and the microbubble generator 2 via a three-way valve 13.

The microbubble generator 2 is a device that generates microbubbles by gas-liquid shearing the liquid phase supplied from the drain pipe 7 and the hydrogen gas supplied through the trap 12. The micro bubble generator 2 includes Asp's micro bubble generator MA3FS.
Was used. The discharge port of the microbubble generator 2 is connected to the base end of the supply pipe 8, and the liquid phase containing the microbubbles is supplied from the supply pipe 8 into the cup 10 of the four-necked flask 1.

  In the reaction by the apparatus, an amount of liquid phase that does not sink the edge of the cup 10 is accommodated in the four-necked flask 1, a catalyst is accommodated in the cup 10, and only four liquid phases that have passed through the hydrogen gas and the cup 10 are accommodated. The microbubble generator 2 is continuously supplied from the neck flask 1 through the drain tube 7. Further, hydrogen gas is continuously supplied to the microbubble generator 2 through the trap 12, and a liquid phase containing microbubbles is further supplied from the microbubble generator 2 through the supply pipe 8 into the cup 10 of the four-necked flask 1. Supply continuously. The liquid phase in the four-necked flask 1 is adjusted to a specific temperature by heating directly through a water bath or an oil bath using the hot plate 4 as necessary. This reaction is carried out at normal pressure.

  The substrate reaction rate in Examples described later was determined as the production rate of the target product from the peak area in the chromatogram of gas chromatography or liquid chromatography.

[Example 1]
Using the apparatus of FIG. 1, a hydrogen reduction reaction of styrene represented by the following formula was performed. A styrene-methanol solution of 20 mmol of styrene and 40 mL of methanol was used for the liquid phase, 0.1% by weight of 10% palladium / carbon with respect to styrene was used for the catalyst, and the hydrogen gas flow rate was measured with a hydrogen gas flow meter 14, the reaction rate was 0.5 mL / min, the stirring speed was 20 rpm, the circulation flow rate of the liquid phase was 10 L / hour, the temperature of the liquid phase was 30 ° C., and the reaction was performed for 1 hour. The disappearance of styrene in the liquid phase was confirmed by gas chromatography, and the reaction was terminated. The reaction rate of styrene was 100%.

  Although the fluid mixture of the liquid phase and microbubbles discharged from the microbubble generator 2 is at normal pressure, immediately before the discharge port of the microbubble generator 2, the fluid is 0.4 due to the shearing of hydrogen gas in the liquid phase. A pressure of ˜0.6 MPa is applied to the liquid phase. However, in this embodiment, since the apparatus of FIG. 1 is used, the solid catalyst is not sucked into the microbubble generator 2. Therefore, the above-mentioned result in the present example is a result of the gas-liquid contact reaction proceeding only in the four-necked flask 1 at normal pressure. From this, it became clear that by supplying hydrogen gas as microbubbles to the substrate, the hydrogen reduction reaction of the above formula, which was conventionally performed under high pressure conditions, can be performed at normal pressure.

[Example 2]
As shown in the following formula, the hydrogen reduction reaction was performed under the same conditions as in Example 1 except that the substrate was replaced with indene, the reaction time was 2 hours, and 10 cups were removed from the apparatus of FIG. The reaction rate of indene was 100%.

[Example 3]
As shown in the following formula, Example 1 except that the substrate was replaced with 3,7-dimethylocta-2,6-dien-1-al, the reaction time was 3 hours, and 10 cups were removed from the apparatus of FIG. The hydrogen reduction reaction was performed under the same conditions. The reaction rate of 3,7-dimethylocta-2,6-dien-1-al was 100%.

[Example 4]
As shown in the following formula, the substrate was replaced with 1-methyl-4- (propan-2-ylidene) cyclohex-1-ene, the reaction time was 6 hours, and 10 cups were removed from the apparatus of FIG. A hydrogen reduction reaction was carried out under the same conditions as in Example 1. The reaction rate of 1-methyl-4- (propan-2-ylidene) cyclohex-1-ene was 53% 1-methyl-4- (propan-2-ylidene) cyclohexane and 47% 1-isopropyl-4-methylcyclohexane. there were.

[Example 5]
As shown in the following formula, the hydrogen reduction reaction was carried out under the same conditions as in Example 1 except that the substrate was replaced with phenylacetylene, the reaction time was 7 hours, and 10 cups were removed from the apparatus of FIG. The reaction rate of phenylacetylene was 100%.

[Example 6]
As shown in the following formula, the substrate is replaced with the compound of the following formula (4), the reaction night solvent is replaced with a mixed solvent of 100 mL of toluene and 100 mL of methanol, the reaction temperature is 60 ° C., and the reaction time is 15 hours. The hydrogen reduction reaction was carried out under the same conditions as in Example 1. The reaction rate of the compound of (4) was 99.0%.

