Method for producing hydride

Abstract

To further improve selectivity of a hydride to be produced.SOLUTION: A method for producing a hydride includes a step of making a compound having a double bond and / or a triple bond contact with a mixed gas containing an ammonia gas and a hydrogen gas and reducing the compound having a double bond and / or a triple bond to obtain a hydride.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a hydride, and more specifically to a method for producing a hydride by reducing a compound having a double bond and / or a triple bond with hydrogen. [Background technology]

[0002] For example, a production method is known in which nitrobenzene, a raw material compound having a double bond, is reduced and hydrogenated with hydrogen to produce aniline, a hydride (see Patent Document 1). Conventionally, fossil fuels such as butane have been used as the hydrogen source in such aniline production methods.

[0003] In recent years, various attempts have been made to reduce dependence on fossil fuels, which may cause the generation of greenhouse gases that accelerate global warming. For example, a method for producing a hydride is known in which ammonia is used as a hydrogen source instead of a hydrogen source derived from a fossil fuel in the hydrogenation described in Patent Document 1 (see Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 49-231 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-181197 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in some cases, the selectivity of the target hydride is not sufficient according to the above-mentioned prior art methods for producing hydrides. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above problems, and have found that the above problems can be solved by using ammonia in particular when hydrogenating a raw material compound, thereby completing the present invention.

[0007] That is, the present invention provides the following [1] to

[10] . [1] A method for producing a hydride, comprising the step of contacting a compound having a double bond and / or a triple bond with a mixed gas containing ammonia gas and hydrogen gas to reduce the compound having a double bond and / or a triple bond to form a hydride. [2] The method for producing a hydride according to [1], wherein the concentration of ammonia gas in the mixed gas is at least 0.01% by volume. [3] The method for producing a hydride according to [2], wherein the concentration of ammonia gas in the mixed gas is 0.05 to 2.5% by volume. [4] The method for producing a hydride according to any one of [1] to [3], wherein the mixed gas further contains nitrogen gas. [5] The method for producing a hydride according to any one of [1] to [4], wherein the compound having a double bond and / or a triple bond is an aromatic compound. [6] The method for producing a hydride according to any one of [1] to [5], wherein the compound having a double bond and / or a triple bond is at least one selected from the group consisting of phenol, benzene, and nitrobenzene. [7] The method for producing a hydride according to any one of [1] to [6], wherein the hydride is at least one selected from the group consisting of cyclohexanone, cyclohexanol, cyclohexane, cyclohexene, and aniline. [8] The method for producing a hydride according to any one of [1] to [7], wherein the compound having a double bond and / or a triple bond is nitrobenzene, and the hydride is aniline. [9] The method for producing a hydride according to any one of [1] to [8], wherein the hydrogen gas is hydrogen gas derived from ammonia.

[10] The method for producing a hydride according to any one of [1] to [9], wherein the ammonia gas is derived from hydrogen produced using renewable energy and nitrogen. [Effects of the Invention]

[0008] According to the present invention, the selectivity of the hydride to be produced can be further improved, and the target hydride can be produced more efficiently. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Method for producing hydrides> The method for producing a hydride according to this embodiment will be specifically described below. The method for producing a hydride of the present embodiment includes a step of contacting a compound having a double bond and / or a triple bond with a mixed gas containing ammonia gas and hydrogen gas to reduce the compound having a double bond and / or a triple bond to form a hydride (hereinafter, this may be referred to as a contacting and hydrogenating step).

[0010] First, the "compound having a double bond and / or a triple bond" and the "mixed gas" that are applied to the method for producing a hydride according to this embodiment will be described.

[0011] (1) Compounds having double and / or triple bonds In this embodiment, the "compound having a double bond and / or a triple bond" is not particularly limited as long as it is a compound having a structure containing a double bond and / or a triple bond.

[0012] In this embodiment, examples of the "compound having a double bond" that is a raw material compound include compounds having one double bond such as ethylene, propylene, butylene, isobutylene, pentene, cyclopentene, hexene, and cyclohexene, and compounds having two or more double bonds such as pentadiene, hexadiene, heptadiene, benzene, nitrobenzene, and phenol.

[0013] In this embodiment, examples of the "compound having a triple bond" that is a raw material compound include acetylene and propyne.

