Cyclic diene-containing composition, production method of aldehyde, production method of alcohol, and production method of cyclic diene-containing composition

Abstract

To provide a cyclic diene-containing composition capable of efficiently producing aldehyde such as alicyclic aldehyde while preventing catalytic activity of a hydroformylation reaction catalyst from lowering, and recovering an expensive rhodium metal from a process liquid after hydroformylation reaction at a high recovery rate, and a production method of aldehyde using the cyclic diene-containing composition.SOLUTION: A cyclic diene-containing composition includes a cyclic diene oxide at a rate of 1.2 GC area% or less. A production method of aldehyde hydroformylation-reacts a cyclic diene in the cyclic diene-containing composition to produce aldehyde, and includes setting a content ratio of the cyclic diene oxide included in the cyclic diene-containing composition to be equal to or lower than a prescribed threshold value. However, the cyclic diene excludes the cyclic diene oxide.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cyclic diene-containing composition, a method for producing an aldehyde, a method for producing an alcohol, and a method for producing a cyclic diene-containing composition. [Background technology]

[0002] Aldehydes such as alicyclic aldehydes are useful as raw materials for plasticizer additives, adhesives, disinfectants, etc. Furthermore, alcohols such as alicyclic alcohols obtained by hydrogenating aldehydes such as alicyclic aldehydes are useful as raw material monomers for improving the heat resistance, flex resistance, or low retardation of polyurethane resins, polyester resins, and polycarbonate resins. Specifically, alicyclic aldehydes such as tricyclodecane dicarbaldehyde and alicyclic alcohols such as tricyclodecane dimethanol and pentacyclopentadecanedimethanol have attracted attention from the viewpoints of high functionality in various applications and excellent industrial productivity.

[0003] A known method for producing an alicyclic aldehyde such as tricyclodecane dicarbaldehyde involves heating a C5 hydrocarbon fraction obtained by thermal cracking a hydrocarbon-containing composition such as naphtha, coal, or natural gas, to dimerize cyclic dienes (also referred to as "cyclic dienes" in the present invention) such as cyclopentadiene in the C5 hydrocarbon fraction to form cyclic dienes such as dicyclopentadiene, purifying the C5 hydrocarbon fraction after the dimerization reaction to obtain a composition containing a high concentration of cyclic dienes such as dicyclopentadiene (hereinafter referred to as a "cyclic diene-containing composition"), and subjecting the obtained cyclic diene-containing composition to a hydroformylation reaction in the presence of an organophosphorus complex catalyst containing a metal of Groups 8 to 10 of the long form periodic table (hereinafter sometimes simply referred to as a "Group 8 to 10 metal") to convert the cyclic diene into an alicyclic aldehyde corresponding to the cyclic diene.

[0004] The catalyst used in the hydroformylation reaction of the cyclic diene-containing composition described above contains an expensive Group 8 to 10 metal such as rhodium. Therefore, if factors that inhibit the hydroformylation reaction exist in the reaction system, the amount of catalyst used must be increased, which results in an increase in production costs. Therefore, it is ideal to remove factors that inhibit the hydroformylation reaction as much as possible.

[0005] As a method for obtaining an alicyclic aldehyde by subjecting the above-mentioned cyclic diene-containing composition to a hydroformylation reaction, for example, Patent Document 1 discloses in its Examples a technology for producing bisformyltricyclodecane by hydroformylating highly purified dicyclopentadiene. Furthermore, Patent Document 2 focuses on conjugated dienes contained in dicyclopentadiene as impurities that inhibit the hydroformylation reaction, and discloses a technique for reducing the amount of these conjugated dienes.

[0006] However, the techniques disclosed in Patent Documents 1 and 2 have the problem that the production process becomes complicated and the capital investment, production costs, and utility costs increase in order to remove as many impurities as possible from the cyclic diene-containing composition and separate and recover a high-purity cyclic diene.

[0007] Furthermore, even if the impurities contained in the cyclic diene-containing composition are reduced from an economical standpoint, it has not been fully elucidated what impurities affect the activity of the hydroformylation catalyst, or what impurities affect the recovery rate of expensive rhodium metal when the hydroformylation catalyst is recovered from the process liquid after the hydroformylation reaction and reused. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-139181 [Patent Document 2] Japanese Patent Application Publication No. 11-80067 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention aims to solve these problems. Specifically, the present invention aims to provide a cyclic diene-containing composition containing a cyclic diene such as dicyclopentadiene, which is used as a starting material for aldehydes such as tricyclodecane dicarbaldehyde, and which can efficiently produce aldehydes while suppressing a decrease in the catalytic activity of a hydroformylation catalyst, and which can recover expensive rhodium metal at a high recovery rate from the process solution after the hydroformylation reaction, as well as a method for producing the same.

[0010] Another object of the present invention is to provide a method for producing an aldehyde, which comprises using the cyclic diene-containing composition to produce an aldehyde corresponding to the cyclic diene.

[0011] Another object of the present invention is to provide a method for producing an alcohol, which comprises producing an aldehyde by the above-mentioned production method and then producing an alcohol from the aldehyde. [Means for solving the problem]

[0012] As a result of extensive investigations into solving the above problems, the present inventors have found that the above problems can be solved by setting the content of cyclic diene oxide in a cyclic diene-containing composition to a predetermined value or less. That is, the present invention provides the following.

[0013] [1] A cyclic diene-containing composition comprising a cyclic diene, A cyclic diene-containing composition, wherein the content of cyclic diene oxide in the cyclic diene composition is 1.2 GC area % or less. (However, the cyclic diene does not include the cyclic diene oxide.)

[0014] [2] The cyclic diene-containing composition according to [1], wherein the cyclic diene content is 60 GC area % or more.

[0015] [3] The cyclic diene-containing composition according to [1] or [2], wherein the content of the cyclic diene oxide is 0.5 GC area % or less, preferably 0.35 GC area % or less, more preferably 0.25 GC area % or less, even more preferably 0.14 GC area % or less, and particularly preferably 0.05 GC area % or less.

[0016] [4] The cyclic diene-containing composition according to any one of [1] to [3], wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of the peaks with elution times between 17.7 and 18.8 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃ Sample volume: 0.3 μL (split ratio: 1 / 30)

[0017] [5] The cyclic diene-containing composition according to any one of [1] to [4], wherein the cyclic diene is a polycyclic diene.

[0018] [6] The cyclic diene-containing composition according to [5], wherein the cyclic diene is dicyclopentadiene.

[0019] [7] The cyclic diene-containing composition according to any one of [1] to [6], wherein the cyclic diene oxide is a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

[0020] [8] The cyclic diene-containing composition according to any one of [1] to [7], wherein the cyclic diene oxide comprises at least one selected from the group consisting of a cyclic diene having a carbonyl group, a cyclic diene having a hydroxyl group, and a cyclic monoene having an epoxy group.

[0021] [9] The cyclic diene is dicyclopentadiene, and The cyclic diene-containing composition according to any one of [6] to [8], wherein the cyclic diene oxide comprises at least one compound selected from the group consisting of a compound in which one enantiomer is represented by the following general formula (I), a compound in which one enantiomer is represented by the following general formula (II), and a compound in which one enantiomer is represented by the following general formula (III):

[0022] [ka]

[0023] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0024]

[10] A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of [1] to [9] to a hydroformylation reaction to produce an aldehyde.

[0025]

[11] A method for producing an alcohol, comprising producing an aldehyde by the production method according to

[10] , and producing an alcohol from the aldehyde.

[0026]

[12] A method for producing an aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition, comprising: A method for producing an aldehyde, comprising adjusting the content of cyclic diene oxide contained in the cyclic diene-containing composition to a predetermined threshold value or less. (However, the cyclic diene does not include the cyclic diene oxide.)

[0027]

[13] The method for producing an aldehyde according to

[12] , wherein the content of the cyclic diene oxide in the cyclic diene-containing composition is 1.2 GC area % or less.

[0028]

[14] The method for producing an aldehyde according to

[12] or

[13] , wherein the cyclic diene content in the cyclic diene-containing composition is 60 GC area % or more.

[0029]

[15] The method for producing an aldehyde according to

[13] or

[14] , wherein the content of the cyclic diene oxide in the cyclic diene-containing composition is 0.5 GC area % or less, preferably 0.35 GC area % or less, more preferably 0.25 GC area % or less, even more preferably 0.14 GC area % or less, and particularly preferably 0.05 GC area % or less.

[0030]

[16] The method for producing an aldehyde according to any one of

[12] to

[15] , wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of the peaks with elution times between 17.7 and 18.8 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃ Sample volume: 0.3 μL (split ratio: 1 / 30)

[0031]

[17] The method for producing an aldehyde according to any one of

[12] to

[16] , wherein the cyclic diene is a polycyclic diene.

[0032]

[18] The method for producing an aldehyde according to

[17] , wherein the cyclic diene is dicyclopentadiene.

[0033]

[19] The method for producing an aldehyde according to any one of

[12] to

[18] , wherein the cyclic diene oxide is a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

[0034]

[20] The method for producing an aldehyde according to any one of

[12] to

[19] , wherein the cyclic diene oxide comprises at least one selected from the group consisting of a cyclic diene having a carbonyl group, a cyclic diene having a hydroxyl group, and a cyclic monoene having an epoxy group.

[0035]

[21] The cyclic diene is dicyclopentadiene, and The method for producing an aldehyde according to any one of

[18] to

[20] , wherein the cyclic diene oxide comprises at least one compound selected from the group consisting of a compound of which one enantiomer is represented by the following general formula (I), a compound of which one enantiomer is represented by the following general formula (II), and a compound of which one enantiomer is represented by the following general formula (III).

[0036] [ka]

[0037] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0038]

[22] The method for producing an aldehyde according to any one of

[18] to

[21] , wherein the cyclic diene is dicyclopentadiene and the aldehyde is tricyclodecane dicarbaldehyde.

[0039]

[23] The cyclic diene-containing composition is a composition obtained by distilling and purifying a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition, The method for producing an aldehyde according to any one of

[12] to

[22] , comprising carrying out the distillation purification so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

[0040]

[24] The method for producing an aldehyde according to any one of

[12] to

[23] , comprising controlling storage conditions of the cyclic diene-containing composition so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

[0041]

[25] The method for producing an aldehyde according to

[24] , wherein the control of the storage conditions includes controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

[0042]

[26] The method for producing an aldehyde according to

[24] , wherein the control of the storage conditions includes adding an antioxidant to the cyclic diene-containing composition.

[0043]

[27] A method for producing an alcohol, comprising producing an aldehyde by the production method according to any one of

[12] to

[26] , and producing an alcohol from the aldehyde.

[0044]

[28] The cyclic diene is dicyclopentadiene, the aldehyde is tricyclodecane dicarbaldehyde, and the alcohol is tricyclo[5.2.1.0 2,6 ] The method for producing an alcohol according to

[27] , wherein the alcohol is decanedimethanol.

[0045]

[29] A method for producing a cyclic diene-containing composition containing a cyclic diene, comprising distilling and purifying a hydrocarbon decomposition product obtained by thermal decomposition of a hydrocarbon-containing composition, the method comprising: A method for producing a cyclic diene-containing composition, comprising adjusting the content of cyclic diene oxide contained in the cyclic diene-containing composition to a predetermined threshold value or less. (However, the cyclic diene does not include the cyclic diene oxide.)

[0046]

[30] The method for producing a cyclic diene-containing composition according to

[29] , comprising carrying out the distillation purification so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

[0047]

[31] A method for producing a cyclic diene-containing composition according to

[29] or

[30] , comprising controlling storage conditions of the cyclic diene-containing composition so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

[0048]

[32] The method for producing a cyclic diene-containing composition according to

[31] , wherein the control of the storage conditions includes controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

[0049]

[33] The method for producing a cyclic diene-containing composition according to

[31] , wherein the control of the storage conditions includes adding an antioxidant to the cyclic diene-containing composition.

