Method for producing formate and method for producing formic acid

Abstract

The present invention relates to a method for producing a formic acid salt, the method comprising reacting hydrogen with carbon dioxide, a hydrogencarbonate, or a carbonic acid salt in the presence of a solvent using a catalyst, wherein the solvent for the reaction is a two-phase system including an organic solvent and an aqueous solvent that are present separately from each other and the catalyst is at least one compound selected from among ruthenium complexes represented by the general formula (1) given in the description, tautomers and stereoisomers thereof, and salt compounds of these.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a formate, a method for producing formic acid, a catalyst for producing a formate, and a ruthenium complex. [Background technology]

[0002] Due to issues such as global warming and the depletion of fossil fuels, there are high hopes for hydrogen energy as the next generation energy source.

[0003] Formic acid is attracting attention as an excellent compound for hydrogen storage because the dehydrogenation reaction requires low energy and is easy to handle. To use formic acid as a hydrogen storage material, it is necessary to obtain a highly concentrated formic acid solution to reduce transportation costs.

[0004] Therefore, a method for producing formic acid from carbon dioxide (CO2) and hydrogen (H2) in the presence of a catalyst has been investigated. For example, Non-Patent Document 1 describes a method for producing formic acid by reacting carbon dioxide with hydrogen in a hydrogenation reactor in the presence of a metal complex catalyst. Furthermore, a technology for efficiently extracting hydrogen from the produced formic acid is also important. For example, Patent Document 1 studies a metal complex catalyst for extracting hydrogen from formic acid. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japan Special Publication No. 2016-539793 [Non-patent literature]

[0006] [Non-Patent Document 1] E. Pidko et al.,ChemCatChem 2014,6,1526-1530 Summary of the Invention [Problem to be solved by the invention]

[0007] Furthermore, in the technology described in Patent Document 1, a method for producing hydrogen from formic acid is considered, but the ease of producing formic acid and separating and recovering the catalyst is not considered. The technology described in Non-Patent Document 1 produces formate from hydrogen and carbon dioxide in an amine solvent using a metal complex catalyst, but there is room for improvement in the separation and extraction of formic acid from the catalyst and solvent, and there is a need for the development of a catalyst that can produce formic acid in a higher yield.

[0008] Therefore, the present invention provides a method for producing formate, which is a precursor of formic acid, in high yield and allows the catalyst to be reused; a method for producing formic acid; a catalyst for producing formate; and a ruthenium complex that can be used as a catalyst for converting hydrogen into formate with high efficiency. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that hydrogen can be converted to formate with high efficiency by using a metal complex having a specific structure as a catalyst. They have also discovered a method for producing formate and formic acid that allows the catalyst to be recovered and reused with high efficiency, and have completed the present invention.

[0010] The means for solving the above problems are as follows. [1] A method for producing a formate by reacting hydrogen with carbon dioxide, a bicarbonate, or a carbonate in the presence of a solvent using a catalyst, comprising: the reaction is a two-phase system in which the solvent is separated into an organic solvent and an aqueous solvent, The method for producing a formate, wherein the catalyst is at least one selected from a ruthenium complex represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt compound thereof:

[0011] [ka]

[0012] (In the general formula (1), R represents a hydrogen atom or an alkyl group, Each Q1 independently represents CH2, NH, or O; Each R1 independently represents an alkyl group or an aryl group (provided that when Q1 represents NH or O, at least one R1 represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand. [2] The method for producing a formate salt according to [1], wherein the ruthenium complex represented by the general formula (1) is a ruthenium complex represented by the following general formula (3):

[0013] [ka]

[0014] (In the general formula (3), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand. [3] The method for producing a formate salt according to [1], wherein R1 represents a phenyl group. [4] The method for producing a formate salt according to [2], wherein R3 represents a phenyl group. [5] The method for producing a formate salt according to [4], wherein A represents CH and Q2 represents NH. [6] The method for producing a formate salt according to any one of [1] to [5], wherein R0 represents a hydrogen atom or a methyl group. [7] The method for producing a formate salt according to any one of [1] to [6], wherein the X represents a chlorine atom. [8] The method for producing a formate salt according to any one of [1] to [7], wherein the n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine. [9] The method for producing a formate salt according to any one of [1] to [8], wherein the organic solvent contains toluene or dioxane.

[10] The method for producing a formate salt according to any one of [1] to [9], further comprising using an ammonium salt as a phase transfer catalyst.

[11] The method for producing a formate salt according to any one of [1] to

[10] , further comprising adding a ligand represented by the following general formula (4):

[0015] [ka]

[0016] (In the general formula (4), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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.

[12] A step of producing a formate salt by the method according to any one of [1] to

[11] ; and a second step of protonating at least a portion of the formate salt to produce formic acid.

[13] A catalyst for producing formate by reacting hydrogen with carbon dioxide, hydrogencarbonate or carbonate, the catalyst comprising a ruthenium complex represented by the following general formula (2):

[0017] [ka]

[0018] (In the general formula (2), R represents a hydrogen atom or an alkyl group, Each Q1 independently represents CH2, NH, or O; Each R2 independently represents an alkyl group or an aryl group (provided that at least one R2 represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[14] A ruthenium complex represented by the following general formula (3):

[0019] [ka]

[0020] (In the general formula (3), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[15] The ruthenium complex according to

[14] , wherein R3 represents a phenyl group.

[16] The ruthenium complex according to

[14] or

[15] , wherein A represents CH and Q2 represents NH.

[17] The ruthenium complex according to any one of

[14] to

[16] , wherein R0 represents a hydrogen atom or a methyl group.

[18] The ruthenium complex according to any one of

[14] to

[17] , wherein the X represents a chlorine atom.

[19] The ruthenium complex according to any one of

[14] to

[18] , wherein n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide a ruthenium complex that can be used as a catalyst for converting hydrogen into formate with high efficiency, a catalyst for producing formate, a method for producing formate in high yield and capable of reusing the catalyst, and a method for producing formic acid. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 is a schematic diagram showing an example of a three-compartment electrodialysis apparatus. DETAILED DESCRIPTION OF THE INVENTION

[0023] Hereinafter, embodiments of the present invention will be described in detail. A method for producing a formate according to a first embodiment of the present invention is a method for producing a formate by reacting hydrogen with carbon dioxide, a hydrogen carbonate, or a carbonate in the presence of a solvent using a catalyst, the method comprising: The reaction is carried out in a two-phase system in which the solvent is separated into an organic solvent and an aqueous solvent, The catalyst is at least one selected from the group consisting of a ruthenium complex represented by the following general formula (1), a tautomer or stereoisomer thereof, and a salt compound thereof, in the method for producing a formate salt.

[0024] [ka]

[0025] In general formula (1), R represents a hydrogen atom or an alkyl group. Each Q1 independently represents CH2, NH, or O; Each R1 independently represents an alkyl group or an aryl group (provided that when Q1 represents NH or O, at least one R1 represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[0026] A method for producing formic acid according to a second embodiment of the present invention includes a step of producing a formate by the method for producing a formate, and a second step of protonating at least a portion of the formate by electrodialysis to produce formic acid and water.

[0027] A catalyst for producing a formate according to a third embodiment of the present invention is a catalyst used in producing a formate by reacting hydrogen with carbon dioxide, a bicarbonate, or a carbonate, and contains a ruthenium complex represented by the following general formula (2):

[0028] [ka]

[0029] (In the general formula (2), R represents a hydrogen atom or an alkyl group, Each Q1 independently represents CH2, NH, or O; Each R2 independently represents an alkyl group or an aryl group (provided that at least one R2 represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[0030] Moreover, a ruthenium complex according to a fourth embodiment of the present invention is represented by the following general formula (3).

[0031] [ka]

[0032] (In the general formula (3), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[0033] The ruthenium complexes represented by the general formulae (1) to (3) may produce stereoisomers depending on the coordination mode or conformation of the ligands, but may be a mixture of these stereoisomers or a pure isomer.

[0034] [Methods for producing formic acid and formic salt] A method for producing a formate according to a first embodiment of the present invention is a method for producing a formate by reacting hydrogen with carbon dioxide, a hydrogen carbonate, or a carbonate in the presence of a solvent using a catalyst, the method comprising: The reaction is carried out in a two-phase system in which the solvent is separated into an organic solvent and an aqueous solvent, The catalyst is at least one selected from a ruthenium complex represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt compound thereof (hereinafter, sometimes simply referred to as a "ruthenium complex"), in the method for producing a formate salt.

