Electrolytic reaction device

Abstract

To make effective use of ammonia and produce a nitrogen-containing compound at room temperature.SOLUTION: A target substance is dissolved in liquid ammonia to prepare a solvent 1. The solvent 1, in which the target substance is dissolved, is electrolyzed by electrolysis means to provide a nitrogen-containing compound.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an electrolytic reaction device that produces a nitrogen-containing compound by electrolyzing an object using ammonia as a solvent. [Background technology]

[0002] Nitrogen-containing compounds (organic compounds with amino groups, cyano groups, etc.) are the main raw materials for the synthesis of pharmaceuticals, resins, etc., and are essential compounds as intermediates in the synthesis of organic compounds.

[0003] Nitrogen-containing compounds, such as nitrile compounds, are synthesized using copper cyanide or sodium cyanide as a nitrogen source or by a catalytic reaction using ammonia (see Patent Documents 1 and 2). By applying chemical cyanation or electrolytic cyanation techniques such as those described in Patent Document 1, aromatic nitrile compounds can be produced efficiently.

[0004] However, chemical and electrolytic cyanation techniques require highly toxic substances (CuCN, NaCN) as nitrogen sources to obtain nitrogen compounds, and the technology for synthesizing nitrile compounds using ammonia requires high temperatures, high pressures, and expensive catalysts to obtain nitrile compounds.

[0005] Furthermore, in the amination reaction to synthesize compounds having amino groups, it is difficult to directly introduce amino groups into organic compounds, and the synthesis process requires high temperatures, high pressures, and expensive catalysts. In addition, the process involves many intermediates, making the synthesis process complicated. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2021-070667 [Patent Document 2] Patent Publication No. 2021-138644 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and aims to provide an electrolytic reaction apparatus (electrolytic reaction apparatus using liquid ammonia) that can directly obtain nitrogen-containing compounds by effectively utilizing ammonia without using highly toxic substances (CuCN, NaCN) as a nitrogen source. [Means for solving the problem]

[0008] To achieve the above object, the electrolytic reaction device of the present invention according to claim 1 is characterized by comprising an electrolytic solution in which an object is dissolved in a solvent mainly containing ammonia, and electrolysis means for obtaining a nitrogen-containing compound from the object by electrolyzing the electrolytic solution.

[0009] In the present invention according to claim 1, a target substance (e.g., an organic substance) is electrolyzed in a solvent (liquid ammonia) containing ammonia as a main component, thereby obtaining nitrogen-containing compounds from the target substance using ammonia as a nitrogen source. In other words, nitrogen-containing compounds such as amines, imines, nitriles, amides, and imides can be obtained directly at room temperature by effectively using ammonia and without using highly toxic substances (CuCN, NaCN) as a nitrogen source.

[0010] Note that liquid ammonia as a solvent containing ammonia as the main component does not only mean 100% pure ammonia, but also includes ammonia containing impurities, etc. Furthermore, hydrogen (H2) obtained on the reduction side of the electrolytic reactor can be used as various fuels (for example, fuel for fuel cells).

[0011] The electrolytic reaction apparatus of the present invention according to claim 2 is the electrolytic reaction apparatus according to claim 1, characterized in that the target substance is an organic substance and the solvent is liquid ammonia.

[0012] In the present invention according to claim 2, a nitrogen-containing compound can be obtained from an organic substance by electrolyzing the organic substance in liquid ammonia (nitrogen source).

[0013] The electrolytic reaction device of the present invention according to claim 3 is characterized in that in the electrolytic reaction device according to claim 2, the organic substance as the target is an aliphatic compound or an aromatic compound having at least one functional group selected from the group consisting of an alkyl group, an aldehyde group, a carboxyl group, an amino group, an imide group, a hydroxyl group, a carbonyl group, an ether group, a nitro group, and a sulfo group.

[0014] In the present invention according to claim 3, an aliphatic compound or an aromatic compound containing at least one functional group selected from the group consisting of an alkyl group, an aldehyde group, a carboxyl group, an amino group, an imide group, a hydroxyl group, a carbonyl group, an ether group, a nitro group, and a sulfo group can be electrolyzed in liquid ammonia (nitrogen source).

