Production method for aldehyde, production method for alcohol, production method for cyclic diene-containing composition, and cyclic diene-containing composition

Abstract

Provided is a method for producing an aldehyde by subjecting a cyclic diene in a cyclic diene-containing composition to a hydroformylation reaction, said production method for aldehyde including configuring the content ratio of an oxygen-containing compound included in the cyclic diene-containing composition to no more than a predetermined threshold value. Also provided is a method for producing a cyclic diene-containing composition that contains a cyclic diene by distilling and purifying a hydrocarbon decomposition product obtained via pyrolysis of a hydrocarbon-containing composition, said production method for a cyclic diene-containing composition including configuring the content ratio of an oxygen-containing compound included in the cyclic diene-containing composition to no more than a predetermined threshold value.

Description

Method for producing aldehyde, method for producing alcohol, method for producing cyclic diene-containing composition, and cyclic diene-containing composition

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

[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 the corresponding cyclic diene 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 of 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 increased 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, an experimental example in Patent Document 1 discloses a technology for producing bisformyltricyclodecane by hydroformylating highly purified dicyclopentadiene. Also, Patent Document 2 focuses on conjugated dienes contained in dicyclopentadiene as impurities that inhibit the hydroformylation reaction, and discloses a technology for reducing the 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.

[0008] JP2005-139181A JP11-80067A

[0009] The present invention aims to solve these problems. Specifically, the present invention aims to provide a method for producing an aldehyde such as tricyclodecane dicarbaldehyde corresponding to a cyclic diene such as dicyclopentadiene using a cyclic diene-containing composition, which suppresses a decrease in the catalytic activity of a hydroformylation catalyst, thereby efficiently producing an aldehyde, and which enables the recovery of expensive rhodium metal at a high recovery rate from the process solution after the hydroformylation reaction.

[0010] Another object of the present invention is 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.

[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 method for producing an aldehyde and then producing an alcohol from the aldehyde.

[0012] As a result of extensive investigations aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by adjusting the content ratio of oxygen-containing compounds contained in a cyclic diene-containing composition to a predetermined value or less.

[0013] [1] A method for producing an aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition, the method comprising adjusting the content ratio of an oxygen-containing compound in the cyclic diene-containing composition to a predetermined threshold value or less.

[0014] [2] The method for producing an aldehyde according to [1], wherein the oxygen-containing compound is a cyclic diene oxide (provided that the cyclic diene does not include the cyclic diene oxide).

[0015] [3] The method for producing an aldehyde according to [2], wherein the content of the cyclic diene oxide contained in the cyclic diene-containing composition is 1.2 GC area % or less.

[0016] [4] The method for producing an aldehyde according to [2] or [3], wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60 GC area % or more.

[0017] [5] The method for producing an aldehyde according to [3] or [4], 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.

[0018] [6] The method for producing an aldehyde according to any one of [2] to [5], wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analysis is performed under the following GC measurement conditions, and the total content of peaks with elution times of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC apparatus: gas chromatogram measuring apparatus (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 min) → heating at 10°C / min → 300°C (holding time: none) Injection port temperature: 200°C Detector temperature: 300°C Sample amount: 0.3 μL (split ratio: 1 / 30)

[0019] [7] The method for producing an aldehyde according to any one of [2] to [6], wherein the cyclic diene is a polycyclic diene.

[0020] [8] The method for producing an aldehyde according to [7], wherein the cyclic diene is dicyclopentadiene.

[0021] [9] The method for producing an aldehyde according to any one of [2] to [8], 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.

[0022]

[10] The method for producing an aldehyde according to any one of [2] to [9], wherein the cyclic diene oxide contains 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.

[0023]

[11] The method for producing an aldehyde according to any one of [8] to

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

[0024]

[0025] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0026]

[12] The method for producing an aldehyde according to

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

[0027]

[13] The method for producing an aldehyde according to any one of [2] to

[12] , wherein 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, and the method includes carrying out the distillation and 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.

[0028]

[14] The method for producing an aldehyde according to any one of [2] to

[13] , 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.

[0029]

[15] The method for producing an aldehyde according to

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

[0030]

[16] The method for producing an aldehyde according to

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

[0031]

[17] A method for producing an alcohol, comprising producing an aldehyde by the production method according to any one of [1] to

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

[0032]

[18] 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

[17] , wherein the alcohol is decanedimethanol.

[0033]

[19] The method for producing an aldehyde according to [1], wherein the oxygen-containing compound is a peroxide.

[0034]

[20] The method for producing an aldehyde according to

[19] , wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.8 mmol / L or less.

[0035]

[21] The method for producing an aldehyde according to

[20] , wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

[0036]

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

[19] to

[21] , wherein the peroxide contains a peroxide of an alkene compound.

[0037]

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

[19] to

[22] , wherein the concentration of the peroxide is measured by the following Measurement Method 1. <Measurement Method 1> Under a nitrogen atmosphere, a mixed solution of chloroform and acetic acid is added to a cyclic diene-containing composition, and then a saturated aqueous potassium iodide solution is added and stirred, and the mixture is further diluted with distilled water to prepare a measurement sample. The obtained measurement sample is subjected to iodine reduction titration using a 0.01 mol / L aqueous sodium thiosulfate solution as a standard solution, and the concentration of peroxide (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

[0038]

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

[19] to

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

[0039]

[25] The method for producing an aldehyde according to

[24] , wherein the polycyclic diene is dicyclopentadiene.

[0040]

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

[19] to

[25] , wherein 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, and the method comprises carrying out the distillation and purification so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

[0041]

[27] The method for producing an aldehyde according to

[26] , wherein the hydrocarbon decomposition product contains an antioxidant.

[0042]

[28] The method for producing an aldehyde according to

[26] or

[27] , comprising adding an antioxidant to the hydrocarbon decomposition product so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or lower than a predetermined threshold value.

[0043]

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

[26] to

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

[0044]

[30] The method for producing an aldehyde according to

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

[0045]

[31] The method for producing an aldehyde according to

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

[0046]

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

[19] to

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

[0047]

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

[19] to

[32] , and producing a corresponding alcohol from the obtained aldehyde.

[0048]

[34] 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

[33] , wherein the alcohol is decanedimethanol.

[0049]

[35] 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, the method comprising reducing the content ratio of oxygen-containing compounds contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0050]

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

[35] , wherein the oxygen-containing compound is a cyclic diene oxide (provided that the cyclic diene does not include the cyclic diene oxide).

[0051]

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

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

[0052]

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

[36] or

[37] , 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.

[0053]

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

[36] to

[38] , 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.

[0054]

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

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

[0055]

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

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

[0056]

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

[36] to

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

[0057]

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

[41] or

[42] , 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.

[0058]

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

[36] to

[43] , wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analysis is performed under the following GC measurement conditions, and the total content of peaks with elution times of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC apparatus: gas chromatogram measuring apparatus (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 min) → heating at 10°C / min → 300°C (holding time: none) Injection port temperature: 200°C Detector temperature: 300°C Sample amount: 0.3 μL (split ratio: 1 / 30)

[0059]

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

[36] to

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

[0060]

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

[45] , wherein the cyclic diene is dicyclopentadiene.

[0061]

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

[36] to

[46] , 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.

[0062]

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

[36] to

[47] , 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.