[0035] A method for producing formic acid according to a second embodiment of the present invention includes a step (first step) of producing a formate by the method for producing a formate according to the first embodiment, and a second step of protonating at least a portion of the formate by electrodialysis to produce formic acid and water.

[0036] <First step> The first step is a step in which hydrogen is reacted with carbon dioxide, hydrogen carbonate or carbonate in the presence of a solvent using a catalyst to produce a formate in a reaction solution. In the first embodiment of the present invention, the reaction of hydrogen with carbon dioxide, a bicarbonate, or a carbonate is preferably carried out in a two-phase system in which an organic solvent and an aqueous solvent are present in separate states, and the reaction is preferably carried out in a solution containing a catalyst dissolved in an organic solvent.

[0037] The method for producing a formate salt according to the first embodiment of the present invention can be carried out, for example, as follows: A reaction vessel equipped with a stirrer is prepared, and a solvent is introduced into the reaction vessel. If necessary, a phase transfer catalyst may also be added. A catalyst is added to the reaction vessel and dissolved in a solvent to prepare a catalyst solution. Then, hydrogen, carbon dioxide, a bicarbonate, or a carbonate is introduced into the reaction vessel to carry out the reaction.

[0038] (solvent) The solvent according to the embodiment of the present invention is not particularly limited as long as it can form a two-phase system in which the organic solvent and the aqueous solvent exist in a separated state, and preferably includes a solvent that dissolves the catalyst and becomes homogeneous. 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. Examples of organic solvents include toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, and mixed solvents thereof. From the viewpoint of separability from the aqueous solvent, it is preferable that the organic solvent contains toluene or dioxane, and toluene is more preferable.

[0039] (catalyst) As described above, the catalyst used in the method for producing a formate according to the first embodiment of the present invention is a ruthenium complex represented by general formula (1). The ruthenium complex represented by general formula (1) is soluble in organic solvents but insoluble in water. Because the formate produced by the reaction is easily soluble in water, the reaction in a two-phase system facilitates separation of the catalyst and the formate, making it easy to separate and recover the catalyst and the formate from the reaction system, enabling the production of formate in high yield. According to the method of this embodiment, the formate produced by the reaction can be separated from the catalyst by a simple operation, and the expensive catalyst can be reused.

[0040] The catalyst used in the embodiment of the present invention is at least one selected from a ruthenium complex represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt compound thereof.

[0041] [ka]

[0042] (In the general formula (1), R represents a hydrogen atom or an alkyl group, Each Q1 independently represents CH2, NH, or O; Each R1 independently represents an alkyl group or an aryl group (provided that when Q1 represents NH or O, at least one R1 represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[0043] In general formula (1), 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, or a 2-ethylhexyl group. From the viewpoint of ease of procurement of raw materials, an alkyl group having 6 or less carbon atoms is preferred, and a methyl group is preferred. In general formula (1), R0 is preferably a hydrogen atom or a methyl group.

[0044] In general formula (1), each R1 independently represents an alkyl group or an aryl group, provided that when Q1 represents NH or O, at least one R1 represents an aryl group. Examples of the alkyl group represented by R1 include linear, branched, and cyclic substituted or unsubstituted alkyl groups. The alkyl group represented by R1 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, and a t-butyl group is preferred.

[0045] The aryl group represented by R1 includes 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.

[0046] 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. The alkyl group represented by R5 may be a linear, branched, or cyclic substituted or unsubstituted alkyl group. 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, or 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.

[0047] The aryl group represented by R5 includes 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.

[0048] 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.

[0049] 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.

[0050] X represents a halogen atom, preferably a chlorine atom.

[0051] n represents an integer of 0 to 3, and represents the number of ligands coordinated to ruthenium. From the viewpoint of catalyst stability, n is preferably 2 or 3.

[0052] When a plurality of Ls are present, each L independently represents a neutral or anionic ligand. 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. 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).

[0053] In general formula (1), it is preferred that A represents CH and Q1 represents NH. It is also preferred that n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0054] The ruthenium complexes represented by the general formula (1) may be used singly or in combination of two or more kinds.

[0055] The ruthenium complex represented by the above general formula (1) is preferably a ruthenium complex represented by the following general formula (3).

[0056] [ka]

[0057] (In the general formula (3), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[0058] R0, A, R5, X, n, and L in general formula (3) have the same meanings as R0, A, R5, X, n, and L in general formula (1), respectively, and the preferred ranges are also the same.

[0059] The aryl group represented by R3 in the general formula (3) has the same meaning as the aryl group represented by R1 in the general formula (1), and the preferred ranges are also the same. In general formula (3), it is preferred that A represents CH and Q2 represents NH.

[0060] The ruthenium complexes represented by general formula (1), general formula (2), and general formula (3) may be produced by known methods, such as those described in Non-Patent Document 1.

[0061] The amount of the ruthenium complex used as a catalyst is not particularly limited as long as it can produce a formate. To fully demonstrate catalytic function, the amount of the ruthenium complex used as a catalyst is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and even more preferably 1 μmol or more per liter of the organic phase (organic solvent) and aqueous phase solvent (aqueous solvent). From the viewpoint of cost, the amount is preferably 1 mol or less, more preferably 10 mmol or less, and even more preferably 1 mmol or less. When two or more ruthenium complexes are used, the total amount used may be within the above range.

[0062] In the method for producing a formate salt according to an embodiment of the present invention, it is preferable that the ligand that forms the complex represented by general formula (1) is present in excess in the reaction mixture, and therefore it is preferable to further add the ligand of the complex to be used. That is, in the method for producing a formate salt according to an embodiment of the present invention, it is preferable to further add a ligand represented by the following general formula (4).

[0063] [ka]

[0064] (In the general formula (4), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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.

[0065] R0, Q2, R3, A, and R5 in general formula (4) have the same meanings as R0, Q2, R3, A, and R5 in general formula (3), respectively, and the preferred ranges are also the same.

[0066] By adding an excess amount of the complex-forming ligand to the reaction system, even if the ligand is oxidized and deteriorated by oxygen or impurities contained in the system, the deteriorated ligand is exchanged for the added ligand, restoring the catalytic function, thereby improving the stability of the catalyst.

[0067] The addition of the ligand represented by the above general formula (4) to the reaction mixture may be carried out when the reaction mixture is prepared or during the reaction. However, from the viewpoint of process control, it is preferably carried out when the reaction mixture is prepared.

[0068] (phase transfer catalyst) The method for producing a formate salt according to the first embodiment of the present invention requires a two-phase reaction, and a phase-transfer catalyst may be used to facilitate the transfer of materials between the two phases. Examples of phase-transfer catalysts include quaternary ammonium salts (ammonium salts), quaternary phosphates, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptands, nitrogen-containing linear polyethers, polyethylene glycols and alkyl ethers thereof, and the like. Among these, quaternary ammonium salts are preferred because they facilitate the transfer of materials between an aqueous solvent and an organic solvent even under mild reaction conditions.

[0069] Examples of quaternary ammonium salts include methyltrioctylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium iodide, trimethylphenylammonium bromide, tributylammonium tribromide, tetrahexylammonium hydrogensulfate, decyltrimethylammonium bromide, diallyldimethylammonium chloride, dodecyltrimethylammonium bromide, dimethyldioctadecylammonium bromide, tetraethylammonium tetrafluoroborate, ethyltrimethylammonium iodide tris(2-hydroxyethyl)methylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium bromide, and tetraethylammonium iodide, with methyltrioctylammonium chloride being preferred.

[0070] The amount of the phase transfer catalyst used is not particularly limited as long as it allows for the production of formate. 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 liter of organic phase and aqueous phase solvent, in order to efficiently assist the transfer of carbonate or bicarbonate. 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. When two or more phase transfer catalysts are used, the total amount used may be within the above range.