[0014] In this embodiment, a suitable "compound having a double bond and / or a triple bond" is, for example, an aromatic compound. In this embodiment, the "compound having a double bond and / or a triple bond" is preferably an aromatic compound.

[0015] In this embodiment, the "aromatic compound" includes an aromatic carbocyclic compound which may have a substituent and an aromatic heterocyclic compound which may have a substituent, and also includes a compound having a structure in which multiple ring structures are fused. Here, the aromatic heterocyclic compound may include not only a compound in which the heterocycle itself exhibits aromaticity, but also a compound in which an aromatic ring is fused to a heterocycle which does not exhibit aromaticity.

[0016] Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself exhibits aromaticity include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.

[0017] Specific examples of aromatic heterocyclic compounds in which an aromatic ring is condensed with a heterocycle that does not exhibit aromaticity include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0018] Specific examples of the "aromatic compound" include phenol, benzene, and nitrobenzene. The "aromatic compound" is preferably at least one selected from the group consisting of benzene and nitrobenzene, and more preferably nitrobenzene.

[0019] Here, the phrase "optionally having a substituent" can include both cases where all hydrogen atoms constituting the compound or group are unsubstituted, and cases where one or more hydrogen atoms are partially or entirely substituted with a substituent.

[0020] In this embodiment, examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a monovalent heterocyclic group, a substituted amino group, an acyl group, an imine residue, an amide group, an acid imide group, a substituted oxycarbonyl group, an alkenyl group, an alkynyl group, a cyano group, and a nitro group.

[0021] (2) Hydrides In the present embodiment, specific examples of the "hydride" that can be produced include cyclohexanone, cyclohexanol, cyclohexane, cyclohexene, and aniline. The "hydride" is preferably at least one selected from the group consisting of cyclohexane, cyclohexene, and aniline, and more preferably aniline.

[0022] In the method for producing a hydride according to this embodiment, it is preferable that the "compound having a double bond and / or a triple bond" is nitrobenzene and the "hydride" is aniline, as described above.

[0023] Here, for example, when the "compound having a double bond and / or a triple bond" is nitrobenzene and the "hydride" that is the target of the "hydride selectivity" is aniline, the "by-product" is a product that includes intermediate products other than the hydride, and the target of the "by-product selectivity" is nitrosobenzene.

[0024] (Contacting and Hydrogenation Step) In the method for producing a hydride of the present embodiment, as described above, the compound having a double bond and / or a triple bond described above is brought into contact with a mixed gas containing ammonia gas and hydrogen gas, and the compound having a double bond and / or a triple bond is reduced to form a hydride.

[0025] When the compound having a double bond and / or a triple bond is brought into contact with the mixed gas, the state of the compound having a double bond and / or a triple bond is not particularly limited, and specifically, it may be in a gaseous (gas phase) state or a liquid (liquid phase) state.

[0026] When the compound having a double bond and / or triple bond is brought into contact with the mixed gas, the conditions for the contact, such as the temperature conditions and the pressure conditions, are not particularly limited, and any suitable conditions known in the art that correspond to the target hydride can be used.

[0027] The conditions for carrying out the method for producing a hydride according to this embodiment are, for example, preferably a temperature of 50 to 400°C and a pressure of 0 to 30 MPaG, and more preferably a temperature of 100 to 300°C and a pressure of 0 to 7 MPaG.

[0028] Specifically, for example, when the target hydride is aniline and the compound having a double bond and / or triple bond is nitrobenzene, the conditions for carrying out the method for producing a hydride of the present embodiment are preferably a temperature of 175 to 370°C and a pressure of 0 to 0.5 MPaG, and more preferably a temperature of 190 to 300°C and a pressure of 0 to 0.4 MPaG.

[0029] When the target hydrogenated product is cyclohexane and the compound having a double bond and / or triple bond is benzene, specifically, the temperature is preferably 50 to 350°C and the pressure is preferably 1 to 20 MPaG, and more preferably the temperature is 100 to 250°C and the pressure is preferably 2 to 7 MPaG.

[0030] When the target hydrogenated product is cyclohexene and the compound having a double bond and / or triple bond is benzene, specifically, the temperature is preferably 50 to 250°C and the pressure is preferably 1 to 20 MPaG, and more preferably the temperature is 100 to 200°C and the pressure is preferably 2 to 7 MPaG.

