Method for producing reaction product, and system for producing reaction product

Abstract

A method for producing a reaction product according to the present invention comprises: a supply step for supplying a gas and a liquid to a reactor; a reaction step for producing a reaction product from a starting compound contained in a raw material in the reactor using a catalyst; and a discharge step for intermittently discharging a portion of a liquid containing the reaction product from the reactor. A reaction product production system 100 according to the present invention comprises: a reactor 10 for producing a reaction product from a starting compound contained in a raw material using a catalyst; a supply mechanism 20 for supplying a gas and a liquid to the reactor 10; and a discharge mechanism 40 for intermittently discharging a portion of a liquid containing the reaction product from the reactor 10.

Description

Reaction product manufacturing method and reaction product manufacturing system

[0001] The present invention relates to a method for producing a reaction product and a system for producing a reaction product.

[0002] Generally, reaction techniques for obtaining compounds by chemically reacting raw materials include batch and continuous processes. Continuous processes have advantages such as eliminating the time required to charge raw materials and being more scalable than batch processes, and have been studied as a means of scaling up. For example, Non-Patent Document 1 discloses a continuous hydroformylation reaction using equipment equipped with a liquid containing a catalyst and a substrate, and a reactor pressurized with carbon monoxide and hydrogen.

[0003] Auto-tandem catalytic reductive hydroformylation with continuous multiphase catalyst recycling, S.Puschel et al., Catalysis Science & Technology 2022, 12, 728-736

[0004] When a reaction is carried out in a continuous system containing a gas phase and a liquid phase, in order to obtain a reaction product safely and stably, many other devices and parts in the production facility other than the reactor must also be pressure-resistant, which poses a cost problem.

[0005] In view of the above problems, the present invention provides a new method and system for producing a reaction product that is suitable for scale-up.

[0006] The present invention provides a method for producing a reaction product, comprising: a supply step of supplying a gas and a liquid to a reactor; a reaction step of producing a reaction product from a starting compound contained in a raw material in the reactor using a catalyst; and a discharge step of intermittently discharging a portion of the liquid containing the reaction product from the reactor.

[0007] The present invention further provides a reaction product manufacturing system comprising: a reactor that produces a reaction product from a starting compound contained in a raw material using a catalyst; a supply mechanism that supplies a gas and a liquid to the reactor; and a discharge mechanism that intermittently discharges a portion of the liquid containing the reaction product from the reactor.

[0008] According to the present invention, a new method and system for producing a reaction product suitable for scale-up can be provided.

[0009] FIG. 1 is a schematic diagram showing an example of a system for producing a reaction product.

[0010] A method for producing a reaction product according to a first aspect of the present invention includes a supply step of supplying a gas and a liquid to a reactor; a reaction step of producing a reaction product from a starting compound contained in a raw material in the reactor using a catalyst; and a discharge step of intermittently discharging a portion of the liquid containing the reaction product from the reactor.

[0011] In a second aspect of the present invention, for example, in the method for producing a reaction product according to the first aspect, the raw material contains a gas capable of reacting with the starting compound, and the gas contains the gas.

[0012] In a third aspect of the present invention, for example, in the method for producing a reaction product according to the second aspect, the gas contains hydrogen, and the reaction is a hydrogenation reaction of the starting compound with the hydrogen.

[0013] In a fourth aspect of the present invention, for example, in the method for producing a reaction product according to any one of the first to third aspects, the liquid has an organic phase and an aqueous phase.

[0014] In a fifth aspect of the present invention, for example, in the method for producing a reaction product according to the fourth aspect, the organic phase contains the catalyst, and the aqueous phase contains the starting compound.

[0015] In a sixth aspect of the present invention, for example, in the method for producing a reaction product according to any one of the first to fifth aspects, the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and the reaction product is formate.

[0016] In a seventh aspect of the present invention, for example, in the method for producing a reaction product according to any one of the first to sixth aspects, the discharging step is carried out while the supplying step is being carried out.

[0017] In an eighth aspect of the present invention, for example, in the method for producing a reaction product according to any one of the first to seventh aspects, the discharge step is carried out by opening and closing a discharge valve disposed in a discharge path for discharging the liquid from the reactor.

[0018] In a ninth aspect of the present invention, for example, in the method for producing a reaction product according to any one of the first to eighth aspects, the average residence time of the liquid in the reactor is 1 minute or more and 180 minutes or less.

[0019] In a tenth aspect of the present invention, for example, in the method for producing a reaction product according to any one of the first to ninth aspects, an inlet of a discharge path for discharging the liquid from the reactor is located below the liquid level in the reactor when the reactor is stationary.

[0020] In an eleventh aspect of the present invention, for example, the method for producing a reaction product according to any one of the first to tenth aspects, further comprises a separation step of separating the liquid discharged in the discharge step into an organic phase and an aqueous phase under normal pressure.

[0021] In a twelfth aspect of the present invention, for example, in the method for producing a reaction product according to any one of the first to eleventh aspects, the catalyst is a metal catalyst.

[0022] In a thirteenth aspect of the present invention, for example, in the method for producing a reaction product according to the twelfth aspect, the metal catalyst contains ruthenium.

[0023] In a fourteenth aspect of the present invention, for example, in the method for producing a reaction product according to the fourth or fifth aspect, the organic phase contains toluene.

[0024] A reaction product manufacturing system according to a fifteenth aspect of the present invention comprises: a reactor that produces a reaction product from a starting compound contained in a raw material using a catalyst; a supply mechanism that supplies a gas and a liquid to the reactor; and a discharge mechanism that intermittently discharges a portion of the liquid containing the reaction product from the reactor.

[0025] In a sixteenth aspect of the present invention, for example, the reaction product production system according to the fifteenth aspect further comprises a separation mechanism that separates the liquid discharged by the discharge mechanism into an organic phase and an aqueous phase under normal pressure.

[0026] In a seventeenth aspect of the present invention, for example, the reaction product production system according to the fifteenth or sixteenth aspect is used in the production method according to any one of the first to fourteenth aspects.

[0027] The present invention will be described in detail below, but the following description is not intended to limit the present invention to a specific embodiment.

[0028] [Method for Producing Reaction Product] The method for producing a reaction product according to this embodiment includes a supply step of supplying a gas and a liquid to a reactor, a reaction step of producing a reaction product from a starting compound contained in the raw material using a catalyst in the reactor, and a discharge step of intermittently discharging a portion of the liquid containing the reaction product from the reactor.

[0029] Hereinafter, the liquid supplied to the reactor in the supply step may be referred to as "liquid L" and the gas may be referred to as "gas G." Hereinafter, the liquid containing the reaction product may be referred to as "reaction liquid."

[0030] The production method according to this embodiment can produce a reaction product by a reaction in a system having a gas phase and a liquid phase using a catalyst, and is suitable for mass production of the reaction product. According to the production method according to this embodiment, a reaction product can be produced, for example, with an excellent conversion rate using various reactions. The production method according to this embodiment is a semi-batch process in which a portion of the reaction liquid is intermittently discharged from the reactor in the discharge step, so that the reaction product can be obtained stably, and further, the reaction liquid can be discharged under normal pressure. Therefore, compared to a continuous process, equipment costs can be reduced. Furthermore, the production method according to this embodiment can simultaneously perform the supply step, reaction step, and discharge step, so that time efficiency can be improved compared to a batch process.

[0031] 1 is a schematic diagram showing an example of a production system suitable for the production method according to this embodiment. The production system 100 according to this embodiment includes a reactor 10 that produces a reaction product from a starting compound contained in a raw material using a catalyst, a supply mechanism 20 that supplies a gas G and a liquid L to the reactor 10, and a discharge mechanism 40 that intermittently discharges a portion of the reaction liquid from the reactor 10.

[0032] The supply mechanism 20 continuously or intermittently supplies the gas G and the liquid L to the reactor 10. The supply mechanism 20 includes, for example, a liquid supply device and a gas supply device 27.

[0033] The liquid supply device includes, for example, an organic phase supply device 21 and an aqueous phase supply device 24. The organic phase supply device 21 includes a container 22 that contains an organic phase, and an organic phase supply path 23 for supplying the organic phase from the container 22 to the reactor 10. The aqueous phase supply device 24 includes a container 25 that contains an aqueous phase, and an aqueous phase supply path 26 for supplying the aqueous phase from the container 25 to the reactor 10. The containers 22 and 25 are, for example, tanks.

[0034] The gas supply device 27 includes, for example, a cylinder 28 containing the gas G, and a gas supply path 29 for supplying the gas G from the cylinder 28 to the reactor 10 .

[0035] The discharge mechanism 40 is, for example, a reaction liquid discharge path 41. The reaction liquid discharge path 41 preferably includes a discharge valve 42 disposed in the discharge path for discharging the liquid (reaction liquid) from the reactor 10. The discharge valve 42 can control the flow of the reaction liquid; for example, opening the discharge valve 42 allows the reaction liquid to flow, and closing the discharge valve 42 stops the flow of the reaction liquid. The reaction liquid discharge path 41 is preferably equipped with a back pressure valve 43. This allows the production system 100 to operate stably. In FIG. 1 , the back pressure valve 43 is located downstream of the discharge valve 42, but the order of the back pressure valve 43 and the discharge valve 42 is not limited to this.