[0071] (carbon dioxide and hydrogen) The hydrogen used in the embodiment of the present invention can be either hydrogen gas cylinders or liquid hydrogen. Examples of hydrogen sources that can be used include hydrogen generated during the iron smelting process and hydrogen generated during the soda production process. Hydrogen generated by the electrolysis of water can also be used. The carbon dioxide used in the embodiment of the present invention may be pure carbon dioxide gas or a mixed gas containing components other than carbon dioxide. Carbon dioxide gas and other gases may be introduced separately, or may be mixed before being introduced. Examples of components other than carbon dioxide include inert gases such as nitrogen and argon, water vapor, and any other components contained in exhaust gases. Carbon dioxide may be from a carbon dioxide gas cylinder, liquid carbon dioxide, supercritical carbon dioxide, dry ice, or the like. Hydrogen gas and carbon dioxide gas may be introduced into the reaction system either individually or as a mixed gas. The ratio of hydrogen to carbon dioxide used is preferably equal on a molar basis or hydrogen in excess. When a hydrogen cylinder is used as the hydrogen used in the method for producing a formate according to an embodiment of the present invention, the pressure is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and even more preferably 0.5 MPa or more, from the viewpoint of ensuring sufficient reactivity. Moreover, since the equipment tends to become large, the pressure is preferably 50 MPa or less, more preferably 20 MPa or less, and even more preferably 10 MPa or less. The pressure of carbon dioxide used in the method for producing a formate according to an embodiment of the present invention is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and even more preferably 0.5 MPa or more, from the viewpoint of ensuring sufficient reactivity. However, since the equipment tends to become large, the pressure is preferably 50 MPa or less, more preferably 20 MPa or less, and even more preferably 10 MPa or less.

[0072] The hydrogen gas and carbon dioxide gas may be bubbled (injected) into the catalyst solution. Alternatively, after introducing a gas containing hydrogen gas and carbon dioxide, the catalyst solution and the hydrogen gas and carbon dioxide gas may be stirred with a stirring device, by rotating the reaction vessel, or the like.

[0073] The method for introducing carbon dioxide, hydrogen, a catalyst, a solvent, and the like used in the reaction into a reaction vessel is not particularly limited, and all of the raw materials may be introduced at once, some or all of the raw materials may be introduced stepwise, some or all of the raw materials may be introduced continuously, or a combination of these introduction methods may be used.

[0074] (bicarbonate and carbonate) The bicarbonates and carbonates used in the first embodiment of the present invention include carbonates and bicarbonates of alkali metals or alkaline earth metals. Examples of hydrogen carbonates include sodium hydrogen carbonate and potassium hydrogen carbonate, with potassium hydrogen carbonate being preferred from the viewpoint of high solubility in water. Examples of carbonates include sodium carbonate, potassium carbonate, potassium sodium carbonate, and sodium sesquicarbonate.

[0075] 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.

[0076] The solvent for the basic solution 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. The solvent preferably contains water, and more preferably is water. The base used in the basic solution is not particularly limited as long as it can react with carbon dioxide to produce a bicarbonate or carbonate, and is preferably a hydroxide. Examples include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium hydroxide, sodium hydroxide, diazabicycloundecene, triethylamine, sodium hydroxide, and potassium hydroxide. Among the above, hydroxides are preferred, potassium hydroxide and sodium hydroxide are more preferred, and potassium hydroxide is even more preferred.

[0077] 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 formate, the content of the base is preferably 0.1 mol or more per 1 L of aqueous solvent, more preferably 0.5 mol or more, and even more preferably 1 mol or more. From the viewpoint of the reaction efficiency of formate, 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.

[0078] The ratio of the amounts of carbon dioxide and 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 a carbonate from carbon dioxide, in terms of molar ratio. Also, 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.

[0079] The ratio of the amounts of carbon dioxide and base used may be the ratio of the molar amounts of carbon dioxide and base introduced into the reaction vessel, and 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 and base used within the above range, it is possible to prevent excessive addition of carbon dioxide to the reaction vessel, minimize unreacted carbon dioxide, and improve the final formic acid conversion efficiency. Furthermore, the reaction of carbon dioxide with the base can be carried out in the same vessel to produce a formate salt by hydrogenating carbon dioxide via a bicarbonate or carbonate salt. Unreacted carbon dioxide can be recovered from the reaction vessel and recycled.

[0080] Although there are no particular limitations on the method and order of introducing carbon dioxide and a base into a reaction vessel, it is preferable to introduce carbon dioxide into the reaction vessel after introducing the base. Furthermore, the introduction of carbon dioxide and the base may be carried out continuously or intermittently, with respect to either or both of them.

[0081] 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.

[0082] 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 bicarbonate or carbonate produced, 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.

[0083] The bicarbonate and carbonate produced by the reaction of carbon dioxide with a base can be used in the reaction of hydrogen with the bicarbonate or carbonate in the method for producing a formate according to an embodiment of the present invention. Furthermore, the production of the bicarbonate or carbonate by the reaction of carbon dioxide with a base in a reaction vessel may be used as the introduction of the bicarbonate or carbonate into the reaction vessel in the method for producing a formate.

[0084] (Reaction conditions) The reaction conditions in the method for producing a formate according to the embodiment of the present invention are not particularly limited, and the reaction conditions can be appropriately changed during the reaction. The shape of the reaction vessel used in the reaction is not particularly limited. In the method for producing a formate according to an embodiment of the present invention, examples of the reaction between hydrogen and carbon dioxide, bicarbonate, or carbonate include a reaction between hydrogen and carbon dioxide, a reaction between hydrogen and bicarbonate, and a reaction between hydrogen and carbonate. In the reaction between hydrogen and carbon dioxide, the carbonation reaction of carbon dioxide and the production reaction of formate by hydrogenation of carbonate proceed simultaneously.

[0085] There are no particular limitations on the method and order of introducing hydrogen, carbon dioxide, bicarbonate or carbonate into the reaction vessel. For example, in the reaction of hydrogen with carbon dioxide, it is preferable to introduce hydrogen and carbon dioxide simultaneously. Hydrogen and carbon dioxide may be introduced alone or as a mixed gas. Furthermore, the introduction of either or both of hydrogen and carbon dioxide may be carried out continuously or intermittently. In the reaction between hydrogen and a bicarbonate and the reaction between hydrogen and a carbonate, it is preferable to introduce the bicarbonate or carbonate into the reaction vessel and then introduce hydrogen. One or both of the hydrogen and the bicarbonate or carbonate may be introduced continuously or intermittently.

[0086] The reaction temperature in the reaction between hydrogen and carbon dioxide, hydrogencarbonate, or carbonate is not particularly limited, but in order to allow the reaction to proceed efficiently, it is preferably 30° C. or higher, more preferably 40° C. or higher, and even more preferably 50° C. or higher. From the viewpoint of energy efficiency, it is preferably 200° C. or lower, more preferably 150° C. or lower, and even more preferably 100° C. or lower. The reaction temperature can be adjusted by heating or cooling, and is preferably increased by heating. In addition, in the reaction between hydrogen and carbon dioxide, for example, hydrogen and carbon dioxide may be introduced into a reaction vessel and then heated to increase the temperature, or carbon dioxide may be introduced into the reaction vessel, the temperature may be increased, and then hydrogen may be introduced. In the reaction between hydrogen and a bicarbonate or a carbonate, for example, it is preferable to introduce (produce) the bicarbonate or carbonate into a reaction vessel, then introduce hydrogen and raise the temperature.

[0087] The reaction time for the reaction of hydrogen with carbon dioxide, hydrogencarbonate, or carbonate is not particularly limited, but is preferably 0.5 hours or longer, more preferably 1 hour or longer, and even more preferably 2 hours or longer from the viewpoint of ensuring a sufficient amount of formate produced, and is preferably 24 hours or shorter, more preferably 12 hours or shorter, and even more preferably 6 hours or shorter from the viewpoint of cost.

[0088] <Second process> The second step is a step of protonating at least a portion of the formate salt by electrodialysis to produce formic acid and water.

[0089] In an embodiment of the present invention, the formate salt produced in the first step is eluted into the aqueous phase, and an aqueous formate salt solution can be obtained by separating the aqueous phase. It is preferable to separate the aqueous phase in the first step and treat the resulting aqueous formate solution using an electrodialysis device in the second step to produce formic acid. The aqueous phase to be separated is the aqueous phase after completion of the first step.