[0063]

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

[46] to

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

[0064]

[0065] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0066]

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

[36] to

[49] , wherein the hydrocarbon-containing composition is naphtha.

[0067]

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

[35] , wherein the oxygen-containing compound is a peroxide.

[0068]

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

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

[0069]

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

[51] or

[52] , wherein the hydrocarbon decomposition product contains an antioxidant.

[0070]

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

[51] to

[53] , comprising adding an antioxidant to the hydrocarbon decomposition product so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

[0071]

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

[51] to

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

[0072]

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

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

[0073]

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

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

[0074]

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

[51] to

[57] , wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.8 mmol / L or less.

[0075]

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

[51] to

[57] , wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60.0 GC area% or more.

[0076]

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

[58] or

[59] , wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

[0077]

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

[51] to

[60] , wherein the peroxide concentration is measured by the following Measurement Method 1. <Measurement Method 1> Under a nitrogen atmosphere, a mixed solution of chloroform and acetic acid is added to the cyclic diene-containing composition, and then a saturated aqueous potassium iodide solution is added and stirred, and the mixture is further diluted with distilled water to prepare a measurement sample. The obtained measurement sample is subjected to iodine reduction titration using a 0.01 mol / L aqueous sodium thiosulfate solution as a standard solution, and the peroxide concentration (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

[0078]

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

[51] to

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

[0079]

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

[62] , wherein the polycyclic diene is dicyclopentadiene.

[0080]

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

[51] to

[63] , wherein the hydrocarbon-containing composition is naphtha.

[0081]

[65] A cyclic diene-containing composition containing a cyclic diene, wherein the content of a cyclic diene oxide in the cyclic diene composition is 1.2 GC area % or less (provided that the cyclic diene excludes the cyclic diene oxide).

[0082]

[66] The cyclic diene-containing composition according to

[65] , wherein the content of the cyclic diene is 60 GC area % or more.

[0083]

[67] The cyclic diene-containing composition according to

[65] or

[66] , 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.

[0084]

[68] The cyclic diene-containing composition according to any one of

[65] to

[67] , wherein the content ratio of the cyclic diene oxide is measured by the following Measurement Method 1. <Measurement Method 1> Analysis is performed under the following GC measurement conditions, and the total content ratio of peaks having an elution time of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC apparatus: gas chromatogram measuring apparatus (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 min) → heating at 10°C / min → 300°C (holding time: none) Injection port temperature: 200°C Detector temperature: 300°C Sample amount: 0.3 μL (split ratio: 1 / 30)

[0085]

[69] The cyclic diene-containing composition according to any one of

[65] to

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

[0086]

[70] The cyclic diene-containing composition according to

[69] , wherein the cyclic diene is dicyclopentadiene.

[0087]

[71] The cyclic diene-containing composition according to any one of

[65] to

[70] , 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.

[0088]

[72] The cyclic diene-containing composition according to any one of

[65] to

[71] , 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.

[0089]

[73] The cyclic diene-containing composition according to any one of

[70] to

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

[0090]

[0091] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0092]

[74] The cyclic diene-containing composition according to any one of

[65] to

[73] , wherein the concentration of peroxide in the cyclic diene composition is 2.8 mmol / L or less.

[0093]

[75] The cyclic diene-containing composition according to

[74] , wherein the concentration of the peroxide is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

[0094]

[76] The cyclic diene-containing composition according to

[74] or

[75] , wherein the peroxide comprises a peroxide of an alkene compound.

[0095]

[77] A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of

[65] to

[76] to a hydroformylation reaction to produce an aldehyde.

[0096]

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

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

[0097] According to the present invention, in a method for producing an aldehyde such as tricyclodecane dicarbaldehyde corresponding to a cyclic diene such as dicyclopentadiene using a cyclic diene-containing composition, a decrease in the catalytic activity of a hydroformylation catalyst can be suppressed, and the method can efficiently produce an aldehyde, and can recover expensive rhodium metal with a high recovery rate from the process solution after the hydroformylation reaction. Furthermore, the method can efficiently produce a corresponding alcohol from the aldehyde produced from the cyclic diene-containing composition of the present invention.

[0098] Furthermore, 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 from the process liquid after the hydroformylation reaction at a high recovery rate.

[0099] 1 is a schematic system diagram illustrating one embodiment of a production process for separating and recovering a cyclic diene-containing composition of the present invention from a C5 hydrocarbon fraction according to the present invention. FIG. 2 is a graph showing the relationship between the content (GC area %) of cyclic diene oxide (DCPD oxide) and the reaction rate constant (k2) in Experimental Examples 1 to 7. FIG. 3 is a graph showing the relationship between the content (GC area %) of cyclic diene oxide (DCPD oxide) and the rate of decrease in the reaction rate constant (k2) in Experimental Examples 1 to 7. FIG. 4 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 Experimental Examples 1 to 7. FIG. 5 is a diagram showing a gas chromatogram of the DCPD-containing composition obtained in Reference Experimental Example 2.

[0100] The present invention will be described in detail below, but the present invention is not limited to the following description and can be practiced in any modified form without departing from the gist of the present invention.

[0101] Unless otherwise specified, numerical ranges expressed using "to" in this specification mean a range including the numerical values ​​before and after "to" as the lower and upper limits, respectively. "A to B" means A or greater and B or less. In this specification, "including A or B" means "including A," "including B," or "including A and B," unless otherwise specified. In this specification, "GC area %" refers to the compositional proportion of each component measured using a gas chromatograph (GC) measurement device and a gas chromatography total area method. It is calculated as the area content (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 are explained in the experimental examples described below. In this specification, "mass %" refers to the content percentage of a given component in a total amount of 100% by mass, and "wt %" refers to the content percentage of a given component in a total amount of 100% by weight. "mass %" and "wt %" are synonymous. The term "any" 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 20% above and below 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.

[0102] In this specification, "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 oil, 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.

[0103] In this specification, the "method for producing an aldehyde of the present invention," the "method for producing an alcohol of the present invention," the "method for producing a cyclic diene-containing composition of the present invention," and the "cyclic diene-containing composition of the present invention" are collectively referred to as "the present invention."

[0104] First, in the present invention, the "oxygen-containing compound" (hereinafter, sometimes referred to as the "oxygen-containing compound of the present invention") whose content in the cyclic diene-containing composition is equal to or less than a predetermined threshold value, and the cyclic diene contained in the cyclic diene-containing composition will be described.

[0105] A cyclic diene-containing composition according to a first embodiment of the present invention, a method for producing an aldehyde according to a second embodiment of the present invention, a method for producing an alcohol according to a third embodiment of the present invention, and a method for producing a cyclic diene-containing composition according to a fourth embodiment of the present invention (hereinafter, the inventions of the first to fourth embodiments may be collectively referred to as "the present invention").

[0106] <Oxygen-Containing Compound> The oxygen-containing compound of the present invention is not particularly limited as long as the effects of the present invention can be achieved by adjusting the content ratio in the cyclic diene-containing composition to a predetermined value or less. Specific examples of the oxygen-containing compound include the cyclic diene oxides described below and the peroxides described below, which can more significantly achieve the effects of the present invention. The oxygen-containing compound of the present invention may be one of these, or two or more of these. Details of the cyclic diene oxides and peroxides will be described later.

[0107] 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.