[0015] The electrolytic reaction device of the present invention according to claim 4 is characterized in that in the electrolytic reaction device according to claim 2, the organic matter as the target contains at least one of sugars (glucose, xylose, mannan, glucan, xylan, etc.), proteins (plant, animal, microbial, etc.), lipids (triglycerides, free fatty acids, wax, steroids, etc.), lignin (phenylpropanoids and polyphenols, which are components that constitute lignin), extracted components (phenolic compounds, terpenoids, alkaloids, etc.), other inorganic substances (potassium, magnesium, etc.), and vitamins.

[0016] In the present invention according to claim 4, organic substances containing any one of the following can be electrolyzed in liquid ammonia (nitrogen source): sugars (glucose, xylose, mannan, glucan, xylan, etc.), proteins (plant, animal, microbial, etc.), lipids (triglycerides, free fatty acids, wax, steroids, etc.), lignin (phenylpropanoids and polyphenols, which are components that make up lignin), extractive components (phenolic compounds, terpenoids, alkaloids, etc.), other inorganic substances (potassium, magnesium, etc.), and vitamins.

[0017] The electrolytic reaction device of the present invention according to claim 5 is the electrolytic reaction device according to claim 3, characterized in that the organic substance as the target is an organic substance containing at least one of m-methylanisole, m-anisaldehyde, propylbenzene, hexanal, benzoic acid, and p-coumaric acid.

[0018] In the present invention according to claim 5, a nitrogen-containing compound can be obtained by electrolyzing an organic substance containing at least one of m-methylanisole, m-anisaldehyde, propylbenzene, hexanal, benzoic acid, and p-coumaric acid in liquid ammonia (nitrogen source).

[0019] The electrolytic reaction device of the present invention according to claim 6 is characterized in that in the electrolytic reaction device according to claim 3 or claim 4, the nitrogen-containing compound contains at least one of amine, imine, nitrile, amide, and imide.

[0020] According to the sixth aspect of the present invention, a nitrogen-containing compound containing at least one of amine, imine, nitrile, amide, and imide can be obtained.

[0021] The electrolytic reaction device of the present invention according to claim 7 is characterized in that in the electrolytic reaction device according to any one of claims 2 to 5 (claim 6), the electrolytic solution is a solvent from which the insoluble components have been separated (a solvent from which the insoluble components have been separated and from which the soluble components have been dissolved) in a separation means that separates a dissolved material containing organic matter into a dissolved component that dissolves in the liquid and an insoluble component using a solvent containing ammonia as a main component.

[0022] In the present invention according to claim 7, liquid ammonia in which the dissolving components of the material to be dissolved, including organic substances, are dissolved as the target can be used as the electrolyte. After the target is electrolyzed to obtain a nitrogen-containing compound, the ammonia is vaporized to obtain the nitrogen-containing compound (product) with the solvent removed. The vaporized ammonia can be used as fuel for combustion means.

[0023] The electrolytic reaction apparatus of the present invention according to claim 8 is characterized in that in the electrolytic reaction apparatus according to claim 7, the material to be dissolved that is separated into a dissolved component and an undissolved component by the separation means is biomass.

[0024] In the present invention according to claim 8, liquid ammonia in which the dissolved components of biomass containing organic matter, from which undissolved components have been separated by the biomass separation means, are dissolved as the target substance, can be used as the electrolyte. After the nitrogen-containing compound is obtained, the ammonia is vaporized and the obtained ammonia can be liquefied and used for separation by the biomass separation means. [Effects of the Invention]

[0025] The electrolytic reactor of the present invention (electrolytic reactor using ammonia) effectively utilizes ammonia without using highly toxic substances (CuCN, NaCN) as a nitrogen source, and can directly produce nitrogen-containing compounds (nitrogen-containing compounds such as amines, imines, nitriles, amides, and imides) at room temperature. [Brief explanation of the drawings]