[0090] In the second step, as described above, the aqueous formate solution obtained in the first step may be used as is, or may be used after adjusting the formate concentration by concentrating or diluting it, as necessary. An example of a method for diluting the aqueous solution of formate is to add pure water. Examples of methods for concentrating the aqueous formate solution include a method in which water is distilled off from the aqueous formate solution, and a method in which the aqueous formate solution is concentrated using a separation membrane unit equipped with a reverse osmosis membrane. From the viewpoint of suppressing loss of formate due to concentration diffusion in a highly concentrated aqueous formate solution during treatment using an electrodialysis apparatus, it is preferred to separate the aqueous phase in the first step, adjust the formate concentration in the aqueous phase by dilution, and then use the resulting aqueous phase in the second step. By obtaining a highly concentrated aqueous formate solution in the first step, adjusting the formate concentration by dilution to a concentration suitable for electrodialysis, and then subjecting the solution to the second step, the TON can be further increased, and formic acid can be produced in a higher yield and with greater productivity.

[0091] The degree of concentration adjustment (preferably dilution) of the formate aqueous solution obtained in the first step can be appropriately selected. The formate concentration in the formate aqueous solution after concentration adjustment is preferably a concentration suitable for electrodialysis, preferably 2.5 mol / L or more, more preferably 3 mol / L or more, and even more preferably 5 mol / L or more. Furthermore, from the viewpoint of suppressing formate loss due to concentration diffusion of the high-concentration formate aqueous solution during treatment using an electrodialysis device, the formate concentration is preferably 20 mol / L or less, more preferably 15 mol / L or less, and even more preferably 10 mol / L or less.

[0092] Pure water can be used for dilution. Alternatively, the water produced in the second step may be used for dilution. Reusing the water produced in the second step for dilution is preferable because it has the advantage of reducing the cost of wastewater treatment and the environmental load.

[0093] In the method for producing formic acid according to an embodiment of the present invention, an acid may be added to the aqueous formate solution obtained in the first step, followed by decarboxylation before use in the second step. That is, the aqueous phase in the first step may be separated, an acid may be added, followed by decarboxylation before use in the second step. The aqueous solution of formate obtained in the first step may contain unreacted carbonate or bicarbonate produced by a side reaction, and electrodialysis of a solution containing carbonate or bicarbonate may generate carbon dioxide, potentially reducing the dialysis efficiency. Therefore, by adding an acid to the aqueous solution of formate obtained in the first step and performing a decarbonation treatment followed by electrodialysis, the TON can be further increased, and formic acid can be produced in a higher yield and with greater productivity.

[0094] Examples of acids used in the decarboxylation treatment include formic acid, citric acid, acetic acid, malic acid, lactic acid, succinic acid, tartaric acid, butyric acid, fumaric acid, propionic acid, hydrochloric acid, nitric acid, and sulfuric acid, and it is preferable to use formic acid. The amount of acid used is preferably 50% or more, more preferably 80% or more, of the amount of carbon dioxide present in the solution, from the viewpoint of suppressing the amount of carbon dioxide generated during electrodialysis treatment. Furthermore, from the viewpoint of suppressing deterioration of the electrodialysis apparatus by maintaining a neutral pH of the formate solution during electrodialysis treatment, the amount of acid used is preferably 150% or less, more preferably 120% or less, of the amount of carbon dioxide present in the solution.

[0095] In an embodiment of the present invention, the proportion of formate protonated in the second step is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, relative to the initial molar amount of formate in the formate aqueous solution, from the viewpoint of increasing the purity of the recovered aqueous formic acid solution.

[0096] Examples of electrodialysis devices include a two-compartment electrodialysis device using a bipolar membrane and an anion exchange membrane or a cation exchange membrane, and a three-compartment electrodialysis device using a bipolar membrane, an anion exchange membrane, and a cation exchange membrane.

[0097] Figure 1 is a schematic diagram showing an example of a three-compartment electrodialysis apparatus. The electrodialysis apparatus shown in Figure 1 includes multiple bipolar membranes, anion exchange membranes, and cation exchange membranes. These bipolar membranes, anion exchange membranes, and cation exchange membranes are arranged between an anode and a cathode, forming a base tank, a sample tank (salt tank), and an acid tank. By circulating and supplying an aqueous solution of formate to the sample tank while applying electricity, the formate is converted to formic acid, and formic acid is recovered from the acid tank, water is recovered from the sample tank, and hydroxide is recovered from the base tank.

[0098] The two-compartment electrodialysis apparatus comprises a plurality of bipolar membranes and cation exchange membranes, which are alternately arranged between an anode and a cathode. A salt chamber is formed between each bipolar membrane and the cation exchange membrane arranged on the cathode side thereof, and a base chamber is formed between each bipolar membrane and the cation exchange membrane arranged on the anode side thereof. By circulating an aqueous formate solution through the salt chambers while applying current, the formate being circulated through the salt chambers is converted to formic acid while producing hydroxide in the base chamber.

[0099] In the second step, the formate salt can be protonated in a simple manner to give a formic acid solution.

[0100] Next, a catalyst for producing formate salts according to a third embodiment of the present invention will be described.

[0101] [Catalyst for producing formate salts] A catalyst for producing a formate according to a third embodiment of the present invention is a catalyst used in producing a formate by reacting hydrogen with carbon dioxide, a bicarbonate, or a carbonate, and contains a ruthenium complex represented by the following general formula (2):

[0102] [ka]

[0103] (In the general formula (2), R represents a hydrogen atom or an alkyl group, Each Q1 independently represents CH2, NH, or O; Each R2 independently represents an alkyl group or an aryl group (provided that at least one R2 represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[0104] R0, A, R5, X, n, and L in general formula (2) have the same meanings as R0, A, R5, X, n, and L in general formula (1), respectively, and the preferred ranges are also the same.

[0105] The alkyl group and aryl group represented by R2 in general formula (2) have the same meanings as the alkyl group and aryl group represented by R1 in general formula (1), respectively, and the preferred ranges are also the same.

[0106] The ruthenium complex represented by the general formula (2) is preferably a ruthenium complex represented by the general formula (3) above.

[0107] The reaction for producing a formate using the catalyst for producing a formate according to the third embodiment of the present invention may be carried out in a single phase or a two-phase system. The solvent used in the catalyst for producing a formate salt according to the third embodiment of the present invention is not particularly limited as long as it allows the production of a formate salt, and examples thereof include water, methanol, ethanol, ethylene glycol, glycerin, toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, tetrahydrofuran, and mixed solvents thereof.

[0108] When producing a formate using the catalyst for producing a formate according to the third embodiment of the present invention, the types and amounts of hydrogen, carbon dioxide, hydrogencarbonate, and carbonate used, reaction conditions, and the like can also be appropriately selected from those described in the method for producing a formate according to the first embodiment.

[0109] Next, a ruthenium complex represented by general formula (3) according to a fourth embodiment of the present invention will be described.

[0110] [Ruthenium complex represented by general formula (3)] The ruthenium complex represented by the general formula (3) is a novel compound. The ruthenium complex according to the fourth embodiment of the present invention is represented by the following general formula (3).

[0111] [ka]

[0112] (In the general formula (3), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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; X represents a halogen atom; n represents 0 to 3, When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

[0113] R0, A, R5, X, n, and L in general formula (3) have the same meanings as R0, A, R5, X, n, and L in general formula (1), respectively, and the preferred ranges are also the same.

[0114] The aryl group represented by R3 in the general formula (3) has the same meaning as the aryl group represented by R1 in the general formula (1), and the preferred ranges are also the same.

[0115] In general formula (3), it is preferred that A represents CH and Q2 represents NH.

[0116] The ruthenium complex represented by general formula (3) can be produced, for example, by adding a tridentate ligand represented by the following general formula (4) and a ruthenium compound represented by the following general formula (5) to a reaction system.

[0117] [ka]

[0118] (In the general formula (4), R represents a hydrogen atom or an alkyl group, Each Q2 independently represents NH or O; Each R3 independently represents an aryl 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.

[0119] R0, Q2, R3, A, and R5 in general formula (4) have the same meanings as R0, Q2, R3, A, and R5 in general formula (3), respectively, and the preferred ranges are also the same.

[0120] [RuHX[L]n(CO)] (5)

[0121] (In general formula (5), X 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.)

[0122] X, n, and L in the general formula (5) have the same meanings as X, n, and L in the general formula (3), respectively, and the preferred ranges are also the same.

[0123] In producing the ruthenium complex represented by general formula (3), it is preferable to use a solvent. Specific examples of the solvent to be used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as methylene chloride and chlorobenzene, ethers such as diethyl ether, tetrahydrofuran, methyl tert-butyl ether, and cyclopentyl methyl ether, alcohols such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, 2-butanol, and tert-butyl alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,2-propanediol, and glycerin, amides such as dimethylformamide and dimethylacetamide, nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide, and water, with tetrahydrofuran being preferred. These solvents may be used either alone or in appropriate combination of two or more.