[0050]

[34] The method for producing a cyclic diene-containing composition according to any one of

[29] to

[33] , wherein the content of the cyclic diene oxide in the cyclic diene-containing composition is 1.2 GC area % or less.

[0051]

[35] The method for producing a cyclic diene-containing composition according to any one of

[29] to

[34] , wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60 GC area % or more.

[0052]

[36] The method for producing a cyclic diene-containing composition according to

[34] or

[35] , wherein the content of the cyclic diene oxide contained in the cyclic diene-containing composition is 0.5 GC area % or less, preferably 0.35 GC area % or less, more preferably 0.25 GC area % or less, even more preferably 0.14 GC area % or less, and particularly preferably 0.05 GC area % or less.

[0053]

[37] The method for producing a cyclic diene-containing composition according to any one of

[29] to

[36] , wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of the peaks with elution times between 17.7 and 18.8 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃ Sample volume: 0.3 μL (split ratio: 1 / 30)

[0054]

[38] The method for producing a cyclic diene-containing composition according to any one of

[29] to

[37] , wherein the cyclic diene is a polycyclic diene.

[0055]

[39] The method for producing a cyclic diene-containing composition according to

[38] , wherein the cyclic diene is dicyclopentadiene.

[0056]

[40] The method for producing a cyclic diene-containing composition according to any one of

[29] to

[39] , wherein the cyclic diene oxide is a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

[0057]

[41] The method for producing a cyclic diene-containing composition according to any one of

[29] to

[40] , wherein the cyclic diene oxide comprises at least one selected from the group consisting of a cyclic diene having a carbonyl group, a cyclic diene having a hydroxyl group, and a cyclic monoene having an epoxy group.

[0058]

[42] The cyclic diene is dicyclopentadiene, and The method for producing a cyclic diene-containing composition according to any one of

[39] to

[41] , wherein the cyclic diene oxide comprises at least one compound selected from the group consisting of a compound in which one enantiomer is represented by the following general formula (I), a compound in which one enantiomer is represented by the following general formula (II), and a compound in which one enantiomer is represented by the following general formula (III).

[0059] [ka]

[0060] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0061]

[43] The method for producing a cyclic diene-containing composition according to any one of

[29] to

[42] , wherein the hydrocarbon-containing composition is naphtha. [Effects of the Invention]

[0062] According to the present invention, it is possible to provide a cyclic diene-containing composition that is used as a starting material for aldehydes such as alicyclic aldehydes, and that enables efficient production of aldehydes from the cyclic diene-containing composition while suppressing a decrease in the catalytic activity of a hydroformylation reaction catalyst, and enables recovery of expensive rhodium metal with a high recovery rate from the process liquid after the hydroformylation reaction. Furthermore, according to the present invention, the cyclic diene-containing composition can be used to efficiently produce an aldehyde and further an alcohol corresponding to the cyclic diene. [Brief explanation of the drawings]

[0063] [Figure 1] FIG. 1 is a schematic system diagram illustrating one embodiment of a production process for separating and recovering the cyclic diene-containing composition of the present invention from a C5 hydrocarbon fraction according to the present invention. [Figure 2] 1 is a graph showing the relationship between the content (GC area %) of cyclic diene oxide (DCPD oxide) and the reaction rate constant (k2) in Examples 1 to 7. [Figure 3] 1 is a graph showing the relationship between the content (GC area %) of cyclic diene oxide (DCPD oxide) and the rate of decrease in reaction rate constant (k2) in Examples 1 to 7. [Figure 4] 1 is a graph showing the relationship between the content (GC area %) of cyclic diene oxide (DCPD oxide) and the recovery rate of rhodium (Rh) in Examples 1 to 7. [Figure 5] FIG. 1 is a diagram showing a gas chromatogram of the DCPD-containing composition obtained in Reference Experimental Example 2. DETAILED DESCRIPTION OF THE INVENTION

[0064] The present invention will be described in detail below, but the present invention is not limited to the following description and can be practiced with any modifications within the scope of the gist of the present invention.

[0065] Unless otherwise specified, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits, and "A to B" means A or more and B or less. In this specification, unless otherwise specified, "including A or B" means "including A," "including B," or "including A and B." In this specification, "GC area %" refers to the composition ratio of each component measured using a gas chromatograph (GC) measuring device and a gas chromatography total area method, and is calculated as the area content ratio (unit: GC area %) of each peak component when the total area of ​​the GC peaks of all products on the gas chromatogram is taken as 100%. Details of the GC measurement conditions will be explained in the experimental examples below. In this specification, "mass %" indicates the content ratio of a specified component contained in a total amount of 100 mass %, and "wt %" indicates the content ratio of a specified component contained in a total amount of 100 wt %. "% by mass" and "% by weight" have the same meaning. "Optional" or "optionally" means that the subsequently described circumstance may or may not occur, and thus the description includes both the occurrence and non-occurrence of the circumstance. As used herein, the term "about" can mean above and below 20% of the stated value. For example, about 75°C encompasses the range of 60°C to 90°C. All steps described herein can be performed in any suitable order unless otherwise stated herein or clearly contradicted by context.

[0066] As used herein, "hydrocarbon" refers to naphtha, coal, and natural gas. More specifically, it refers to hydrocarbons such as fossil fuels and refined petroleum products, including naphtha, heavy aromatic naphtha, crude oil, gasoline, kerosene, diesel oil, light oil, heavy oil, extra heavy oil, heavy oil A, heavy oil B, heavy oil C, jet fuel, tar, gas to liquids (GTL), coal to liquids (CTL), coal, coke, natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), sour gas, oil field gas, and oil field concentrate.

[0067] In this specification, the "cyclic diene-containing composition of the present invention," "method for producing an aldehyde of the present invention," "method for producing an alcohol of the present invention," and "method for producing a cyclic diene-containing composition of the present invention" are collectively referred to as "the present invention."

[0068] The cyclic diene-containing composition according to the first embodiment of the present invention, the method for producing an aldehyde according to the second embodiment of the present invention, the method for producing an alcohol according to the third embodiment of the present invention, and the method for producing a cyclic diene-containing composition according to the fourth embodiment of the present invention (hereinafter, the inventions of the first to fourth embodiments may be collectively referred to as "the present invention") will be described below.

[0069] <Cyclic Diene-Containing Composition> The cyclic diene-containing composition of the present invention is a composition containing a cyclic diene as described below, in which the content of cyclic diene oxide in the cyclic diene composition is 1.2 GC area % or less. In the present invention, "cyclic diene oxides" are not included in the cyclic dienes in the cyclic diene-containing composition of the present invention, and the cyclic dienes according to the present invention exclude cyclic diene oxides.

[0070] (cyclic diene) The cyclic diene (also referred to as "cyclic diene") in the present invention is one component that constitutes the cyclic diene-containing composition of the present invention.

[0071] The "cyclic diene" in the method for producing an aldehyde of the present invention described below and the method for producing a cyclic diene-containing composition of the present invention described below can be treated as synonymous with the cyclic diene in the cyclic diene-containing composition of the present invention.

[0072] The cyclic diene in the present invention is not particularly limited as long as it is a compound having a ring structure in the molecule and having two non-conjugated carbon-carbon double bonds in the ring structure, but is preferably a compound that can be used as a starting material when producing an alicyclic alcohol. One embodiment of the cyclic diene includes a polycyclic diene having two or more ring structures in the molecule, each of which has a non-conjugated carbon-carbon double bond. Alternatively, another embodiment of the cyclic diene includes a compound in which a cyclic diene having one ring structure is dimerized.

[0073] Specific examples of the cyclic dienes include dicyclopentadiene, 1,4-cyclohexadiene, methylcyclopentadiene, methyldicyclopentadiene, and methyltetrahydroindene. Among these cyclic dienes, dicyclopentadiene is preferred because it is easily available industrially, has excellent hydroformylation reactivity, and is excellent in the production efficiency of alicyclic alcohols. These cyclic dienes can be used alone or in combination of two or more.

[0074] In the present invention, the lower limit of the content of the cyclic diene (unit: GC area%) in the cyclic diene-containing composition is not particularly limited, but from the viewpoint of producing an aldehyde such as an alicyclic aldehyde in a short reaction time and in a high yield using the cyclic diene-containing composition as a starting material, the cyclic diene content can be 60.0 GC area% or more, preferably 63.0 GC area% or more, more preferably 66.0 GC area% or more, even more preferably 70.0 GC area% or more, particularly preferably 75.0 GC area% or more, and most preferably 80.0 GC area% or more, relative to 100% of the total GC area of ​​the cyclic diene-containing composition. On the other hand, in the present invention, the upper limit of the content of the cyclic diene (unit: GC area%) in the cyclic diene-containing composition is not particularly limited, but from the viewpoint of economic efficiency such as the production costs required for purifying and separating the cyclic diene-containing composition, and from the viewpoint of fluidity at room temperature and excellent handleability, the upper limit can be 99.95 GC area% or less, preferably 99.9 GC area% or less, more preferably 97.5 GC area% or less, even more preferably 95.0 GC area% or less, particularly preferably 90.0 GC area% or less, and most preferably 85.0 GC area% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition.

[0075] The upper and lower limits can be arbitrarily combined. For example, the content of the cyclic diene in the cyclic diene-containing composition of the present invention (unit: GC area%) is not particularly limited, but can be 60.0 GC area% or more and 99.95 GC area% or less, preferably 63.0 GC area% or more and 99.9 GC area% or less, more preferably 66.0 GC area% or more and 97.5 GC area% or less, even more preferably 70.0 GC area% or more and 95.0 GC area% or less, particularly preferably 75.0 GC area% or more and 90.0 GC area% or less, and most preferably 80.0 GC area% or more and 85.0 GC area% or less, relative to 100% of the total GC area of ​​the cyclic diene-containing composition.

[0076] In the cyclic diene-containing composition and production method thereof of the present invention, and the aldehyde production method of the present invention, the lower limit of the GC area ratio of the cyclic diene oxide content (unit: GC area %) to the cyclic diene content (unit: GC area %) is not particularly limited, but from the viewpoint of economic efficiency such as the production costs required for purification and separation of the cyclic diene-containing composition, it can be set to 0.00001 or more, preferably 0.00002 or more, more preferably 0.00004 or more, even more preferably 0.00006 or more, and particularly preferably 0.00008 or more. On the other hand, in the present invention, the upper limit of the GC area ratio can be set to 0.040 or less, preferably 0.015 or less, more preferably 0.0035 or less, even more preferably 0.0025 or less, and particularly preferably 0.0015 or less, from the viewpoints of suppressing a decrease in the catalytic activity of the hydroformylation catalyst and recovering expensive rhodium metal at a high recovery rate. The upper and lower limits can be combined arbitrarily. For example, the GC area ratio of the content of cyclic diene oxide (unit: GC area %) to the content of cyclic diene (unit: GC area %) in the present invention is not particularly limited, but can be 0.00001 or more and 0.040 or less, preferably 0.00002 or more and 0.015 or less, more preferably 0.00004 or more and 0.0035 or less, even more preferably 0.00006 or more and 0.0025 or less, and particularly preferably 0.00008 or more and 0.0015 or less.

[0077] The method for measuring the content of the cyclic diene in the cyclic diene-containing composition will be described in detail below. Methods for controlling the content of the cyclic diene in the cyclic diene-containing composition include, for example, extraction methods, methods for controlling the amount by adjusting purification conditions or distillation conditions, and combinations of these methods.