[0026] [Figure 1] 1 is a conceptual diagram of an electrolytic reaction device of the present invention. [Figure 2] 1 is an overall configuration diagram of an electrolysis device according to an embodiment of the present invention. [Figure 3] FIG. 1 is a conceptual diagram illustrating a first embodiment of electrolysis. [Figure 4] FIG. 10 is a conceptual diagram illustrating a second embodiment of electrolysis. [Figure 5] FIG. 10 is a conceptual diagram illustrating a third embodiment of electrolysis. [Figure 6] FIG. 10 is a conceptual diagram illustrating a fourth embodiment of electrolysis. [Figure 7] FIG. 10 is a conceptual diagram illustrating a fifth embodiment of electrolysis. [Figure 8] FIG. 10 is a conceptual diagram illustrating a sixth embodiment of electrolysis. DETAILED DESCRIPTION OF THE INVENTION

[0027] The concept of the electrolytic reaction apparatus of the present invention will be explained based on Fig. 1. Fig. 1 shows a conceptual diagram of the outline of the electrolytic reaction apparatus of the present invention.

[0028] The electrolytic reactor of the present invention has an electrolyte 1 in which organic matter (dissolved components: ◯) as the target substance is dissolved in liquid ammonia (nitrogen source), which is a solvent mainly composed of ammonia, and nitrogen-containing compounds (△) are produced from the organic matter by electrolyzing the electrolyte 1. The solvent mainly composed of ammonia does not only mean 100% pure liquid ammonia, but also includes those containing impurities.

[0029] After electrolyzing organic matter to obtain nitrogen-containing compounds, the ammonia is vaporized to obtain nitrogen-containing compounds (products) with the solvent (ammonia) removed. The vaporized ammonia can be liquefied and reused for biomass separation or used as fuel for combustion.

[0030] Nitrogen-containing compounds can be obtained from organic matter by electrolyzing it in liquid ammonia (a nitrogen source).

[0031] An embodiment of the electrolytic reaction apparatus of the present invention will be described with reference to Fig. 2. Fig. 2 shows the overall configuration of an electrolytic reaction apparatus according to one embodiment of the present invention.

[0032] The electrolytic reactor 4 is configured to obtain an electrolytic solution 9 in which a target substance is dissolved in a solvent mainly composed of ammonia from a pretreatment means 5, which serves as a separation means. The pretreatment means 5 supplies liquid ammonia as a solvent to a material 6 to be dissolved (for example, coal or biomass), thereby obtaining dissolved components 7 (target organic substances: indicated by circles) that dissolve in the liquid.

[0033] As the pretreatment means, a biomass separation means can be used, which supplies liquid ammonia as a solvent to biomass, which is the material to be dissolved, and obtains dissolved components (target organic matter) that dissolve in the liquid and undissolved components. The liquid ammonia with the dissolved components (organic matter) dissolved therein serves as the electrolyte 9 of the electrolytic reactor 4.

[0034] The electrolytic reactor 4 has an anode 11, where an oxidation reaction occurs when electrons are removed, and a cathode 12, where a reduction reaction occurs when electrons are given. The anode 11 and the cathode 12 are connected to a power source 13, which operates the electrolytic reactor 4. When the electrolytic reactor 4 is operated, the dissolved components 7 (organic substances) are electrolyzed in the liquid ammonia (nitrogen source), and nitrogen-containing compounds 14 (indicated by triangles) are produced.

[0035] Hydrogen (H2) is generated on the cathode 12 side, and the obtained hydrogen (H2) can be used as various fuels (for example, fuel for fuel cells).

[0036] After the nitrogen-containing compound 14 (indicated by a triangle mark) is produced, the ammonia is vaporized, and the solvent (ammonia) of the electrolytic solution 9 is removed to obtain the nitrogen-containing compound 14. The vaporized ammonia may be used as a fuel for the combustion means, or may be liquefied and reused as a solvent for the pretreatment means 5.

[0037] By electrolyzing dissolved components 7 (organic matter) in liquid ammonia (nitrogen source), nitrogen-containing compounds 14 can be obtained from the dissolved components 7 (organic matter). In other words, nitrogen-containing compounds such as amines, imines, nitriles, amides, and imides can be obtained directly at room temperature by effectively using ammonia and without using highly toxic substances (CuCN, NaCN) as nitrogen sources.