[0124] The production of the ruthenium complex represented by general formula (3) is preferably carried out in an inert gas or air atmosphere. Examples of inert gases include argon gas and nitrogen gas, with argon gas being preferred. These gases and air may be used alone or as a mixed gas. The reaction temperature is appropriately selected usually within the range of -50°C to 300°C, preferably -20°C to 250°C, and more preferably 30°C to 200°C. The reaction time varies depending on the base, solvent, reaction temperature, and other conditions, but is usually selected appropriately from the range of 1 minute to 72 hours, preferably 1 minute to 24 hours, more preferably 5 minutes to 12 hours.

[0125] The ruthenium complex represented by general formula (3) produced by the above production method can be subjected to post-treatment, isolation, and purification as necessary. Specific examples of post-treatment methods include concentration, solvent substitution, washing, extraction, stripping, filtration, and crystallization by adding a poor solvent. These methods can be used alone or in combination. Specific examples of isolation and purification methods include drying of the reaction solution, column chromatography, recrystallization, and washing of crystals with a poor solvent. These methods can be used alone or in combination.

[0126] The ruthenium complex represented by general formula (3) is suitable for industrial use and can carry out reactions under mild reaction conditions with high catalytic activity. For example, it can be used to produce formates by hydrogenation reduction of carbon dioxide or bicarbonates in the presence of a hydrogen donor. [Example]

[0127] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0128] [Catalyst Synthesis] (Synthesis Example 1) Synthesis of Ru catalyst 1 Ru catalyst 1 was synthesized by the following procedure. Under an inert atmosphere, 40 mg (0.1 mmol) of Ligand A was added to a suspension of 95.3 mg (0.1 mmol) of [RuHCl(PPh3)3(CO)] in 5 ml of tetrahydrofuran (THF), and the mixture was stirred and heated at 65°C for 3 hours to carry out the reaction, followed by cooling 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. The solid was filtered and dried under vacuum to give Ru catalyst 1 (55 mg, 97%) as yellow crystals. In the Ru catalyst 1 and ligand A shown below, tBu represents a tertiary butyl group.

[0129] [ka]

[0130] 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=9.5Hz),37.7(t,J=6.0Hz),37.9 (t,J=6.5Hz),119.5(t,J=4.5Hz),136.4(s),163.4(t,J=5.0Hz),209.8(s).

[0131] (Synthesis Example 2) Synthesis of Ru catalyst 2 Ru catalyst 2 was synthesized by the following procedure. Under an inert atmosphere, 83.9 mg (0.21 mmol) of the following ligand B was added to a slurry of 200.0 mg (0.21 mmol) of [RuHCl(PPh3)3(CO)] in 5 mL of benzene. The mixture was heated in a sealed vessel at 100° C. for 8 hours to give a clear pink solution. The solvent was removed in vacuo to give a pink solid. To remove free PPh3, the residue was washed with pentane (5 mL) and the washings were passed through a silica column. The residue was dissolved in benzene (1 mL) and passed through a column, which was washed with more benzene (5 mL), and finally the product was eluted with THF. The solvent THF was removed under vacuum to give a pink solid, Ru catalyst 2, in 95.3% (113 mg) yield. In the Ru catalyst 2 and ligand B shown below, tBu represents a tertiary butyl group.

[0132] [ka]

[0133] 31 P{ 1 H}NMR(C6D6):226.65(brs). 1 H NMR(C6D6):6.71(t,J=8.2Hz,1H),6.09(d,J=8.2Hz,2H),1.72(vt,J=7.6Hz),1.20(vt,J=7.3Hz),-14.07(t,J=20.7Hz,1H). 13 C{ 1 H}NMR(C6D6):206.84(t,J=10.2Hz),163.20(t,J=3.9Hz),142.0(s),102.30(s),4 3.18(t,J=3.0Hz),40.70(t,J=7.6Hz),30.50(vt,J=3.8Hz),27.85(vt,J=2.8Hz).

[0134] (Synthesis Example 3) Synthesis of Ru catalyst 3 Ru catalyst 3 was synthesized by the following procedure. Under an inert atmosphere, to a suspension of [RuHCl(PPh)(CO)] (953 mg, 1 mmol) in THF (15 mL) was added Ligand C (397 mg, 1 mmol), and the mixture was stirred and heated at 65°C for 12 h, then cooled to room temperature. The precipitated pale yellow solid was filtered, washed with ether (3 mL x 3), and dried under vacuum to give Ru catalyst 3 (519 mg, 92%). In the Ru catalyst 3 and ligand C shown below, tBu represents a tertiary butyl group.

[0135] [ka]

[0136] 31 P{ 1 H}NMR(CDCl3):135.6(s). 1 H NMR(CDCl3):δ-26.11(t,J=16.0Hz,1H),1.32(t,J=7.28Hz,18H),1.41(t,J= 7.68Hz,18H),6.87(t,J=8.04Hz,1H),7.14(d,J=8.04Hz,2H),9.51(br,2H). 13 C{ 1 H}NMR(125MHz,CD3OD):28.62(t,J=2.7Hz),28.87(t,J=3.4Hz),39.34(t,J=10.8Hz),41.1 0(t,J=9.1Hz),99.75(t,J=3.5Hz),143.05(s),164.32(t,J=7.3Hz),207.41(t,J=10.7Hz).

[0137] (Synthesis Example 4) Synthesis of Ru catalyst 5 Ru catalyst 5 was synthesized by the following procedure. A mixture of 0.51 g (0.54 mmol) of [RuHCl(PPh3)3(CO)] and 0.30 g (0.63 mmol) of the ligand E in 25 mL of benzene was refluxed overnight under an inert atmosphere to give a clear yellow solution, which was then allowed to cool to room temperature. The solvent was completely removed under vacuum and 30 mL of diethyl ether was added to give a yellow solid. The yellow solid was recrystallized using dichloromethane / diethyl ether to give a pale yellow solid. The solid was collected on a filter and dried under vacuum overnight to give Ru catalyst 5 in 0.29 g, 85% yield. In the Ru catalyst 5 and ligand E shown below, Ph represents a phenyl group.

[0138] [ka]

[0139] 1 H NMR(300MHz,CD2Cl2):δ-13.65(t,J=19.9Hz,1H),4.13(dt,J=16.6Hz,J=4.8Hz,2H),4.64(dt,J=16.6Hz,J=4.5Hz,2H),6.82-7.85(m,23H). 31 P{ 1 H}NMR(121.51MHz,CD2Cl2):δ50.4(s)

[0140] (Synthesis Example 5) Synthesis of Ru catalyst 7 Ru catalyst 7 was synthesized by the following procedure. Under an inert atmosphere, 142.6 mg of ligand G and 284.6 mg of [RuHCl(PPh3)3(CO)] were mixed in 5 mL of benzene and the suspension was refluxed overnight. The resulting yellow precipitate was collected on a filter and washed four times with 5 mL of ether. The precipitate was dried in vacuo to give 154.0 mg of Ru catalyst 7. In the Ru catalyst 7 and ligand G shown below, Ph represents a phenyl group.

[0141] [ka]

[0142] 31 P{ 1H}NMR(CDC3):95.58(br,s),29.71(s). 1 H NMR(400MHz,CD2Cl2)δ9.92(s,2H),8.11(q,J=6.6Hz,4H),7.38-7.24(m,4H),7.20(t,J=7.5Hz,3H),7.16-7.04(m,4H),7.0 4-6.92(m,14H),6.87(td,J=7.6,2.1Hz,6H),6.51(d,J=8.0Hz,1H),6.61(d,J=8.0Hz,2H),-7.22(dt,J=89.2,23.1Hz,1H).

[0143] (Synthesis Example 6) Synthesis of Ru catalyst 8 Ru catalyst 8 was synthesized by the following procedure. Under an inert atmosphere, 161.0 mg of the ligand H and 242.4 mg of [RuHCl(PPh3)3(CO)] were mixed with 6 mL of THF and stirred at 64 °C overnight. After cooling to room temperature, the solvent was removed in vacuo, and the residue was washed twice with 3 mL of diethyl ether. The resulting pale yellow powder was further dried in vacuo to give 110.2 mg of Ru catalyst 8. In the Ru catalyst 8 and ligand H shown below, Ph represents a phenyl group.