[0108] By using the oxygen-containing compound of the present invention to control the content of cyclic diene oxide in the cyclic diene-containing composition to a predetermined threshold or less, it is possible to efficiently produce an alicyclic aldehyde from the cyclic diene-containing composition while suppressing a decrease in the catalytic activity of the hydroformylation catalyst in the production of the aldehyde of the present invention, and to recover expensive rhodium metal at a high recovery rate from the process liquid after the hydroformylation reaction.Furthermore, by using the oxygen-containing compound of the present invention to control the concentration of peroxide in the cyclic diene-containing composition to a predetermined threshold or less, it is possible to efficiently produce an alicyclic aldehyde while suppressing a decrease in the catalytic activity of the hydroformylation catalyst even when the peroxide is repeatedly recovered and reused from the reaction liquid after the hydroformylation reaction.

[0109] <Cyclic Diene> The cyclic diene (also referred to as "cyclic diene") in the present invention is one component constituting the cyclic diene-containing composition of the present invention.

[0110] 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.

[0111] 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 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 the two ring structures having a non-conjugated carbon-carbon double bond. Alternatively, another embodiment of the cyclic diene includes a compound obtained by dimerization of a cyclic diene having one ring structure.

[0112] 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 industrially readily available, 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.

[0113] In the following, first, the cyclic diene-containing composition and the method for producing the cyclic diene-containing composition of the present invention will be described, and then the method for producing an aldehyde and the method for producing an alcohol of the present invention will be described in that order.

[0114] <Cyclic Diene-Containing Composition> The cyclic diene-containing composition of the present invention is a composition containing the above-mentioned cyclic diene, in which the content of cyclic diene oxide in the cyclic diene composition is 1.2 GC area % or less. However, as described above, the cyclic diene does not include the cyclic diene oxide.

[0115] In the present invention, the lower limit of the content (unit: GC area%) of the cyclic diene 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, it 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 cyclic diene content (unit: GC area%) in the cyclic diene-containing composition is not particularly limited, but from the viewpoint of economic efficiency such as the production cost 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.

[0116] The upper and lower limits can be arbitrarily combined. For example, the content ratio of the cyclic diene in the cyclic diene-containing composition in 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 the total GC area of ​​the cyclic diene-containing composition (100%).

[0117] In the cyclic diene-containing composition and production method thereof of the present invention, as well as 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 cost 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 viewpoint of suppressing a decrease in the catalytic activity of the hydroformylation catalyst and recovering expensive rhodium metal at a high recovery rate. The above 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.

[0118] The method for measuring the content of the cyclic diene in the cyclic diene-containing composition will be described in detail below. Examples of methods for controlling the content of the cyclic diene in the cyclic diene-containing composition include an extraction method, a method for controlling the amount by adjusting purification conditions or distillation conditions, and a combination of these methods.

[0119] (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 suppress a decrease in the catalytic activity of the hydroformylation reaction catalyst, thereby efficiently producing an aldehyde from the cyclic diene-containing composition, and to recover expensive rhodium metal at a high recovery rate from the process liquid after the hydroformylation reaction.

[0120] 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.

[0121] The "cyclic diene oxide" in the cyclic diene-containing composition and method for producing the same 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.

[0122] 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.

[0123] The cyclic diene oxide in the present invention is not particularly limited, but as a first embodiment, it can be a compound having a skeleton selected from a tricyclodecene skeleton and a tricyclodecadiene skeleton and having an oxygen-containing functional group.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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 in the present invention, isopropylnorbornene, and methyltetrahydroindene. Specific examples of the oxide of the unsaturated hydrocarbon compound include a compound containing a carbonyl group, a compound containing a hydroxyl group, or a compound containing an epoxy group.

[0128] 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).

[0129]

[0130] [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.]

[0131] These cyclic diene oxides may be used alone or in combination of two or more.

[0132] The content of cyclic diene oxides in the present invention can be measured by the following measurement method 1. <Measurement method 1> Analysis is performed under the following GC measurement conditions, and the total content of peaks with elution times from 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC apparatus: Gas chromatogram measurement apparatus (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 x 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)

[0133] 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, 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 solution 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 oxide can be set to 0.0001 GC area % or more relative to the cyclic diene-containing composition, 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.

[0134] The upper and lower limits can be arbitrarily combined. 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% or more and 1.2 GC area% or less, preferably 0.0003 GC area% or more and 0.5 GC area% or less, more preferably 0.001 GC area% or more and 0.35 GC area% or less, even more preferably 0.002 GC area% or more and 0.25 GC area% or less, particularly preferably 0.005 GC area% or more and 0.14 GC area% or less, and most preferably 0.01 GC area% or more and 0.05 GC area% or less.

[0135] (Peroxide) In the method for producing a cyclic diene-containing composition of the present invention and the method for producing an aldehyde of the present invention, when the oxygen-containing compound is a peroxide, by controlling the concentration of the peroxide contained 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, even when the cyclic diene-containing composition is repeatedly recovered and reused from the reaction liquid after the hydroformylation reaction, the cyclic diene-containing composition can be hydroformylated to efficiently produce an aldehyde corresponding to the cyclic diene while suppressing a decrease in the catalytic activity of the hydroformylation catalyst.

[0136] The cyclic diene-containing composition of the present invention preferably further has a peroxide content of 2.8 mmol / L or less.

[0137] In the method for producing a cyclic diene-containing composition of the present invention and the method for producing an aldehyde of the present invention, by controlling the concentration of peroxide contained 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 alicyclic aldehyde, even when the cyclic diene-containing composition is repeatedly recovered and reused from the reaction solution after the hydroformylation reaction, the cyclic diene-containing composition can be hydroformylated to efficiently produce an aldehyde corresponding to the cyclic diene while suppressing a decrease in the catalytic activity of the hydroformylation catalyst.

[0138] The peroxide in the present invention is not particularly limited, and examples thereof include peroxides of alkene compounds. Examples of the alkene compounds include the cyclic dienes in the present invention, isopropylnorbornene, methyltetrahydroindene, etc. Specific examples of the peroxides of alkene compounds include compounds having a four-membered ring structure composed of two carbon molecules and two oxygen molecules, or compounds having a hydroperoxy group at the vinyl position. More specific examples of the peroxides of alkene compounds include compounds represented by the following formula when the alkene compound is dicyclopentadiene, a cyclic diene:

[0139]

[0140] The peroxide concentration in the present invention can be measured by the following Measurement Method 1. More specific measurement methods are as described in the Examples section below. <Measurement Method 1> Under a nitrogen atmosphere, a mixed solution of chloroform and acetic acid is added to a cyclic diene-containing composition, and then a saturated aqueous potassium iodide solution is added and stirred, and the mixture is further diluted with distilled water to prepare a measurement sample. The obtained measurement sample is subjected to iodine reduction titration using a 0.1 N aqueous sodium thiosulfate solution as a standard solution, and the peroxide concentration (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

[0141] When an aldehyde is produced by a hydroformylation reaction using the cyclic diene-containing composition of the present invention as a starting material, the upper limit of the peroxide concentration in the cyclic diene-containing composition of the present invention is usually 2.8 mmol / L or less, preferably 2.0 mmol / L or less, more preferably 1.0 mmol / L or less, even more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less, from the viewpoint of efficiently producing an alicyclic aldehyde corresponding to the cyclic diene while suppressing a decrease in the catalytic activity of the hydroformylation reaction catalyst, even when the peroxide is repeatedly recovered and reused from the reaction liquid after the hydroformylation reaction. On the other hand, the lower limit of the concentration of the peroxide is not particularly limited, and it is acceptable for the peroxide to be substantially absent (0.0 mmol / L). However, from the viewpoint of economic efficiency, such as the production costs required for purifying and separating the cyclic diene-containing composition, the concentration of the peroxide can be 0.001 mmol / L or more relative to the cyclic diene-containing composition, preferably 0.005 mmol / L or more, more preferably 0.01 mmol / L or more, even more preferably 0.02 mmol / L or more, and particularly preferably 0.03 mmol / L or more.