[0036] According to the above configuration, the reaction solution can be easily discharged without stopping the operation of the manufacturing system 100, thereby improving time efficiency. Furthermore, the reaction solution can be discharged into an environment under atmospheric pressure while maintaining stable operation of the manufacturing system 100, and subsequent processes can be carried out under atmospheric pressure. This reduces the number of high-pressure resistant parts required for the manufacturing system 100, thereby achieving cost reduction and miniaturization.

[0037] The shape of the reactor 10 is not particularly limited, but it is preferably a tank-type reactor.

[0038] The production system 100 can produce reaction products using various reactions with, for example, excellent conversion rates. Furthermore, the production system 100 is suitable for, for example, reusing catalysts. Furthermore, exhaust and waste can be reduced.

[0039] The manufacturing system 100 may further include a controller 50 that controls each component of the manufacturing system 100. The controller 50 is, for example, a DSP (Digital Signal Processor) that includes an A / D conversion circuit, an input / output circuit, an arithmetic circuit, a storage device, etc. The controller 50 stores a program for appropriately operating the manufacturing system 100.

[0040] Unless otherwise specified, each of the paths in the manufacturing system 100 is made up of, for example, metal or resin piping.

[0041] The manufacturing method according to this embodiment will be described in detail below with reference to FIG.

[0042] In the supply step, a gas G and a liquid L are supplied to the reactor 10 by the supply mechanism 20. At least one of the supplied gas G and liquid L contains raw materials for the reaction in the reaction step. In the reaction step, a reaction product is produced from a starting compound contained in the raw materials using a catalyst in the reactor 10. In the discharge step, a portion of the reaction liquid is intermittently discharged from the reactor 10 by the discharge mechanism 40.

[0043] The manufacturing method according to this embodiment may further include a preparation step prior to the supply step.

[0044] <Preparation Step> In the preparation step, a predetermined amount of liquid L is prepared in the reactor 10. The preparation step may be performed before constructing the production system 100. In the preparation step, the inside of the reactor 10 may be pressurized to the pressure of the reaction in the reaction step. By supplying the gas G to be used in the supply step in the preparation step, the inside of the reactor 10 can be replaced with an atmosphere suitable for the reaction step.

[0045] <Supply Step> In the supply step, the gas G and the liquid L are each continuously or intermittently supplied to the reactor 10 by the supply mechanism 20. In the supply step, it is preferable that the gas G and the liquid L are each continuously supplied to the reactor 10.

[0046] The liquid L preferably has an organic phase and an aqueous phase. In the supply step, the gas G and the liquid L having an organic phase and an aqueous phase are each continuously or intermittently supplied to the reactor 10, preferably, the gas G and the liquid L having an organic phase and an aqueous phase are each continuously supplied.

[0047] The organic phase supply path 23 may be equipped with a liquid feed pump 30 for feeding the organic phase. The aqueous phase supply path 26 may be equipped with a liquid feed pump 31 for feeding the aqueous phase. The liquid feed pumps 30 and 31 can supply the liquid L to the reactor 10 at a desired liquid supply flow rate.

[0048] Each path and pump may be heated, which allows for the transfer of higher concentrations of raw materials as the organic and aqueous phases and stabilizes the temperature during the reaction process.

[0049] The production system 100 may be provided with a two-way switching valve 32 that can switch the flow direction of the liquid L between within the system or to the purge line. In the production system 100, the two-way switching valve may be disposed in the liquid supply path after the organic phase supply path 23 and the aqueous phase supply path 26 join, or a two-way switching valve may be disposed in each of the organic phase supply path 23 and the aqueous phase supply path 26.

[0050] In Fig. 1, the organic phase supply path 23 and the aqueous phase supply path 26 join together, and then the gas supply path 29 joins them up to the reactor 10, but the system structure is not limited to this. For example, the organic phase supply path 23, the aqueous phase supply path 26, and the gas supply path 29 may be independent of each other.

[0051] <Reaction Step> In the reaction step, a reaction product is produced from the starting compounds contained in the raw materials using a catalyst in the reactor 10. That is, in the reaction step, a reaction to produce the reaction product is carried out. The reaction step is typically carried out while the supply step is being carried out. This makes it possible to eliminate time required other than the reaction, such as the time required to charge the raw materials, in the production method.

[0052] The raw material is contained in at least one of a gas G and a liquid L. The reaction product is typically an organic compound.

[0053] Examples of the reaction of the starting compound include a hydrogenation reaction, a reduction reaction other than a hydrogenation reaction, a dehydration condensation reaction, and a hydrolysis reaction, and the hydrogenation reaction is preferred.

[0054] In the reaction step, the liquid L in the reactor 10 may be stirred. This promotes the reaction. The reactor 10 may be equipped with a stirring blade 33. The stirring conditions are not particularly limited and can be set appropriately taking into consideration the amount of the liquid L, etc. The reactor 10 may be equipped with a baffle. For example, the reactor 10 may be equipped with one or more baffles on the inner wall surface.

[0055] In the reaction step, the contents (liquid L and gas G) in the reactor 10 may be heated. This promotes the reaction. The heating temperature is not particularly limited, but in order to efficiently proceed with the reaction, it is, for example, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, or even 80°C or higher. From the viewpoint of suppressing side reactions and energy efficiency, the heating temperature is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower. For example, the gas G and liquid L may be heated to 90°C. The production system 100 may further include a heating device (not shown) that heats the gas G and liquid L supplied to the reactor 10. The heating device may be integrated with the reactor 10 or may be a separately provided constant temperature bath.

[0056] The reaction time for the reaction to produce a reaction product is not particularly limited and can be set to a time appropriate for the reaction. That is, the time (average residence time) for which the liquid (reaction liquid) resides in the reactor 10 is not particularly limited and can be set to a time appropriate for the reaction. The average residence time of the liquid in the reactor 10 may be 1 minute or more, 5 minutes or more, 10 minutes or more, 30 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, or even 60 minutes or more, from the viewpoint of ensuring sufficient reactivity. Furthermore, the average residence time of the liquid in the reactor may be 180 minutes or less, 120 minutes or less, or even 60 minutes or less, from the viewpoint of increasing production efficiency per hour. The average residence time of the liquid in the reactor 10 is preferably 1 minute or more and 180 minutes or less, more preferably 1 minute or more and 120 minutes or less, and even more preferably 5 minutes or more and 60 minutes or less.

[0057] The reaction pressure is not particularly limited, but from the viewpoint of improving the conversion rate, it may be, for example, 0.1 MPa or more, 0.2 MPa or more, 0.5 MPa or more, 1 MPa or more, 4 MPa or more, 4.5 MPa or more, 5 MPa or more, or even 6 MPa or more. The upper limit of the reaction pressure is not particularly limited, but from the viewpoint of cost, it is preferably 20 MPa or less, more preferably 10 MPa or less. The inside of the reactor 10 may be pressurized with a gaseous raw material.

[0058] <Discharge Step> In the discharge step, a portion of the liquid (reaction liquid) containing the reaction product in the reactor 10 is intermittently discharged from the reactor 10 by the discharge mechanism 40. The discharge step is typically carried out while the reaction step is being carried out. Furthermore, the discharge step is typically carried out while the supply step is being carried out. This makes it possible to eliminate time required other than for the reaction, such as the time required to discharge the reaction liquid.

[0059] The reaction mixture may further contain raw materials as the case may be.

[0060] The discharge step may be performed by opening and closing the discharge valve 42 disposed in the reaction liquid discharge path 41. For example, in the discharge step, the following steps 1 to 3 may be repeated in this order. Step 1: Open the discharge valve 42. Step 2: Confirm that the amount of discharged liquid has reached a predetermined value. Step 3: Close the valve.

[0061] The time during which the discharge valve is open, i.e., the time for one discharge in the discharge step, is, for example, 10 minutes or less, preferably 5 minutes or less, and more preferably 1 minute or less. The lower limit of the time is not particularly limited, but is, for example, 1 second or more.

[0062] In step 2, the amount of liquid is confirmed, for example, by measuring it at the outlet or by a flow meter provided in the reaction liquid discharge path 41.

[0063] The discharge valve 42 may include two or more valves. For example, if the discharge valve 42 includes an upstream valve 42a and a downstream valve 42b, the discharge process may involve repeating the following steps 11 to 13 in this order. Step 11: Close the valves 42a and 42b. Step 12: Open the valve 42a, and close the valve 42b. Step 13: Close the valve 42a, and open the valve 42b.