[0144] [ka]

[0145] 31 PNMR(162MHz,THF-d8)δ90.19(s). 1 H NMR(400MHz,THF-d8)δ9.26(s,2H),7.94(br,4H),7.74(t,J=4.6Hz,4H),7.43-7.32(br12H),2.26(d,J=2.2Hz,3H),-13.63(t,J=21.6Hz,1H).

[0146] Example 1 In an argon-atmosphere glovebox, 2 mL of N,N-dimethylformamide (DMF) was placed in a glass vial equipped with a rare earth metal stir bar. Then, 2.23 mmol of azabicycloundecene (DBU) (333 μL) was added. Next, 10 mg of a 6.6 mg / mL stock solution of catalyst 7 (6.6 mg of catalyst 7 dissolved in 1 mL of DMF) was added. Finally, the autoclave was sealed and removed from the glovebox. The autoclave was connected to a H2 / CO2 (1:1 mixture) supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar (1 bar = 0.1 MPa) at room temperature and heated to the desired temperature (90 °C) while stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with the H2 / CO2 mixture (1:1). After stirring the reaction mixture for 1.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released upon cooling. 300 μL of dimethyl sulfoxide (DMSO) was added as an internal standard, and a 100 μL sample was dissolved in 0.5 mL of DO. 1 The amount of potassium formate produced was quantified by 1 H NMR analysis.

[0147] Example 2 In an argon-atmosphere glovebox, potassium bicarbonate (10 mmol, 1.0 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 2 mL of water and 0.12 μmol (108 μg, equivalent to 10 μL of a 12.6 mg / mL solution in DMF) of catalyst 7 were added. Finally, the autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. The reaction mixture was stirred for 2.5 hours, after which the reaction mixture was cooled in an ice bath and, once cooled, the pressure was carefully released. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO. The amount of potassium formate was determined. 1 1 H NMR analysis.

[0148] Example 3 In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10 μL of a 6.6 mg / mL stock solution of catalyst 1 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released upon cooling. The upper layer containing the catalyst and trimethylammonium chloride was removed, leaving the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0149] Example 4 In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10 μL of a 6.6 mg / mL stock solution of catalyst 5 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0150] Example 5 In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10 μL of a 12.6 mg / mL stock solution of catalyst 7 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 4.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0151] Example 6 In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10 μL of a 6.3 mg / mL stock solution of catalyst 8 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 12 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0152] Example 7 In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of dioxane and 10 μL of a 12.6 mg / mL stock solution of catalyst 7 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to the desired temperature (typically 90°C) with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 4.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0153] Example 8 In this example, catalyst 1 was exposed to air in its solid state for 20 hours before use. In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10 μL of a 6.3 mg / mL stock solution of the exposed catalyst 1 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0154] Example 9 In this example, catalyst 5 was exposed to air in its solid state for 20 hours before use. In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 7.0 μL of a 9.0 mg / mL aerated catalyst 5 stock solution (9.0 mg of catalyst 5 dissolved in 1 mL of DMF) were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0155] Example 10 In this example, catalyst 7 was exposed to air in its solid state for 20 hours before use. In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10.5 μL of a 10.6 mg / mL stock solution of the exposed catalyst 7 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to 90 °C with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 4.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0156] Example 11 In this example, catalyst 8 was exposed to air in its solid state for 20 hours before use. In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10.5 μL of a 5.8 mg / mL stock solution of the exposed catalyst 8 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to the desired temperature (typically 90°C) with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 12 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0157] Comparative Example 1 In this example, catalyst 2 was exposed to air in its solid state for 20 hours before use. In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10 μL of a 6.7 mg / mL stock solution of the exposed catalyst 2 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to the desired temperature (typically 90°C) with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0158] Comparative Example 2 In this example, catalyst 3 was exposed to air in its solid state for 20 hours before use. In an argon-atmosphere glovebox, potassium bicarbonate (5 mmol, 0.5 g) was weighed into a glass vial equipped with a rare earth metal stir bar. Solid methyltrioctylammonium chloride (54 μmol, 22 mg) was then added. Next, 1 mL of toluene and 10 μL of a 6.6 mg / mL stock solution of the exposed catalyst 3 were added. Finally, 1 mL of water was added, and the vial was placed in an autoclave. The autoclave was sealed and removed from the glovebox. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 5 bar at room temperature and heated to the desired temperature (typically 90°C) with stirring. Once the desired temperature was reached, the autoclave was further pressurized to 40 bar with H2. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0159] The above examples and comparative examples are listed in Table 1. The TON (Turnover Number) in the table indicates the amount (molar amount) of formic acid or formate produced relative to the amount (molar amount) of catalyst used.

[0160] [Table 1]

[0161] Examples 3 to 11, in which formate salts were produced using the production method according to the first embodiment, exhibited high TON (Turnover Number) and were excellent in formate production efficiency. It was also confirmed that Examples 1 and 2, in which formate salts were produced using the ruthenium complex according to the fourth embodiment as a catalyst, exhibited high TON.

[0162] Example 12 In this example, catalyst 7 was exposed to air in its solid state for 20 hours before use. In an argon-filled glove box, potassium hydroxide (50 mmol, 2.8 g) was weighed into a glass vial equipped with a rare earth metal stir bar, and 4.2 mL of distilled water was added to prepare a 10 mol / L potassium hydroxide solution. Next, 10.5 μL of a 10.6 mg / mL stock solution of catalyst 7 exposed to air and solid methyltrioctylammonium chloride (54 μmol, 22 mg) were added to 5 mL of toluene. Finally, 5 mL of the toluene containing catalyst 7 and methyltrioctylammonium chloride was added to 5 mL of 10 mol / L potassium hydroxide solution, and the vial was placed in a 300 mL autoclave. The autoclave was then sealed and removed from the glove box. The autoclave was connected to a CO2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 0.4 MPa at room temperature. The solution was stirred for 1 h, after which the CO2 was carefully released. The autoclave was then connected to an H2 supply line and purged to remove traces of CO2 and other impurities, after which the solution was heated to 90°C with stirring, and pressurized with H2 to approximately 0.5 MPa. After stirring the reaction mixture for 18 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0163] Example 13 In this example, catalyst 7 was exposed to air in its solid state for 20 hours before use. In an argon-filled glove box, potassium hydroxide (50 mmol, 2.8 g) was weighed into a glass vial equipped with a rare earth metal stir bar, and 4.2 mL of distilled water was added to prepare a 10 mol / L potassium hydroxide solution. Next, 10.5 μL of a 10.6 mg / mL stock solution of catalyst 7 exposed to air and solid methyltrioctylammonium chloride (54 μmol, 22 mg) were added to 5 mL of toluene. Finally, 5 mL of the toluene containing catalyst 7 and methyltrioctylammonium chloride was added to 5 mL of 10 mol / L potassium hydroxide solution, and the vial was placed in a 300 mL autoclave. The autoclave was then sealed and removed from the glove box. The autoclave was connected to a CO2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 0.1 MPa at room temperature. The solution was stirred for 1 h, after which the CO2 was carefully released. The autoclave was then connected to an H2 supply line and purged to remove traces of CO2 and other impurities.The solution was then heated to 90°C with stirring, and after the temperature was raised, H2 was pressurized to approximately 0.4 MPa. After stirring the reaction mixture for 18 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0164] Example 14 In this example, catalyst 7 was exposed to air in its solid state for 20 hours before use. In an argon-filled glove box, potassium hydroxide (50 mmol, 2.8 g) was weighed into a glass vial equipped with a rare earth metal stir bar, and 4.2 mL of distilled water was added to prepare a 10 mol / L potassium hydroxide solution. Next, 10.5 μL of a 10.6 mg / mL stock solution of catalyst 7 exposed to air and solid methyltrioctylammonium chloride (54 μmol, 22 mg) were added to 5 mL of toluene. Finally, 5 mL of the toluene containing catalyst 7 and methyltrioctylammonium chloride was added to 5 mL of 10 mol / L potassium hydroxide solution, and the vial was placed in a 300 mL autoclave. The autoclave was then sealed and removed from the glove box. The autoclave was connected to a CO2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 0.1 MPa at room temperature. Next, the autoclave was connected to an H2 supply line and pressurized to approximately 0.4 MPa. Finally, the solution was heated to 90 °C. After stirring the reaction mixture for 18 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0165] Example 15 In this example, catalyst 7 was exposed to air in its solid state for 20 hours before use. In an argon-filled glove box, potassium hydroxide (50 mmol, 2.8 g) was weighed into a glass vial equipped with a rare earth metal stir bar, and 4.2 mL of distilled water was added to prepare a 10 mol / L potassium hydroxide solution. Next, 10.5 μL of a 10.6 mg / mL stock solution of catalyst 7 exposed to air and solid methyltrioctylammonium chloride (54 μmol, 22 mg) were added to 5 mL of toluene. Finally, 5 mL of the toluene containing catalyst 7 and methyltrioctylammonium chloride was added to 5 mL of 10 mol / L potassium hydroxide solution, and the vial was placed in a 300 mL autoclave. The autoclave was then sealed and removed from the glove box. The autoclave was connected to an H2 supply line and first purged to remove traces of oxygen and other impurities. The autoclave was then pressurized to approximately 0.1 MPa at room temperature. Next, the autoclave was connected to a CO2 supply line and pressurized to approximately 0.4 MPa. Finally, the solution was heated to 90 °C. After stirring the reaction mixture for 18 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released once cooled. The upper layer containing the catalyst and trimethylammonium chloride could be removed, leaving behind the lower layer containing potassium formate and unreacted potassium bicarbonate. 100 μL of DMSO was added as an internal standard, and 100 μL of the aqueous layer was taken and dissolved in 0.5 mL of DO to quantify the potassium formate. 1 H NMR was performed.