[0142] The upper and lower limits can be combined arbitrarily. For example, the concentration of peroxide in the cyclic diene-containing composition is not particularly limited, and may be substantially free (0.0 mmol / L), or may be 0.001 mmol / L or more and 2.8 mmol / L or less, preferably 0.005 mmol / L or more and 2.0 mmol / L or less, more preferably 0.01 mmol / L or more and 1.0 mmol / L or less, even more preferably 0.02 mmol / L or more and 0.6 mmol / L or less, and particularly preferably 0.03 mmol / L or more and 0.3 mmol / L or less.

[0143] Methods for controlling the content of cyclic diene oxide in the cyclic diene-containing composition, and further the concentration of peroxide, 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.

[0144] <Method for 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.

[0145] 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 the oxygen-containing compound of the present invention, such as the cyclic diene oxide or peroxide, contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0146] One method for ensuring that the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value is to obtain a hydrocarbon decomposition product by thermal decomposition of a hydrocarbon-containing composition, as described below, and then purify the product by distillation to produce a cyclic diene-containing composition. During this distillation purification, it is preferable to control the distillation purification conditions. In this case, the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, are typically high-boiling components having boiling points higher than those of the cyclic dienes in the cyclic diene-containing composition. Therefore, these oxygen-containing compounds 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, as described below, allowing their content to be appropriately controlled.

[0147] Furthermore, as a method for ensuring that the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold, an antioxidant can be added to the hydrocarbon decomposition products obtained by thermal decomposition of the hydrocarbon-containing composition so that the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, 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 inclusion of an antioxidant in the hydrocarbon decomposition products can prevent the oxidation of cyclic dienes, such as dicyclopentadiene, to produce oxygen-containing compounds, such as cyclic diene oxides and peroxides, derived from the cyclic diene. The type and suitable amount of antioxidant to be added here will be described in detail in the section describing the method for producing an aldehyde of the present invention.

[0148] Furthermore, in the cyclic diene-containing composition of the present invention, storage conditions may be controlled so that the content ratio of the oxygen-containing compound of the present invention, such as the cyclic diene oxide or peroxide, is below the threshold value. In this case, methods 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 in the case of adding an antioxidant, controlling the dissolved oxygen concentration can also suppress the generation of cyclic diene-derived cyclic diene oxides and peroxides due to the oxidation of cyclic dienes such as dicyclopentadiene.

[0149] 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.

[0150] 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 control 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.

[0151] When the oxygen-containing compound is a cyclic diene oxide, 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, particularly 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. When the oxygen-containing compound is a peroxide, the threshold value of the peroxide concentration in the method for producing a cyclic diene-containing composition of the present invention is preferably 2.8 mmol / L or less, more preferably 2.0 mmol / L or less, even more preferably 1.0 mmol / L or less, particularly preferably 0.6 mmol / L or less, and most preferably 0.3 mmol / L or less, as the peroxide concentration in the produced cyclic diene-containing composition. The same applies to the threshold value in the method for producing an aldehyde of the present invention described below.

[0152] 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 oxygen-containing compound content and cyclic diene content.

[0153] (Method for Producing 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.

[0154] When producing the cyclic diene-containing composition, the distillation purification is carried out so that the content of the oxygen-containing compound 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 alicyclic 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 to recover expensive rhodium metal at a high recovery rate from the process liquid after the hydroformylation reaction.

[0155] The hydrocarbon-containing composition may be naphtha, coal, or natural gas. Of these, naphtha is preferred from the viewpoint of excellent productivity and quality of the resulting cyclic diene-containing composition.

[0156] (Ethylene Production Facility) The ethylene production facility in the present invention refers to 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.

[0157] The embodiment of the ethylene production apparatus is not particularly limited, and may be any configuration as long as it includes a distillation facility for a C5 hydrocarbon fraction and separates and refines naphtha cracking products, and examples thereof include 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 obtained cracked gas is quenched and separated; Step (3): A compression step in which the quenched and separated cracked gas is compressed; and Step (4): A refining step in which the compressed cracked gas is separated into each fraction and refined to obtain the main products ethylene and propylene.

[0158] (C5 Hydrocarbon Fraction) In the present invention, the C5 hydrocarbon fraction refers to a fraction containing hydrocarbons having 5 carbon atoms as the main component, which is obtained by separating heavy oil from hydrocarbon cracking products obtained by thermally cracking a hydrocarbon-containing composition such as naphtha, and then separating and removing hydrogen and hydrocarbons having 1 to 4 carbon atoms. Specific examples of the C5 hydrocarbon fraction include mixtures containing C5 hydrocarbons such as isoprene, isopentane, normal pentane, and cyclopentadiene as the main components. 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.

[0159] 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%.

[0160]

[0161] (Distillation purification of hydrocarbon cracking products or C5 hydrocarbon fraction) In the present invention, the distillation purification of the hydrocarbon cracking products or the C5 hydrocarbon fraction may be carried out by a single distillation operation, or by a combination of multiple distillation operations. When a combination of multiple distillation operations is carried out, 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 in combination may be employed.

[0162] In particular, from the viewpoint of keeping the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxide and peroxide, contained in the cyclic diene-containing composition of the present invention below a predetermined threshold value, specifically, keeping the content of the cyclic diene oxide below 1.2 GC area % or keeping the peroxide concentration below 2.8 mmol / L, a method in which distillation operations under the same or different conditions are combined and carried out two or more times is preferred. When distillation operations are carried out multiple times, by using two or more distillation columns and controlling the number of theoretical plates or reflux ratio of each distillation column within the following ranges, separation and removal of oxygen-containing compounds, which would not be achieved sufficiently with a single distillation column, can be reliably achieved.

[0163] 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, oxygen-containing compounds can be efficiently separated and removed, and the content ratio of oxygen-containing compounds can be efficiently controlled to be equal to or less than the predetermined threshold value.

[0164] 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 or more and 28 or less, preferably 23 or more and 27 or less, and to set the number of theoretical plates of the second distillation column to 10 or more and 20 or less, preferably 13 or more and 17 or less. By setting the numbers in this manner, oxygen-containing compounds can be efficiently separated and removed, and the content ratio of oxygen-containing compounds can be efficiently controlled to be equal to or less than the predetermined threshold value.

[0165] (Specific Embodiment of Method for Producing Cyclic Diene-Containing Composition) One 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.

[0166] Step (I): A dimerization step in which a C5 hydrocarbon fraction, which will be described later and which is 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.

[0167] 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.