[0064] The transition from step 12 to step 13 may be performed by simultaneously operating valves 42a and 42b, or by closing valve 42a and then opening valve 42b. According to the above configuration, the discharge step can be performed while maintaining stable operation of the production system 100, and the reaction liquid can be discharged to an environment under normal pressure. This reduces the number of high-pressure resistant parts required for the production system 100, thereby enabling cost reduction and miniaturization.

[0065] The inlet 41a of the reaction liquid discharge path 41 is preferably located below the liquid level in the reactor 10 when the production system 100 is stationary, and more preferably located below the liquid level in the reactor 10 both when the production system 100 is stationary and when it is operating. That is, the inlet 41a of the reaction liquid discharge path 41 is preferably always in contact with the liquid in the reactor 10. This allows the discharge mechanism 40 to discharge the reaction liquid from the reactor 10 without discharging a large amount of gas outside the system.

[0066] 1, the reaction liquid discharge path 41 extends from the top of the reactor 10 toward the liquid surface, but is not limited thereto. For example, in the discharge step, the reaction liquid may be discharged downward from the bottom of the reactor 10.

[0067] The amount of the reaction liquid discharged at one time, i.e., the amount of a portion of the reaction liquid, may be, for example, 1% or more and 70% or less of the amount (volume) of liquid in the reactor 10 at the start of discharge, or 2% or more and 50% or less, or even 5% or more and 30% or less.

[0068] In the discharge step, for example, the reaction liquid may be discharged intermittently so that the average discharge rate per unit time (liquid discharge flow rate) and the supply rate of liquid L per unit time in the supply step (liquid supply flow rate) are substantially the same. That is, the supply step and the discharge step may be performed so that the liquid volume in the reactor does not change substantially. "The liquid discharge flow rate and the liquid supply flow rate being substantially the same" means that the ratio (flow rate S / flow rate D) of the liquid supply flow rate (flow rate S) to the liquid discharge flow rate (flow rate D) is in the range of 0.9 to 1.1. The flow rate S / flow rate D is preferably in the range of 0.95 to 1.05, and more preferably 1.

[0069] The amount of reaction liquid discharged at one time in the discharge step may be the same as the amount of liquid in the reactor 10 that has increased since the previous discharge.

[0070] In the discharging step, it is preferable to intermittently discharge a portion of the reaction liquid so that the above-mentioned average residence time is satisfied.

[0071] When the liquid discharge flow rate and the liquid supply flow rate are substantially the same, the average residence time [min] can be calculated using the average liquid volume [L] in the reactor 10 and the liquid supply flow rate [L / min] according to the following formula: Average residence time = (Average liquid volume in the reactor) / (Liquid supply flow rate) Here, the average liquid volume in the reactor is the liquid volume [L] in the reactor at the start of system operation (i.e., the amount of liquid L prepared in the reactor 10 in the preparation step) plus the average liquid volume in the reactor 10 that increased from the previous discharge (or from the prepared amount of liquid L) to the next discharge (hereinafter, sometimes referred to as the "average liquid increase") × 1 / 2 [L]. The average liquid increase can be calculated by multiplying the liquid supply flow rate by the average time during which no discharge is performed between intermittent discharges. When the discharge step is performed by opening and closing the discharge valve 42, the "average time during which no discharge is performed between intermittent discharges" is the average time from when the discharge valve 42 is closed to when it is opened again. Therefore, the average liquid volume in the reactor is calculated by the following formula: In the formula below, the "average time of the period during which no discharge is performed between intermittent discharges" is referred to as the "average time during which the discharge valve is closed." Average liquid volume in the reactor = liquid volume in the reactor at the start of system operation + (liquid supply flow rate × average time during which the discharge valve is closed × 1 / 2)

[0072] In the discharging step, a certain amount of the reaction liquid may be repeatedly discharged from the reactor 10 .

[0073] The feeding step, the reacting step, and the discharging step may be carried out simultaneously.

[0074] <Other Steps> The production method according to this embodiment may include other steps in addition to the supply step, reaction step, and discharge step. For example, when the liquid L has an organic phase and an aqueous phase, the production method according to this embodiment may further include a separation step in which the reaction liquid discharged in the discharge step is separated into an organic phase and an aqueous phase under atmospheric pressure (i.e., into a solution containing an organic solvent and a solution containing an aqueous solvent). For example, the production system 100 may further include a separation mechanism (not shown) that separates the reaction liquid discharged from the reactor 10 into an organic phase and an aqueous phase, and the separation mechanism may be a mechanism that separates the reaction liquid into an organic phase and an aqueous phase under atmospheric pressure. The separation mechanism may be a known separation device capable of separating an organic phase and an aqueous phase. As a result, the number of high-pressure-resistant components required for the production system 100 can be reduced, thereby achieving cost reduction and miniaturization. Atmospheric pressure is the pressure of the ambient environment (e.g., 0.1 MPa).

[0075] For example, if the reaction product is eluted into the aqueous phase, the reaction product can be recovered from the aqueous phase. The separated aqueous phase may be used to supply liquid L in the supply step. This allows the starting compounds remaining in the liquid phase to react. If the catalyst is contained in the organic phase, the catalyst can be recovered from the organic phase, allowing the catalyst to be easily reused. The separated organic phase may be used to supply liquid L in the supply step.

[0076] The organic phase and the aqueous phase can be separated using a separator employing a known separation method, such as static separation, centrifugation, or separation using an oil-water separation filter. From the viewpoint of simplicity, static separation and separation using an oil-water separation filter are preferred.

[0077] The production method according to this embodiment may further include a cooling step of cooling the reaction liquid discharged in the discharging step. The cooling step is preferably carried out before the separating step.

[0078] The gas G and the liquid L used in the manufacturing method according to this embodiment will be described in detail below.

[0079] <Gas G> The gas G may contain at least a portion of the raw material. The gas G may contain a gas capable of reacting with the starting compound. The gas contains, for example, hydrogen. When the gas contains hydrogen, the reaction of the starting compound in the reaction step is typically a hydrogenation reaction. However, the reaction of the starting compound is not limited to a hydrogenation reaction, and may be a reduction reaction other than a hydrogenation reaction, a dehydration condensation reaction, a hydrolysis reaction, or the like.

[0080] Examples of hydrogen sources that can be used include hydrogen generated during the iron smelting process and hydrogen generated during the sodium hydroxide production process. Hydrogen generated by the electrolysis of water can also be used.

[0081] The gas G may comprise the starting compound. For example, if the starting compound is carbon dioxide, the gas G may comprise the starting compound.

[0082] The carbon dioxide may be pure carbon dioxide gas or may be mixed with other components other than carbon dioxide. Examples of the components other than carbon dioxide include inert gases such as nitrogen and argon, water vapor, and any other components contained in exhaust gases, etc. The ratio of hydrogen and carbon dioxide used may be equal on a molar basis, but an excess of hydrogen is preferred.

[0083] <Liquid L> As described above, the liquid L preferably has an organic phase and an aqueous phase. That is, the liquid L contains an organic solvent and an aqueous solvent. In this specification, the aqueous phase means the part of the liquid that is a solution containing an aqueous solvent. The organic phase means the part of the liquid that is a solution containing an organic solvent. In this specification, the aqueous solvent and the organic solvent may be collectively referred to as solvents.

[0084] The aqueous phase contains an aqueous solvent and may further contain a starting compound.

[0085] Examples of aqueous solvents include water, methanol, ethanol, ethylene glycol, glycerin, and mixtures thereof, with water being preferred from the viewpoint of low environmental impact.

[0086] The aqueous phase may include an aqueous solvent and a starting compound.

[0087] The starting compound is, for example, an inorganic substance. Examples of the inorganic substance include carbon dioxide, bicarbonate, and carbonate. That is, the starting compound may be at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate.

[0088] Examples of bicarbonates and carbonates include carbonates or bicarbonates of alkali metals or alkaline earth metals. Examples of bicarbonates include sodium bicarbonate and potassium bicarbonate, with potassium bicarbonate being preferred from the viewpoint of high solubility in water. That is, in the production method according to this embodiment, the starting compound preferably contains potassium bicarbonate as the bicarbonate. Examples of carbonates include sodium carbonate, potassium carbonate, potassium sodium carbonate, and sodium sesquicarbonate.

[0089] Bicarbonates and carbonates can be produced by the reaction of carbon dioxide with a base. For example, bicarbonates or carbonates may be produced by introducing carbon dioxide into a basic solution.

[0090] The solvent for the basic solution used in producing the bicarbonate or carbonate is not particularly limited, and examples thereof include water, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, and mixed solvents thereof. It is preferable for the solvent to contain water, and water is more preferable. The base used in the basic solution is not particularly limited as long as it can react with carbon dioxide to produce the bicarbonate or carbonate, and a hydroxide is preferable. Examples include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium hydroxide, sodium hydroxide, diazabicycloundecene, and triethylamine. Of the above, a hydroxide is preferable, with potassium hydroxide and sodium hydroxide being more preferable, and potassium hydroxide being even more preferable.

