Production method for cyclopentanone and purified cyclopentanone

Abstract

A production method for cyclopentanone according to the present invention includes a transfer hydrogenation step for passing a first fluid that contains furfuryl alcohol, water, and hydrogen through a solid-bed flow reactor packed with a hydrogenation catalyst to obtain a reaction product that includes cyclopentanone and water, an extraction step for extracting the cyclopentanone from the reaction product by means of an extraction solvent to obtain an oil phase that contains the cyclopentanone, and a recovery step for recovering the cyclopentanone from the oil phase.

Description

Cyclopentanone manufacturing method and purified cyclopentanone product

[0001] The present disclosure relates to a method for producing cyclopentanone and a purified cyclopentanone product.

[0002] Cyclopentanone is used in a variety of applications, such as as a raw material for producing jasmine-based fragrances, lactone-based fragrances, and as a semiconductor cleaning agent. Conventionally, known methods for producing cyclopentanone include a production method based on a ketonization reaction of adipic acid and a production method based on a dehydrogenation reaction of cyclopentanol. For example, Patent Document 1 describes a method for producing cyclopentanone by a vapor-phase dehydrogenation reaction of cyclopentanol in the presence of a specific catalyst.

[0003] JP 2017-178824 A

[0004] Conventional methods for producing cyclopentanone have a problem in that they use petroleum-derived raw materials.

[0005] An object of the present disclosure is to provide a method for producing cyclopentanone that can efficiently produce cyclopentanone using readily available raw materials from biomass. Another object of the present disclosure is to provide a purified cyclopentanone product.

[0006] The present disclosure relates to, for example, the following [1] to [4]. [1] A method for producing cyclopentanone, comprising: a rearrangement hydrogenation step of contacting a first fluid containing furfuryl alcohol, water, and hydrogen with a hydrogenation catalyst to obtain a reaction product containing cyclopentanone and water; an extraction step of extracting cyclopentanone from the reaction product with an extraction solvent to obtain an oil phase containing cyclopentanone; and a recovery step of recovering cyclopentanone from the oil phase. [2] The production method according to [1], wherein the recovery step comprises: a separation step of removing at least a portion of the extraction solvent from the oil phase; and a purification step of purifying cyclopentanone from the remainder of the separation step. [3] The production method according to [1] or [2], wherein the extraction solvent comprises at least one selected from the group consisting of aromatic hydrocarbons and alicyclic hydrocarbons. [4] A purified cyclopentanone product comprising: cyclopentanone; and at least one trace component selected from the group consisting of furfural, 4-hydroxy-2-cyclopentenone, furfuryl alcohol, 2-cyclopentenone, toluene, ethylbenzene, ethylcyclohexane, and dimethylcyclohexane; wherein the cyclopentanone content is 98% by mass or more; the trace component contents are 0.1% by mass or more and less than 2% by mass; and the proportion of 4-hydroxy-2-cyclopentenone and furfuryl alcohol in the trace components is less than 50% by mass.

[0007] The present disclosure provides a method for producing cyclopentanone that can efficiently produce cyclopentanone using readily available raw materials from biomass. The present disclosure also provides a purified cyclopentanone product obtained by the production method.

[0008] Fig. 1 is a schematic diagram showing an example of a manufacturing apparatus for carrying out the manufacturing method of this embodiment. Fig. 2 is a schematic diagram showing a manufacturing apparatus for Comparative Example 1. Fig. 3 is a schematic diagram showing another example of a manufacturing apparatus for carrying out the manufacturing method of this embodiment.

[0009] Preferred embodiments of the present disclosure will be described in detail below.

[0010] The method for producing cyclopentanone of the present embodiment includes a rearrangement hydrogenation step of contacting a first fluid containing furfuryl alcohol, water, and hydrogen with a hydrogenation catalyst to obtain a reaction product containing cyclopentanone and water; an extraction step of extracting cyclopentanone from the reaction product with an extraction solvent to obtain an oil phase containing cyclopentanone; and a recovery step of recovering cyclopentanone from the oil phase.

[0011] According to the production method of this embodiment, cyclopentanone can be efficiently produced using furfuryl alcohol, which is easily available from biomass, as a raw material.

[0012] Each step of the manufacturing method of this embodiment will be described in detail below.

[0013] (Rearrangement-hydrogenation step) The rearrangement-hydrogenation step is a step of contacting a first fluid containing furfuryl alcohol, water, and hydrogen with a hydrogenation catalyst to obtain a reaction product containing cyclopentanone and water. In the rearrangement-hydrogenation step, cyclopentanone is produced by a rearrangement-hydrogenation reaction (rearrangement reaction and hydrogenation reaction) of furfuryl alcohol.