[0168] Step (III): A step for removing low boiling components, in which the C5 fraction heavy composition from the bottom of the column 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 in the dimerization reaction of step (I), are removed from the top of the column, while a fraction rich in cyclic dienes such as dicyclopentadiene is taken out from the bottom of the column.

[0169] Step (IV): A step for 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 oxygen-containing compounds of the present invention, such as the above-mentioned cyclic diene oxides and peroxides, which have boiling points higher than those 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 out from the top of the column.

[0170] The steps (I) to (IV) will be described in more detail below.

[0171] [Step (I)] The C5 hydrocarbon fraction is first supplied to a dimerization step (I), in which 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, etc., but typically, the dimerization temperature is set within the range of 50 to 110°C and the reaction time is set within the 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.

[0172] [Step (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. This unreacted C5 hydrocarbon fraction contains isoprene, piperylene (i.e., 1,3-pentadiene), and the like, which are sent to separate purification processes as needed. For example, since the boiling point of the cyclic diene dicyclopentadiene is 170°C and the boiling points of the other unreacted components are approximately 30 to 50°C, the product from the dimerization step (I) is fed to a distillation column in this recovery step (II) to take advantage of this difference in boiling point. The 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 extracted from the bottom. Distillation is usually carried out under atmospheric pressure, but if it is desired to increase the recovery amounts of the C5 hydrocarbon fraction and the C6 hydrocarbon fraction, reduced-pressure distillation or steam distillation is performed.

[0173] [Step (III)] The C5 heavy fraction composition withdrawn from the bottom of the distillation column in step (II) is liquefied in a condenser, if necessary, and then sent to a low-boiling component removal step (III) (light-boiling component removal column) for distillation. The C5 heavy fraction composition sent to this 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 C5 heavy fraction composition are removed from the top of the light-boiling component removal column, while a fraction rich in cyclic dienes such as dicyclopentadiene is withdrawn from the bottom of the column.

[0174] 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 during 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 components, it is easy to remove cyclic monoenes such as vinylnorbornene, and the C5 hydrocarbon fraction and C6 hydrocarbon fraction, but it is difficult to remove similar co-dimer components such as propenylnorbornene. Therefore, a distillation column with 50 to 100 plates has conventionally been required as the low-boiling component removal column.

[0175] The light-boiler 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 5 carbon atoms is 2.0 GC area % or less. The distillation conditions in the light-boiler removal column are controlled within the following ranges: a vacuum degree of 5 to 200 torr, preferably 10 to 50 torr; a column bottom temperature of 50 to 120°C, preferably 80 to 110°C; a theoretical plate number of 22 to 28, preferably 23 to 27; and a reflux ratio of 20 to 30, preferably 23 to 27. Under these conditions, the oxygen-containing compounds of the present invention contained in the C5 fraction heavy composition obtained from the bottom of the light-boiler removal column in step (II) can be efficiently removed from the bottom effluent obtained from the bottom of the light-boiler removal column, and further 90 mass % or more of cyclic monoenes such as vinylnorbornene and similar co-dimers can be removed. Specifically, the content of cyclic dienes such as cyclopentadiene in the bottom distillate can be 0.5 GC area % or less, and the content of hydrocarbons having 5 carbon atoms can be 2.0 GC area % or less.

[0176] [Step (IV)] In the low-boiling component removal step (III), the fraction (column bottoms liquid) rich in cyclic dienes such as dicyclopentadiene is extracted from the bottom of the low-boiling component removal column and sent to the high-boiling component removal step (IV) (heavy-boiling component removal column) for distillation. The high-boiling components removed in this step (IV) are the oxygen-containing compounds of the present invention and high-boiling co-dimers such as methylbicyclononadiene, which are dimers of cyclopentadiene and isoprene, each of which has a boiling point higher than that of the cyclic dienes such as dicyclopentadiene produced as a by-product in the dimerization reaction in step (I). When low-boiling products such as cyclopentadiene trimers are present, these low-boiling products are also removed.

[0177] The distillation conditions in the heavy-boiler 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 pressure from 5 to 100 torr, preferably from 10 to 50 torr; bottom temperature from 50 to 120°C, preferably from 70 to 110°C; number of theoretical plates from 10 to 20, preferably from 13 to 17; and reflux ratio from 1.8 to 4.5, preferably from 2.0 to 2.8. Under these conditions, the cyclic diene-containing composition of the present invention, which contains a high content of cyclic dienes such as dicyclopentadiene and has an appropriately controlled content of the oxygen-containing compound of the present invention, can be obtained from the top of the heavy-boiler removal column.

[0178] In the present invention, the high-boiling component removal column is preferably controlled so that, in the cyclic diene-containing composition obtained from the top of the column, the content of cyclic diene oxides as the oxygen-containing compounds of the present invention is 1.2 GC area % or less, preferably the content of cyclopentadiene, etc. is 60 GC area % or more, and the content of cyclic diene oxides as the oxygen-containing compounds of the present invention is 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.

[0179] Alternatively, the high-boiling component removal column is preferably controlled so that the concentration of peroxides as the oxygen-containing compounds of the present invention in the cyclic diene-containing composition obtained from the top of the column is 2.8 mmol / L or less, preferably so that the concentration of cyclopentadiene or the like is 60 GC area % or more and the concentration of peroxides as the oxygen-containing compounds of the present invention is 2.0 mmol / L or less.

[0180]

[0013] Examples of methods 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 include 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 theoretical plate number of the heavy-boiling component removal column within a range of 10 to 20 and the reflux ratio within a range of 1.8 to 4.5, the oxygen-containing compound of the present invention can be efficiently separated and removed from the cyclic diene-containing composition of the present invention obtained from the top of the heavy-boiling component removal column, thereby controlling the content ratio of the oxygen-containing compound of the present invention to the predetermined threshold value or less. Furthermore, if the residence time of the feed liquid in the distillation column exceeds 15 minutes, the oxygen-containing compound of the present invention may be generated in the column, or the bottom effluent may contain a large amount of heavy fractions such as tricyclopentadiene. 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. Furthermore, the amount of hold liquid at the column bottom decreases, and the liquid in the column bottom may become empty during normal distillation column operation, which may hinder stable operation.

[0181] 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.

[0182] 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.

[0183] In the method for producing a cyclic diene-containing composition of the present invention, when the content ratio of the oxygen-containing compound of the present invention 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). Furthermore, in the method for producing a cyclic diene-containing composition of the present invention, the antioxidant may be added to the produced cyclic diene-containing composition.

[0184] [One embodiment of the production equipment for a cyclic diene-containing composition] Next, one embodiment of the production equipment for a cyclic diene-containing composition of the present invention will be described with reference to the accompanying drawing. In Fig. 1, first, a C5 hydrocarbon fraction obtained by thermal cracking of a hydrocarbon-containing composition such as naphtha is supplied to a dimerization vessel 1 via a pipe 10, where dimerization of a cyclic diene precursor such as cyclopentadiene is carried out to produce a cyclic diene such as dicyclopentadiene corresponding to the cyclic diene precursor [dimerization step (I)]. After the dimerization reaction, the contents of the dimerization vessel 1 are sent via a pipe 11 to a 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-component removal column 3 [light-boiling component removal step (III)] for distillation. In light-component removal column 3, cyclic monoenes such as vinylnorbornene, which have lower boiling points than cyclic dienes such as cyclopentadiene, the C5 hydrocarbon fraction, the C6 hydrocarbon fraction, and similar co-dimers are removed from the top of light-component removal column 3 via pipe 15, and the fraction rich in cyclic dienes such as dicyclopentadiene is sent from the bottom of light-component removal column 3 via pipe 14 to the final heavy-component removal column 4 [high-boiling component removal step (IV)] for distillation. In the heavy-boiling component removal column 4, the high-boiling oxygen-containing compounds 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.