[0078] (cyclic diene oxide) In the cyclic diene-containing composition and production method thereof of the present invention, and the aldehyde production method of the present invention, when the oxygen-containing compound is a cyclic diene oxide, by setting the content of cyclic diene oxide in the cyclic diene-containing composition to a predetermined value or less, when the cyclic diene-containing composition is used as a starting material for an aldehyde, it becomes possible to efficiently produce an aldehyde from the cyclic diene-containing composition while suppressing a decrease in the catalytic activity of a hydroformylation reaction catalyst, and to recover expensive rhodium metal at a high recovery rate from the process liquid after the hydroformylation reaction.

[0079] The cyclic diene oxide in the present invention is a compound in which a functional group containing oxygen is introduced into the above-mentioned cyclic diene.

[0080] The "cyclic diene oxide" in the cyclic diene-containing composition of the present invention, the method for producing an aldehyde of the present invention, and the method for producing a cyclic diene-containing composition of the present invention can be treated as having the same meaning as the cyclic diene oxide in the present invention.

[0081] In the cyclic diene-containing composition of the present invention and the process for producing an aldehyde of the present invention, by setting the content of cyclic diene oxide in the cyclic diene-containing composition to a predetermined value or less, when the cyclic diene-containing composition is used as a starting material for an aldehyde such as an alicyclic aldehyde, a decrease in the catalytic activity of the hydroformylation reaction catalyst can be suppressed, and an aldehyde corresponding to the cyclic diene can be produced from the cyclic diene-containing composition efficiently, i.e., in a short reaction time and in a high yield, and expensive rhodium metal can be recovered at a high recovery rate from the process solution after the hydroformylation reaction.

[0082] The cyclic diene oxide in the present invention is not particularly limited, but a first embodiment thereof is a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

[0083] The oxygen-containing functional group is not particularly limited, but may be at least one selected from the group consisting of a carbonyl group, a hydroxyl group, and an epoxy group.

[0084] More specifically, a first embodiment of the cyclic diene oxide of the present invention is at least one selected from the group consisting of a compound having a carbonyl group and a tricyclodecadiene skeleton, a compound having a hydroxyl group and a tricyclodecadiene skeleton, and a compound having an epoxy group and a tricyclodecene skeleton.

[0085] The cyclic diene oxide in the present invention is not particularly limited, but in a second embodiment, it may be at least one selected from the group consisting of cyclic dienes having a carbonyl group, cyclic dienes having a hydroxyl group, and cyclic monoenes having an epoxy group.

[0086] The cyclic diene oxide in the present invention is not particularly limited, but as a third embodiment, an oxide of an unsaturated hydrocarbon compound can be mentioned. In the present invention, the "oxide of an unsaturated hydrocarbon compound" is a compound in which a functional group containing oxygen is introduced into an unsaturated hydrocarbon compound. Examples of the unsaturated hydrocarbon compound include the cyclic diene of the present invention, isopropylnorbornene, and methyltetrahydroindene. Specific examples of the oxide of the unsaturated hydrocarbon compound include a compound having a carbonyl group, a compound having a hydroxyl group, and a compound having an epoxy group.

[0087] In the first, second, and third embodiments of the cyclic diene oxide of the present invention, when the cyclic diene is dicyclopentadiene, more specific examples include at least one selected from the group consisting of compounds one of whose enantiomers is represented by the following general formula (I), compounds one of whose enantiomers is represented by the following general formula (II), and compounds one of whose enantiomers is represented by the following general formula (III).

[0088] [ka]

[0089] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0090] These cyclic diene oxides may be used alone or in combination of two or more.

[0091] The content of cyclic diene oxide in the present invention can be measured by the following measurement method 1. <Measurement method 1> Analyze under the following GC measurement conditions and measure the total content ratio of the peaks with elution times between 17.7 and 18.8 minutes. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃ Sample volume: 0.3 μL (split ratio: 1 / 30)

[0092] The upper limit of the content of cyclic diene oxide in the cyclic diene-containing composition of the present invention is 1.2 GC area % or less, preferably 0.5 GC area % or less, more preferably 0.35 GC area % or less, even more preferably 0.25 GC area % or less, particularly preferably 0.14 GC area % or less, and most preferably 0.05 GC area % or less, from the viewpoints of efficiently producing an aldehyde corresponding to the cyclic diene from the cyclic diene-containing composition using the cyclic diene-containing composition as a starting material while suppressing a decrease in the catalytic activity of the hydroformylation reaction catalyst, and recovering expensive rhodium metal at a high recovery rate from the process liquid after the hydroformylation reaction. On the other hand, the lower limit of the content of the cyclic diene oxide is not particularly limited, and it is acceptable for the cyclic diene oxide to be substantially free of the cyclic diene oxide (0.0 GC area %). However, from the viewpoint of economic efficiency, such as the production costs required for purifying and separating the cyclic diene-containing composition, the content of the cyclic diene-containing composition can be 0.0001 GC area % or more, preferably 0.0003 GC area % or more, more preferably 0.001 GC area % or more, even more preferably 0.002 GC area % or more, particularly preferably 0.005 GC area % or more, and most preferably 0.01 GC area % or more.

[0093] The upper and lower limits can be combined arbitrarily. For example, the content of cyclic diene oxide in the cyclic diene-containing composition is not particularly limited, and it may be substantially free (0.0 GC area%), or may be 0.0001 GC area% to 1.2 GC area%, preferably 0.0003 GC area% to 0.5 GC area%, more preferably 0.001 GC area% to 0.35 GC area%, even more preferably 0.002 GC area% to 0.25 GC area%, particularly preferably 0.005 GC area% to 0.14 GC area%, and most preferably 0.01 GC area% to 0.05 GC area%.

[0094] Methods for controlling the content of cyclic diene oxide in the cyclic diene-containing composition include, for example, an extraction method, a method for controlling the amount by adjusting purification conditions or distillation conditions, a method for adding an antioxidant as described below, and a combination of these methods.

[0095] <Method of producing cyclic diene-containing composition> The method for producing the cyclic diene-containing composition of the present invention is not particularly limited, and examples thereof include the method for producing the cyclic diene-containing composition of the present invention.

[0096] The method for producing a cyclic diene-containing composition of the present invention is a method for producing a cyclic diene-containing composition containing a cyclic diene by distilling and purifying a hydrocarbon decomposition product obtained by thermal decomposition of a hydrocarbon-containing composition, and is characterized in that it includes reducing the content of cyclic diene oxide contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0097] As a method for controlling the content of cyclic diene oxide in the cyclic diene-containing composition to a predetermined threshold or less, a method for producing a cyclic diene-containing composition by thermal decomposition of a hydrocarbon-containing composition to obtain a hydrocarbon decomposition product, which is then purified by distillation, as described below, can be mentioned. During this distillation purification, it is preferable to control the distillation purification conditions. In this case, the cyclic diene oxides in the present invention are usually high-boiling components having a boiling point higher than that of the cyclic diene in the cyclic diene-containing composition of the present invention. Therefore, these cyclic diene oxides can be removed together with other high-boiling components, for example, in the distillation purification step in the production method for the cyclic diene-containing composition of the present invention described below, and their content can be appropriately controlled.

[0098] Furthermore, as a method for controlling the content of cyclic diene oxide contained in the cyclic diene-containing composition to be equal to or less than a predetermined threshold, there can be mentioned a method of adding an antioxidant to the hydrocarbon decomposition product obtained by thermal decomposition of the hydrocarbon-containing composition so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold. That is, the hydrocarbon decomposition products obtained by thermal decomposition of the hydrocarbon-containing composition may contain an antioxidant. In the method for producing a cyclic diene-containing composition of the present invention, the hydrocarbon decomposition product contains an antioxidant, which can suppress the oxidation of cyclic dienes such as dicyclopentadiene to produce cyclic diene oxides derived from the cyclic dienes. The type and suitable amount of antioxidant to be added here will be described in detail in the section explaining the method for producing an aldehyde of the present invention.

[0099] In addition, in the cyclic diene-containing composition of the present invention, storage conditions may be controlled so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than the threshold value. In this case, examples of a method for controlling the storage conditions of the cyclic diene-containing composition include adding an antioxidant to the cyclic diene-containing composition to be stored, or controlling the dissolved oxygen concentration of the cyclic diene-containing composition to be stored. As with the addition of an antioxidant, controlling the dissolved oxygen concentration can also suppress the generation of cyclic diene-derived cyclic diene oxides due to oxidation of cyclic dienes such as dicyclopentadiene.

[0100] When an antioxidant is added to the cyclic diene-containing composition, the type of antioxidant and the lower limit or upper limit of the amount of antioxidant added are the same as the type of antioxidant and the lower limit or upper limit of the amount of antioxidant added described in the method for producing an aldehyde of the present invention, which will be described later.

[0101] When the control of the storage conditions includes controlling the dissolved oxygen concentration of the cyclic diene-containing composition to be stored, the control method of the dissolved oxygen concentration and the dissolved oxygen concentration are synonymous with the control method of the dissolved oxygen concentration and the dissolved oxygen concentration described in the aldehyde production method of the present invention described below.

[0102] The threshold value of the cyclic diene oxide content in the method for producing a cyclic diene-containing composition of the present invention is preferably 1.2 GC area % or less, more preferably 0.5 GC area % or less, even more preferably 0.35 GC area % or less, particularly preferably 0.25 GC area % or less, especially preferably 0.14 GC area % or less, and most preferably 0.05 GC area % or less, as the cyclic diene oxide content in the produced cyclic diene-containing composition. The same applies to the threshold value in the aldehyde production method of the present invention described below.

[0103] In the method for producing a cyclic diene-containing composition of the present invention, the production conditions and the like are controlled so as to obtain a cyclic diene-containing composition having the above-mentioned suitable cyclic diene oxide content and cyclic diene content.

[0104] (Method of producing a cyclic diene-containing composition) The method for producing the cyclic diene-containing composition of the present invention is not particularly limited, and examples include a method in which a hydrocarbon-containing composition is thermally decomposed in a hydrocarbon decomposition product treatment facility such as an ethylene production facility described below, and the resulting hydrocarbon decomposition product is purified by distillation to obtain the cyclic diene-containing composition; or a method in which the hydrocarbon decomposition product is separated and purified to obtain a C5 hydrocarbon fraction described below, and the resulting C5 hydrocarbon fraction is purified by distillation to obtain the cyclic diene-containing composition.

[0105] When producing the cyclic diene-containing composition, the distillation purification is carried out so that the content of the cyclic diene oxide in the cyclic diene-containing composition is equal to or less than a predetermined threshold value. This makes it possible to suppress a decrease in the catalytic activity of the hydroformylation reaction catalyst using the cyclic diene-containing composition as a starting material, efficiently produce an aldehyde corresponding to the cyclic diene from the cyclic diene-containing composition, i.e., in a short reaction time and in a high yield, and also recover expensive rhodium metal at a high recovery rate from the process liquid after the hydroformylation reaction.

[0106] The hydrocarbon-containing composition may be naphtha, coal, or natural gas. Among these, naphtha is preferred from the viewpoint of excellent productivity and quality of the resulting cyclic diene-containing composition.

[0107] (Ethylene production facility) The ethylene production facility in the present invention is a production facility for obtaining a C5 hydrocarbon fraction, which will be described later, as one of the fractions separated and purified from naphtha cracking products, and refers to a facility that thermally cracks naphtha at high temperatures to produce hydrogen, hydrocarbons having a carbon number of 4 such as methane, ethane, ethylene, propane, propylene, butane, or butadiene, hydrocarbons having a carbon number of 5, aromatic hydrocarbons such as benzene, and other heavy oils, and then separates and refines these.