[0091] The content of the base in the basic solution is not particularly limited as long as it allows the production of bicarbonate and carbonate. From the viewpoint of ensuring the production amount of a reaction product (e.g., formate), the content of the base is preferably 0.1 mol or more, more preferably 0.5 mol or more, and even more preferably 1 mol or more, per 1 L of aqueous solvent. From the viewpoint of reaction efficiency, the content of the base is preferably 30 mol or less, more preferably 20 mol or less, and even more preferably 15 mol or less. However, if the solubility of the base in the aqueous phase is exceeded, the solution will become suspended.

[0092] The ratio of the amounts of carbon dioxide to base used in the reaction of carbon dioxide and base is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more, in terms of producing carbonate from carbon dioxide. Furthermore, from the viewpoint of carbon dioxide utilization efficiency, it is preferably 8.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less. The ratio of the amounts of carbon dioxide to base used is expressed as the molar amount (mol) of CO2 / the molar amount (mol) of base. By setting the ratio of the amounts of carbon dioxide to base used within the above range, excessive carbon dioxide input can be suppressed, unreacted carbon dioxide can be minimized, and the conversion efficiency of the final product (e.g., formic acid) in the production method according to this embodiment is likely to be improved.

[0093] The reaction temperature in the reaction of carbon dioxide with a base to produce a bicarbonate or a carbonate is not particularly limited, but in order to dissolve carbon dioxide in the aqueous phase, the reaction temperature is preferably 0° C. or higher, more preferably 10° C. or higher, and even more preferably 20° C. or higher. The reaction temperature is also preferably 100° C. or lower, more preferably 80° C. or lower, and even more preferably 40° C. or lower.

[0094] The reaction time for producing a bicarbonate or carbonate by the reaction of carbon dioxide with a base is not particularly limited, but is, for example, preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 2 hours or more from the viewpoint of ensuring a sufficient amount of produced bicarbonate or carbonate, and is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 6 hours or less from the viewpoint of cost.

[0095] In the production method according to this embodiment, formate may be synthesized by a hydrogenation reaction between hydrogen and at least one starting compound selected from the group consisting of carbon dioxide, bicarbonate, and carbonate. Formate has the advantages of being easy to handle due to its high hydrogen storage density, safety, and chemical stability, and capable of storing hydrogen and carbon dioxide for a long period of time. At least a portion of the formate produced by the production method according to this embodiment can be protonated to produce formic acid.

[0096] The formate salts and formic acid thus obtained have a wide range of applications in various fields, such as use as a silage additive, a feed preservative, a leather tanning agent, a textile dyeing agent, a rubber coagulant, an antifreeze agent, a cleaning agent for precision machinery, a neutralizing agent, a precipitant for heavy metals, a deicing agent, a cutting fluid, a heat transfer fluid, a lubricant, a hydride ion source, and a hydrogen supply source.

[0097] The organic phase contains an organic solvent. The organic phase may further contain a catalyst used in the reaction in the reaction step. It is preferable that the organic phase contains the catalyst and the aqueous phase contains the starting compound. It is preferable that the organic phase contains the catalyst and a solvent that dissolves the catalyst to make the organic phase homogeneous.

[0098] Examples of organic solvents include toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, methylcyclohexane, cyclopentyl methyl ether, and mixed solvents thereof. From the viewpoint of separability from the aqueous solvent, it is preferable for the organic solvent to contain toluene or dioxane, and it is more preferable for the organic solvent to contain toluene.

[0099] <Catalyst> In the production method according to this embodiment, the catalyst is, for example, a metal catalyst. The metal catalyst contains, for example, ruthenium.

[0100] In the production method according to this embodiment, it is preferable to use, as a catalyst, at least one compound selected from the group consisting of a metal complex represented by the following general formula (1A), a tautomer thereof, a stereoisomer thereof, and a salt thereof:

[0101]

[0102] (In general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can be coordinated to M; each Q independently represents a bridged structure that contains a typical element of Groups 14 to 16 and connects Y and X; each Y independently represents an atomic group containing a typical element of Groups 14 to 16 that can be coordinated to M; M represents a metal atom; Z represents a halogen atom or a hydrogen atom; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

[0103] In this specification, "Group n" means "Group n of the periodic table."

[0104] Examples of the typical elements of Groups 13 to 15 of the periodic table for X include a boron atom, a carbon atom, a silicon atom, a germanium atom, a tin atom, a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, and a selenium atom, of which a boron atom, a carbon atom, a silicon atom, a germanium atom, a tin atom, a nitrogen atom, a phosphorus atom, an arsenic atom, and a sulfur atom are preferred, a carbon atom, a nitrogen atom, a phosphorus atom, and a sulfur atom are more preferred, and a carbon atom or a nitrogen atom is even more preferred.

[0105] X may be a zero- to monovalent atomic group. Examples of the atomic group represented by X include an alkyl group, an alkenyl group, an alkoxy group, an aromatic ring, and a heterocyclic ring, which may have a substituent or may be bonded to another substituent to form a ring.

[0106] Examples of the alkyl group for X include linear, branched, and cyclic substituted or unsubstituted alkyl groups. The alkyl group for X is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, or a 2-ethylhexyl group, and is preferably an alkyl group having 6 or less carbon atoms, and more preferably a methyl group.

[0107] The alkenyl group for X includes linear, branched, and cyclic substituted or unsubstituted alkenyl groups. The alkenyl group for X is preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an n-propenyl group, an i-propenyl group, a t-butenyl group, or an n-octenyl group, and is preferably an alkenyl group having 6 or less carbon atoms.

[0108] The alkoxy group for X includes a linear, branched, or cyclic substituted or unsubstituted alkoxy group. The alkoxy group for X is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group.

[0109] Examples of the aromatic ring in X include a phenyl ring and a naphthyl ring.

[0110] Examples of the heterocyclic ring for X include a pyrrolidine ring, a piperidine ring, a pyrroline ring, an imidazoline ring, an imidazolidine ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, and a quinazoline ring.

[0111] The zero- to monovalent atomic group represented by X preferably represents an atomic group containing a heteroaromatic ring formed together with two carbon atoms and a nitrogen atom, and this may have a substituent or may be bonded to another substituent to form a ring.

[0112] The zero- to monovalent atomic group represented by X is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and even more preferably a pyridine ring.

[0113] When the zero- to monovalent atomic group represented by X has a substituent, examples of the substituent include those in Substituent Group A, and an alkyl group is preferred, and a methyl group is more preferred.

[0114] The bridged structure represented by Q, which connects Y and X and contains a typical element of Groups 14 to 16 of the periodic table, may have a double bond, a monocyclic structure or a fused ring structure, or may have a substituent.

[0115] Q can introduce various structures as described above. For example, the number of atoms in the portion between Y and X is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2.

[0116] The atom contained between Y and X is not particularly limited, but is preferably a carbon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom, more preferably a carbon atom, a nitrogen atom, or an oxygen atom, still more preferably a carbon atom or an oxygen atom, and particularly preferably a carbon atom.

[0117] Q may have a monocyclic structure. In other words, the bridged structure represented by Q may contain a cyclic structure.

[0118] When Q has a monocyclic structure, the monocyclic structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the monocyclic structure and Y and / or Z in general formula (1A). Examples of the divalent substituent include an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, a heteroatom such as an oxygen atom or a sulfur atom, or a combination of these bonded in series.

[0119] Each Q preferably independently represents CH2, NH, or O, and CH2 and NH may further have a substituent, and more preferably represents CH2 or NH.

[0120] Q may have a fused ring structure. In other words, the bridged structure represented by Q may contain a fused ring structure.

[0121] When Q has a fused ring structure, the fused ring structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the fused ring structure and Y and / or X in general formula (1A). The divalent substituent is the same as the divalent substituent sandwiched between the monocyclic structure and Y and / or X in general formula (1A) described above.

[0122] Q may have a substituent. When Q does not have either a monocyclic structure or a fused ring structure, the substituent is a substituent of the Q portion in the ring structure formed by including Q, Y, X, and M in general formula (1A).

[0123] When Q has a monocyclic structure or a fused ring structure, the substituent is a substituent of the monocyclic structure or the fused ring structure, or a substituent of Q in another ring structure formed by including Q, Y, X, and M in general formula (1A).

[0124] The substituent that Q may have may be, for example, one having a hetero atom, or another atom or atomic group.

[0125] Examples of the substituent having a hetero atom include an alkoxy group having 1 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an acyl group having 2 to 18 carbon atoms, an aroyl group having 7 to 18 carbon atoms, a dialkylamino group having 2 to 18 carbon atoms, an oxygen atom, and a sulfur atom.

[0126] Examples of the other atoms or atomic groups include aromatic groups having 3 to 18 carbon atoms, alkyl groups having 1 to 18 carbon atoms, halogen atoms, etc. Examples of the aromatic groups include aryl groups having 6 to 20 carbon atoms such as phenyl, xylyl, naphthyl, and biphenyl.