[0185] The order of carrying out the above steps (I) to (IV), particularly steps (II) to (IV), is not particularly limited, and the order of carrying out the steps can be changed as long as the effects of the present invention are not impaired.

[0186] <Method for Producing Aldehyde> The method for producing an aldehyde of the present invention is a method for producing an aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition. The method for producing an aldehyde of the present invention is a production method including reducing the content of the oxygen-containing compound of the present invention, such as the cyclic diene oxide or peroxide, contained in the cyclic diene-containing composition to a predetermined threshold value or less.

[0187] 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.

[0188] 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.

[0189] The method for reducing the content of the oxygen-containing compound of the present invention, such as the cyclic diene oxide or peroxide, contained in the cyclic diene-containing composition to a predetermined threshold value or less is not particularly limited, and an example thereof includes a method, as described above, 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.

[0190] In the method for producing an aldehyde of the present invention, the hydrocarbon decomposition product can also contain an antioxidant, as described above in the method for producing a cyclic diene-containing composition of the present invention. The antioxidant in the method for producing an aldehyde of the present invention can be treated as synonymous with the antioxidant 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 suppress the oxidation of cyclic dienes such as dicyclopentadiene to produce the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, which are derived from the cyclic dienes.

[0191] 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 the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, contained 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 the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, derived from the cyclic dienes.

[0192] Furthermore, in the aldehyde production method of the present invention, storage conditions may be controlled so that the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, contained in the cyclic diene-containing composition is below the threshold value. In this case, methods for controlling the storage conditions of the cyclic diene-containing composition include adding an antioxidant to the cyclic diene-containing composition being stored, or controlling the dissolved oxygen concentration of the cyclic diene-containing composition being 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 the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides derived from the cyclic diene.

[0193] 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 the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides 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.

[0194] Examples of 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-hydroxybenzoyl ... ,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-methylbenzenepropanoate)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.

[0195] These antioxidants may be used alone or in combination of two or more.

[0196] When the hydrocarbon decomposition product contains an antioxidant, or when an antioxidant is added to the hydrocarbon decomposition product, the content or lower limit of the antioxidant content or amount added is not particularly limited, as long as it is an amount that can reduce the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, to the threshold value or less. For 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 antioxidant content or amount added is not particularly limited, as long as it can maintain the quality of the cyclic diene-containing composition of the present invention and keep the increase in production costs for purification and other processes 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.

[0197] 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 the antioxidant is not particularly limited, as long as it is an amount that can keep the content of the oxygen-containing compound of the present invention, such as the cyclic diene oxide or peroxide, below 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 it can maintain the quality of the cyclic diene-containing composition of the present invention and keep the increase in production costs for purification and the like within an acceptable range. For example, the content of the antioxidant in the cyclic diene-containing composition 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.

[0198] When the content of the antioxidant in the hydrocarbon decomposition product or the cyclic diene-containing composition is equal to or greater than the lower limit, the generation of oxygen-containing compounds can be effectively suppressed by a sufficient amount of antioxidant, and the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, can be easily reduced to below the threshold value. On the other hand, when the content of the antioxidant is equal to or less than the upper limit, the quality of the cyclic diene-containing composition of the present invention can be maintained at a good level, and increases in production costs for purification and the like can be kept within an acceptable range. Furthermore, the risk of the antioxidant precipitating at the bottom of the distillation column and causing pipe blockage can be reduced.

[0199] In the method for producing an aldehyde of the present invention, when the dissolved oxygen concentration of the stored cyclic diene-containing composition is controlled so that the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, contained in the cyclic diene-containing composition is below the threshold, the control of the dissolved oxygen concentration can be performed, for example, by flowing an inert gas such as nitrogen through the cyclic diene-containing composition or under the storage atmosphere of the cyclic diene-containing composition. Even in this case, the control concentration of the dissolved oxygen is not particularly limited, as long as it is a concentration that can keep the content of the oxygen-containing compounds of the present invention, such as the cyclic diene oxides and peroxides, in the cyclic diene-containing composition below the threshold. However, from the viewpoint of the effect of inhibiting the production of oxygen-containing compounds, it is preferable to set the dissolved oxygen concentration of the cyclic diene-containing composition to 100 ppm by volume or less, particularly 50 ppm by volume or less. On the other hand, from the viewpoint of economics, such as the production costs required for reducing the dissolved oxygen concentration, an excessively low dissolved oxygen concentration is not recommended. Generally, the dissolved oxygen concentration in the cyclic diene-containing composition is 1 ppm by volume or more.

[0200] In the method for producing an aldehyde according to 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 JP-A-2001-10999, an aldehyde can be produced by hydroformylating the cyclic diene contained in the cyclic diene-containing composition according to 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.

[0201] 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:

[0202]

[0203] The rhodium compound used in this hydroformylation step is not limited to the form of its precursor, as long as it forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. ２ , Rh ２ O ３ , Rh ４ (CO) １２ , Rh ６ (CO) １６ , Rh(NO ３ ) ３ A catalyst precursor substance such as the above 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.

[0204] In a preferred embodiment of the present invention, Rh(acac)(CO) ２is 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.

[0205] The organophosphorus compound which forms a catalyst for the hydroformylation reaction with the rhodium compound includes known phosphites and known phosphines. Among these, the phosphites include those 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 an optionally substituted 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.

[0206] 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.

[0207] As the phosphine, sterically hindered alkylphosphines are particularly effective in the hydroformylation reaction of dicyclopentadiene. 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] 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. Typically, the molar ratio of hydrogen to carbon monoxide (hydrogen / carbon monoxide) in the introduced gas composition can be set within the range of 0.2 to 5.0.

[0213] 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 can reduce 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.

[0214] <Extraction of Tricyclodecanedicarbaldehyde> After completion of the hydroformylation reaction, the method for extracting and separating the product tricyclodecanedicarbaldehyde from the reaction product liquid 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 tricyclodecanedicarbaldehyde, the product in the reaction product liquid, can be extracted into the extraction solvent layer.

[0215] The extraction solvent is not particularly limited, and examples thereof include alcohol.

[0216] 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 alcohol 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 preferred because they have relatively low boiling points, are available at relatively low cost, and are liquids that are easy to handle. These alcohols may be used alone or in combination. Furthermore, extraction may be performed in the presence of water in the alcohol. The addition of water facilitates the distribution of aldehydes and catalyst components into each layer.

[0217] From the viewpoint of efficiently extracting the product tricyclodecane dicarbaldehyde from the hydroformylation reaction solvent, it is preferable that the hydroformylation reaction solvent and the extraction solvent have excellent liquid-liquid separation properties, specifically, it is preferable that there is 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 water / methanol mixed solution.

[0218] 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.