[0038] The soluble component 7 (organic substance) is obtained by dissolving the soluble component 7 in the liquid ammonia solvent in the pretreatment means 5. For example, an aliphatic compound or an aromatic compound having at least one functional group selected from the group consisting of an alkyl group, an aldehyde group, a carboxyl group, an amino group, an imide group, a hydroxyl group, a carbonyl group, an ether group, a nitro group, and a sulfo group is used as the soluble component 7 (organic substance).

[0039] This allows a nitrogen-containing compound 14 to be obtained by electrolyzing dissolved components 7 (organic matter) of an aliphatic or aromatic compound having at least one functional group selected from the group consisting of an alkyl group, an aldehyde group, a carboxyl group, an amino group, an imide group, a hydroxyl group, a carbonyl group, an ether group, a nitro group, and a sulfo group in liquid ammonia (nitrogen source).

[0040] The dissolved components 7 (organic matter) can include at least one of the following: sugars (glucose, xylose, mannan, glucan, xylan, etc.), proteins (plant, animal, microbial, etc.), lipids (triglycerides, free fatty acids, wax, steroids, etc.), lignin (phenylpropanoids, polyphenols, etc., which are components that make up lignin), extractive components (phenolic compounds, terpenoids, alkaloids, etc.), other inorganic substances (potassium, magnesium, etc.), and vitamins.

[0041] More specifically, the dissolved component 7 (organic substance) is an organic substance containing at least one of m-methylanisole, m-anisaldehyde, propylbenzene, hexanal, benzoic acid, and p-coumaric acid.

[0042] As a result, nitrogen-containing compound 14 can be obtained by electrolyzing an organic substance containing at least one of m-methylanisole, m-anisaldehyde, propylbenzene, hexanal, benzoic acid, and p-coumaric acid in liquid ammonia (nitrogen source).

[0043] The nitrogen-containing compound 14 obtained contains at least one of amine, imine, nitrile, amide, and imide.

[0044] Specific examples of the dissolved component 7 (organic substance) and the nitrogen-containing compound 14 will be described with reference to FIGS.

[0045] 3 to 8 show specific examples of dissolved components 7 (organic substances: see FIG. 2) that are the subject of electrolysis, and nitrogen-containing compounds 14 (see FIG. 2) that are produced by electrolysis.

[0046] <First Example> As shown in Figure 3(a), m-methylanisole, an aromatic alkyl group, is used as the dissolved component 7 (organic substance: see Figure 2). When m-methylanisole is electrolyzed in liquid ammonia (nitrogen source), the methyl group is converted to a cyano group, as shown in Figure 3(b). This produces m-methoxybenzonitrile with a cyano group (-CN) as the nitrogen-containing compound 14 (see Figure 2).

[0047] <Second Example> As shown in Figure 4(a), the aromatic alkyl propylbenzene is used as the dissolved component 7 (organic substance: see Figure 2). When propylbenzene is electrolyzed in liquid ammonia (nitrogen source), an amino group is added to the propyl group as shown in Figure 4(b), and the propyl group is converted to a cyano group as shown in Figure 4(c). This simultaneously produces 1-phenylpropan-1-amine and benzonitrile as nitrogen-containing compounds 14 (see Figure 2).

[0048] <Third Example> As shown in Figure 5(a), m-anisaldehyde, an aromatic aldehyde, is used as the dissolved component 7 (organic substance: see Figure 2). When anisaldehyde is electrolyzed in liquid ammonia (nitrogen source), the aldehyde group is converted to a cyano group as shown in Figure 5(b), an amino group as shown in Figure 5(c), and an amide group as shown in Figure 5(d). This simultaneously produces m-methoxybenzonitrile, m-methoxyaniline, and m-methoxybenzamide as nitrogen-containing compounds 14 (see Figure 2).

[0049] <Fourth Example> As shown in Figure 6(a), hexanal, an aliphatic aldehyde without an aromatic ring, is used as the dissolved component 7 (organic substance: see Figure 2). When hexanal is electrolyzed in liquid ammonia (nitrogen source), the aldehyde group is converted to an amide group as shown in Figure 6(b), and then to a cyano group as shown in Figure 6(c). This results in the production of hexanamide and hexanenitrile as nitrogen-containing compounds 14 (see Figure 2).