[0127] The number of carbon atoms in Q is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0128] Y may be a zero- to monovalent atomic group. Each Y independently represents a zero- to monovalent atomic group containing a typical element of Groups 14 to 16 of the periodic table that can be coordinated to M, and may further have a substituent. As the typical element of Groups 14 to 16 of the periodic table, a carbon atom, a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, or a selenium atom is preferred, a carbon atom, a nitrogen atom, a phosphorus atom, or an arsenic atom is more preferred, a nitrogen atom or a phosphorus atom is still more preferred, and a phosphorus atom is particularly preferred.

[0129] In formula (1A), it is preferred that both Y's represent a nitrogen atom or a phosphorus atom, or that one Y represents a phosphorus atom and the other Y represents a nitrogen atom.

[0130] When the zero- to monovalent atomic group represented by Y has a substituent, examples of the substituent include those in Substituent Group A, and an alkyl group or an aryl group is preferred, and an ethyl group, a t-butyl group, or a phenyl group is more preferred.

[0131] M represents a metal atom, and examples thereof include those containing elements of Groups 8 to 11 of the periodic table, such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold. Among these, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, and copper are preferred, ruthenium, rhodium, iridium, nickel, and palladium are more preferred, ruthenium, rhodium, iridium, and palladium are even more preferred, and ruthenium (Ru) is particularly preferred.

[0132] Z preferably represents a halogen atom, more preferably a chlorine atom.

[0133] n represents an integer of 0 to 3, and represents the number of ligands coordinated to the metal atom represented by M. From the viewpoint of catalyst stability, n is preferably 2 or 3.

[0134] When a plurality of Ls are present, each L independently represents a neutral or anionic ligand.

[0135] Examples of the neutral ligand represented by L include ammonia, carbon monoxide, phosphines (e.g., triphenylphosphine, tris(4-methoxyphenyl)phosphine), phosphine oxides (e.g., triphenylphosphine oxide), sulfides (e.g., dimethyl sulfide), sulfoxides (e.g., dimethyl sulfoxide), ethers (e.g., diethyl ether), nitriles (e.g., p-methylbenzonitrile), heterocyclic compounds (e.g., pyridine, N,N-dimethyl-4-aminopyridine, tetrahydrothiophene, tetrahydrofuran), and the like, and preferably triphenylphosphine.

[0136] Examples of the anionic ligand represented by L include a hydride ion (hydrogen atom), a nitrate ion, and a cyanide ion, and preferably a hydride ion (hydrogen atom).

[0137] In general formula (1A), it is preferred that X represents a heterocycle, Q represents CH2, NH, or O, Y represents a phosphorus atom, and M represents ruthenium.

[0138] It is also preferred that Z represents a chlorine atom, n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0139] In the production method according to this embodiment, the metal complex represented by general formula (1A) is preferably a metal complex represented by the following general formula (2A).

[0140]

[0141] (In general formula (2A), X1 represents a heteroaromatic ring formed together with two carbon atoms and a nitrogen atom, which may have a substituent, or may be bonded to another substituent to form a ring; each Q1 independently represents CH2, NH, or O, and CH2 and NH may further have a substituent; each Y1 independently represents a phosphorus atom or a nitrogen atom; each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent; M represents a metal atom; Z represents a halogen atom or a hydrogen atom; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

[0142] M, Q1, Z, n, and L in general formula (2A) have the same meanings as M, Q, Z, n, and L in general formula (1A), respectively, and the preferred ranges are also the same.

[0143] The heteroaromatic ring formed together with the two carbon atoms and nitrogen atom represented by X is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and even more preferably a pyridine ring.

[0144] Examples of the substituent that X1 may have include those in Substituent Group A, and an alkyl group is preferable, and a methyl group is more preferable.

[0145] Y represents a phosphorus atom or a nitrogen atom, and both Y may represent a nitrogen atom or a phosphorus atom, or one Y may represent a phosphorus atom and the other Y may represent a nitrogen atom. It is preferable that both Y are nitrogen atoms or phosphorus atoms, and it is more preferable that both Y are nitrogen atoms.

[0146] Examples of the alkyl group represented by R include linear, branched, and cyclic substituted or unsubstituted alkyl groups. The alkyl group represented by R is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, and a 2-ethylhexyl group. From the viewpoint of catalytic activity, an alkyl group having 12 or less carbon atoms is preferred, an ethyl group or a t-butyl group is preferred, and a t-butyl group is more preferred.

[0147] Examples of the aryl group represented by R include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. An aryl group having 12 or less carbon atoms is preferred, and a phenyl group is more preferred.

[0148] When R further has a substituent, examples of the substituent include those in Substituent Group A, and a methyl group, an ethyl group, an i-propyl group, a t-butyl group, and a phenyl group are preferred, and an ethyl group, an i-propyl group, or a t-butyl group is more preferred.

[0149] In general formula (2A), it is preferable that X1 represents a pyridine ring or a triazine ring, Q1 represents CH2, NH, or O, Y1 represents a phosphorus atom, R represents an ethyl group, a t-butyl group, or a phenyl group, and M represents ruthenium.

[0150] It is also preferred that Z represents a chlorine atom, n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0151] In the production method according to this embodiment, the metal complex represented by general formula (2A) is preferably a metal complex represented by the following general formula (3A).

[0152]

[0153] (In general formula (3A), R represents a hydrogen atom or an alkyl group; each A independently represents CH, CR, or N, and R represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group; each Q independently represents CH, NH, or O, and CH and NH may further have a substituent; Y represents a phosphorus atom or a nitrogen atom; each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent; M represents a metal atom; Z represents a halogen atom or a hydrogen atom; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

[0154] Y1, R, Q1, M, Z, n, and L in general formula (3A) have the same meanings as Y1, R, Q1, M, Z, n, and L in general formula (2A), respectively, and the preferred ranges are also the same.

[0155] In general formula (3A), R0 represents a hydrogen atom or an alkyl group. Examples of the alkyl group represented by R0 include linear, branched, and cyclic substituted or unsubstituted alkyl groups. The alkyl group represented by R0 is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, and a 2-ethylhexyl group. From the viewpoint of ease of raw material procurement, an alkyl group having 6 or less carbon atoms is preferred, and a methyl group is preferred.

[0156] In formula (3A), R0 is preferably a hydrogen atom or a methyl group.

[0157] Each A independently represents CH, CR5, or N, and R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group.

[0158] Examples of the alkyl group represented by R5 include linear, branched, and cyclic substituted or unsubstituted alkyl groups. The alkyl group represented by R5 is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, and a 2-ethylhexyl group. From the viewpoint of ease of raw material procurement, an alkyl group having 12 or less carbon atoms is preferred, and a methyl group is preferred.

[0159] The aryl group represented by R5 includes a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. An aryl group having 12 or less carbon atoms is preferred, and a phenyl group is more preferred.

[0160] The aralkyl group represented by R5 includes a substituted or unsubstituted aralkyl group having 30 or less carbon atoms, such as a trityl group, a benzyl group, a phenethyl group, a tritylmethyl group, a diphenylmethyl group, and a naphthylmethyl group, and is preferably an aralkyl group having 12 or less carbon atoms.

[0161] The alkoxy group represented by R5 is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group.

[0162] In general formula (3A), it is preferable that X1 represents a pyridine ring or a triazine ring, Q1 represents CH2, NH, or O, Y1 represents a phosphorus atom, R represents an ethyl group, a t-butyl group, or a phenyl group, and M represents ruthenium.

[0163] It is also preferred that Z represents a chlorine atom, n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0164] In the production method according to this embodiment, the metal complex represented by general formula (3A) is preferably a ruthenium complex represented by the following general formula (4A).

[0165] The ruthenium complex represented by general formula (4A) is soluble in organic solvents and insoluble in water, and is particularly suitable as a catalyst for the production of organic compounds. The ruthenium complex represented by general formula (4A) is suitable as a catalyst, for example, for the production of formate salts. Since the formate salt produced by the reaction is easily soluble in water, the reaction in a two-phase system makes it easy to separate the catalyst and the formate salt, making it easy to separate and recover the catalyst and the formate salt from the reaction system, enabling the production of formate salts with high yields and facilitating the reuse of expensive catalysts.

[0166]

[0167] (In general formula (4A), R represents a hydrogen atom or an alkyl group; each Q independently represents CH, NH, or O, and CH and NH may further have a substituent; each R independently represents an alkyl group or an aryl group (provided that when Q represents NH or O, at least one R represents an aryl group); each A independently represents CH, CR, or N; R represents an alkyl group, aryl group, aralkyl group, amino group, hydroxy group, or alkoxy group; Z represents a halogen atom; n represents 0 to 3; and when a plurality of Ls are present, each L independently represents a neutral or anionic ligand.)

[0168] R0, A, Q1, Z, L, and n in general formula (4A) have the same meanings as R0, A, Q1, Z, L, and n in general formula (3A), respectively, and the preferred ranges are also the same.

