Method for producing hydride

Abstract

The present invention further improves the selectivity of a hydride to be produced. Provided is a method for producing a hydride that comprises a step for bringing a compound having a double bond and / or a triple bond into contact with a mixed gas containing ammonia gas and hydrogen gas to reduce the compound having a double bond and / or a triple bond into a hydride.

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 to produce a hydride.

Background Art

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

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

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, depending on the method for producing a hydride according to the prior art as described above, it may be difficult to say that the selectivity of the target hydride is sufficient.

Means for Solving the Problems

[0006] The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using ammonia, particularly when hydrogenating a raw material compound, and have thus completed the present invention.

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

[10] . [1] A method for producing a hydride, comprising a step of bringing a compound having a double bond and / or a triple bond into contact with a mixed gas containing ammonia gas and hydrogen gas to reduce the compound having the double bond and / or the triple bond to obtain 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. The method for producing a hydride according to any one of [1] to [9], wherein the ammonia gas is an ammonia gas derived from hydrogen produced using renewable energy and nitrogen.

Advantages of the Invention

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

Embodiments for Carrying Out the Invention

[0009] <Method for Producing Hydride> Hereinafter, the method for producing a hydride according to the present embodiment will be specifically described. The method for producing a hydride according to the present embodiment includes a step of bringing a compound having a double bond and / or a triple bond into contact with a mixed gas containing ammonia gas and hydrogen gas to reduce the compound having a double bond and / or a triple bond to obtain a hydride (hereinafter, may be referred to as a contact and hydrogenation step).

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

[0011] (1) Compound having a double bond and / or a triple bond In the present 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 the present embodiment, examples of the "compound having a double bond" as the starting compound include compounds having one double bond such as ethylene, propylene, butylene, isobutylene, pentene, cyclopentene, hexene, 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" which is a raw material compound include acetylene, propyne and the like.

[0014] In this embodiment, examples of the preferable "compound having a double bond and / or a triple bond" include aromatic compounds. In this embodiment, the "compound having a double bond and / or a triple bond" is preferably an aromatic compound.

[0015] In this embodiment, examples of the "aromatic compound" include an aromatic carbocyclic compound which may have a substituent, and an aromatic heterocyclic compound which may have a substituent, and compounds having a structure in which a plurality of ring structures are fused are also included. Here, the aromatic heterocyclic compound may include a compound in which an aromatic ring is fused to a heterocyclic ring which does not exhibit aromaticity in addition to a compound in which the heterocyclic ring itself exhibits aromaticity.

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

[0017] Specific examples of the compound in which an aromatic ring is fused to a heterocyclic ring which does not exhibit aromaticity among the aromatic heterocyclic compounds include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.

[0018] Specific examples of the "aromatic compound" include, for example, 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, "optionally having a substituent" can include both cases where all hydrogen atoms constituting the compound or group are unsubstituted and cases where some or all of one or more hydrogen atoms are substituted by a substituent.

[0020] In the present 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) Hydride In the present embodiment, specific examples of the "hydride" that can be produced include, for example, 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 the present embodiment, as described above, it is preferable that the "compound having a double bond and / or a triple bond" is nitrobenzene and the "hydride" is aniline.

[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 "selectivity of hydride" is aniline, the "by-product" is a product containing intermediate products other than the hydride, and the target of the "selectivity of by-product" is nitroso benzene.

[0024] (Contact 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 already described is brought into contact with a mixed gas containing ammonia gas and hydrogen gas to reduce the compound having a double bond and / or a triple bond to obtain a hydride.

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

[0026] When bringing a compound having a double bond and / or a triple bond into contact with a mixed gas, the implementation conditions such as temperature conditions and pressure conditions are not particularly limited, and can be any conventionally known suitable conditions corresponding to the target hydride.

[0027] In the production method of the hydride of this embodiment, the implementation conditions are preferably, for example, 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] In the production method of the hydride of this embodiment, specifically, for example, when the target hydride is aniline and the compound having a double bond and / or a triple bond is nitrobenzene, preferably the temperature is 175 to 370°C and the pressure is 0 to 0.5 MPaG, and more preferably the temperature is 190 to 300°C and the pressure is 0 to 0.4 MPaG.

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

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

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

[0032] The contacting and hydrogenating step according to the method for producing a hydride of the present embodiment can be carried out using any conventionally known suitable reactor, specifically, for example, a heat-exchange type flow reactor or a batch reactor. In the contacting and hydrogenating step, the reactor is preferably composed of a pressure-resistant container, and as the material of the reactor, carbon steel or stainless steel is preferably used from the viewpoints of ensuring pressure resistance and corrosion resistance.

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

[0034] (Mixed gas) The preparation of the mixed gas in the method for producing a hydride of the present embodiment can be carried out using any conventionally known suitable apparatus, such as a cylinder or a pipe equipped with a flow rate 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 contacted with the compound having a double bond and / or a triple bond already described may contain additional gas in addition to ammonia gas and hydrogen gas.

[0036] Hereinafter, the gas that the mixed gas can contain in the method for producing a hydride of the present embodiment will be specifically described.

[0037] (1) Ammonia gas In the method for producing a hydride according to 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, still 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 of the target hydride.

[0038] In the method for producing a hydride according to this 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. Further, from the viewpoint of further reducing the environmental impact, it is preferably derived from nitrogen and hydrogen produced using renewable energy, or from nitrogen and hydrogen produced by a decomposition process of decomposing fossil fuel at high temperature, and the carbon dioxide or carbon generated in the decomposition process is recovered and stored while producing the ammonia gas.