[0014] Furfuryl alcohol can be obtained, for example, by hydrogenating furfural obtained by hydrolysis of hemicellulose. In the present embodiment, the method for producing furfuryl alcohol is not particularly limited, and may be the above-mentioned method or another method.

[0015] The first fluid may contain an oxygen-containing organic component including furfuryl alcohol, water, and hydrogen.

[0016] The proportion of furfuryl alcohol in the oxygen-containing organic component may be, for example, 50 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, 98 mol% or more, 99 mol% or more, or 99.5 mol% or more, or may be 100 mol%.

[0017] The oxygen-containing organic component is an organic component having an oxygen atom. The oxygen-containing organic component may further contain other components in addition to furfuryl alcohol. Examples of other components include products of hemicellulose hydrolysis (e.g., furfural, formic acid, acetic acid, hydroxymethylfurfural, etc.), by-products of the hydrogenation reaction of furfural (e.g., tetrahydrofurfuryl alcohol, methylfuran, methyltetrahydrofuran, etc.), and intermediate products and by-products of the rearrangement hydrogenation reaction of furfuryl alcohol to cyclopentanone (e.g., 4-hydroxy-2-cyclopentenone, 2-cyclopentenone, cyclopentanol, levulinic acid, butanal, etc.).

[0018] The hydrogen-oil ratio (molar ratio of hydrogen to oxygen-containing organic components) in the first fluid may be, for example, 1 or more, and from the viewpoint of further promoting the hydrogenation reaction, it may be 2 or more, 3 or more, or 4 or more. Moreover, the hydrogen-oil ratio in the first fluid may be, for example, 50 or less, and from the viewpoint of further improving the selectivity in the rearrangement hydrogenation reaction, it may be 40 or less, 30 or less, or 20 or less. That is, the hydrogen-oil ratio in the first fluid may be, for example, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 2 to 50, 2 to 40, 2 to 30, 2 to 20, 3 to 50, 3 to 40, 3 to 30, 3 to 20, 4 to 50, 4 to 40, 4 to 30, or 4 to 20.

[0019] In the first fluid, the mass ratio of water to the oxygen-containing organic component (water / oxygen-containing organic component) may be, for example, 5 or more, and from the viewpoint of further suppressing the polymerization of furfuryl alcohol, it may be 7 or more, 10 or more, or 15 or more. Furthermore, the mass ratio of water to the oxygen-containing organic component (water / oxygen-containing organic component) may be, for example, 100 or less, and from the viewpoint of further improving the recovery efficiency of cyclopentanone, it may be 70 or less, 50 or less, or 40 or less. That is, the mass ratio of water to the oxygen-containing organic component (water / oxygen-containing organic component) may be, for example, 5 to 100, 5 to 70, 5 to 50, 5 to 40, 7 to 100, 7 to 70, 7 to 50, 7 to 40, 10 to 100, 10 to 70, 10 to 50, 10 to 40, 15 to 100, 15 to 70, 15 to 50, or 15 to 40.

[0020] The first fluid may further contain components other than the oxygen-containing organic component, water, and hydrogen. Examples of such components include toluene and benzene. The proportion of the other components in the first fluid may be, for example, 5 vol% or less, 3 vol% or less, 2 vol% or less, 1 vol% or less, or 0.5 vol% or less, or even 0 vol%. That is, the total amount of the oxygen-containing organic component, water, and hydrogen in the first fluid may be, for example, 95 vol% or more, 97 vol% or more, 98 vol% or more, 99 vol% or more, or 99.5 vol% or more, or even 100 vol% based on the total amount of the first fluid.

[0021] The hydrogenation catalyst is not particularly limited as long as it is a catalyst that can convert at least a portion of 4-hydroxy-2-cyclopentenone and 2-cyclopentenone to cyclopentanone. The hydrogenation catalyst may be appropriately selected from solid catalysts used in known hydrogenation reactions.

[0022] The hydrogenation catalyst may be, for example, a catalyst in which an active metal is supported on a carrier.

[0023] The support may be, for example, an inorganic oxide support, such as a support containing an inorganic oxide such as silica, alumina, or titania.

[0024] Examples of the active metal include platinum and palladium.