[0108] The embodiment of the ethylene production apparatus is not particularly limited, and may have any configuration as long as it includes a distillation facility for a C5 hydrocarbon fraction and separates and purifies naphtha cracking products. For example, the ethylene production apparatus may have a configuration including facilities for sequentially performing the following steps (1) to (4): Step (1): A thermal cracking step in which raw materials such as naphtha, coal, and natural gas are thermally cracked in a cracking furnace. Step (2): A quenching step in which the resulting cracked gas is quenched and separated. Step (3): Compression step of compressing the quenched and separated cracked gas Step (4): The compressed cracked gas is separated and purified into its various fractions to obtain the main products, ethylene and propylene.

[0109] (C5 hydrocarbon fraction) The C5 hydrocarbon fraction in the present invention is a fraction containing hydrocarbons with a carbon number of 5 as a main component, which is obtained by separating heavy oil from a hydrocarbon cracking product obtained by thermally cracking a hydrocarbon-containing composition such as naphtha, and then separating and removing hydrogen and hydrocarbons with a carbon number of 1 to 4. Specific examples of the C5 hydrocarbon fraction include a mixture containing C5 hydrocarbons such as isoprene, isopentane, normal pentane, and cyclopentadiene as main components. Here, the C5 hydrocarbon fraction contains a small amount of a C4 hydrocarbon fraction and a small amount of a C6 hydrocarbon fraction for separation performance reasons. Furthermore, since the C5 hydrocarbon fraction contains cyclopentadiene, the cyclopentadiene polymerizes over time to form dicyclopentadiene, resulting in the presence of dicyclopentadiene in the C5 hydrocarbon fraction.

[0110] An example of the composition of the C5 hydrocarbon fraction is shown in Table 1. Although it varies depending on the type of hydrocarbon-containing composition such as naphtha subjected to thermal cracking, the C5 hydrocarbon fraction generally contains cyclopentadiene and dicyclopentadiene in a total amount in the range of 10 to 35 mass%.

[0111] [Table 1]

[0112] (Distillation and refining of hydrocarbon cracking products or C5 hydrocarbon fractions) In the present invention, the distillation purification of the hydrocarbon cracking product or the C5 hydrocarbon fraction may be carried out in a single distillation operation or in a combination of multiple distillation operations. When multiple distillation operations are carried out in combination, a method of carrying out multiple distillation operations under the same conditions or a method of carrying out two or more distillation operations under different conditions may be employed.

[0113] In particular, from the viewpoint of keeping the content of cyclic diene oxide contained in the cyclic diene-containing composition of the present invention below a predetermined threshold, specifically, keeping the content of cyclic diene oxide below 1.2 GC area %, a method in which distillation operations under the same or different conditions are combined and carried out two or more times is preferred. When the distillation operation is carried out multiple times, two or more distillation columns are used and the number of theoretical plates or reflux ratio of each distillation column is controlled within the ranges described below, thereby reliably achieving separation and removal of cyclic diene oxides, which cannot be achieved in a single distillation column.

[0114] For example, when two distillation columns are used in the distillation purification, i.e., when a first distillation column and a second distillation column are included, it is preferable to set the reflux ratio of the first distillation column to 20 or more and 30 or less, preferably 23 or more and 27 or less, and the reflux ratio of the second distillation column to 1.8 or more and 4.5 or less, preferably 2.0 or more and 2.8 or less. By doing so, cyclic diene oxides can be efficiently separated and removed, and the content of cyclic diene oxides can be efficiently controlled to be equal to or less than the predetermined threshold value.

[0115] Furthermore, when the distillation purification includes a first distillation column and a second distillation column, it is preferable to set the number of theoretical plates of the first distillation column to 22 to 28, preferably 23 to 27, and the number of theoretical plates of the second distillation column to 10 to 20, preferably 13 to 17. By setting the numbers in this manner, cyclic diene oxides can be efficiently separated and removed, and the content of cyclic diene oxides can be efficiently controlled to be equal to or less than the predetermined threshold value.

[0116] (Specific embodiment of the method for producing a cyclic diene-containing composition) A specific embodiment of the method for producing a cyclic diene-containing composition of the present invention includes a method in which the following steps (I) to (IV) are carried out in order.

[0117] Step (I): A dimerization step in which a C5 hydrocarbon fraction (described below) obtained by thermal cracking of a hydrocarbon-containing composition such as naphtha is introduced into a dimerization tank and heated, and cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction are dimerized to form cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors.

[0118] Step (II): A recovery step in which the effluent from step (I) is introduced into a recovery column and distilled, and unreacted components from step (I) are recovered from the top of the column, while a heavy C5 fraction composition rich in cyclic dienes such as dicyclopentadiene is taken out from the bottom of the column.

[0119] Step (III): A step for removing low boiling components in which the C5 fraction heavy composition from the column bottom in step (II) is introduced into a low boiling component removal column for distillation, and low boiling cyclic monoenes such as vinylnorbornene, which have a boiling point lower than that of cyclic dienes such as dicyclopentadiene and are by-produced during the dimerization reaction in step (I), are removed from the column top, while a fraction rich in cyclic dienes such as dicyclopentadiene is taken from the column bottom.

[0120] Step (IV): A step of removing high boiling components in which the fraction rich in cyclic dienes such as dicyclopentadiene from the bottom of the column in step (III) is introduced into a high boiling component removal column for distillation, and the cyclic diene oxide of the present invention, which has a boiling point higher than that of cyclic dienes such as dicyclopentadiene, and high boiling similar co-dimers produced as by-products during the dimerization reaction of step (I) are removed from the bottom of the column, while the cyclic diene-containing composition of the present invention, which contains a high content of cyclic dienes such as dicyclopentadiene, is taken from the top of the column.

[0121] The steps (I) to (IV) will be described in more detail below.

[0122] [Process (I)] The C5 hydrocarbon fraction is first supplied to the dimerization step (I), where cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction are dimerized to produce cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors. The conditions for the dimerization are not particularly limited and are appropriately selected depending on the content of cyclic diene precursors such as cyclopentadiene in the C5 hydrocarbon fraction, and other factors. Typically, the dimerization temperature is set within a range of 50 to 110°C, and the reaction time is set within a range of 1 to 6 hours, and 30 to 99 mass% of the cyclic diene precursors such as cyclopentadiene contained in the C5 hydrocarbon fraction is dimerized.

[0123] [Process (II)] The product from the dimerization step (I) is then sent to the unreacted component recovery step (II) to separate and recover the unreacted C5 hydrocarbon fraction, which contains isoprene, piperylene (i.e., 1,3-pentadiene), etc., and is sent to a separate purification process as needed. For example, the boiling point of the cyclic diene dicyclopentadiene is 170°C, while the boiling points of the other unreacted components are about 30 to 50°C, so in this recovery step (II), the product from the dimerization step (I) is fed to a distillation column that takes advantage of this difference in boiling points. An unreacted C5 hydrocarbon fraction is recovered from the top of the distillation column, and a heavy C5 fraction composition rich in cyclic dienes such as dicyclopentadiene is taken out from the bottom. Distillation is usually carried out under normal pressure, but when it is desired to increase the recovery amount of the C5 hydrocarbon fraction and the C6 hydrocarbon fraction, reduced pressure distillation or steam distillation is carried out.

[0124] [Process (III)] The heavy C5 fraction composition withdrawn from the bottom of the distillation column in step (II) is liquefied in a condenser as necessary and then sent to a low-boiling component removal step (III) (light-boiling component removal column) for distillation. The heavy C5 fraction composition sent to step (III) is controlled so that the content of cyclic dienes such as dicyclopentadiene is usually within the range of 50 to 95 mass%. The low boiling components contained in the heavy C5 fraction composition are removed from the top of the low boiling component removal column, while a fraction rich in cyclic dienes such as dicyclopentadiene is taken out from the bottom of the column.

[0125] Here, the low-boiling components include the C5 hydrocarbon fraction and C6 hydrocarbon fraction that could not be recovered in step (II), as well as low-boiling cyclic monoenes such as vinylnorbornene, which have a boiling point lower than that of dicyclopentadiene produced as a by-product in the dimerization reaction in step (I), and similar co-dimers such as propenylnorbornene, which is a co-dimer of cyclopentadiene and piperylene. Of these low boiling point components, it is easy to remove cyclic monoenes such as vinylnorbornene, and C5 hydrocarbon fractions and C6 hydrocarbon fractions, but it is difficult to remove similar co-dimer components such as propenylnorbornene. Therefore, conventionally, a distillation column with 50 to 100 plates is required as the low boiling point component removal column.

[0126] The low-boiling component removal column is preferably controlled so that the content of cyclic dienes such as cyclopentadiene in the bottom effluent obtained from the column bottom is 0.5 GC area % or less and the content of hydrocarbons having a carbon number of 5 is 2.0 GC area % or less. The distillation conditions in the light-removal column are controlled as follows: vacuum degree 5 to 200 torr, preferably 10 to 50 torr; column bottom temperature 50 to 120°C, preferably 80 to 110°C; theoretical plate number 22 to 28, preferably 23 to 27; and reflux ratio 20 to 30, preferably 23 to 27. Under these conditions, the bottom effluent obtained from the bottom of the light-removal column can efficiently remove cyclic diene oxides contained in the C5 fraction heavy composition obtained from the bottom of the light-removal column in step (II), and can further remove 90 mass% or more of cyclic monoenes such as vinylnorbornene and similar co-dimers. Specifically, the content of cyclic dienes such as cyclopentadiene can be reduced to 0.5 GC area% or less and the content of hydrocarbons having 5 carbon atoms can be reduced to 2.0 GC area% or less in the bottom distillate.

[0127] [Process (IV)] In the low-boiling component removal step (III), the fraction (tower bottom liquid) rich in cyclic dienes such as dicyclopentadiene taken out from the bottom of the low-boiling component removal column is sent to the high-boiling component removal step (IV) (heavy-boiling component removal column) and subjected to distillation. The high-boiling components removed in step (IV) are cyclic diene oxides of the present invention, which have boiling points higher than those of cyclic dienes such as dicyclopentadiene produced as a by-product in the dimerization reaction of step (I), and high-boiling analogous co-dimers such as methylbicyclononadiene, which are dimers of cyclopentadiene and isoprene. When low-molecular weight products such as cyclopentadiene trimers are present, these low-molecular weight products are also removed.

[0128] The distillation conditions in the high-boiling component removal column in step (IV), particularly the distillation temperature, affect the thermal decomposition of dicyclopentadiene and significantly affect the purity of the final product, so it is preferable to pay attention to them so as to obtain the desired cyclic diene-containing composition. The heavy-boiler removal column is preferably a packed column to minimize pressure loss within the column, and is operated under controlled conditions of a pressure of 5 to 100 torr, preferably 10 to 50 torr, a column bottom temperature of 50 to 120°C, preferably 70 to 110°C, a theoretical plate number of 10 to 20, preferably 13 to 17, and a reflux ratio of 1.8 to 4.5, preferably 2.0 to 2.8. Under these conditions, a cyclic diene-containing composition of the present invention containing a high content of cyclic dienes such as dicyclopentadiene and having an appropriately controlled content of the cyclic diene oxide of the present invention is obtained from the top of the heavy-boiler removal column.

[0129] In the present invention, the high-boiling component removal column is preferably controlled so that the cyclic diene-containing composition obtained from the top of the column has a cyclic diene oxide content of 1.2 GC area % or less, preferably a cyclopentadiene content of 60 GC area % or more, and a cyclic diene oxide content of 0.5 GC area % or less, more preferably 0.35 GC area % or less, even more preferably 0.25 GC area % or less, particularly preferably 0.14 GC area % or less, and especially preferably 0.05 GC area % or less.