[0166] The results of Examples 12 to 15 are shown in Table 2. The CO2 / base amount (mol / mol) in Table 2 indicates the ratio of the amount of CO2 (molar amount) charged into a 300 mL autoclave to the amount of KOH (molar amount) used. The molar amount of CO2 charged was calculated using the gas equation of state from the volume of the autoclave minus the volume of the basic aqueous solution added, the CO2 charging pressure, and the ambient temperature at the time of CO2 charging.

[0167] [Table 2]

[0168] Example 12, in which formic acid was produced using the production method according to the first embodiment, exhibited a high TON (Turnover Number (the amount of formic acid produced (mol) relative to the amount of catalyst charged (mol))), and it was confirmed that potassium hydroxide was used as a base and formic acid was produced by the reaction of hydrogen and carbon dioxide. Furthermore, Example 13 exhibited a high TON (Turnover Number (the amount of formic acid produced (mol) relative to the amount of catalyst charged (mol))) depending on the ratio of CO2 / base amount, even when the CO2 charging pressure was 1 MPa, and it was confirmed that formic acid was produced from hydrogen and carbon dioxide.

[0169] Examples 14 and 15, in which formic acid was produced using the production method according to the first embodiment, showed a high TON (Turnover Number (the amount of formic acid produced (mol) relative to the amount of catalyst charged (mol))), and it was confirmed that potassium hydroxide was used as a base and formic acid was produced by the reaction of hydrogen and carbon dioxide. There are no particular restrictions on the timing of heating the solution, but it is preferable to heat it after introducing hydrogen and carbon dioxide into the reaction vessel.

[0170] Example 16 In a glove box under inert gas, 5 mL of water was weighed out and placed in a glass vial equipped with a stirring rod, and 5 mmol of calcium carbonate was added. Then, a solution of 0.6 μmol of Ru catalyst 7 and 270 μmol of methyltrioctylammonium chloride mixed in 5 mL of toluene was added, and the glass vial was then placed in an autoclave, which was then sealed and taken out of the glove box. The autoclave was heated to 90°C while stirring. Once the target temperature was reached, a gas containing 50 vol% hydrogen and 50 vol% carbon dioxide was introduced into the autoclave and pressurized to 4 MPa. After stirring the reaction mixture for 4.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The organic phase of the reaction solution (a solution containing the homogeneous catalyst) was separated, and the unreacted calcium carbonate precipitated in the aqueous phase was removed to obtain an aqueous solution containing calcium formate. 100 μL of the aqueous solution containing calcium formate was then taken and dissolved in 0.5 mL of DO, and 100 μL of DMSO was added as an internal standard to quantify the calcium formate. 1 1 H NMR analysis.

[0171] Example 17 In a glove box under inert gas, 5 mL of water was weighed out and placed in a glass vial equipped with a stirring rod, and 5 mmol of calcium carbonate was added. Then, a solution of 0.6 μmol of Ru catalyst 7 and 270 μmol of methyltrioctylammonium chloride mixed in 5 mL of toluene was added, and the glass vial was then placed in an autoclave, which was then sealed and taken out of the glove box. The autoclave was heated to 90°C while stirring. Once the target temperature was reached, a gas containing 50 vol% hydrogen and 50 vol% carbon dioxide was introduced into the autoclave and pressurized to 4 MPa. After stirring the reaction mixture for 18 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The organic phase of the reaction solution (a solution containing the homogeneous catalyst) was separated, and the unreacted calcium carbonate precipitated in the aqueous phase was removed to obtain an aqueous solution containing calcium formate. 100 μL of the aqueous solution containing calcium formate was then taken and dissolved in 0.5 mL of DO, and 100 μL of DMSO was added as an internal standard to quantify the calcium formate. 1 1 H NMR analysis.

[0172] The results of Examples 16 and 17 are shown in Table 3.

[0173] [Table 3]

[0174] Examples 16 and 17, in which formic acid was produced by the production method according to the first embodiment, showed a high TON (Turnover Number (the amount of formic acid produced (mol) relative to the amount of catalyst charged (mol))), and it was confirmed that formic acid could be efficiently produced by using calcium carbonate as a base and reacting hydrogen, an alkaline earth metal salt, and carbon dioxide or a carbonate.

[0175] Examples 18 to 21 In a glove box under inert gas, 1 mL of water was weighed into a glass vial equipped with a stirring rod, and potassium bicarbonate in the range of 2.5 to 14 mmol was added. Then, a solution of 0.12 μmol of Ru catalyst 1 and 54 μmol of methyltrioctylammonium chloride mixed in 1 mL of toluene was added, and the vial was placed in an autoclave, which was then sealed and taken out of the glove box. The autoclave was heated to 90°C while stirring. Once the desired temperature was reached, the autoclave was pressurized with hydrogen to 4 MPa. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The upper layer of the reaction mixture was removed, leaving behind the lower aqueous solution containing potassium formate and unreacted potassium bicarbonate. 100 μL of the lower aqueous solution was taken and dissolved in 500 μL of heavy water. 300 μL of dimethyl sulfoxide was added as an internal standard, and the potassium formate was then quantified. 1 H NMR was performed.

[0176] Examples 22 to 24 In a glove box under inert gas, 1 mL of water was weighed into a glass vial equipped with a stirring rod, and sodium bicarbonate was added in an amount ranging from 5 to 10 mmol. Then, a solution of 0.12 μmol of Ru catalyst 1 and 54 μmol of methyltrioctylammonium chloride mixed in 1 mL of toluene was added, and the vial was then placed in an autoclave, which was then sealed and taken out of the glove box. The autoclave was heated to 90°C while stirring. Once the desired temperature was reached, the autoclave was pressurized with hydrogen to 4 MPa. After stirring the reaction mixture for 2.5 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The upper layer of the reaction mixture was removed, leaving behind the lower aqueous solution containing sodium formate and unreacted potassium bicarbonate. 100 μL of the lower aqueous solution was taken and dissolved in 500 μL of heavy water. 300 μL of dimethyl sulfoxide was added as an internal standard, and the sodium formate was then quantified. 1 H NMR was performed.

[0177] Examples 18 to 24 are listed in Table 4.

[0178] [Table 4]

[0179] Examples 18 to 24, in which formate salts were produced using the production method according to the first embodiment, exhibited high TON (Turnover Number) and excellent formate salt production efficiency. It was confirmed that formic acid could be produced efficiently even when potassium bicarbonate or sodium bicarbonate was used as the base and the base concentration was changed.