[0050] <Fifth Example> As shown in Figure 7(a), benzoic acid, an aromatic carboxylic acid, is used as the dissolved component 7 (organic substance: see Figure 2). When benzoic acid is electrolyzed in liquid ammonia (nitrogen source), the carboxyl group is converted to an amide group as shown in Figure 7(b), the carboxyl group is converted to a cyano group as shown in Figure 7(c), and the carboxyl group is converted to an amino group as shown in Figure 7(d). As a result, benzamide, benzonitrile, and aniline are produced as nitrogen-containing compounds 14 (see Figure 2).

[0051] <Sixth Example> As shown in Figure 8(a), p-coumaric acid, an organic compound found in large amounts in biomass, is used as dissolved component 7 (organic matter: see Figure 2). When p-coumaric acid is electrolyzed in liquid ammonia (nitrogen source), p-hydroxybenzonitrile and 2-(4-hydroxyphenyl)acetonitrile are produced as nitrogen-containing compounds 14 (see Figure 2), as shown in Figures 8(b) and 8(c).

[0052] In the electrolytic reaction device 4 having the above configuration, for example, dissolved components 7 (organic substances) containing aliphatic or aromatic compounds having at least one functional group selected from the group consisting of alkyl, aldehyde, carboxyl, amino, imide, hydroxyl, carbonyl, ether, nitro, and sulfo groups can be electrolyzed in liquid ammonia (nitrogen source) at room temperature to obtain nitrogen-containing compounds 14, such as nitriles, amines, imines, amides, and imides.

[0053] Therefore, nitrogen-containing compounds such as amines, imines, nitriles, amides, and imides can be obtained at room temperature by effectively utilizing ammonia and without using highly toxic substances (CuCN, NaCN) as nitrogen sources. [Industrial Applicability]

[0054] The present invention can be used in the industrial field of electrolytic reaction devices that produce nitrogen-containing compounds by electrolyzing an object using ammonia as a solvent. [Explanation of symbols]

[0055] 1, 9 Electrolyte 4. Electrolytic reactor 5 Pretreatment methods 6 Parts to be melted 7 Dissolved components (organic substances) 11 Anode 12 Cathode 13 Power supply 14 Nitrogen-containing compounds

Claims

1. an electrolyte in which an object is dissolved in a solvent mainly composed of ammonia; and an electrolysis means for obtaining a nitrogen-containing compound from the target by electrolyzing the electrolytic solution. An electrolytic reaction device characterized by:

2. 2. The electrolytic reactor according to claim 1, the target object is an organic matter, The solvent is liquid ammonia An electrolytic reaction device characterized by:

3. 3. The electrolytic reactor according to claim 2, The organic matter as the target is It is an aliphatic or aromatic compound having at least one functional group selected from the group consisting of an alkyl group, an aldehyde group, a carboxyl group, an amino group, an imide group, a hydroxyl group, a carbonyl group, an ether group, a nitro group, and a sulfo group. An electrolytic reaction device characterized by:

4. 3. The electrolytic reactor according to claim 2, The organic matter as the target is Contains at least one of the following: sugars, proteins, lipids, lignin, extractives, minerals, or vitamins An electrolytic reaction device characterized by:

5. 4. The electrolytic reactor according to claim 3, The organic matter as the target is It is an organic substance containing at least one of m-methylanisole, m-anisaldehyde, propylbenzene, hexanal, benzoic acid, and p-coumaric acid. An electrolytic reaction device characterized by:

6. The electrolytic reactor according to claim 3 or claim 4, The nitrogen-containing compound is Contains at least one of amine, imine, nitrile, amide, and imide An electrolytic reaction device characterized by:

7. The electrolytic reactor according to any one of claims 2 to 5, The electrolyte solution is A solvent containing ammonia as a main component is used in a separation means for separating a material to be dissolved containing organic matter into a soluble component that dissolves in a liquid and an insoluble component, and the solvent from which the insoluble component is separated is used. An electrolytic reaction device characterized by:

8. 8. The electrolytic reactor according to claim 7, The material to be dissolved that is separated into a dissolved component and an insoluble component by the separation means is biomass. An electrolytic reaction device characterized by:

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