[0130] A method for controlling the composition of the cyclic diene-containing composition obtained from the top of the heavy-boiling component removal column to the above-mentioned composition can be exemplified by a method in which the bottom temperature of the heavy-boiling component removal column is controlled to a range of 50 to 120°C, the degree of vacuum is controlled to a range of 5 to 100 torr, the number of theoretical plates is controlled to a range of 10 to 20, and the reflux ratio is controlled to a range of 1.8 to 4.5, and the distillation column feed liquid has a residence time in the column of 15 minutes or less, preferably 10 to 15 minutes. If the bottom temperature of the heavy-boiling component removal column is less than 50°C, the content of C5 hydrocarbons such as cyclopentadiene in the bottom effluent will be high, and if it exceeds 120°C, the content of heavy fractions such as tricyclopentadiene in the bottom effluent will be high. In either case, the content of cyclic dienes such as dicyclopentadiene in the bottom effluent will be low. By controlling the number of theoretical plates of the heavy-boiling component removal column within the range of 10 to 20 and the reflux ratio within the range of 1.8 to 4.5, it is possible to efficiently separate and remove cyclic diene oxides from the cyclic diene-containing composition of the present invention obtained from the top of the heavy-boiling component removal column, and to control the cyclic diene oxide content to the predetermined threshold value or less. Furthermore, if the residence time of the feed liquid in the distillation column exceeds 15 minutes, cyclic diene oxides may be produced in the column, and the amount of heavy fractions such as tricyclopentadiene in the column bottom effluent may increase. Furthermore, if the residence time in the column is less than 10 minutes, the bottom portion of the distillation column becomes small, making it difficult to install a meter for measuring the liquid level. In addition, the amount of liquid held at the bottom of the column becomes small, and during normal operation of the distillation column, the liquid in the bottom of the column becomes empty, which may hinder stable operation.

[0131] A specific method for realizing the above residence time is to design the inner diameter of the bottom of the distillation column to a size that corresponds to the amount of the components effluent from the bottom of the column.

[0132] The pressure of the distillation column may be controlled by introducing into the distillation column a gas (pressure control gas) that is present in the naphtha cracking product treatment equipment and does not contain hydrocarbons having 5 or more carbon atoms.

[0133] In the method for producing a cyclic diene-containing composition of the present invention, when the content of cyclic diene oxide in the resulting cyclic diene-containing composition is controlled by adding an antioxidant to the hydrocarbon decomposition product obtained by thermal decomposition of the aforementioned hydrocarbon-containing composition, the antioxidant may be added in a required amount, for example, before carrying out step (II). In the method for producing a cyclic diene-containing composition of the present invention, an antioxidant may be added to the produced cyclic diene-containing composition.

[0134] [One embodiment of a production facility for a cyclic diene-containing composition] Next, one embodiment of the production equipment for the cyclic diene-containing composition of the present invention will be described with reference to the accompanying drawing. In Fig. 1, a C5 hydrocarbon fraction obtained by thermal cracking of a hydrocarbon-containing composition such as naphtha is first supplied to dimerization vessel 1 via line 10, where dimerization of cyclic diene precursors such as cyclopentadiene is carried out to produce cyclic dienes such as dicyclopentadiene corresponding to the cyclic diene precursors [dimerization step (I)]. After the dimerization reaction, the content of dimerization vessel 1 is sent via line 11 to distillation column 2 [unreacted component recovery step (II)] and subjected to distillation. In distillation column 2, the unreacted C5 hydrocarbon fraction is removed from the top of distillation column 2 via pipe 13, and the bottom liquid (heavy C5 fraction composition) rich in cyclic dienes such as dicyclopentadiene is sent from the bottom of distillation column 2 via pipe 12 to light-boiling component removal column 3 [light-boiling component removal step (III)] for distillation. In the light-removal column 3, cyclic monoenes such as vinylnorbornene, which have lower boiling points than cyclic dienes such as cyclopentadiene, as well as C5 hydrocarbon fractions, C6 hydrocarbon fractions, and similar co-dimers, are removed from the top of the light-removal column 3 via pipe 15, and the fraction rich in cyclic dienes such as dicyclopentadiene is sent from the bottom of the light-removal column 3 via pipe 14 to the final heavy-removal column 4 [heavy-boiling component removal step (IV)] for distillation. In the heavy-boiling component removal column 4, the high-boiling cyclic diene oxides of the present invention, which have boiling points higher than those of cyclic dienes such as dicyclopentadiene, similar co-dimers, and remaining oligomers are removed from the bottom of the heavy-boiling component removal column 4 via pipe 16, and a cyclic-diene-containing composition containing a high content of cyclic dienes such as dicyclopentadiene is obtained from the top of the heavy-boiling component removal column 4 via pipe 17.

[0135] The order in which the above steps (I) to (IV), particularly steps (II) to (IV), are carried out is not particularly limited, and the order in which the steps are carried out can be changed as long as the effects of the present invention are not impaired.

[0136] <Method for producing aldehyde> The method for producing an aldehyde of the present invention is a method for producing an aldehyde by subjecting a cyclic diene in a cyclic diene-containing composition to a hydroformylation reaction. The method for producing an aldehyde of the present invention is a production method that includes adjusting the content of cyclic diene oxide contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0137] The cyclic diene in the aldehyde production method of the present invention can be treated as having the same meaning as the cyclic diene in the cyclic diene-containing composition of the present invention described above.

[0138] In the method for producing an aldehyde of the present invention, the cyclic diene-containing composition of the present invention can be used as the cyclic diene-containing composition.

[0139] The method for reducing the content of cyclic diene oxide in the cyclic diene-containing composition to a predetermined threshold or less is not particularly limited, and an example thereof includes, as described above, a method in which a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition such as naphtha is distilled and purified to obtain the cyclic diene-containing composition. During this distillation purification, it is preferable to control the conditions for the distillation purification.

[0140] In the method for producing an aldehyde of the present invention, the hydrocarbon decomposition product may also contain an antioxidant, as described above in the method for producing a cyclic diene-containing composition of the present invention. The antioxidant used in the method for producing an aldehyde of the present invention can be treated as having the same meaning as the antioxidant used in the method for producing a cyclic diene-containing composition of the present invention. When the hydrocarbon decomposition product contains an antioxidant, it is possible to inhibit the oxidation of cyclic dienes such as dicyclopentadiene and the like, resulting in the generation of cyclic diene oxides derived from the cyclic dienes.

[0141] Furthermore, in the method for producing an aldehyde of the present invention, as described above in the method for producing a cyclic diene-containing composition of the present invention, an antioxidant can be added to the hydrocarbon decomposition product so that the content of cyclic diene oxides in the cyclic diene-containing composition is equal to or less than a predetermined threshold. By adding an antioxidant to the hydrocarbon decomposition product, it is possible to suppress the oxidation of cyclic dienes such as dicyclopentadiene to produce cyclic diene-derived cyclic diene oxides.

[0142] In the method for producing an aldehyde of the present invention, the storage conditions may be controlled so that the content of the cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than the threshold value. In this case, examples of a method for controlling the storage conditions of the cyclic diene-containing composition include adding an antioxidant to the cyclic diene-containing composition to be stored, or controlling the dissolved oxygen concentration of the cyclic diene-containing composition to be stored. As with the addition of an antioxidant, controlling the dissolved oxygen concentration can also prevent cyclic dienes such as dicyclopentadiene from being oxidized to produce cyclic diene oxides derived from the cyclic diene.

[0143] The type of antioxidant used in the present invention is not particularly limited as long as it has excellent dispersibility and solubility in the reaction system and can suppress the oxidation of the cyclic diene and the generation of cyclic diene oxides derived from the cyclic diene, and those skilled in the art can appropriately select and use, for example, known phenolic compounds, known sulfur-based compounds, known phosphorus-based compounds, known amine-based compounds, etc., which are used as antioxidants. Among these, phenolic compounds, particularly hindered phenolic compounds, are preferred, and it is preferable to use at least one of these.

[0144] The phenolic compounds include t-butylcatechol, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), N,N'-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide], pentaerythritol tetrakis[3-[3,5-di(t-butyl)-4-hydroxyphenyl]propionate], 2,2thio[diethylbis-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4-hydroxybenzoylpropanol ... ,4',4''-[(2,4,6-trimethylbenzene-1,3,5-triyl)tris(methylene)]tris(2,6-di-t-butylphenol), bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid)ethylenebis(oxyethylene), 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanuric acid, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-S-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, and the like.

[0145] These antioxidants may be used alone or in combination of two or more.

[0146] When the hydrocarbon decomposition product contains an antioxidant, or when an antioxidant is added to the hydrocarbon decomposition product, the lower limit of the content or amount of the antioxidant is not particularly limited, as long as it is an amount that can make the content of the cyclic diene oxide according to the present invention equal to or less than the threshold value. As an example, the content of the antioxidant in the hydrocarbon decomposition product is preferably 30 ppm by mass or more, more preferably 50 ppm by mass or more, and even more preferably 100 ppm by mass or more. On the other hand, when an antioxidant is added to the hydrocarbon decomposition product, the content or upper limit of the amount of the antioxidant is not particularly limited as long as the quality of the cyclic diene-containing composition of the present invention can be maintained at a satisfactory level and the increase in production costs for purification, etc. can be kept within an acceptable range. For example, the content of the antioxidant in the hydrocarbon decomposition product is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, and even more preferably 300 ppm by mass or less. The above upper and lower limits can be combined in any manner.

[0147] Furthermore, when the cyclic diene-containing composition according to the present invention contains an antioxidant, or when an antioxidant is added to the cyclic diene-containing composition, the lower limit of the content or amount of antioxidant added is not particularly limited, as long as it is an amount that can make the content ratio of the cyclic diene oxide according to the present invention equal to or less than the threshold value. For example, the content of the antioxidant in the cyclic diene-containing composition is preferably 30 ppm by mass or more, more preferably 50 ppm by mass or more, and even more preferably 100 ppm by mass or more. On the other hand, when the cyclic diene-containing composition contains an antioxidant, the upper limit of the content or amount of the antioxidant is not particularly limited as long as the quality of the cyclic diene-containing composition of the present invention can be maintained at a good level and the increase in production costs for purification, etc. can be kept within an acceptable range. For example, the content of the antioxidant in the cyclic diene-containing composition is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and even more preferably 300 ppm by mass or less. The above upper and lower limits can be combined in any manner.

[0148] When the content of antioxidant in the hydrocarbon decomposition product or the cyclic diene-containing composition is equal to or greater than the above-mentioned lower limit, the production of cyclic diene oxides can be effectively suppressed with a sufficient amount of antioxidant, making it easier to reduce the content of cyclic diene oxides to the above-mentioned threshold value or less. On the other hand, when the content of the antioxidant is equal to or less than the above upper limit, the quality of the cyclic diene-containing composition of the present invention can be maintained at a good level, and an increase in production costs for purification, etc. can be kept within an acceptable range. Furthermore, the risk of the antioxidant precipitating at the bottom of the distillation column and clogging the piping can be reduced.

[0149] Furthermore, in the aldehyde production method of the present invention, when the dissolved oxygen concentration of the stored cyclic diene-containing composition is controlled so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is below the threshold, the control of the dissolved oxygen concentration can be carried out, for example, by circulating an inert gas such as nitrogen through the cyclic diene-containing composition or under the storage atmosphere of the cyclic diene-containing composition. In this case, there is no particular limitation on the concentration of dissolved oxygen to be controlled, as long as it is a concentration that can reduce the content of cyclic diene oxide in the cyclic diene-containing composition to the threshold value or less, but from the viewpoint of the effect of inhibiting the production of cyclic diene oxide, it is preferable to set the dissolved oxygen concentration of the cyclic diene-containing composition to 100 volume ppm or less, particularly 50 volume ppm or less. On the other hand, from the viewpoint of economics such as the production cost required for reducing the dissolved oxygen concentration, an excessively low dissolved oxygen concentration is not preferable, and therefore the dissolved oxygen concentration in the cyclic diene-containing composition is usually 1 volume ppm or more.