[0025] The amount of the active metal supported in the hydrogenation catalyst is not particularly limited. The amount of the active metal supported may be, for example, 0.01 mass% or more, 0.02 mass% or more, 0.025 mass% or more, or 0.03 mass% or more, based on the total amount of the hydrogenation catalyst. Furthermore, the amount of the active metal supported may be, for example, 1 mass% or less, 0.5 mass% or less, 0.3 mass% or less, or 0.1 mass% or less, based on the total amount of the hydrogenation catalyst. That is, the amount of the active metal supported may be, for example, 0.01 to 1 mass%, 0.01 to 0.5 mass%, 0.01 to 0.3 mass%, 0.01 to 0.1 mass%, 0.02 to 1 mass%, 0.02 to 0.5 mass%, 0.02 to 0.3 mass%, 0.02 to 0.1 mass%, 0.025 to 1 mass%, 0.025 to 0.5 mass%, 0.025 to 0.3 mass%, 0.025 to 0.1 mass%, 0.03 to 1 mass%, 0.03 to 0.5 mass%, 0.03 to 0.3 mass%, 0.03 to 0.1 mass%, 0.1 to 1 mass%, 0.1 to 0.5 mass%, 0.1 to 0.3 mass%, or 0.1 to 0.1 mass%, based on the total amount of the hydrogenation catalyst.

[0026] The reactor used in the transfer hydrogenation step is not particularly limited as long as it can be filled with a hydrogenation catalyst and can bring the first fluid into contact with the filled hydrogenation catalyst, and is preferably, for example, a solid-bed flow reactor. Examples of solid-bed flow reactors include a cylindrical reactor, a radial flow reactor, a tubular reactor (single-tubular reactor, multi-tubular reactor), a double-tubular reactor, etc.

[0027] The reaction temperature of the rearrangement hydrogenation reaction (e.g., the temperature of the packed section of a solid-bed flow reactor packed with a hydrogenation catalyst) may be, for example, 150°C or higher, and from the viewpoint of further improving the selectivity of the rearrangement reaction, it may be 170°C or higher, 180°C or higher, or 190°C or higher. The reaction temperature of the rearrangement hydrogenation reaction may be, for example, 250°C or lower, and from the viewpoint of further suppressing the polymerization of furfuryl alcohol, it may be 230°C or lower, 220°C or lower, or 210°C or lower. That is, the reaction temperature of the rearrangement hydrogenation reaction may be, for example, 150°C to 250°C, 150°C to 230°C, 150°C to 220°C, 150°C to 210°C, 170°C to 250°C, 170°C to 230°C, 170°C to 220°C, 170°C to 210°C, 180°C to 250°C, 180°C to 230°C, 180°C to 220°C, 180°C to 210°C, 190°C to 250°C, 190°C to 230°C, 190°C to 220°C, or 190°C to 210°C.

[0028] The reaction pressure of the rearrangement hydrogenation reaction (e.g., the pressure in the packed section of a solid-bed flow reactor packed with the hydrogenation catalyst) may be, for example, 1.0 MPaG or more, and from the viewpoint of further accelerating the hydrogenation reaction, may be 2.0 MPaG or more, 2.5 MPaG or more, or 3.0 MPaG or more. The reaction pressure of the rearrangement hydrogenation reaction (e.g., the pressure in the packed section of a solid-bed flow reactor packed with the hydrogenation catalyst) may be, for example, 20.0 MPaG or less, and from the viewpoint of further improving the reaction selectivity, may be 15.0 MPaG or less, 10.0 MPaG or less, or 8.0 MPaG or less. That is, the reaction pressure of the rearrangement hydrogenation reaction may be, for example, 1.0 to 20.0 MPaG, 1.0 to 15.0 MPaG, 1.0 to 10.0 MPaG, 1.0 to 8.0 MPaG, 2.0 to 20.0 MPaG, 2.0 to 15.0 MPaG, 2.0 to 10.0 MPaG, 2.0 to 8.0 MPaG, 2.5 to 20.0 MPaG, 2.5 to 15.0 MPaG, 2.5 to 10.0 MPaG, 2.5 to 8.0 MPaG, 3.0 to 20.0 MPaG, 3.0 to 15.0 MPaG, 3.0 to 10.0 MPaG, or 3.0 to 8.0 MPaG.