[0219] 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, if tricyclodecanedicarbaldehyde has relatively low solubility in the extraction solvent, the volume ratio can be appropriately selected from a range of 10:1 to 1:10. Furthermore, in order to increase the amount of tricyclodecanedicarbaldehyde 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 extraction operation, a hydroformylation reaction solvent such as methylcyclohexane may be added to the reaction product solution in an amount of approximately 5 to 20 mass %, thereby improving the catalyst removal rate by adding the hydroformylation reaction solvent.

[0220] The temperature for the extraction operation is not particularly limited and can be equal to or lower than the hydroformylation reaction temperature. The method for the extraction operation is also not particularly limited and includes, for example, a method in which an extraction solvent is added to the hydroformylation reactor after the hydroformylation reaction to perform extraction treatment, and a method in which the hydroformylation reaction product liquid withdrawn from the hydroformylation reactor is introduced into an extraction tank to perform extraction treatment.

[0221] 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.

[0222] The cyclic diene-containing composition of the present invention used as a raw material for producing the aldehyde of the present invention has a content of the oxygen-containing compound of the present invention, such as the above-mentioned cyclic diene oxide or peroxide, which is equal to or less than a predetermined threshold value. Therefore, expensive rhodium metal can 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, allowing for efficient repeated hydroformylation reactions.

[0223] <Method for Producing Alcohol> The method for producing alcohol of the present invention is a method for producing alcohol, which comprises producing an aldehyde by the method for producing an aldehyde of the present invention, and producing an alcohol from the aldehyde.

[0224] The method for producing an alcohol from an 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, an alcohol can be produced by subjecting the aldehyde obtained by the method for producing an aldehyde of the present invention to a known hydrogenation reaction as it is, or by dimerizing the obtained aldehyde and then subjecting it to a known hydrogenation reaction.

[0225] 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.

[0226] 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.

[0227] The present invention will be described in more detail below using experimental examples instead of working examples, but the present invention is not limited to the following experimental examples as long as it does not deviate from the gist of the present invention. The following experimental examples are merely illustrative and are not intended to limit any of the embodiments described herein. The following experimental examples do not limit the present invention in any way. The values ​​of various manufacturing conditions and evaluation results in the following experimental examples have the meaning of preferred upper or lower limit values ​​in embodiments of the present invention, and preferred ranges may be ranges defined by a combination of the above-mentioned upper or lower limit values ​​and the values ​​of the following experimental examples or values ​​of the experimental examples.

[0228] The compounds used in the following experimental examples are as follows: DCPD: dicyclopentadiene (manufactured by 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 mass% and a chromium loading of 2 mass%, produced in accordance with the description in Experimental 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 (trade name: methylcyclohexane, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Methanol (trade name: methanol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0229] Reference Experimental Example 1 Production of Heavy Oil by Thermal Cracking of Naphtha Using commercially available naphtha as a hydrocarbon-containing composition and a naphtha cracking plant manufactured by Mitsubishi Chemical Corporation, thermal cracking of the naphtha was carried out according to the naphtha thermal cracking method disclosed in Japanese Patent Publication No. 7-39354 to obtain a hydrocarbon cracked product. The obtained hydrocarbon cracked product was supplied to a distillation column and fractionated to recover a C5 hydrocarbon fraction composed mainly of hydrocarbons having 5 carbon atoms. The obtained C5 hydrocarbon fraction was then supplied to a reactive distillation column, and cyclopentadiene contained in the C5 hydrocarbon fraction was dimerized and converted to dicyclopentadiene, while separation and purification were carried out under the conditions described below, thereby recovering a C5 fraction heavy composition containing the cyclic diene dicyclopentadiene from the bottom of the distillation column.

[0230] <Distillation purification of heavy oil> 1,895 g of the obtained C5 hydrocarbon fraction was charged into a distillation column with 40 plates, and fractional distillation was carried out under the following fractional distillation conditions, and the distillate was collected at the top of the distillation column in approximately 100 g portions.

[0231] <Fractionation conditions> Column bottom temperature: 40 to 140°C Column top temperature: 24 to 80°C Pressure: 1 to 10 kPa (7.5 to 75 torr) Residence time of the liquid fed to the distillation column in the column: about 19 hours

[0232] The collected fractions were analyzed using a gas chromatograph (GC) measuring device and a gas chromatography total area method under the following GC measurement conditions, and a fraction containing 99% DCPD (hereinafter referred to as "DCPD with a purity of 99%) was selected.

[0233] <GC measurement conditions> GC apparatus: GC-2025 (high-performance general-purpose gas chromatograph, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 min) → 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)

[0234] 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 retention times 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.

[0235] Reference Experimental Example 2 Distillative Purification of Dicyclopentadiene (DCPD) 1,494.1 g of the above-mentioned DCPD having a purity of 99% as a cyclic diene 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 shown in Table 1 in the order of distillation, and these were used as DCPD-containing compositions.

[0236] 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) (referred to as "compound (I)"), the compound one enantiomer of which is represented by the general formula (II) (referred to as "compound (II)"), and the compound one enantiomer of which is represented by the general formula (III) (referred to as "compound (III)"), which constitute the DCPD oxide, were measured according to the following measurement method 1.

[0237] <Measurement Method 1> Analysis was performed under the following GC measurement conditions, and the total content ratio of peaks with elution times from 17.7 minutes to 18.8 minutes was measured. (GC Measurement Conditions) GC Apparatus: Gas Chromatography Apparatus (Product Name: GC-2025, Shimadzu Corporation) Detector: Hydrogen Flame Ionization Detector (FID) Carrier Gas: Helium (Column Flow Rate: 1.65 mL / min) Column: Capillary Column (Product Name: DB-1, Agilent Technologies, Size: Length 30 m x Inner Diameter 0.25 mm, Film Thickness 1.00 μm) Column Temperature: 50°C (Hold Time 5 Minutes) → Heat Up at 10°C / min → 300°C (Hold Time: None) Injection Port Temperature: 200°C Detector Temperature: 300°C Sample Volume: 0.3 μL (Split Ratio: 1 / 30)

[0238] 5 shows the gas chromatogram of the DCPD-containing composition obtained in Reference Experimental Example 2. Peak (1) at an elution time of 17.73 to 17.88 minutes corresponds to compound (I), peak (2) at an elution time of 18.26 to 18.36 minutes corresponds to compound (II), and peak (3) at an elution time of 18.52 to 18.70 minutes corresponds to compound (III).

[0239] Experimental 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 a hydroformylation catalyst and 109.34 g of Rh(acac)(CO) as a catalyst under a nitrogen atmosphere. ２After charging 14.3 mg (0.0556 mmol), 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 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 quickly injected through the gas inlet valve so that the pressure in the reactor became 3 MPaG, and the reaction was allowed to proceed until hydrogen and carbon monoxide were no longer consumed by the reaction. Thereafter, while maintaining this pressure, the temperature of the reaction solution was raised to 100°C, and the reaction was allowed to proceed until hydrogen and carbon monoxide were no longer consumed by the reaction. The time from the introduction of the mixed gas of hydrogen and carbon monoxide into the reactor until hydrogen and carbon monoxide were no longer consumed by the reaction was defined as the reaction time of the hydroformylation reaction (also referred to simply as "reaction time" in this specification) and was used as an index of reaction efficiency. During the reaction, the amount of mixed gas consumed in the reaction was automatically introduced into the autoclave via an automatic pressure regulating valve, and the reaction was carried out while constantly maintaining the pressure in the reactor at 3 MPaG. After completion of the reaction, the reaction solution in the reactor was cooled to room temperature, and the remaining gas in the reactor was released to obtain 237.68 g of a hydroformylation reaction product liquid.