[0031] When the target hydrogenated product is cyclohexanone or cyclohexanol and the compound having a double bond and / or triple bond is phenol, specifically, the temperature is preferably 100 to 220°C and the pressure is 0 to 1 MPaG, and more preferably the temperature is 140 to 160°C and the pressure is 0 to 0.3 MPaG.

[0032] The contacting and hydrogenating steps in the hydrogenation production method of the present embodiment can be carried out using any suitable conventionally known reactor, specifically, for example, a heat exchange type flow reactor or a batch reactor. In the contacting and hydrogenating steps, the reactor is preferably constructed of a pressure-resistant vessel, and carbon steel or stainless steel is preferably used as the reactor material from the viewpoint of ensuring pressure resistance and corrosion resistance.

[0033] Hereinafter, a mixed gas that can be used in the method for producing a hydride according to this embodiment will be specifically described.

[0034] (mixed gas) The mixed gas in the method for producing a hydride according to the present embodiment can be prepared using any suitable conventionally known device, such as a cylinder or a pipe equipped with a flow control valve.

[0035] In the method for producing a hydride of the present embodiment, the mixed gas containing ammonia gas and hydrogen gas that is brought into contact with the compound having a double bond and / or a triple bond described above may contain an additional gas in addition to ammonia gas and hydrogen gas.

[0036] Hereinafter, gases that may be contained in the mixed gas in the method for producing a hydride according to this embodiment will be specifically described.

[0037] (1) Ammonia gas In the method for producing a hydride of this embodiment, the concentration of ammonia gas in the mixed gas is preferably at least 0.01% by volume, more preferably 0.01 to 10% by volume, even more preferably 0.02 to 7.5% by volume, particularly preferably 0.03 to 5.0% by volume, and even more preferably 0.05 to 2.5% by volume, from the viewpoint of further improving the selectivity for the target hydride.

[0038] In the method for producing a hydride according to the present embodiment, the origin of the ammonia gas contained in the mixed gas is not particularly limited. The ammonia gas contained in the mixed gas may be, for example, ammonia gas (ammonia) derived from biomass, and from the viewpoint of further reducing the environmental load, it is preferable that the ammonia gas be derived from nitrogen and hydrogen produced using renewable energy, or from nitrogen and hydrogen produced by a decomposition process of decomposing fossil fuels at high heat, wherein the hydrogen is produced while recovering and storing carbon dioxide or carbon generated in the decomposition process.

[0039] Here, "hydrogen produced using renewable energy" refers to hydrogen (gas) produced by any suitable conventional method known in the art, specifically, for example, by electrolyzing water (HO), using electricity obtained from solar power generation, wind power generation, geothermal power generation, or even thermal power generation using biomass fuel.

[0040] Furthermore, "hydrogen produced by a decomposition process in which fossil fuels are decomposed at high heat, and which is produced while recovering and storing the carbon dioxide or carbon generated in the decomposition process" refers to hydrogen (gas) produced by using any suitable conventionally known method, such as steam reforming or thermal decomposition of liquefied natural gas (LNG) or methane, recovering the generated carbon dioxide or carbon by any suitable conventionally known method, specifically, for example, a chemical absorption method using an amine, and storing the recovered hydrogen or gas underground; or it refers to hydrogen (gas) produced by directly thermally decomposing methane, separating and recovering the (solid) carbon, and storing the recovered hydrogen or gas.

[0041] Ammonia gas (ammonia) used in the hydride production method of the present embodiment can be produced by any suitable conventionally known production method, for example, by directly contacting nitrogen with "hydrogen produced using renewable energy or produced by a decomposition process in which fossil fuels are decomposed at high heat, and which is produced while recovering and storing carbon dioxide or carbon generated in the decomposition process," in the presence of a predetermined catalyst, as described above.

[0042] (2) Hydrogen gas In the method for producing a hydride of this embodiment, the concentration of hydrogen gas in the mixed gas is preferably 50 to 99.999% by volume, more preferably 75 to 99.99% by volume, and even more preferably 75 to 99.95% by volume, from the viewpoint of further improving the reaction rate of the target hydride.

[0043] In the method for producing a hydride of the present embodiment, the hydrogen gas contained in the mixed gas is preferably hydrogen gas derived from ammonia, from the viewpoint of further reducing the environmental load.

[0044] Here, the "hydrogen gas derived from ammonia" includes, for example, hydrogen gas produced by any suitable conventionally known ammonia reforming method.