[0029] The WHSV (ratio of the weight of the oxygen-containing organic component fed to the reactor per unit time to the weight of the catalyst packed in the reactor) in the rearrangement hydrogenation reaction is, for example, 0.005 h －１ From the viewpoint of further improving the reaction selectivity, it may be 0.01 h －１ That's it, 0.015h －１ or more or 0.02h －１ The WHSV in the rearrangement hydrogenation reaction may be, for example, 1.0 h －１ From the viewpoint of promoting the rearrangement hydrogenation reaction, the reaction time may be 0.5 h or less. －１ Below, 0.2h －１ Less than or equal to 0.1h －１ That is, the WHSV in the rearrangement hydrogenation reaction may be, for example, 0.005 to 1.0 h －１ , 0.005~0.5h －１ ,0.005~0.2h －１ ,0.005~0.1h －１ , 0.01~1.0h －１ , 0.01~0.5h －１ ,0.01~0.2h －１ , 0.01~0.1h －１ ,0.015~1.0h －１ ,0.015~0.5h －１ ,0.015~0.2h －１ ,0.015~0.1h －１ ,0.02~1.0h －１ ,0.02~0.5h －１ ,0.02~0.2h －１ , or 0.02 to 0.1 h －１ It may be.

[0030] In the rearrangement hydrogenation reaction, the conversion rate of furfuryl alcohol may be, for example, 70% or more, and from the viewpoint of further suppressing polymerization of furfuryl alcohol during recycling, it may be 80% or more, 90% or more, 95% or more, or 98% or more. Furthermore, in the rearrangement hydrogenation reaction, the conversion rate of furfuryl alcohol may be, for example, 100% or less, and from the viewpoint of improving reaction selectivity, it may be 99.9% or less, 99.8% or less, or 99.5% or less. The rearrangement hydrogenation step may be one in which the conditions of the rearrangement hydrogenation reaction are appropriately adjusted so that the conversion rate falls within the above range. That is, in the rearrangement hydrogenation reaction, the conversion rate of furfuryl alcohol may be, for example, 70 to 100%, 70 to 99.9%, 70 to 99.8%, 70 to 99.5%, 80 to 100%, 80 to 99.9%, 80 to 99.8%, 80 to 99.5%, 90 to 100%, 90 to 99.9%, 90 to 99.8%, 90 to 99.5%, 95 to 100%, 95 to 99.9%, 95 to 99.8%, 95 to 99.5%, 98 to 100%, 98 to 99.9%, 98 to 99.8%, or 98 to 99.5%.

[0031] In the rearrangement hydrogenation step, a reaction product containing cyclopentanone and water is obtained. The reaction product may be, for example, a liquid phase obtained by gas-liquid separation of the second fluid recovered from the outlet of the solid-bed flow reactor.

[0032] The reaction product may be a fluid (third fluid) that includes water and an oxygen-containing organic component that includes cyclopentanone.

[0033] The reaction product may further contain oxygen-containing organic components other than cyclopentanone. For example, the reaction product may contain components contained in the first fluid (e.g., furfuryl alcohol, water, etc.). The reaction product may also contain intermediate products and by-products of the rearrangement hydrogenation reaction from furfuryl alcohol to cyclopentanone (e.g., 4-hydroxy-2-cyclopentanone, 2-cyclopentenone, cyclopentanol, levulinic acid, butanal, etc.).

[0034] (Extraction Step) The extraction step is a step in which cyclopentanone is extracted from the reaction product (third fluid) obtained in the rearrangement hydrogenation step using an extraction solvent to obtain an oil phase containing cyclopentanone. In the extraction step, oxygen-containing organic components including cyclopentanone are extracted from the reaction product containing a large amount of water using the extraction solvent, and water that forms an azeotrope with cyclopentanone is separated as an aqueous phase. One extraction solvent may be used alone, or two or more extraction solvents may be used in combination.

[0035] The extraction solvent may be any solvent that can separate from water and extract cyclopentanone. Examples of the extraction solvent include aromatic hydrocarbons (e.g., benzene, toluene, xylene, mesitylene, 1,2,3,5-tetramethylbenzene, etc.) and alicyclic hydrocarbons (e.g., cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, etc.).

[0036] The extraction solvent preferably contains at least one selected from the group consisting of aromatic hydrocarbons and alicyclic hydrocarbons. Furthermore, in the extraction step, it is preferred that 50% by mass or more (more preferably 70% by mass or more, more preferably 90% by mass or more, particularly preferably 100% by mass) of the extraction solvent be selected from the group consisting of aromatic hydrocarbons and alicyclic hydrocarbons, and all of the extraction solvent may be selected from the group consisting of aromatic hydrocarbons and alicyclic hydrocarbons. Preferred examples of aromatic hydrocarbons include benzene and toluene. Preferred examples of alicyclic hydrocarbons include cyclohexane and methylcyclohexane.