[0180] Examples 25 to 28 In a glove box under inert gas, 1 mL of water was weighed out and placed in a glass vial equipped with a stirring rod, and 5 mmol of potassium bicarbonate was added. Then, a solution containing 0.059 to 0.006 μmol of Ru catalyst 1 and 54 μmol of methyltrioctylammonium chloride was added to 1 mL of toluene. The vial was then placed in an autoclave, which was then sealed and taken out of the glove box. The autoclave was heated to 90°C while stirring. Once the desired temperature was reached, the autoclave was pressurized with hydrogen to 4 MPa. After stirring the reaction mixture for 18 to 48 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The upper layer of the reaction mixture was removed, leaving behind the lower aqueous solution containing potassium formate and unreacted potassium bicarbonate. 100 μL of the lower aqueous solution was taken and dissolved in 500 μL of heavy water. 300 μL of dimethyl sulfoxide was added as an internal standard, and the potassium formate was then quantified. 1 H NMR was performed.

[0181] Examples 25 to 28 are listed in Table 5.

[0182] [Table 5]

[0183] Examples 25 to 28, in which formate salts were produced using the production method according to the first embodiment, exhibited high TON (Turnover Number) and excellent formate salt production efficiency. It was confirmed that formate salts could be produced efficiently even when the catalyst concentration was changed.

[0184] Examples 29 to 43 In a glove box under inert gas, 1 mL of water was weighed out and placed in a glass vial equipped with a stirring rod, and 5 mmol of potassium bicarbonate was added. Then, a solution of 0.12 μmol of Ru catalyst 1 and 54 μmol of methyltrioctylammonium chloride mixed in 1 mL of toluene was added, and the vial was then placed in an autoclave, which was then sealed and taken out of the glove box. The autoclave was heated to a temperature between 65 and 120°C while stirring. Once the desired temperature was reached, the autoclave was pressurized with hydrogen at a pressure between 0.5 and 6 MPa. After stirring the reaction mixture for 16 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The upper layer of the reaction mixture was removed, leaving behind the lower aqueous solution containing potassium formate and unreacted potassium bicarbonate. 100 μL of the lower aqueous solution was taken and dissolved in 500 μL of heavy water. 300 μL of dimethyl sulfoxide was added as an internal standard, and the potassium formate was then quantified. 1 H NMR was performed.

[0185] Examples 29 to 43 are listed in Tables 6 and 7.

[0186] [Table 6]

[0187] [Table 7]

[0188] Examples 29 to 43, in which formate salts were produced using the production method according to the first embodiment, showed high TON (Turnover Number) and excellent production efficiency of formate salts. It was confirmed that formate salts could be produced efficiently even when the reaction temperature and hydrogen pressure were changed.

[0189] Examples 44 to 48 In a glove box under inert gas, 1 mL of water was weighed into a glass vial equipped with a stir bar, and potassium bicarbonate in an amount of 5 mmol was added. Then, a solution containing 0.13 μmol of Ru catalyst 1 and 42 to 57 μmol of benzyltriethylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium bromide, or tetrabutylammonium iodide as a phase transfer catalyst was added to 1 mL of toluene. The vial was then placed in an autoclave, which was then sealed and removed from the glove box. The autoclave was heated to 90°C while stirring. Once the desired temperature was reached, the autoclave was pressurized with hydrogen to 4.5 MPa. After stirring the reaction mixture for 18 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The upper layer of the reaction mixture was removed, leaving behind the lower aqueous solution containing potassium formate and unreacted potassium bicarbonate. 100 μL of the lower aqueous solution was taken and dissolved in 500 μL of heavy water. 300 μL of dimethyl sulfoxide was added as an internal standard, and the potassium formate was then quantified. 1 H NMR was performed.

[0190] Examples 44 to 48 are listed in Table 8.

[0191] [Table 8]

[0192] Examples 44 to 48, in which formate salts were produced using the production method according to the first embodiment, exhibited high TON (Turnover Number) and excellent production efficiency of formate salts. It was confirmed that formate salts could be produced efficiently even when the type of phase transfer catalyst was changed.

[0193] Example 49 In a glove box under inert gas, 1 mL of toluene was weighed into a glass vial equipped with a stir bar, 0.12 μmol of ligand A and 0.12 μmol of [RuHCl(PPh3)3(CO)] were added, and the toluene solution was heated to 65°C and stirred for 3 hours. Then, 54 μmol of methyltrioctylammonium chloride, 1 mL of water, and 5 mmol of potassium bicarbonate were added to the toluene solution, and the vial was placed in an autoclave, which was then sealed and removed from the glove box. The autoclave was heated to 90°C while stirring. Once the desired temperature was reached, the autoclave was pressurized with hydrogen to 4 MPa. After stirring the reaction mixture for 18 hours, the reaction mixture was cooled in an ice bath and the pressure was carefully released. The upper layer of the reaction mixture was removed, leaving behind the lower aqueous solution containing potassium formate and unreacted potassium bicarbonate. 100 μL of the lower aqueous solution was taken and dissolved in 500 μL of heavy water. 300 μL of dimethyl sulfoxide was added as an internal standard, and the potassium formate was then quantified. 1 H NMR was performed.

[0194] Example 49 is described in Table 9.

[0195] [Table 9]

[0196] Even when the entire reaction series from the synthesis of the Ru catalyst to the synthesis of formate was carried out in the same glass vial, a high TON (Turnover Number) was observed, confirming excellent formate production efficiency. [Industrial Applicability]

[0197] The present invention can provide a method for producing formate, which is a precursor of formic acid, in high yield and allows the catalyst to be reused; a method for producing formic acid; a catalyst for producing formate; and a ruthenium complex that can be used as a catalyst for converting hydrogen into formate with high efficiency.

[0198] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese patent applications filed on September 3, 2020 (Patent Application No. 2020-148562), February 12, 2021 (Patent Application No. 2021-021223), February 12, 2021 (Patent Application No. 2021-021224), February 12, 2021 (Patent Application No. 2021-021225), May 10, 2021 (Patent Application No. 2021-079887), and May 17, 2021 (Patent Application No. 2021-083416), the contents of which are incorporated herein by reference.

Claims

1. A method for producing a formate by reacting hydrogen with carbon dioxide, a bicarbonate, or a carbonate in the presence of a solvent using a catalyst, comprising: the reaction is a two-phase system in which the solvent is separated into an organic solvent and an aqueous solvent, The catalyst is at least one selected from a ruthenium complex represented by the following general formula (1), a tautomer or stereoisomer thereof, or a salt compound thereof: Furthermore, a method for producing a formate using a phase transfer catalyst. 【Chemistry 1】 (In general formula (1), R ０ represents a hydrogen atom or an alkyl group, Q １ are each independently CH ２ , NH, or O; R １ each independently represents an alkyl group or an aryl group (provided that Q １ When represents NH or O, R １ at least one of which represents an aryl group; Each A is independently CH, CR ５ , or N, R ５ represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group; X represents a halogen atom; n represents 0 to 3; When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

2. The method for producing a formate salt according to claim 1, wherein the ruthenium complex represented by the general formula (1) is a ruthenium complex represented by the following general formula (3): 【Chemistry 2】 (In general formula (3), R ０ represents a hydrogen atom or an alkyl group, Q ２ each independently represents NH or O; R ３ each independently represents an aryl group; Each A is independently CH, CR ５ , or N, R ５ represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group; X represents a halogen atom; n represents 0 to 3; When a plurality of L's are present, each L independently represents a neutral or anionic ligand.

3. The R １ The method for producing a formate salt according to claim 1 , wherein represents a phenyl group.

4. The R ３ The method for producing a formate salt according to claim 2 , wherein represents a phenyl group.

5. A represents CH, and Q ２ The method for producing a formate salt according to claim 4, wherein represents NH.

6. The R ０ The method for producing a formate salt according to any one of claims 1 to 5, wherein represents a hydrogen atom or a methyl group.

7. The method for producing a formate salt according to any one of claims 1 to 6, wherein X represents a chlorine atom.

8. The method for producing a formate salt according to any one of claims 1 to 7, wherein n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

9. The method for producing a formate salt according to any one of claims 1 to 8, wherein the organic solvent comprises toluene or dioxane.

10. The method for producing a formate salt according to claim 1, wherein an ammonium salt is used as the phase transfer catalyst.

11. The method for producing a formate salt according to any one of claims 1 to 10, further comprising adding a ligand represented by the following general formula (4): 【Transformation 3】 (In general formula (4), R ０ represents a hydrogen atom or an alkyl group, Q ２ each independently represents NH or O; R ３ each independently represents an aryl group; Each A is independently CH, CR ５ , or N, R ５ represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group.

12. A step of producing a formate by the method for producing a formate according to any one of claims 1 to 11; and a second step of protonating at least a portion of the formate salt to produce formic acid.

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