[0150] In the method for producing an aldehyde of the present invention, the method for producing an aldehyde by the hydroformylation reaction is not particularly limited, and can be carried out according to a conventional method. For example, according to the method described in Japanese Patent Application Laid-Open No. 2001-10999, an aldehyde can be produced by hydroformylating the cyclic diene contained in the cyclic diene-containing composition of the present invention using hydrogen and carbon monoxide in a hydroformylation reaction solvent comprising a hydrocarbon compound in the presence of a catalyst comprising a rhodium compound and an organophosphorus compound.

[0151] Specifically, when the cyclic diene in the cyclic diene-containing composition of the present invention is dicyclopentadiene, tricyclodecane dicarbaldehyde can be produced by hydroformylating the dicyclopentadiene contained in the cyclic diene-containing composition using hydrogen and carbon monoxide in a hydroformylation reaction solvent comprising a hydrocarbon compound in the presence of a catalyst comprising a rhodium compound and an organophosphorus compound, as shown in the following reaction formula (I), according to the method described in JP 2001-10999 A:

[0152] [ka]

[0153] The rhodium compound used in this hydroformylation step may take any form of precursor, so long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. Rhodium compounds include Rh(acac)(CO)2, Rh2O3, and Rh4(CO) 12 , Rh6(CO) 16 Alternatively, a catalyst precursor such as Rh(NO3)3 may be introduced into the reaction mixture together with an organophosphorus compound to form a catalytically active rhodium metal hydride carbonyl phosphorus complex in the reaction vessel, or a rhodium metal hydride carbonyl phosphorus complex catalyst may be prepared in advance and then introduced into the reaction vessel.

[0154] In a preferred embodiment of the present invention, Rh(acac)(CO)2 is used as a rhodium precursor material and reacted with an organophosphorus compound in the presence of a solvent, and then introduced into a reactor together with an excess of free organophosphorus compound to form a catalytically active rhodium-organophosphorus complex catalyst.

[0155] The organophosphorus compounds which form catalysts for the hydroformylation reaction with the rhodium compounds include known phosphites and known phosphines. Among these, the phosphite is a compound represented by the general formula P(-OR 11 )(-OR 12 )(-OR 13 )(wherein, R 11 , R 12 and R 13 R represents an optionally substituted aryl group or alkyl group. 11 , R 12 and R 13 Specific examples of the alkyl group include aryl groups such as phenyl and naphthyl groups which may be substituted with a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, methoxy group, etc.; aliphatic alkyl groups such as methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.; and alicyclic alkyl groups such as cyclopentyl and cyclohexyl groups which may be substituted with a lower alkyl group such as a methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group, etc.

[0156] Specific examples of suitable phosphites include tris(2-t-butylphenyl)phosphite, tris(3-methyl-6-t-butylphenyl)phosphite, tris(3-methoxy-6-t-butylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, and di(2-t-butylphenyl)(t-butyl)phosphite. The phosphites are not limited to these. These phosphites may be used alone or in combination of two or more.

[0157] As the phosphine, sterically hindered alkylphosphines are particularly effective in the hydroformylation reaction of dicyclopentadiene, and specific examples include tricyclopropylphosphine, tricyclobutylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, tricycloheptylphosphine, and tricyclooctylphosphine. The phosphines are not limited to these. These phosphines may be used alone or in combination of two or more.

[0158] The amount of the organic phosphorus compound used is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques.

[0159] The amount of the rhodium catalyst used is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques.

[0160] The hydroformylation reaction of dicyclopentadiene can be carried out without using a solvent, but is more preferably carried out using an organic solvent that is inert to the reaction.

[0161] The temperature and pressure for the hydroformylation reaction of dicyclopentadiene are not particularly limited and can be appropriately set by a person skilled in the art according to well-known techniques. The reaction temperature is usually 40 to 160°C, preferably 80 to 140°C, and the reaction pressure is usually 1 to 15 MPa.

[0162] The molar ratio of hydrogen to carbon monoxide in the hydrogen / carbon monoxide mixed gas used in the reaction is not particularly limited and can be appropriately set by a person skilled in the art according to well-known techniques. Usually, the molar ratio of hydrogen to carbon monoxide (hydrogen / carbon monoxide) in the introduced gas composition can be set to be within the range of 0.2 to 5.0.

[0163] The hydroformylation reaction is carried out by a continuous feed method in which the cyclic diene-containing composition of the present invention as a raw material is fed alone or as a mixed solution of the cyclic diene-containing composition of the present invention and a solvent to a reactor containing a rhodium-organophosphorus complex catalyst, a solvent, and a mixed gas of hydrogen and carbon monoxide. This method reduces the production of cyclopentadiene, which inhibits the hydroformylation reaction due to thermal decomposition of dicyclopentadiene, the cyclic diene in the cyclic diene-containing composition of the present invention, in the reactor, thereby maintaining a good reaction rate and yield. In order to maintain the fluidity of the cyclic diene-containing composition of the present invention, it is preferable to dilute it with the aforementioned solvent and feed it to the reactor at a temperature at which it does not depolymerize and produce cyclopentadiene.

[0164] <Extraction of tricyclodecane dicarbaldehyde> After completion of the hydroformylation reaction, the method for extracting and separating the product tricyclodecane dicarbaldehyde from the reaction mixture is not particularly limited, and can be appropriately determined by a person skilled in the art according to well-known techniques. For example, the reaction product liquid obtained after the hydroformylation reaction, or a diluted product liquid obtained by diluting the reaction product liquid with a hydrocarbon compound that can be used as a hydroformylation reaction solvent, is mixed with an extraction solvent, and then the mixture is separated, whereby tricyclodecane dicarbaldehyde, which is the product in the reaction product liquid, can be extracted into the extraction solvent layer.

[0165] The extraction solvent is not particularly limited, and examples thereof include alcohol.

[0166] The alcohol is not particularly limited, and examples thereof include primary alcohols having 1 to 3 carbon atoms and polyhydric alcohols having 2 to 6 carbon atoms. Examples of the primary alcohols include methanol, ethanol, and propanol. Examples of the polyhydric alcohols having 2 to 6 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, isomers of pentanediol, neopentyl glycol, hexanediol, glycerin, pentaerythritol, and trimethylolpropane. Among these, methanol, ethylene glycol, propanediol, and butanediol are preferably used because they have a relatively low boiling point, are available at relatively low cost, and are liquids that are easy to handle. These alcohols may be used alone or in combination of two or more. Alternatively, extraction may be carried out in the presence of water in addition to the alcohol, as the addition of water facilitates the distribution of the aldehyde and catalyst components into each layer.

[0167] From the viewpoint of efficiently extracting the product tricyclodecane dicarbaldehyde from the hydroformylation reaction solvent, the hydroformylation reaction solvent and the extraction solvent preferably have excellent liquid-liquid separation properties, specifically, a significant difference in density between the two solvents. From this viewpoint, examples of combinations of the hydroformylation reaction solvent and the extraction solvent include methylcyclohexane and ethylene glycol, or methylcyclohexane and a mixed solution of water and methanol.

[0168] The volume ratio of the extraction solvent to the reaction product liquid is not particularly limited, and can be determined based on, for example, the solubility of tricyclodecane dicarbaldehyde in the extraction solvent and the content of tricyclodecane dicarbaldehyde in the reaction product liquid.

[0169] For example, if the tricyclodecanedicarbaldehyde to be separated has high solubility in the extraction solvent and is present at a low concentration in the reaction product solution, tricyclodecanedicarbaldehyde can be effectively extracted by using an extraction solvent with a low volume ratio (extraction solvent / reaction product solution).As the product concentration increases, the volume ratio (extraction solvent / reaction product solution) required to extract tricyclodecanedicarbaldehyde from the reaction product solution increases. On the other hand, when tricyclodecane dicarbaldehyde has a relatively low solubility in the extraction solution, the volume ratio can be appropriately selected from the range of 10:1 to 1:10. Furthermore, in order to increase the amount of tricyclodecane dicarbaldehyde extracted using a small amount of extraction solvent, it is effective to divide the extraction solvent and perform the extraction operation several times. In the final stage of the extraction operation, a hydroformylation reaction solvent such as methylcyclohexane may be added to the reaction product liquid in an amount of about 5 to 20 mass %, which can improve the catalyst removal rate by adding the hydroformylation reaction solvent.

[0170] The temperature for the extraction operation is not particularly limited, and can be set to the hydroformylation reaction temperature or lower. The extraction method is not particularly limited, and examples thereof include a method in which an extraction solvent is added to the hydroformylation reactor after the hydroformylation reaction to carry out extraction treatment, and a method in which the hydroformylation reaction product liquid withdrawn from the hydroformylation reactor is introduced into an extraction tank to carry out extraction treatment.

[0171] The layer containing the reaction product liquid recovered after the extraction operation contains the hydroformylation catalyst and the hydroformylation solvent. Therefore, this layer can be returned to the hydroformylation reactor and reused. In this case, the catalyst components rhodium, organophosphorus ligand, or solvent may be added to the layer to be reused. The extraction operation described above can be carried out as both a batch process and a continuous process.

[0172] The cyclic diene-containing composition of the present invention used as a raw material for producing an aldehyde in the present invention has a cyclic diene oxide content of not more than a predetermined threshold value. This allows expensive rhodium metal to be recovered at a high recovery rate from the process solution after the hydroformylation reaction, and the recovered rhodium metal can be reused as a catalyst to efficiently carry out the hydroformylation reaction repeatedly.

[0173] <Alcohol production method> The alcohol production method of the present invention is a method for producing an alcohol, which comprises producing an aldehyde by the aldehyde production method of the present invention and producing an alcohol from the aldehyde.

[0174] The method for producing an alcohol from the aldehyde is not particularly limited and can be carried out according to a conventional method. For example, according to the method described in JP-A-2001-10999, the aldehyde obtained by the method for producing an aldehyde of the present invention can be directly subjected to a known hydrogenation reaction, or the obtained aldehyde can be dimerized and then subjected to a known hydrogenation reaction to produce an alcohol.

[0175] Specifically, when the cyclic diene in the cyclic diene-containing composition of the present invention is dicyclopentadiene, the dicyclopentadiene contained in the cyclic diene-containing composition is hydroformylated to obtain tricyclodecane dicarbaldehyde, and then the obtained tricyclodecane dicarbaldehyde is subjected to a hydrogenation reaction in the presence of a hydrogenation catalyst and hydrogen to obtain tricyclo[5.2.1.0 2,6 ]Decanedimethanol can be produced.

[0176] The hydrogenation catalyst used in the hydrogenation reaction may be a known solid catalyst in which a metal such as Ru, Ni, Cr, or Cu is supported on a carrier. The conditions for the hydrogenation reaction are usually a temperature of 60 to 200° C. and a hydrogen pressure of about 0.1 to 20 MPaG. [Example]

[0177] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. The following examples are merely illustrative and are not intended to limit any of the embodiments described herein. The following examples do not limit the present invention in any way. The values ​​of various manufacturing conditions and evaluation results in the following examples and the like have the meaning of preferred upper or lower limit values ​​in the embodiments of the present invention, and a preferred range may be a range defined by a combination of the above-mentioned upper or lower limit value and the values ​​of the following examples or values ​​of the examples themselves.