[0039] Here, "hydrogen produced using renewable energy" refers to, for example, hydrogen (gas) produced by electrolyzing water (H2O) by an arbitrarily suitable method known in the art, specifically, using electric power obtained by solar power generation, wind power generation, geothermal power generation, or further thermal power generation using biomass fuel.

[0040] Also, "hydrogen produced by a decomposition process of decomposing fossil fuel at high temperature, and the carbon dioxide or carbon generated in the decomposition process is recovered and stored while producing the hydrogen" refers to, for example, hydrogen (gas) produced by using an arbitrarily suitable method known in the art, such as steam reforming or thermal decomposition of liquefied natural gas (LNG) or methane, and the generated carbon dioxide or carbon is recovered by an arbitrarily suitable method known in the art, specifically, for example, a chemical absorption method using an amine or the like, and stored in the ground while producing the hydrogen, or hydrogen (gas) produced by directly thermally decomposing methane to separate and recover (solid) carbon and storing it while producing the hydrogen.

[0041] In producing ammonia gas (ammonia) used in the method for producing a hydride according to the present embodiment, any conventionally known and suitable production method can be used. For example, in the presence of a predetermined catalyst, hydrogen that "has been produced using renewable energy or has been produced by a decomposition process of decomposing fossil fuel at high temperature, and in which carbon dioxide or carbon generated in the decomposition process has been recovered and stored" and nitrogen are directly contacted to produce ammonia gas.

[0042] (2) Hydrogen gas In the method for producing a hydride according to the present 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 according to 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, examples of the "hydrogen gas derived from ammonia" include hydrogen gas produced by any conventionally known and suitable ammonia reforming.

[0045] Specifically, ammonia reforming can be carried out using any conventionally known and suitable catalyst for ammonia reforming containing 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. Since the decomposition reaction of ammonia is an endothermic reaction, it can preferably be carried out using a reactor having any conventionally known and suitable configuration equipped with a heating device.

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

[0047] However, according to the method for producing a hydride of the present embodiment, since ammonia gas is contained in the mixed gas, even when using the "hydrogen gas derived from ammonia" produced by, for example, ammonia reforming as described above, the step of removing ammonia from the hydrogen produced by ammonia reforming is not necessarily carried out, and the inevitably contained ammonia (gas) can be effectively utilized as a component of the mixed gas for producing a hydride.

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

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

[0050] In the present 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 viewpoints of further reducing the production cost and further improving the reaction rate of the hydride.

[0051] In the method for producing a hydride according to this embodiment, when bringing the compound having a double bond and / or a triple bond, which has already been described, into contact with the mixed gas, which has also already been described, from the viewpoint of more efficiently producing the target hydride, 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).

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

[0053] As a catalyst that can be suitably applied to the method for producing a hydride according to this embodiment, a conventionally known arbitrary suitable catalyst corresponding 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 mode.

[0054] Examples of the catalyst that can be suitably applied to the method for producing a hydride according to 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. As such a catalyst, an arbitrary suitable catalyst that is commercially available can be selected and used.

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

[0056] In the method for producing a hydride according to this embodiment, in addition to the above "contacting and hydrogenating step", for example, a conventionally known arbitrary suitable purification step for increasing the purity of the target hydride may be carried out.

Examples

[0057] Hereinafter, examples according to the present invention will be shown. The present invention is not limited to the following examples at all.

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

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

[0060] Next, a raw material gas generated by supplying nitrobenzene (in liquid form) as a raw material at 0.06 mL / min to a mixed gas in which hydrogen gas was 60 mL / min, nitrogen gas containing 0.2 volume% of ammonia gas was 100 mL / min, and nitrogen gas was 220 mL / min and the gases were merged, was passed through the reaction tube at normal pressure and brought into contact with a reaction temperature of 210°C in the reaction bed to produce aniline. The composition of the raw material gas is also shown in Table 1 below.

[0061] Subsequently, the reaction gas led out from the reaction tube after being brought into contact with the reaction bed was cooled and liquefied, and then 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 - based) of the products (aniline and the by - product nitrosobenzene). The results (conversion rate, selectivity of aniline (aniline selectivity), selectivity of 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 velocities) of ammonia gas and nitrogen gas were 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 other conditions were the same as those 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 velocities) of ammonia gas and nitrogen gas were the same as those shown in Table 1 below.

[0065]

Table 1

[0066] As is clear from Table 1 above, according to Examples 1 to 3 using a raw material gas containing ammonia, the selectivity of aniline, which is the target hydride (aniline selectivity), can be effectively improved as compared with Comparative Example 1 not using ammonia, and the selectivity of nitroso benzene, which is a by-product (nitroso benzene selectivity), can be significantly reduced. Also, as shown in Table 1 above, in Comparative Example 2 where the concentration of ammonia gas in the mixed gas exceeded a predetermined range, as a result, the reaction temperature in the reaction bed decreased to the reactor temperature, and thus the reaction could not proceed to produce aniline.

Claims

The manufacturing method of a hydride, comprising the step of reducing nitrobenzene to aniline by bringing nitrobenzene into contact with a mixed gas containing ammonia gas and hydrogen gas.

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

3. The manufacturing method of the hydride according to Claim 2, wherein the concentration of ammonia gas in the mixed gas is 0.05 - 2.5% by volume.

4. The manufacturing method of the hydride according to Claim 1 or 2, wherein the mixed gas further contains nitrogen gas.

5. The manufacturing method of the hydride according to Claim 1 or 2, wherein the hydrogen gas is hydrogen gas derived from ammonia.

6. The manufacturing method of the hydride according to Claim 1 or 2, wherein the ammonia gas is ammonia gas derived from hydrogen produced using renewable energy and nitrogen.

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