[0169] The alkyl group and aryl group represented by R1 have the same meanings as the alkyl group and aryl group represented by R in general formula (3A), respectively, and the preferred ranges are also the same.

[0170] The metal complexes represented by the general formulae (1A) to (4A) may produce stereoisomers depending on the coordination mode or conformation of the ligand, and may be a mixture of these stereoisomers or a pure isomer.

[0171] The metal complexes represented by general formulas (1A) to (4A) may be produced by known methods, such as those described in E. Pidko et al., ChemCatChem 2014, 6, 1526-1530.

[0172] Specific examples of the ruthenium complex represented by general formula (4A) include the compounds shown below: In the compounds shown below, Et represents an ethyl group, tBu represents a tertiary butyl group, and Ph represents a phenyl group.

[0173]

[0174]

[0175]

[0176] The amount of catalyst (preferably ruthenium complex) used is not particularly limited. From the viewpoint of fully exhibiting the function of the catalyst, the amount of catalyst used is, for example, preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and even more preferably 1 μmol or more, per 1 L of organic phase solvent. Furthermore, from the viewpoint of cost, it is preferably 1 mol or less, more preferably 10 mmol or less, and even more preferably 1 mmol or less, per 1 L of organic phase solvent. Furthermore, from the viewpoint of suppressing a decrease in catalyst efficiency, it may be 500 μmol or less, 400 μmol or less, 250 μmol or less, or 100 μmol or less, per 1 L of organic phase solvent. Note that when two or more catalysts are used, the total amount used may be within the above range.

[0177] <Phase Transfer Catalyst> The production method according to this embodiment may use a phase transfer catalyst. When the liquid L has an aqueous phase and an organic phase, the phase transfer catalyst can facilitate the transfer of substances between the aqueous phase and the organic phase. Examples of phase transfer catalysts include quaternary ammonium salts, quaternary phosphates, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptands, nitrogen-containing linear polyethers, polyethylene glycol and its alkyl ethers, etc. Among these, quaternary ammonium salts are preferred from the viewpoint of facilitating the transfer of substances between the aqueous solvent and the organic solvent even under mild reaction conditions.

[0178] Examples of quaternary ammonium salts include methyltrioctylammonium chloride, benzyltrimethylammonium chloride, trimethylphenylammonium bromide, tributylammonium tribromide, tetrahexylammonium hydrogen sulfate, decyltrimethylammonium bromide, diallyldimethylammonium chloride, dodecyltrimethylammonium bromide, dimethyldioctadecylammonium bromide, tetraethylammonium tetrafluoroborate, ethyltrimethylammonium iodide, tris(2-hydroxyethyl)methylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium bromide, tetraethylammonium iodide, dimethyldioctylammonium bromide, methyltrioctylammonium bromide, and trihexyl(tetradecyl)phosphonium chloride, with methyltrioctylammonium chloride being preferred.

[0179] The amount of the phase transfer catalyst used is not particularly limited. The amount of the phase transfer catalyst used is preferably 0.1 mmol or more, more preferably 0.5 mmol or more, and even more preferably 1 mmol or more, per 1 L of the organic and aqueous solvents. From the viewpoint of cost, the amount is preferably 1 mol or less, more preferably 500 mmol or less, and even more preferably 100 mmol or less, per 1 L of the organic and aqueous solvents. When two or more phase transfer catalysts are used, the total amount used may be within the above range.

[0180] <Other Components> In the production method according to this embodiment, an antioxidant may be added to the liquid L as needed. Examples of antioxidants include phosphorus-based antioxidants, amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants. Examples of these antioxidants that can be used include those disclosed in JP 2016-44190 A. Note that additives such as ultraviolet absorbers and light stabilizers may be added to the liquid L in place of or in addition to the antioxidant. Examples of these additives that can be used include those disclosed in JP 2016-44190 A. When the liquid L has an aqueous phase and an organic phase, the organic phase may contain an antioxidant.

[0181] When an antioxidant is used, the amount used is adjusted, for example, to a range in which the antioxidant dissolves in the liquid L. From the viewpoint of fully exhibiting the function of the antioxidant, the amount used of the antioxidant is preferably 1 mmol or more per 1 L of the solvent. From the viewpoint of reducing the cost of the antioxidant, the amount used of the antioxidant is preferably 100 mmol or less per 1 L of the solvent. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0182] The present invention will be described in more detail below, but is not limited thereto. In the examples, a hydrogenation reaction of hydrogen carbonate using a catalyst was carried out to synthesize a formate.

[0183] [Catalyst Synthesis] A catalyst was synthesized using the following procedure. First, under an inert atmosphere, 40 mg (0.1 mmol) of Ligand A (see below) was added to a suspension of 95.3 mg (0.1 mmol) of [RuHCl(PPh)(CO)] in 5 mL of tetrahydrofuran (THF). The mixture was stirred and heated at 65°C for 3 hours to carry out the reaction. The mixture was then cooled to room temperature (25°C). The resulting yellow solution was filtered, and the filtrate was evaporated to dryness under vacuum. The resulting yellow residual oil was dissolved in a small amount of THF (1 mL), and hexane (10 mL) was slowly added to precipitate a yellow solid, which was then filtered. The filtrate was dried under vacuum to obtain the following catalyst 1 in the form of yellow crystals. In the catalyst 1 and ligand A shown below, tBu represents a tertiary butyl group.

[0184]

[0185] 31 P{ 1 H}(C6D6):90.8(s), 1 H (C6D6): -14.54 (t, 1H, J = 20.0Hz), 1.11 (t, 18H, J = 8.0Hz), 1.51 (t, 18H, J = 8.0Hz), 2.88 (dt, 2H, J = 16.0Hz, J=4.0Hz), 3.76 (dt, 2H, J=16.0Hz, J=4.0Hz), 6.45 (d, 2H, J=8.0Hz), 6.79 (t, 1H, J=8.0Hz). 13 C{ 1 H}NMR (C6D6): 29.8 (s), 30.7 (s), 35.2 (t, J = 9.5 Hz), 37.7 (t, J = 6.0 Hz), 37.9 (t, J=6.5Hz), 119.5 (t, J=4.5Hz), 136.4 (s), 163.4 (t, J=5.0Hz), 209.8 (s).

[0186] [Example 1] (Preparation of Liquid L) In an inert atmosphere glove box, the above catalyst and methyltri-n-octylammonium chloride (phase transfer catalyst) were dissolved in degassed toluene to prepare an organic phase. The catalyst concentration was 60 μmol / L, and the phase transfer catalyst concentration was 54 mmol / L. The atmosphere inside the container (flask) containing the organic phase was replaced with argon gas.

[0187] ​Potassium bicarbonate and degassed ion-exchanged water were added to an argon-substituted container (bottle) and the potassium bicarbonate was dissolved to prepare an aqueous phase. Argon gas was bubbled through the aqueous phase for approximately 3 minutes, and the container was then sealed. The potassium bicarbonate concentration was 1.85 mol / L.

[0188] (Evaluation System) The evaluation system of Example 1 was constructed like production system 100 in FIG. 1 using: a vessel containing an organic phase, a vessel containing an aqueous phase, an organic phase supply path, an aqueous phase supply path, a plunger pump (NPG-50L, manufactured by Nippon Seimitsu Kagaku Co., Ltd.) as a liquid transfer pump, a hydrogen gas cylinder, a hydrogen gas supply path, an autoclave (MMJ-300, manufactured by OM Labotec Co., Ltd.) as a reactor, a siphon tube (16.75 cm) as a reaction liquid discharge path, and a discharge valve, and a back pressure valve (KPB1L0A425P20000, manufactured by Swagelok).

[0189] The siphon tube was installed so that one end was located inside the autoclave and the other end was located outside the autoclave. The autoclave was equipped with a stirring blade. The evaluation system was equipped with a two-way switching valve (Swagelok, SS-41GXS2) that could switch the direction of liquid flow between the system and the purge line.

[0190] (Evaluation) First, the autoclave was pressurized to 0.3 MPa with argon gas and then released three times. After 12.01 g of potassium bicarbonate and 60 mL of degassed ion-exchanged water were added to the autoclave, the autoclave was pressurized to 0.3 MPa with argon gas and then released six times. The potassium bicarbonate concentration was 1.85 mol / L. Three of these operations were carried out without stirring, and three were carried out with stirring. An additional 60 mL of organic phase was added to the autoclave, and the reactor was pressurized to 0.3 MPa with argon gas and then released three times without stirring. Then, the autoclave was pressurized to 0.5 MPa with hydrogen gas and then released three times. At this time, the tip of the siphon tube located inside the autoclave was located below the liquid level (i.e., in the liquid).