[Example 7]
As shown in the following formula, the hydrogen reduction reaction was carried out under the same conditions as in Example 1 except that the substrate was replaced with the compound of the following formula (5), the reaction temperature was 60 ° C., and the reaction time was 7 hours. The reaction rate of the compound of Formula (5) was 99.9%.

[Example 8]
As shown in the following formula, the hydrogen reduction reaction was performed under the same conditions as in Example 1 except that the substrate was replaced with the compound of the following formula (6), the reaction temperature was 60 ° C., and the reaction time was 10 hours. The reaction rate of the compound of Formula (6) was 60.0%.

[Example 9]
As shown in the following formula, the hydrogen reduction reaction was carried out under the same conditions as in Example 1 except that the substrate was replaced with the compound of the following formula (7) and the reaction temperature was 60 ° C. and the reaction time was 10 hours. The reaction rate of the compound of Formula (7) was 90.0%.

[Example 10]
As shown in the following formula, the substrate was replaced with 2-ethyl-2-buten-1-al, the solvent was not used, the reaction temperature was 60 ° C., and the reaction time was 5 hours. Hydrogen reduction reaction was performed. The reaction rate of 2-ethyl-2-buten-1-al was 50%.

[Example 11]
As shown in the following formula, the substrate was replaced with 2-ethylbutanal, the catalyst was replaced with Raney nickel, no solvent was used, the reaction temperature was 60 ° C., and the reaction time was 5 hours. Hydrogen reduction reaction was performed. The reaction rate of 2-ethylbutanal was 50%.

[Example 12]
As shown in the following formula, the substrate is replaced with the compound of the following formula (10), the solvent is replaced with a mixed solvent of 100 mL of toluene and 100 mL of methanol, the reaction temperature is 80 ° C., and the reaction time is 7 hours. The hydrocracking reaction was carried out under the same conditions as in Example 1. The reaction rate of the compound of Formula (10) was 40%.

[Example 13]
As shown in the following formula, the hydrogenolysis reaction was performed under the same conditions as in Example 1 except that the substrate was replaced with the compound of the following formula (11), the reaction temperature was 80 ° C., and the reaction time was 7 hours. The reaction rate of the compound of the following formula (11) was 40%.

[Comparative Example 1]
1, the cup 10 is removed, the drain pipe 7 and the excess hydrogen gas recycling pipe 9 are removed, the side pipe into which these are inserted is sealed, and the base end of the supply pipe 8 is filled with hydrogen gas. A hydrogen reduction reaction was performed in the same manner as in Example 1 except that the balloon (1L) was connected. The reaction rate of styrene was 30%.

[Comparative Example 2]
1, the cup 10 is removed, the drain pipe 7 and the excess hydrogen gas recycling pipe 9 are removed, the side pipe into which these are inserted is sealed, and the base end of the supply pipe 8 is filled with hydrogen gas. A hydrogen reduction reaction was carried out in the same manner as in Example 11 except that the balloon (1L) was connected. The reaction rate of the compound of Formula (11) was 0%.

As is well known, the hydrogen reduction reaction and the hydrogenolysis reaction are highly useful reactions in the industrial production of various compounds. According to the present invention, such a reaction can be carried out at normal pressure. Therefore, according to the present invention, industrial production using hydrogen reduction reaction or hydrocracking reaction can be performed with normal equipment to which the high-pressure gas safety method is not applied, and the cost of manufacturing equipment can be greatly reduced. Be expected.

DESCRIPTION OF SYMBOLS 1 Four neck flask 2 Microbubble generator 3 Stirrer 4 Hot plate 5 Stirring rod 6 Stirring blade 7 Drain pipe 8 Supply pipe 9 Exhaust pipe for excess hydrogen gas recycling 10 Cup 11, 12 Trap 13 Three-way valve 14 For hydrogen gas Flowmeter

Claims (2)

In a method for producing a reaction product produced by gas-liquid contact between a substrate and hydrogen in the presence of a solid catalyst by contacting a liquid phase containing a substrate and hydrogen gas bubbles in the presence of a solid catalyst,
Wherein the substrate is a secondary alcohol or tertiary alcohol,
Microbubbles or nanobubbles der bubble hydrogen gas in the hydrogen gas introduced into the liquid phase is,
The microbubble is a bubble having a diameter of 50 μm or less, the nanobubble is a bubble having a diameter of 1 μm or less,
Conditions for producing a reaction product produced by gas-liquid contact are a reaction pressure of less than 0.5 MPa, a reaction temperature of 20 to 80 ° C. ,
The reaction by gas-liquid contact is a hydrogenolysis reaction with respect to a hydroxyl group of a secondary alcohol or a tertiary alcohol,
Production form of the reaction by the gas-liquid contact, the mixed fluid of microbubbles or nanobubbles and liquid hydrogen gas, characterized in form der Rukoto contacting the solid catalyst, the reaction product of a substrate and hydrogen how to. The method according to claim 1, wherein the substrate is a secondary alcohol or a tertiary alcohol, and the solid catalyst is a catalyst for hydrocracking reaction of a secondary alcohol or a tertiary alcohol .