[0045] Specifically, ammonia reforming can be carried out using any suitable conventionally known ammonia reforming catalyst containing, for example, at least one metal selected from the group consisting of Fe, Co, Ni, Mo, and Mn, or at least one noble metal selected from the group consisting of Pt, Pd, Ir, Rh, and Ru, and preferably using any suitable conventionally known reactor equipped with a heating device, since the ammonia decomposition reaction is an endothermic reaction.

[0046] Note that hydrogen (gas) produced by ammonia reforming inevitably contains unreacted ammonia. When hydrogen produced by ammonia reforming is applied to, for example, a method for producing a hydride, the unavoidably contained ammonia has been removed by any suitable conventional purification method.

[0047] However, according to the method for producing a hydride of the present embodiment, ammonia gas is contained in the mixed gas. Therefore, even when using "hydrogen gas derived from ammonia" produced by ammonia reforming as described above, the ammonia (gas) that may be unavoidably contained can be effectively used as a component of the mixed gas for producing a hydride, without having to perform a step of removing ammonia from the hydrogen produced by ammonia reforming.

[0048] Therefore, according to the method for producing a hydride of the present embodiment, even when "hydrogen gas derived from ammonia" produced by ammonia reforming is used, there is no need to carry out a step for removing the ammonia that is inevitably contained therein, so that the hydride can be produced more simply, and furthermore, there is no need for capital investment for such a step, so that the production cost of the hydride can be further reduced.

[0049] (3) Nitrogen gas In this embodiment, the mixed gas may further contain nitrogen gas in addition to ammonia gas and hydrogen gas, from the viewpoint of further reducing the production cost of the hydride.

[0050] In this embodiment, the concentration of nitrogen gas in the mixed gas is preferably 0.001 to 50% by volume, more preferably 0.01 to 25% by volume, and even more preferably 0.1 to 1% by volume, from the viewpoint of further reducing production costs and further improving the reaction rate of the hydride.

[0051] In the method for producing a hydride of the present embodiment, when the compound having a double bond and / or a triple bond described above is brought into contact with the mixed gas described above, it is preferable to bring the compound having a double bond and / or a triple bond into contact with the mixed gas in the coexistence of a catalyst (in the presence of a catalyst) from the viewpoint of more efficiently producing a target hydride.

[0052] Here, a catalyst that can be used in the method for producing a hydride according to the present embodiment will be specifically described.

[0053] As a catalyst that can be suitably applied to the method for producing a hydride of the present embodiment, any suitable conventionally known catalyst that corresponds to the target hydride and further to the selected "compound having a double bond and / or a triple bond" can be used in a suitable embodiment.

[0054] Examples of catalysts that can be suitably applied to the hydride production method of this embodiment include cobalt-based catalysts, copper-based catalysts, nickel-based catalysts, sponge nickel-based catalysts, copper-chromium-based catalysts, copper-iron-alumina-based catalysts, copper-silicon-based catalysts (Cu-Si catalysts), platinum-based catalysts, palladium catalysts, and ruthenium-based catalysts. Any suitable catalyst available on the market can be selected and used as such a catalyst.

[0055] In the method for producing a hydride of the present embodiment, when applying a catalyst, any suitable conventionally known carrier such as silica gel or alumina and diluent such as silicon carbide corresponding to the selected catalyst and reactor configuration can be further used as a suitable configuration.

[0056] In the method for producing a hydride according to the present embodiment, in addition to the above-mentioned "contacting and hydrogenating step", any suitable purification step known in the art may be carried out, for example, to increase the purity of the target hydride. [Example]

[0057] Examples of the present invention will be described below, but the present invention is not limited to the following examples.

[0058] Example 1 <Production of aniline> 0.5 g of Cu-Si catalyst (E55W manufactured by JGC Catalysts and Chemicals Co., Ltd.) and 1.5 g of silicon carbide (Shinano Random manufactured by Shinano Electric Refining Co., Ltd.) as a diluent were mixed and filled into a quartz reaction tube with an inner diameter of 10 mm to form a reaction bed.

[0059] The temperature of the reaction bed was set to 175° C., and reduction treatment was carried out for 30 minutes at a flow rate (flow rate) of hydrogen gas of 90 mL / min and nitrogen gas of 86 mL / min.