[0037] The amount of extraction solvent used is not particularly limited, and may be any amount that can sufficiently extract cyclopentanone (for example, an amount that can extract 90% or more (preferably 95% or more) of the cyclopentanone in the reaction product).

[0038] The amount of the extraction solvent used may be, for example, 20 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more, relative to 100 parts by mass of the reaction product. The amount of the extraction solvent used may be, for example, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, or 70 parts by mass or less, relative to 100 parts by mass of the reaction product. That is, the amount of the extraction solvent used may be, for example, 20 to 100 parts by mass, 20 to 90 parts by mass, 20 to 80 parts by mass, 20 to 70 parts by mass, 30 to 100 parts by mass, 30 to 90 parts by mass, 30 to 80 parts by mass, 30 to 70 parts by mass, 35 to 100 parts by mass, 35 to 90 parts by mass, 35 to 80 parts by mass, 35 to 70 parts by mass, 40 to 100 parts by mass, 40 to 90 parts by mass, 40 to 80 parts by mass, or 40 to 70 parts by mass, relative to 100 parts by mass of the reaction product.

[0039] The extraction temperature may be, for example, 20°C or higher, and from the viewpoint of operational management efficiency, it may be 30°C or higher, 35°C or higher, or 40°C or higher. The extraction temperature may be, for example, 90°C or lower, and from the viewpoint of target component recovery efficiency, it may be 80°C or lower, 70°C or lower, or 60°C or lower. That is, the extraction temperature may be, for example, 20°C to 90°C, 20°C to 80°C, 20°C to 70°C, 20°C to 60°C, 30°C to 90°C, 30°C to 80°C, 30°C to 70°C, 30°C to 60°C, 35°C to 90°C, 35°C to 80°C, 35°C to 70°C, 35°C to 60°C, 40°C to 90°C, 40°C to 80°C, 40°C to 70°C, or 40°C to 60°C.

[0040] The extraction step may be carried out using a known extraction apparatus. Examples of the extraction apparatus include a mixer-settler type extraction apparatus, a column type extraction apparatus, etc. In the extraction step, these may be used alone, or a plurality of extraction apparatuses may be used in a multi-stage configuration.

[0041] The aqueous phase separated in the extraction step may be treated as wastewater, and the oil phase (fourth fluid) obtained in the extraction step is subjected to the recovery step described below.

[0042] (Recovery Step) The recovery step is a step of recovering cyclopentanone (purified cyclopentanone product) from the oil phase (fourth fluid) obtained in the extraction step.

[0043] The oil phase contains at least a portion of the oxygen-containing organic components contained in the reaction product and the extraction solvent. The recovery step can also be said to be a step of removing the extraction solvent and oxygen-containing organic components other than cyclopentanone to obtain cyclopentanone (purified cyclopentanone product).

[0044] The recovery step may include, for example, a separation step in which at least a portion of the extraction solvent is removed from the oil phase, and a purification step in which cyclopentanone is purified from the remainder of the separation step.

[0045] In the separation step, the method for removing the extracting solvent is not particularly limited, and may be, for example, a method in which the extracting solvent is removed by utilizing the difference in boiling points between the extracting solvent and cyclopentanone. The separation step may be carried out, for example, using a known distillation apparatus.

[0046] In the separation step, most of the extraction solvent may be removed. The remainder of the separation step includes the oxygen-containing organic component and may further include a portion of the extraction solvent. The content of the extraction solvent in the remainder of the separation step may be, for example, 5.0 mass% or less, 3.0 mass% or less, 2.0 mass% or less, 1.0 mass% or less, or even 0 mass%.

[0047] The extraction solvent removed in the separation step may be reused in the extraction step.

[0048] In the purification step, at least a portion of the components other than cyclopentanone (oxygen-containing organic components other than cyclopentanone and the extraction solvent) are removed from the remainder of the separation step to obtain cyclopentanone (purified cyclopentanone product).

[0049] The purification method in the purification step is not particularly limited, and examples thereof include purification by distillation utilizing the difference in boiling points, purification by membrane separation, and the like.

[0050] The purified cyclopentanone product obtained in the recovery step may contain, for example, cyclopentanone and trace components other than cyclopentanone.

[0051] The purified cyclopentanone product may have a cyclopentanone content of, for example, 95% by mass or more, and preferably 98% by mass or more.

[0052] The minor component may be, for example, at least one selected from the group consisting of furfural, 4-hydroxy-2-cyclopentenone, furfuryl alcohol, 2-cyclopentenone, toluene, ethylbenzene, ethylcyclohexane, dimethylcyclohexane, and 1,2,3,5-tetramethylbenzene.