[0191] Next, the autoclave was pressurized to 5.40 MPa with hydrogen gas, and the internal temperature was raised to 90°C while stirring, and the mixture was heated and stirred for approximately 2 hours. The autoclave was pressurized to 6.0 MPa with hydrogen gas. A two-way switching valve was set to the purge line, and the aqueous phase and organic phase were each started to be delivered at approximately 1.15 mL / min using a plunger pump, and the liquid was discharged outside the system. The delivery flow rate was confirmed using an electronic balance (GX-3002A, manufactured by A&D Co., Ltd.) on which each container was placed. The discharge valve was opened to discharge approximately 20 mL of reaction liquid, and then the discharge valve was closed.

[0192] The two-way valve was switched from the purge line to the inside of the system, and the organic and aqueous phases were sent into the system, starting the operation of the system (this was designated as operation time 0 minutes). During operation, the inside of the autoclave was stirred with a stirring blade. From the start of operation, the discharge valve was opened for approximately 10 seconds at 9-minute intervals, and approximately 20 mL of reaction liquid was discharged and collected. The operation was stable, and continuous operation was carried out for 198 minutes. A total of 23 discharges were carried out, including the discharge before the start of operation (operation time 0 minutes), and reaction liquids (fractions) Fr1 to 23 were obtained in order. The average residence time of the liquid in the reactor was 48.0 minutes.

[0193] In order to confirm the reaction stability over time, the conversion rates of reaction solution samples 1-1 to 1-5 consisting of Fr1 to 5, Fr6 to 10, Fr11 to 15, Fr16 to 20, and Fr21 to 23, respectively, were determined by the following method.

[0194] First, the aqueous phase was separated from the reaction solution sample. 1.0000 g of dimethyl sulfoxide (DMSO) was added to 5.0000 g of the aqueous phase as a reference substance, and the mixture was dissolved in an appropriate amount of heavy water. In this way, a measurement sample was prepared. 1 H-NMR measurement was carried out. 1From the H-NMR spectrum, the peak integral value of potassium formate: Ia, and the peak integral value of DMSO: Ib were determined. Furthermore, the conversion rate [%] was calculated using the following formula (1) based on the amount of DMSO used in the preparation of the measurement sample: W [g] (1.0000 g in this case), the molecular weight of DMSO: M (78.13 g / mol), the amount of aqueous phase used in the preparation of the measurement sample: A [g] (5.0000 g in this case), and the amount of potassium bicarbonate contained per gram of aqueous phase before the reaction: B [mol / g] (1.666 mmol in the case of Example 1). The results are shown in Table 1. Conversion rate [%] = {(W / M) × (Ia / (Ib ÷ 6)) / A} ÷ B × 100 (1)

[0195] Example 2 (Preparation of Liquid L) An aqueous phase and an organic phase were prepared in the same manner as in Example 1, except that the concentration of sodium hydrogen carbonate in the aqueous phase was 3.20 mol / L.

[0196] The prepared aqueous phase was heated to 60° C. The aqueous phase heated to 60° C. was used for evaluation.

[0197] (Evaluation System) An evaluation system for Example 2 was constructed in the same manner as in Example 1.

[0198] (Evaluation) First, the autoclave was pressurized to 0.3 MPa with argon gas and then released three times. After 19.20 g of potassium bicarbonate and 51.5 g of degassed ion-exchanged water were added to the autoclave, the autoclave was pressurized to 0.3 MPa with argon gas and then released six times. Three of these operations were carried out without stirring, and three were carried out with stirring. The potassium bicarbonate concentration was 3.20 mol / L. An additional 60 mL of organic phase was added to the autoclave, and the reactor was pressurized to 0.3 MPa with argon gas and then released three times without stirring. Then, the autoclave was pressurized to 0.5 MPa with hydrogen gas and then released three times. At this time, the tip of the siphon tube located inside the autoclave was below the liquid level (i.e., in the liquid).

[0199] Next, the autoclave was pressurized to 5.40 MPa with hydrogen gas, and the internal temperature was raised to 90°C while stirring, and the mixture was heated and stirred for approximately 2 hours. The autoclave was pressurized to 6.0 MPa with hydrogen gas. A two-way switching valve was set to the purge line, and the aqueous phase and organic phase were each started to be delivered at approximately 1.25 mL / min using a plunger pump, and the liquid was discharged outside the system. At this time, the piping of the aqueous phase supply path through which the aqueous phase was delivered was heated so that the temperature of the delivered aqueous phase was maintained at 60°C. The delivery flow rate was confirmed using an electronic balance (GX-3002A, manufactured by A&D Co.) on which each container was placed.

[0200] While the piping of the aqueous phase supply route was still heated, the two-way valve was switched from the purge line to the inside of the system, and the organic and aqueous phases were introduced into the system, starting the system operation (this was designated as operation time 0 minutes). During operation, the autoclave was stirred with a stirring blade. Five minutes after the start of operation, the discharge valve was opened for approximately 10 seconds to discharge approximately 22 mL of reaction liquid. Thereafter, the discharge valve was opened in the same manner for approximately 10 seconds at 9-minute intervals to discharge and recover approximately 22 mL of reaction liquid at a time. A total of 19 discharges were performed as described above, and fractions Fr1 to Fr19 were obtained in order. The operation time was 168 minutes. The average residence time of the liquid in the reactor was 48.5 minutes.

[0201] The conversion rates of reaction solution samples 2-1 to 2-5 consisting of Fr1 to 5, Fr6 to 10, Fr11 to 15, Fr16 to 17, and Fr18 to 19, respectively, were determined in the same manner as in Example 1.

[0202] Example 3 Preparation of Liquid L An aqueous phase and an organic phase were prepared in the same manner as in Example 1, except that the concentration of sodium hydrogen carbonate in the aqueous phase was 3.20 mol / L and the concentration of the catalyst in the organic phase was 250 μmol / L.

[0203] The prepared aqueous phase was heated to 60° C. The aqueous phase heated to 60° C. was used for evaluation.

[0204] (Evaluation System) An evaluation system for Example 3 was constructed in the same manner as in Example 1.

[0205] (Evaluation) First, the autoclave was pressurized to 0.3 MPa with argon gas and then released three times. After 30.75 g of potassium bicarbonate and 82.5 g of degassed ion-exchanged water were added to the autoclave, the autoclave was pressurized to 0.3 MPa with argon gas and then released six times. Three of these operations were carried out without stirring, and three were carried out with stirring. The potassium bicarbonate concentration was 3.20 mol / L. An additional 24 mL of organic phase was added to the autoclave, and the reactor was pressurized to 0.3 MPa with argon gas and then released three times without stirring. Then, the autoclave was pressurized to 0.5 MPa with hydrogen gas and then released three times. At this time, the tip of the siphon tube located inside the autoclave was below the liquid level (i.e., in the liquid).

[0206] Next, the autoclave was pressurized to 5.40 MPa with hydrogen gas, and the internal temperature was raised to 90°C while stirring, and the mixture was heated and stirred for approximately 2 hours. The autoclave was pressurized to 6.0 MPa with hydrogen gas. A two-way switching valve was set to the purge line, and a plunger pump was used to start the delivery of the aqueous phase at approximately 1.48 mL / min and the organic phase at 0.37 mL / min, and the liquid was discharged outside the system. At this time, the piping of the aqueous phase supply path through which the aqueous phase was delivered was heated. The delivery flow rate was confirmed using an electronic balance (GX-3002A, manufactured by A&D Co.) on which each container was placed.

[0207] While the piping of the aqueous phase supply route was still heated, the two-way valve was switched from the purge line to the inside of the system, and the organic and aqueous phases were started to be sent into the system, thereby starting the operation of the system (this was designated as operation time 0 minutes). During operation, the inside of the autoclave was stirred with a stirring blade. The discharge valve was opened for approximately 9 seconds at 10-minute intervals from the start of operation, and approximately 18.5 mL of reaction liquid was discharged and collected. Discharge was performed as described above a total of 22 times, and fractions Fr1 to Fr22 were obtained in order. The operation time was 220 minutes. The average residence time of the liquid in the reactor was 60.0 minutes.

[0208] The conversion rates were determined in the same manner as in Example 1 for reaction solution samples 3-1 to 3-5 consisting of Fr1 to 5, Fr6 to 10, Fr11 to 15, Fr16 to 20, and Fr21 to 22, respectively.

[0209] Example 4 Preparation of Liquid L An aqueous phase and an organic phase were prepared in the same manner as in Example 3, and the prepared aqueous phase was heated to 60° C. The aqueous phase heated to 60° C. was used for evaluation.

[0210] (Evaluation System) An evaluation system for Example 4 was constructed in the same manner as in Example 1, except that the reactor was changed to an autoclave (manufactured by Nitto Koatsu Co., Ltd., 1 L).

[0211] (Evaluation) First, the autoclave was pressurized to 0.3 MPa with argon gas and then released three times. After 102.5 g of potassium bicarbonate and 275.2 g of degassed ion-exchanged water were added to the autoclave, the autoclave was pressurized to 0.3 MPa with argon gas and then released six times. Three of these operations were carried out without stirring, and three were carried out with stirring. The potassium bicarbonate concentration was 3.20 mol / L. An additional 80 mL of organic phase was added to the autoclave, and the reactor was pressurized to 0.3 MPa with argon gas and then released three times without stirring. Then, the autoclave was pressurized to 0.5 MPa with hydrogen gas and then released three times. At this time, the tip of the siphon tube located inside the autoclave was below the liquid level (i.e., in the liquid).