[0178] The compounds used in the following examples are as follows. DCPD: Dicyclopentadiene (Mitsubishi Chemical Corporation) Acetylacetonatodicarbonylrhodium (trade name: Rh(acac)(CO)2 , manufactured by N.E. Chemcat Corporation) Nickel-supported diatomaceous earth catalyst (nickel-chromium-supported diatomaceous earth with a nickel loading of 12% by mass and a chromium loading of 2% by mass, produced in accordance with the description in Example 1 of JP 2005-279587 A) DBPO: (trade name: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by Tokyo Chemical Industry Co., Ltd.) Methylcyclohexane (product name: Methylcyclohexane, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Methanol (product name: Methanol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0179] [Reference Experimental Example 1] <Production of heavy oil through thermal cracking of naphtha> Using commercially available naphtha as a hydrocarbon-containing composition and a naphtha cracking plant manufactured by Mitsubishi Chemical Corporation, the naphtha was thermally cracked according to the naphtha thermal cracking method disclosed in Japanese Patent Publication No. 7-39354 to obtain a hydrocarbon cracking product. The obtained hydrocarbon decomposition product was supplied to a distillation column for fractional distillation to recover a C5 hydrocarbon fraction mainly composed of hydrocarbons having 5 carbon atoms. Next, the obtained C5 hydrocarbon fraction was supplied to a reactive distillation column, and while dimerizing cyclopentadiene contained in the C5 hydrocarbon fraction to convert it to dicyclopentadiene, it was separated and purified under the following conditions to recover a C5 fraction heavy composition containing dicyclopentadiene, which is a cyclic diene, from the bottom of the distillation column.

[0180] <Distillation and purification of heavy oil> 1895 g of the obtained C5 hydrocarbon fraction was charged into a distillation column having 40 stages, and a fractional distillation operation was performed under the following fractional distillation conditions, and about 100 g of the distillate from the top of the distillation column was taken out separately.

[0181] <Fractional distillation conditions> Bottom temperature: 40 - 140 °C Top temperature: 24 - 80 °C Pressure: 1 - 10 kPa (7.5 - 75 torr) Retention time of the distillation column feed liquid in the column: about 19 hours

[0182] The separately taken fractions were analyzed under the following GC measurement conditions using a gas chromatograph (GC) measurement device and the gas chromatography total area method, and a fraction having a DCPD content ratio of 99% (hereinafter referred to as "DCPD with a purity of 99%") was selected.

[0183] <GC measurement conditions> GC device: GC - 2025 (high - performance general - purpose gas chromatograph, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column DB - 1 (manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50 °C (holding time 5 minutes) → heating at 10 °C / min → 300 °C (holding time: none) Injection port temperature: 200 °C Detector temperature: 300 °C Sample volume: 0.3 μL (split ratio: 1 / 30)

[0184] The composition ratio of each component in the gas chromatography total area method was calculated as the area content ratio (unit: GC area%) of each peak component when the total area of ​​the GC peaks of all products observed on the gas chromatogram in the temperature condition region with a retention time of 2.5 to 30 minutes was taken as 100%. Furthermore, the GC area ratio of the total area content ratio (unit: GC area%) of DCPD oxides (described below) to the area content ratio (unit: GC area%) of DCPD among each peak component was calculated.

[0185] [Reference Experimental Example 2] <Distillation purification of dicyclopentadiene (DCPD)> As a cyclic diene, 1494.1 g of the above-mentioned DCPD having a purity of 99% was charged into a simple glass distillation column, and distillation was carried out under conditions of a pressure of 1 to 0.1 kPa, a column bottom temperature of 70 to 90°C, and a column top temperature of 60 to 70°C. The distillate from the top of the distillation column was collected in 200 g portions to obtain distillates 1 to 7 listed in Table 1 in the order of distillation, and these were used as DCPD-containing compositions.

[0186] As the cyclic diene oxides contained in the DCPD-containing composition, the total content of DCPD oxide, and the contents of the compound one enantiomer of which is represented by the general formula (I) (hereinafter referred to as "compound (I)"), the compound one enantiomer of which is represented by the general formula (II) (hereinafter referred to as "compound (II)"), and the compound one enantiomer of which is represented by the general formula (III) (hereinafter referred to as "compound (III)"), which constitute the DCPD oxide, were measured according to the following measurement method 1.

[0187] <Measurement method 1> Analysis was carried out under the following GC measurement conditions, and the total content ratio of the peaks with elution times of 17.7 minutes to 18.8 minutes was measured. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (hold time 5 minutes) → Heat at 10°C / minute → 300°C (hold time: none) Inlet temperature: 200℃ Detector temperature: 300℃ Sample volume: 0.3 μL (split ratio: 1 / 30)

[0188] The gas chromatogram of the DCPD-containing composition obtained in Reference Experimental Example 2 is shown in FIG. Peak (1) with an elution time of 17.73 to 17.88 minutes corresponds to compound (I), peak (2) with an elution time of 18.26 to 18.36 minutes corresponds to compound (II), and peak (3) with an elution time of 18.52 to 18.70 minutes corresponds to compound (III).

[0189] [Example 1] <Hydroformylation reaction> A 500 mL stainless steel autoclave reactor was charged with 109.34 g of DCPD-containing composition distillate 1 as a raw material compound for the hydroformylation catalyst under a nitrogen atmosphere, 14.3 mg (0.0556 mmol) of Rh(acac)(CO)2 as a catalyst, 1052 mg (1.63 mmol) of DBPO, and 84.28 g of methylcyclohexane as an organic solvent. The temperature of the reaction solution in the reactor was then raised to 70 °C while stirring by up-and-down stirring. Next, a mixed gas of hydrogen and carbon monoxide (hydrogen:carbon monoxide = 1:1 (molar ratio)) was rapidly introduced through the gas inlet valve to a pressure of 3 MPaG, and the reaction was continued until the hydrogen and carbon monoxide were no longer consumed by the reaction. Then, while maintaining this pressure, the temperature of the reaction solution was raised to 100 °C, and the reaction was continued until the hydrogen and carbon monoxide were no longer consumed by the reaction. The reaction time of the hydroformylation reaction (also referred to simply as "reaction time" in this specification) was the time from when the mixed gas of hydrogen and carbon monoxide was introduced into the reactor until the hydrogen and carbon monoxide were no longer consumed by the reaction, and was used as an index of reaction efficiency. During the reaction, the mixed gas consumed in the reaction was automatically introduced into the autoclave via an automatic pressure regulating valve, and the reaction was carried out such that the pressure inside the reactor was always maintained at 3 MPaG. After the reaction was completed, the reaction solution in the reactor was cooled to room temperature, and the pressure of the remaining gas in the reactor was released to obtain 237.68 g of a hydroformylation reaction product liquid.

[0190] <Evaluation of Hydroformylation Reaction> The resulting hydroformylation reaction product was analyzed using a gas chromatograph (GC) under the following GC measurement conditions: a gas chromatography (GC) total area method to determine the dicyclopentadiene (DCPD) content (unit: GC area%), and the DCPD and product tricyclodecane dicarbaldehyde (TCDDD) contents (unit: GC area%) in the hydroformylation reaction product. The DCPD conversion (unit: %) and TDD yield (unit: %) were calculated to be 99.4% and 96.5%, respectively. The hydroformylation reaction time was 4.88 hours. The evaluation results are shown in Table 2.

[0191] <GC measurement conditions> GC instrument: Gas chromatogram measuring instrument (trade name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (column flow rate 1.23 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 120 °C (holding time none) → increasing temperature at 10 °C / min → 300 °C (holding time 12 minutes) Inlet temperature: 200 °C Detector temperature: 300 °C Sample volume: 0.3 μL (split ratio: 1 / 30)

[0192] <Extraction operation> To 235.23 g of the obtained hydroformylation reaction product solution, 71.65 g of methanol and 46.85 g of water were added, and then stirred for 40 minutes under a nitrogen atmosphere. Then, it was allowed to stand for 30 minutes to separate into two phases, and the lower layer (a1) and the upper layer (b1) were separated and recovered. To the obtained lower phase (a1), 8.4 g of methylcyclohexane was added and then stirred for 30 minutes. Then, it was allowed to stand for 30 minutes to separate into two phases, and 278.83 g of the lower phase (a2) and a mixed solution of 81.71 g of the upper layer (b1) and the upper layer (b2) were separated and recovered. When the composition of the obtained lower phase (a2) was analyzed by gas chromatography, it was 47% by mass of tricyclodecane dicarbaldehyde, 27% by mass of methanol, 16% by mass of water, 7% by mass of methylcyclohexane, and 3% by mass of other components. Also, regarding the mixed solution of the obtained upper layer (b1) and the upper layer (b2), when the recovery rates of rhodium (Rh) metal and tris(2,4-di-tert-butylphenyl) phosphite were analyzed by fluorescent X-ray analysis and inductively coupled plasma optical emission spectrometry, they were 99% and 99% respectively.

[0193] <Calculation of the reaction rate constant (k2) of the hydroformylation reaction> Assuming that the reaction rate of the hydroformylation reaction can be approximated by a linear function relative to the content of the substrate DCPD, a graph was drawn on an XY graph with the hydroformylation reaction time on the X axis and the natural logarithm of "1 - conversion rate / 100" on the Y axis. The slope of the approximate linear function in the conversion rate range of 60% to 80% was calculated, and this was used as the reaction rate constant (k2) of the hydroformylation reaction (unit: hr -1 ) was decided. The "conversion rate" was calculated in the same manner as described in the evaluation of the hydroformylation reaction. As a result, the reaction rate constant (k2) of the hydroformylation reaction in this Example 1 was 0.98 hr -1 It was.

[0194] The evaluation results for Example 1 are summarized in Table 2.

[0195] [Example 2] The hydroformylation reaction of the raw material compound was carried out under the same conditions as in Example 1, except that DCPD-containing composition distillate 2 was used as the raw material compound in the hydroformylation reaction of Example 1, and the evaluation was similarly carried out. In addition, the rate of decrease in the reaction rate constant (k2) in the hydroformylation reaction was calculated by the following method.

[0196] <Calculation of the Decrease Rate of the Reaction Rate Constant (k2) of the Hydroformylation Reaction> The reaction rate constant (k2) of the hydroformylation reaction calculated by the above-mentioned method was divided by the reaction rate constant (k2) of Example 1 and multiplied by 100 to obtain the "decrease rate of the reaction rate constant (k2) of the hydroformylation reaction." The reaction rate constant (k2) of the hydroformylation reaction in this Example 2 was 0.94 hr -1 The rate of decrease in the reaction rate constant (k2) was 4.1%. The evaluation results in Example 2 are summarized in Table 2.

[0197] [Example 3] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Example 1, except that DCPD-containing composition distillate 3 was used as the raw material compound in the hydroformylation reaction of Example 1, and evaluations were similarly carried out. The rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Example 2. The evaluation results are summarized in Table 2.

[0198] [Example 4] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Example 1, except that DCPD-containing composition distillate 4 was used as the raw material compound in the hydroformylation reaction of Example 1, and evaluations were carried out in the same manner. The rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Example 2. The evaluation results are summarized in Table 2.

[0199] [Example 5] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Example 1, except that DCPD-containing composition distillate 5 was used as the raw material compound in the hydroformylation reaction of Example 1, and evaluations were similarly carried out. The rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Example 2. The evaluation results are summarized in Table 2.

[0200] [Example 6] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Example 1, except that DCPD-containing composition distillate 6 was used as the raw material compound in the hydroformylation reaction of Example 1, and evaluations were carried out in the same manner. The rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Example 2. The evaluation results are summarized in Table 2.