[0060] Next, a mixed gas of hydrogen gas at 60 mL / min, nitrogen gas containing 0.2 vol% ammonia gas at 100 mL / min, and nitrogen gas at 220 mL / min was joined together to produce a raw material gas, which was then supplied with nitrobenzene (liquid) at 0.06 mL / min. The raw material gas was passed through the reaction tube at atmospheric pressure and brought into contact with the reaction bed at a reaction temperature of 210°C, thereby producing aniline. The composition of the raw material gas is also shown in Table 1 below.

[0061] The reaction gas discharged from the reaction tube after contact with the reaction bed was cooled and liquefied, and recovered as a liquid. The recovered liquid was analyzed by gas chromatography to calculate the conversion rate (mol%) of nitrobenzene and the selectivity (mol%, carbon basis) of the products (aniline and the by-product nitrosobenzene). The results (conversion rate, selectivity to aniline (aniline selectivity), and selectivity to nitrosobenzene (nitrosobenzene selectivity)) are shown in Table 1 below.

[0062] Examples 2 and 3 <Production of aniline> Aniline was produced in the same manner as in Example 1, except that the flow rates (flow rates) of ammonia gas and nitrogen gas were set as shown in Table 1 below. The composition of the raw material gas and the results are shown in Table 1 below.

[0063] (Comparative Example 1) <Production of aniline> Aniline was produced in the same manner as in Example 1, except that ammonia gas was not used and the other conditions were as shown in Table 1 below. The composition of the raw material gas and the results are shown in Table 1 below.

[0064] (Comparative Example 2) <Production of aniline> Aniline was produced in the same manner as in Example 1, except that the flow rates (flow rates) of ammonia gas and nitrogen gas were as shown in Table 1 below.

[0065] [Table 1]

[0066] As is clear from Table 1 above, Examples 1 to 3, which use a raw material gas containing ammonia, were able to effectively improve the selectivity of aniline, the target hydrogenated product (aniline selectivity), and significantly reduce the selectivity of nitrosobenzene, the by-product (nitrosobenzene selectivity), compared to Comparative Example 1, which does not use ammonia. Furthermore, as shown in Table 1 above, in Comparative Example 2, in which the concentration of ammonia gas in the mixed gas exceeded the predetermined range, the reaction temperature in the reaction bed fell to the reactor temperature, and as a result, it was not possible to proceed with the reaction to produce aniline.

Claims

1. A method for producing a hydride, comprising: contacting a compound having a double bond and / or a triple bond with a mixed gas containing ammonia gas and hydrogen gas to reduce the compound having a double bond and / or a triple bond to form a hydride, wherein the hydrogen gas is hydrogen gas derived from ammonia.

2. 2. The method for producing a hydride according to claim 1, wherein the concentration of ammonia gas in the mixed gas is at least 0.01% by volume.

3. 3. The method for producing a hydride according to claim 2, wherein the concentration of ammonia gas in the mixed gas is 0.05 to 2.5% by volume.

4. The method for producing a hydride according to claim 1 or 2, wherein the mixed gas further contains nitrogen gas.

5. The method for producing a hydride according to claim 1 or 2, wherein the compound having a double bond and / or a triple bond is an aromatic compound.

6. 3. The method for producing a hydride according to claim 1 or 2, wherein the compound having a double bond and / or a triple bond is at least one selected from the group consisting of phenol, benzene, and nitrobenzene.

7. 3. The method for producing a hydride according to claim 1, wherein the hydride is at least one selected from the group consisting of cyclohexanone, cyclohexanol, cyclohexane, cyclohexene, and aniline.

8. 3. The method for producing a hydride according to claim 1, wherein the ammonia gas is derived from hydrogen produced using renewable energy and nitrogen.

9. The method for producing a hydride according to claim 1 or 2, wherein the step of producing the hydride is a step of contacting a compound having a double bond and / or a triple bond with a mixed gas containing ammonia gas and hydrogen gas in the coexistence of a catalyst, and the catalyst is at least one selected from the group consisting of a cobalt-based catalyst, a copper-based catalyst, a nickel-based catalyst, a sponge nickel-based catalyst, a copper-chromium-based catalyst, a copper-iron-alumina-based catalyst, a copper-silicon-based catalyst (Cu-Si catalyst), a platinum-based catalyst, and a ruthenium-based catalyst.