[0053] Among the above, furfural, 4-hydroxy-2-cyclopentenone, furfuryl alcohol, and 2-cyclopentenone may be unreacted raw materials or by-products of the rearrangement hydrogenation reaction, while toluene, ethylbenzene, ethylcyclohexane, dimethylcyclohexane, and 1,2,3,5-tetramethylbenzene may be the extraction solvent or a reaction product thereof in the extraction step.

[0054] The content of the minor components may be, for example, 0.1% by mass or more, 0.4% by mass or more, or 0.8% by mass or more. The content of the minor components may be, for example, less than 2% by mass, less than 1.5% by mass, or less than 1.2% by mass. That is, the content of the minor components may be, for example, 0.1% by mass or more and less than 2% by mass, 0.1% by mass or more and less than 1.5% by mass, 0.1% by mass or more and less than 1.2% by mass, 0.4% by mass or more and less than 2% by mass, 0.4% by mass or more and less than 1.5% by mass, 0.4% by mass or more and less than 1.2% by mass, 0.8% by mass or more and less than 2% by mass, 0.8% by mass or more and less than 1.5% by mass, or 0.8% by mass or more and less than 1.2% by mass.

[0055] The proportion of 4-hydroxy-2-cyclopentenone and furfuryl alcohol in the minor components may be, for example, less than 50% by mass, preferably 40% by mass or less, and more preferably 30% by mass or less. Because such a purified cyclopentanone product has a low content of components having hydroxy groups, side reactions caused by hydroxy groups can be sufficiently reduced, making it easy to apply to various reactions. The proportion of 4-hydroxy-2-cyclopentenone and furfuryl alcohol in the minor components may be, for example, 0% by mass, 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more. That is, the proportion of 4-hydroxy-2-cyclopentenone and furfuryl alcohol in the trace components may be, for example, 0% by mass or more and less than 50% by mass, 0% by mass or more and less than 40% by mass, 0% by mass or more and less than 30% by mass, 1% by mass or more and less than 50% by mass, 1% by mass or more and less than 40% by mass, 1% by mass or more and less than 30% by mass, 5% by mass or more and less than 50% by mass, 5% by mass or more and less than 40% by mass, 5% by mass or more and less than 30% by mass, 10% by mass or more and less than 50% by mass, 10% by mass or more and less than 40% by mass, 10% by mass or more and less than 30% by mass, 15% by mass or more and less than 50% by mass, 15% by mass or more and less than 40% by mass, 15% by mass or more and less than 30% by mass, 20% by mass or more and less than 50% by mass, 20% by mass or more and less than 40% by mass, or 20% by mass or more and less than 30% by mass.

[0056] FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus for carrying out the manufacturing method of this embodiment.

[0057] The production apparatus 1 in FIG. 1 includes a rearrangement hydrogenation reactor 11 , a gas-liquid separator 12 , an extraction column 13 , a first distillation separator 14 , and a second distillation separator 15 .

[0058] The production apparatus 1 also includes a flow path L1 for transferring a first fluid containing furfuryl alcohol, hydrogen, and water to the rearrangement-hydrogenation reactor 11, a flow path L2 for transferring a second fluid recovered from the outlet of the rearrangement-hydrogenation reactor 11 to the gas-liquid separator 12, a flow path L3 for transferring the gas phase separated in the gas-liquid separator 12, a flow path L4 for transferring the liquid phase (third fluid) separated in the gas-liquid separator 12 to the extraction tower 13, a flow path L5 for supplying an extraction solvent (for example, toluene in FIG. 1 ) to the extraction tower 13, and a flow path L6 for transferring the aqueous phase separated in the extraction tower 13. a flow path L6 for transferring the oil phase (fourth fluid) separated in the extraction column 13 to the first distillation separator 14; a flow path L8 for transferring a part or all of the extraction solvent recovered from the top of the first distillation separator 14 to the flow path L5; a flow path L9 for transferring the fraction (fifth fluid) recovered from the bottom of the first distillation separator 14 to the second distillation separator 15; a flow path L10 for transferring the purified cyclopentanone recovered from the second distillation separator 15; and a flow path L11 for transferring the by-product recovered from the second distillation separator 15.

[0059] The production apparatus 1 is an example of a production apparatus in which the boiling point of the extraction solvent is lower than that of cyclopentanone. When the boiling point of the extraction solvent is higher than that of cyclopentanone, flow path L8 may be a flow path that transfers part or all of the extraction solvent recovered from the bottom of the first distillation separator 14 to flow path L5, and flow path L9 may be a flow path that transfers the fraction (fifth fluid) recovered from the top of the first distillation separator to the second distillation separator 15. Figure 3 is a diagram showing an example of a production apparatus (production apparatus 1') in which the boiling point of the extraction solvent is higher than that of cyclopentanone.