[0201] [Example 7] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Example 1, except that DCPD-containing composition distillate 7 was used as the raw material compound in the hydroformylation reaction of Example 1, and evaluations were carried out in the same manner. The rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Example 2. The evaluation results are summarized in Table 2.

[0202] In addition, in Examples 1 to 7, the contents of Compound (I), Compound (II), and Compound (III) contained in Extracts 1 to 7 were measured according to the above-mentioned Measurement Method 1. The measurement results are shown in Table 2.

[0203] [Table 2]

[0204] FIG. 2 shows the relationship between the content of DCPD oxide (GC area %) in the DCPD-containing compositions (distillates 1 to 7) in Examples 1 to 7 and the reaction rate constant (k2) of the hydroformylation reaction. The relationship between the content of DCPD oxide (GC area %) in the DCPD-containing compositions (distillates 1 to 7) in Examples 1 to 7 and the rate of decrease in the reaction rate constant (k2) is shown in FIG. The relationship between the content of DCPD oxide (GC area %) in the DCPD-containing compositions (distillates 1 to 7) in Examples 1 to 7 and the recovery rate of rhodium (Rh) is shown in FIG.

[0205] FIG. 2 shows that the lower the content of DCPD oxide in the DCPD-containing composition, the higher the value of the reaction rate constant (k2) of the hydroformylation reaction, and the more excellent the reaction efficiency. From FIG. 3, it can be seen that the lower the content of DCPD oxide in the DCPD-containing composition, the lower the rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction, and the more excellent the reaction efficiency. It can be seen from FIG. 4 that the lower the content of DCPD oxide in the DCPD-containing composition, the higher the recovery rate of rhodium (Rh).

[0206] [Example 8] <Alcohol production> A 200 L autoclave reactor was charged with 102.1 g of the lower phase (a2) obtained in Example 1 and 2 g of a nickel-chromium supported diatomaceous earth catalyst as a hydrogenation catalyst. The mixture was stirred at 1200 rpm while the temperature of the reaction solution in the reactor was raised to 160°C. Hydrogen gas was then introduced through the gas inlet valve until the pressure inside the reactor reached 3 MPaG. The reaction was allowed to proceed for 2 hours while maintaining this pressure and the temperature of the reaction solution. During the reaction, hydrogen gas was continuously introduced into the reactor in the amount consumed during the reaction, while maintaining the pressure inside the reactor at 3 MPaG. After the reaction was completed, the reaction mixture was cooled to room temperature, the remaining gas pressure was released, and the nickel-chromium-supported diatomaceous earth catalyst was separated by filtration using a 5 μm filter, yielding 97.2 g of reaction mixture. The content of the starting compound tricyclodecane dicarbaldehyde in the reaction mixture before the reaction and the content of the product tricyclo[5.2.1.0(2,6)]decane dimethanol (hereinafter referred to as "TCDDM") in the reaction mixture after the reaction were analyzed by gas chromatography. The yield of TCDDM was 97.9%. [Explanation of symbols]

[0207] 1 Dimerization tank 2. Distillation tower 3 Low boiling point component removal column 4. High boiling point component removal tower

Claims

1. A cyclic diene-containing composition comprising a cyclic diene, A cyclic diene-containing composition, wherein the content of cyclic diene oxide in the cyclic diene composition is 1.2 GC area % or less. (However, the cyclic diene does not include the cyclic diene oxide.)

2. 2. The cyclic diene-containing composition according to claim 1, wherein the content of the cyclic diene is 60 GC area % or more.

3. The cyclic diene-containing composition according to claim 1, wherein the content of the cyclic diene oxide is 0.5 GC area% or less, preferably 0.35 GC area% or less, more preferably 0.25 GC area% or less, even more preferably 0.14 GC area% or less, and particularly preferably 0.05 GC area% or less.

4. 2. The cyclic diene-containing composition according to claim 1, wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analysis is carried out under the following GC measurement conditions, and the total content ratio of the peaks with elution times of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 minutes) → heating at 10°C / minute → 300°C (holding time: none) Inlet temperature: 200℃ Detector temperature: 300°C Sample volume: 0.3 μL (split ratio: 1 / 30)

5. 2. The cyclic diene-containing composition of claim 1, wherein the cyclic diene is a polycyclic diene.

6. 6. The cyclic diene-containing composition of claim 5, wherein the cyclic diene is dicyclopentadiene.

7. 2. The cyclic diene-containing composition according to claim 1, wherein the cyclic diene oxide is a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

8. 2. The cyclic diene-containing composition according to claim 1, wherein the cyclic diene oxide comprises at least one selected from the group consisting of a cyclic diene having a carbonyl group, a cyclic diene having a hydroxyl group, and a cyclic monoene having an epoxy group.

9. The cyclic diene is dicyclopentadiene, and The cyclic diene-containing composition according to claim 6, wherein the cyclic diene oxide comprises at least one compound selected from the group consisting of a compound in which one enantiomer is represented by the following general formula (I), a compound in which one enantiomer is represented by the following general formula (II), and a compound in which one enantiomer is represented by the following general formula (III): 【Chemical 1】 [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

10. A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of claims 1 to 9 to a hydroformylation reaction to produce an aldehyde.

11. A method for producing an alcohol, comprising producing an aldehyde by the production method according to claim 10 and producing an alcohol from the aldehyde.

12. A method for producing an aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition, comprising: A method for producing an aldehyde, comprising adjusting the content of cyclic diene oxide contained in the cyclic diene-containing composition to a predetermined threshold value or less. (However, the cyclic diene does not include the cyclic diene oxide.)

13. The method for producing an aldehyde according to claim 12, wherein the content of the cyclic diene oxide in the cyclic diene-containing composition is 1.2 GC area % or less.

14. The method for producing an aldehyde according to claim 12, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60 GC area % or more.

15. 14. The method for producing an aldehyde according to claim 13, wherein the content of the cyclic diene oxide in the cyclic diene-containing composition is 0.5 GC area% or less, preferably 0.35 GC area% or less, more preferably 0.25 GC area% or less, even more preferably 0.14 GC area% or less, and particularly preferably 0.05 GC area% or less.

16. The method for producing an aldehyde according to claim 12, wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analysis is carried out under the following GC measurement conditions, and the total content ratio of the peaks with elution times of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 minutes) → heating at 10°C / minute → 300°C (holding time: none) Inlet temperature: 200℃ Detector temperature: 300°C Sample volume: 0.3 μL (split ratio: 1 / 30)

17. The method for producing an aldehyde according to claim 12, wherein the cyclic diene is a polycyclic diene.

18. The method for producing an aldehyde according to claim 17, wherein the cyclic diene is dicyclopentadiene.

19. 13. The method for producing an aldehyde according to claim 12, wherein the cyclic diene oxide is a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

20. The method for producing an aldehyde according to claim 12, wherein the cyclic diene oxide comprises at least one selected from the group consisting of a cyclic diene having a carbonyl group, a cyclic diene having a hydroxyl group, and a cyclic monoene having an epoxy group, which corresponds to the cyclic diene.

21. The cyclic diene is dicyclopentadiene, and 19. The method for producing an aldehyde according to claim 18, wherein the cyclic diene oxide comprises at least one compound selected from the group consisting of a compound of which one enantiomer is represented by the following general formula (I), a compound of which one enantiomer is represented by the following general formula (II), and a compound of which one enantiomer is represented by the following general formula (III): 【Chemistry 2】 [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

22. 19. The method for producing an aldehyde according to claim 18, wherein the cyclic diene is dicyclopentadiene and the aldehyde is tricyclodecane dicarbaldehyde.

23. the cyclic diene-containing composition is a composition obtained by distilling and purifying a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition, The method for producing an aldehyde according to claim 12, comprising carrying out the distillation purification so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

24. 13. The method for producing an aldehyde according to claim 12, comprising controlling storage conditions of the cyclic diene-containing composition so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

25. The method for producing an aldehyde according to claim 24, wherein the control of the storage conditions comprises controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

26. 25. The method for producing an aldehyde according to claim 24, wherein the controlling of the storage conditions comprises adding an antioxidant to the cyclic diene-containing composition.

27. A method for producing an alcohol, comprising producing an aldehyde by the production method according to any one of claims 12 to 26, and producing an alcohol from the aldehyde.

28. The cyclic diene is dicyclopentadiene, the aldehyde is tricyclodecane dicarbaldehyde, and the alcohol is tricyclo[5.2.1.0 ２，６ 28. The method for producing an alcohol according to claim 27, wherein the alcohol is decanedimethanol.

29. A method for producing a cyclic diene-containing composition containing a cyclic diene, comprising distilling and purifying a hydrocarbon decomposition product obtained by thermal decomposition of a hydrocarbon-containing composition, the method comprising: A method for producing a cyclic diene-containing composition, comprising adjusting the content of cyclic diene oxide contained in the cyclic diene-containing composition to a predetermined threshold value or less. (However, the cyclic diene does not include the cyclic diene oxide.)

30. 30. The method for producing a cyclic diene-containing composition according to claim 29, comprising carrying out the distillation purification so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

31. 30. The method for producing a cyclic diene-containing composition according to claim 29, comprising controlling storage conditions of the cyclic diene-containing composition so that the content of cyclic diene oxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

32. 32. The method for producing a cyclic diene-containing composition according to claim 31, wherein the control of the storage conditions comprises controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

33. 32. The method for producing a cyclic diene-containing composition according to claim 31, wherein the controlling of storage conditions comprises adding an antioxidant to the cyclic diene-containing composition.

34. 30. The method for producing a cyclic diene-containing composition according to claim 29, wherein the content of the cyclic diene oxide contained in the cyclic diene-containing composition is 1.2 GC area % or less.

35. The method for producing a cyclic diene-containing composition according to claim 29, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60 GC area % or more.

36. 35. The method for producing a cyclic diene-containing composition according to claim 34, wherein the content of the cyclic diene oxide contained in the cyclic diene-containing composition is 0.5 GC area% or less, preferably 0.35 GC area% or less, more preferably 0.25 GC area% or less, even more preferably 0.14 GC area% or less, and particularly preferably 0.05 GC area% or less.

37. The method for producing a cyclic diene-containing composition according to claim 29, wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analysis is carried out under the following GC measurement conditions, and the total content ratio of the peaks with elution times of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC device: Gas chromatogram measuring device (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: helium (column flow rate 1.65 mL / min) Column: Capillary column (product name: DB-1, manufactured by Agilent Technologies, size: length 30 m × inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 minutes) → heating at 10°C / minute → 300°C (holding time: none) Inlet temperature: 200℃ Detector temperature: 300°C Sample volume: 0.3 μL (split ratio: 1 / 30)

38. 30. The method for producing a cyclic diene-containing composition according to claim 29, wherein the cyclic diene is a polycyclic diene.

39. 39. The method for producing a cyclic diene-containing composition according to claim 38, wherein the cyclic diene is dicyclopentadiene.

40. 30. The method for producing a cyclic diene-containing composition according to claim 29, wherein the cyclic diene oxide is a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

41. 30. The method for producing a cyclic diene-containing composition according to claim 29, wherein the cyclic diene oxide comprises at least one selected from the group consisting of a cyclic diene having a carbonyl group, a cyclic diene having a hydroxyl group, and a cyclic monoene having an epoxy group.

42. The cyclic diene is dicyclopentadiene, and The method for producing a cyclic diene-containing composition according to claim 39, wherein the cyclic diene oxide comprises at least one compound selected from the group consisting of a compound in which one enantiomer is represented by the following general formula (I), a compound in which one enantiomer is represented by the following general formula (II), and a compound in which one enantiomer is represented by the following general formula (III): 【Chemistry 3】 [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

43. 30. The method for producing a cyclic diene-containing composition according to claim 29, wherein the hydrocarbon-containing composition is naphtha.

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