[0212] Next, the autoclave was pressurized to 5.40 MPa with hydrogen gas, and the internal temperature was raised to 90°C while stirring, and the mixture was heated and stirred for approximately 2 hours. The autoclave was pressurized to 6.0 MPa with hydrogen gas. A two-way switching valve was set to the purge line, and a plunger pump was used to start the delivery of the aqueous phase at approximately 4.55 mL / min and the organic phase at 1.14 mL / min, and the liquid was discharged outside the system. At this time, the piping of the aqueous phase supply path through which the aqueous phase was delivered was heated. The delivery flow rate was confirmed using an electronic balance (GX-3002A, manufactured by A&D Co.) on which each container was placed.

[0213] While the piping of the aqueous phase supply route was still heated, the two-way valve was switched from the purge line to the inside of the system, and the organic and aqueous phases were started to be fed into the system, starting the operation of the system (this was designated as operation time 0 minutes). During operation, the inside of the autoclave was stirred with a stirring blade. From the start of operation, the discharge valve was opened for approximately 10 seconds at 10-minute intervals to discharge and recover approximately 56.9 mL of reaction liquid at a time. This discharge was carried out 24 times in total, as described above, and fractions Fr1 to Fr24 were obtained in order. The operation time was 240 minutes. The average residence time of the liquid in the reactor was 75.0 minutes.

[0214] The conversion rates of reaction solution samples 4-1 to 4-5 consisting of Fr1 to 5, Fr6 to 10, Fr11 to 15, Fr16 to 20, and Fr21 to 24 were determined in the same manner as in Example 1.

[0215] Comparative Example 1 Liquid L was prepared in the same manner as in Example 1, and an evaluation system was constructed.

[0216] (Evaluation) First, the autoclave was pressurized to 0.3 MPa with argon gas and then released three times. After 10.01 g of potassium bicarbonate and 50 mL of degassed ion-exchanged water were added to the autoclave, the autoclave was pressurized to 0.3 MPa with argon gas and then released six times. Three of these operations were carried out without stirring, and three were carried out with stirring. An additional 50 mL of organic phase was added to the autoclave, and the autoclave was pressurized to 0.3 MPa with argon gas without stirring and then released three times. Thereafter, the autoclave was pressurized to 0.5 MPa with hydrogen gas and then released three times. At this time, the tip of the siphon tube located in the autoclave was located below the liquid level (i.e., in the liquid).

[0217] Next, the autoclave was pressurized to 5.10 MPa with hydrogen gas, and the internal temperature was raised to 90°C while stirring, followed by heating and stirring for approximately 2 hours. The autoclave was pressurized to 5.5 MPa with hydrogen gas. A two-way switching valve was set to the purge line, and the aqueous phase and organic phase were each started to be delivered at approximately 0.06 mL / min using a plunger pump, and the liquid was discharged outside the system. The discharge valve was opened, and the two-way switching valve was switched from the purge line to the inside of the system, starting the delivery of the organic phase and aqueous phase into the system, thereby starting operation of the system. Even with the discharge valve open, the reaction liquid did not flow out when the pressure inside the autoclave was around 5.5 MPa. However, when the pressure was increased to approximately 6.0 MPa with hydrogen gas, the reaction liquid spurted out forcefully from the autoclave outlet (siphon tube), making it impossible to operate the system stably.

[0218] Comparative Example 2 Liquid L was prepared in the same manner as in Example 1. An evaluation system was constructed in the same manner as in Example 1, except that the length of the siphon tube was 12.75 cm.

[0219] (Evaluation) First, the autoclave was pressurized to 0.3 MPa with argon gas and then released three times. After 12.01 g of potassium bicarbonate and 60 mL of degassed ion-exchanged water were added to the autoclave, the autoclave was pressurized to 0.3 MPa with argon gas and then released six times. Three of these operations were carried out without stirring, and three were carried out with stirring. An additional 60 mL of organic phase was added to the autoclave, and the autoclave was pressurized to 0.3 MPa with argon gas without stirring and then released three times. Thereafter, the autoclave was pressurized to 0.5 MPa with hydrogen gas and then released three times. At this time, the tip of the siphon tube located inside the autoclave was positioned at approximately the same height as the liquid level.

[0220] Next, the autoclave was pressurized to 5.20 MPa with hydrogen gas, and the internal temperature was raised to 90°C while stirring, and the mixture was heated and stirred for approximately 2 hours. At this time, the internal pressure reached a maximum of 5.8 MPa and then decreased to 4.40 MPa. The autoclave was pressurized to 6.3 MPa with hydrogen gas. A two-way switching valve was set to the purge line, and the aqueous and organic phases were each started to be delivered at approximately 1.15 mL / min using a plunger pump, and the liquid was discharged outside the system. The discharge valve was opened, and the two-way switching valve was switched from the purge line to the system interior, starting the delivery of the organic and aqueous phases into the system, thereby starting the system operation (this was designated as operation time 0 minutes). Approximately 68 mL of reaction liquid violently spurted out from the autoclave outlet within the first minute after the start of delivery, and the internal pressure decreased to 5.4 MPa. However, the reaction liquid then flowed out relatively steadily, and the internal pressure was 5.1 MPa to 5.7 MPa. However, hydrogen gas was constantly being discharged from the autoclave outlet, making the system unsuitable for use in generating reaction products. After 210 minutes of operation, a large amount of hydrogen gas, approximately 3,333 L, was consumed.

[0221] The evaluation results of Example 1 are shown in Table 1. The average conversion rate of Example 1 was 71.1%.

[0222]

[0223] The evaluation results of Example 2 are shown in Table 2. The average conversion rate of Example 2 was 62.3%.

[0224]

[0225] The evaluation results of Example 3 are shown in Table 3. The average conversion rate of Example 3 was 62.5%.

[0226]

[0227] The evaluation results of Example 4 are shown in Table 4. The average conversion rate of Example 4 was 66.2%.

[0228]

[0229] By using the systems of Examples 1 to 4, the systems could be operated stably without discharging large amounts of hydrogen gas, and potassium formate could be produced at a high conversion rate by hydrogenating potassium hydrogen carbonate.

[0230] According to the reaction product production method and production system of this embodiment, for example, the target reaction product can be mass-produced easily and at low cost.

Claims

1. A method for producing a reaction product, comprising: a supply step of supplying a gas and a liquid to a reactor; a reaction step of producing a reaction product from a starting compound contained in a raw material in the reactor using a catalyst; and a discharge step of intermittently discharging a portion of the liquid containing the reaction product from the reactor.

2. The method for producing a reaction product according to claim 1, wherein the raw material comprises a gas capable of reacting with the starting compound, and the gas comprises the gas.

3. The method for producing a reaction product according to claim 2, wherein the gas contains hydrogen, and the reaction is a hydrogenation reaction of the starting compound with the hydrogen.

4. The method for producing a reaction product according to claim 1, wherein the liquid has an organic phase and an aqueous phase.

5. The method for producing a reaction product according to claim 4, wherein the organic phase comprises the catalyst and the aqueous phase comprises the starting compound.

6. The method for producing a reaction product according to claim 5, wherein the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and the reaction product is formate.

7. The method for producing a reaction product according to claim 1, wherein the discharging step is carried out while the supplying step is being carried out.

8. The method for producing a reaction product according to claim 1, wherein the discharge step is carried out by opening and closing a discharge valve disposed in a discharge path for discharging the liquid from the reactor.

9. The method for producing a reaction product according to claim 1, wherein the average residence time of the liquid in the reactor is 1 minute or more and 180 minutes or less.

10. The method for producing a reaction product according to claim 1, wherein the inlet of a discharge path for discharging the liquid from the reactor is located below the liquid level in the reactor when the reactor is at rest.

11. The method for producing a reaction product according to claim 1, further comprising a separation step of separating the liquid discharged in the discharge step into an organic phase and an aqueous phase under atmospheric pressure.

12. The method for producing a reaction product according to claim 1, wherein the catalyst is a metal catalyst.

13. The method for producing a reaction product according to claim 12, wherein the metal catalyst comprises ruthenium.

14. The method for producing a reaction product according to claim 4, wherein the organic phase comprises toluene.

15. A reaction product manufacturing system comprising: a reactor that produces a reaction product from a starting compound contained in a raw material using a catalyst; a supply mechanism that supplies a gas and a liquid to the reactor; and a discharge mechanism that intermittently discharges a portion of the liquid containing the reaction product from the reactor.

16. The reaction product manufacturing system according to claim 15, further comprising a separation mechanism that separates the liquid discharged by the discharge mechanism into an organic phase and an aqueous phase under atmospheric pressure.

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