[0060] The manufacturing apparatus 1 and the manufacturing apparatus 1' can easily carry out the above-described manufacturing method.

[0061] Although the preferred embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments.

[0062] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0063] Example 1 A simulation was performed on the production of cyclopentanone using the production apparatus 1 shown in FIG. 1 . The simulation software used was "Aspen Plus" manufactured by Aspen Technology. Specifically, the following process was simulated. First, a first fluid containing a mixture of furfuryl alcohol, hydrogen, and water is supplied to a rearrangement hydrogenation reactor 11 via flow path L1, and a second fluid is obtained in which a portion of the furfuryl alcohol is converted to cyclopentanone. The second fluid is supplied to a gas-liquid separator 12 via flow path L2 and separated into a gas phase and a third fluid consisting of a liquid phase. The third fluid is supplied to an extraction tower 13 via flow path L4 and mixed with an extraction solvent (toluene) supplied via flow path L5. The two streams are stirred by the extraction tower 13 and then separated into an oil phase (fourth fluid) containing toluene and cyclopentanone and an aqueous phase containing water. The fourth fluid is supplied to the first distillation separator 14 via flow path L7, where it is separated into a fraction containing toluene as a main component and a fifth fluid containing cyclopentanone as a main component. The fraction containing toluene as a main component is mixed with the extraction solvent via flow path L8 and recycled to the extraction column 13. The fifth fluid is supplied to the second distillation separator 15 via flow path L9, where it is separated into a purified cyclopentanone product enriched in cyclopentanone and a by-product. The reaction conditions of the rearrangement hydrogenation reactor and the operating conditions of the gas-liquid separator and extraction column are as shown below, and the compositions of the fluids passing through each flow path are shown in Table 1. (Rearrangement Hydrogenation Reactor) Reaction pressure: 5.8 MPaG Reaction temperature: 200°C Hydrogen / oxygen-containing organic component: 6.3 (molar ratio) WHSV: 0.023 h －１ Water: furfuryl alcohol = 20:1 (mass ratio) Catalyst: 0.04% Pd / SiO ２ (Gas-liquid separator) Pressure: 2.0 MPaG Temperature: 40°C (Extraction column) Pressure: 0.5 MPaG Temperature: 50°C Number of stages: 10 stages, countercurrent

[0064] Comparative Example 1 A simulation was performed on the production of cyclopentanone using the production apparatus 2 shown in Figure 2. The simulation software used was "Aspen Plus" manufactured by Aspen Technology, Inc. The production apparatus 2 in Figure 2 includes a rearrangement hydrogenation reactor 21, a gas-liquid separator 22, a first distillation separator 23, and a second distillation separator 24. The production apparatus 2 also includes a flow path L21 for transferring a first fluid containing furfuryl alcohol, hydrogen, and water to the rearrangement-hydrogenation reactor 21, a flow path L22 for transferring a second fluid recovered from the outlet of the rearrangement-hydrogenation reactor 21 to the gas-liquid separator 22, a flow path L23 for transferring the gas phase separated in the gas-liquid separator 22, a flow path L24 for transferring the liquid phase (third fluid) separated in the gas-liquid separator 22 to the first distillation separator 23, a flow path L25 for removing a water-containing fluid from the first distillation separator 23 to the outside of the system, a flow path L26 for transferring a fraction containing cyclopentanone from the first distillation separator 23 to the second distillation separator, a flow path L27 for transferring the purified cyclopentanone product recovered from the second distillation separator, and a flow path L28 for transferring a by-product recovered from the second distillation separator. Specifically, the following process was simulated. First, a first fluid containing a mixture of furfuryl alcohol, hydrogen, and water is supplied to rearrangement hydrogenation reactor 21 via flow path L21, and a second fluid in which a portion of the furfuryl alcohol has been converted to cyclopentanone is obtained. The second fluid is supplied to gas-liquid separator 22 via flow path L22 and separated into a gas phase and a third fluid consisting of a liquid phase. The third fluid is supplied to first distillation separator 23 via flow path L24 and separated into a fraction containing cyclopentanone and a waste liquid enriched in water. The fraction containing cyclopentanone is supplied to second distillation separator 24 via flow path L26 and separated into a purified cyclopentanone product enriched in cyclopentanone and by-products. The reaction conditions of the rearrangement hydrogenation reactor and the operating conditions of the gas-liquid separator were the same as in Example 1, and the compositions of the fluids passing through each flow path are shown in Table 2.

[0065] Comparative Example 2 A simulation was carried out for the same production process as in Example 1, except that furfural was used instead of furfuryl alcohol. Table 3 shows the composition of the fluid passing through each flow path.

[0066] Example 2 A simulation was performed on the production of cyclopentanone using the production apparatus 1' shown in Figure 3. The simulation software used was "Aspen Plus" manufactured by Aspen Technology. Specifically, the simulation was performed on the following process. First, a first fluid containing a mixture of furfuryl alcohol, hydrogen, and water is supplied to a rearrangement hydrogenation reactor 11 via flow path L1, and a second fluid is obtained in which a portion of the furfuryl alcohol is converted to cyclopentanone. The second fluid is supplied to a gas-liquid separator 12 via flow path L2 and separated into a gas phase and a third fluid consisting of a liquid phase. The third fluid is supplied to an extraction tower 13 via flow path L4 and mixed with an extraction solvent (1,2,3,5-tetramethylbenzene) supplied via flow path L5. The two streams are stirred in the extraction tower 13, and then separated into an oil phase (fourth fluid) containing 1,2,3,5-tetramethylbenzene and cyclopentanone and an aqueous phase containing water. The fourth fluid is supplied to the first distillation separator 14 via flow path L7, where it is separated into a fraction containing 1,2,3,5-tetramethylbenzene as a main component and a fifth fluid containing cyclopentanone as a main component. The fraction containing 1,2,3,5-tetramethylbenzene as a main component is mixed with the extraction solvent via flow path L8 and recycled to the extraction column 13. The fifth fluid is supplied to the second distillation separator 15 via flow path L9, where it is separated into a purified cyclopentanone product enriched in cyclopentanone concentration and a by-product. The reaction conditions of the rearrangement hydrogenation reactor and the operating conditions of the gas-liquid separator and extraction column are as shown below, and the composition of the fluid passing through each flow path is shown in Table 4. (Rearrangement hydrogenation reactor) Reaction pressure: 5.8 MPaG Reaction temperature: 200°C Hydrogen / oxygen-containing organic component: 6.3 (molar ratio) WHSV: 0.5 h －１ Water: furfuryl alcohol = 10:1 (mass ratio) Catalyst: 0.04% Pd / SiO ２ (Gas-liquid separator) Pressure: 2.0 MPaG Temperature: 40°C (Extraction column) Pressure: 0.5 MPaG Temperature: 50°C Number of stages: 10 stages, countercurrent

[0067] In Tables 1 to 4, the numerical values ​​of each composition indicate the mass ratio in the flow rate. In Tables 1 to 4, A-1 indicates furfuryl alcohol, A-2 indicates furfural, A-3 indicates 2-cyclopentenone, and A-4 indicates 4-hydroxy-2-cyclopentenone.

[0068]

[0069]

[0070]

[0071]

[0072] 1, 2... production apparatus, 11, 21... rearrangement hydrogenation reactor, 12, 22... gas-liquid separator, 13... extraction column, 14, 23... first distillation separator, 15, 24... second distillation separator.

Claims

1. A method for producing cyclopentanone, comprising: a rearrangement hydrogenation step of contacting a first fluid containing furfuryl alcohol, water, and hydrogen with a hydrogenation catalyst to obtain a reaction product containing cyclopentanone and water; an extraction step of extracting cyclopentanone from the reaction product with an extraction solvent to obtain an oil phase containing cyclopentanone; and a recovery step of recovering cyclopentanone from the oil phase.

2. The method according to claim 1, wherein the recovery step comprises: a separation step of removing at least a portion of the extraction solvent from the oil phase; and a purification step of purifying cyclopentanone from the remainder of the separation step.

3. The method according to claim 1, wherein the extraction solvent comprises at least one selected from the group consisting of aromatic hydrocarbons and alicyclic hydrocarbons.

4. A cyclopentanone refined product comprising: cyclopentanone; and at least one trace component selected from the group consisting of furfural, 4-hydroxy-2-cyclopentenone, 2-cyclopentenone, toluene, ethylbenzene, ethylcyclohexane, and dimethylcyclohexane, wherein the cyclopentanone content is 98% by mass or more, the trace component content is 0.1% by mass or more and less than 2% by mass, and the proportion of 4-hydroxy-2-cyclopentenone and furfuryl alcohol in the trace components is less than 50% by mass.

Images