[0240] <Evaluation of Hydroformylation Reaction> The obtained hydroformylation reaction product liquid was analyzed using a gas chromatograph (GC) measurement device and a gas chromatography total area method under the following GC measurement conditions to determine the dicyclopentadiene (DCPD) content (unit: GC area%) and the contents of DCPD and the product tricyclodecane dicarbaldehyde (TCDD) (unit: GC area%) contained in the hydroformylation reaction product liquid. The DCPD conversion (unit: %) and TCDDD yield (unit: %) were calculated to be 99.4% and 96.5%, respectively. The reaction time of the hydroformylation reaction was 4.88 hours. The evaluation results are shown in Table 2.

[0241] <GC measurement conditions> GC apparatus: gas chromatogram measuring apparatus (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 120°C (no retention time) → heating at 10°C / min → 300°C (retention time 12 min) Injection port temperature: 200°C Detector temperature: 300°C Sample amount: 0.3 μL (split ratio: 1 / 30)

[0242] <Extraction Procedure> 71.65 g of methanol and 46.85 g of water were added to 235.23 g of the obtained hydroformylation reaction product liquid, and then stirred for 40 minutes under a nitrogen atmosphere. The mixture was then allowed to stand for 30 minutes to separate into two phases, and a lower layer (a1) and an upper layer (b1) were separated and recovered. 8.4 g of methylcyclohexane was added to the obtained lower phase (a1), and the mixture was stirred for 30 minutes. The mixture was then allowed to stand for 30 minutes to separate into two phases, and 278.83 g of a lower phase (a2) and 81.71 g of a mixture of the upper layers (b1) and (b2) were separated and recovered. The composition of the obtained lower phase (a2) was analyzed by gas chromatography, and it was found to be 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. Furthermore, the recovery rate of rhodium (Rh) metal and the recovery rate of tris(2,4-di-tert-butylphenyl)phosphite in the resulting mixture of the upper layer (b1) and the upper layer (b2) were analyzed by X-ray fluorescence analysis and inductively coupled plasma atomic emission spectrometry, and were found to be 99% and 99%, respectively.

[0243] <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 ratio 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 approximation equation of the 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 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 Experimental Example 1 was 0.98 hr －１ It was.

[0244] The evaluation results in Experimental Example 1 are summarized in Table 2.

[0245] [Experimental Example 2] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Experimental Example 1, except that DCPD-containing composition distillate 2 was used as the raw material compound in the hydroformylation reaction of Experimental Example 1, and the evaluation was carried out in the same manner. In addition, the rate of decrease in the reaction rate constant (k2) in the hydroformylation reaction was calculated by the following method.

[0246] <Calculation of the rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction> The reaction rate constant (k2) of the hydroformylation reaction calculated by the above method was divided by the reaction rate constant (k2) of Experimental Example 1 and multiplied by 100 to obtain the "rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction." The reaction rate constant (k2) of the hydroformylation reaction in Experimental Example 2 was 0.94 hr －１ The decrease rate of the reaction rate constant (k2) was 4.1%. The evaluation results of Experimental Example 2 are summarized in Table 2.

[0247] [Experimental Example 3] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Experimental Example 1, except that DCPD-containing composition distillate 3 was used as the raw material compound in the hydroformylation reaction of Experimental Example 1, and evaluation was carried out in the same manner. In addition, the rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Experimental Example 2. The evaluation results are summarized in Table 2.

[0248] [Experimental Example 4] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Experimental Example 1, except that DCPD-containing composition distillate 4 was used as the raw material compound in the hydroformylation reaction of Experimental Example 1, and evaluation was carried out in the same manner. In addition, the rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Experimental Example 2. The evaluation results are summarized in Table 2.

[0249] [Experimental Example 5] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Experimental Example 1, except that DCPD-containing composition distillate 5 was used as the raw material compound in the hydroformylation reaction of Experimental Example 1, and evaluation was carried out in the same manner. In addition, the rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Experimental Example 2. The evaluation results are summarized in Table 2.

[0250] [Experimental Example 6] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Experimental Example 1, except that DCPD-containing composition distillate 6 was used as the raw material compound in the hydroformylation reaction of Experimental Example 1, and evaluation was carried out in the same manner. In addition, the rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Experimental Example 2. The evaluation results are summarized in Table 2.

[0251] [Experimental Example 7] The hydroformylation reaction of the raw material compounds was carried out under the same conditions as in Experimental Example 1, except that DCPD-containing composition distillate 7 was used as the raw material compound in the hydroformylation reaction of Experimental Example 1, and evaluation was carried out in the same manner. In addition, the rate of decrease in the reaction rate constant (k2) of the hydroformylation reaction was calculated in the same manner as in Experimental Example 2. The evaluation results are summarized in Table 2.

[0252] In Experimental Examples 1 to 7, the contents of Compound (I), Compound (II), and Compound (III) in Extracts 1 to 7 were measured according to the above-mentioned Measurement Method 1. The measurement results are shown in Table 2.

[0253]

[0254] The relationship between the DCPD oxide content (GC area %) in the DCPD-containing compositions (distillates 1 to 7) in Experimental Examples 1 to 7 and the reaction rate constant (k2) of the hydroformylation reaction is shown in Figure 2. The relationship between the DCPD oxide content (GC area %) in the DCPD-containing compositions (distillates 1 to 7) in Experimental Examples 1 to 7 and the rate of decrease in the reaction rate constant (k2) is shown in Figure 3. The relationship between the DCPD oxide content (GC area %) in the DCPD-containing compositions (distillates 1 to 7) in Experimental Examples 1 to 7 and the rhodium (Rh) recovery rate is shown in Figure 4.

[0255] It can be seen from Fig. 2 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. It can be seen from Fig. 3 that the lower the content of DCPD oxide in the DCPD-containing composition, the lower the value of the rate of decline 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 rhodium (Rh) recovery rate.

[0256] [Experimental Example 8] <Production of alcohol> 102.1 g of the lower phase (a2) obtained in Experimental Example 1 and 2 g of a nickel-chromium-supported diatomaceous earth catalyst as a hydrogenation catalyst were charged into a 200 L autoclave reactor, and the temperature of the reaction solution in the reactor was raised to 160 ° C. while stirring at 1200 rpm. Next, hydrogen gas was injected through the gas inlet valve so that the pressure in the reactor was 3 MPaG, and the reaction was carried out for 2 hours while maintaining this pressure and the temperature of the reaction solution. During the reaction, the amount of hydrogen gas consumed in the reaction was continuously introduced into the reactor while maintaining the pressure in the reactor at 3 MPaG. After completion of the reaction, the reaction solution in the reactor was cooled to room temperature, the remaining gas in the reactor was released, and the nickel-chromium-supported diatomaceous earth catalyst was separated by filtration using a 5 μm filter, yielding 97.2 g of a reaction product liquid. The content of tricyclodecane dicarbaldehyde, a raw material compound, contained in the reaction solution before the reaction and the content of tricyclo[5.2.1.0(2,6)]decane dimethanol (hereinafter referred to as "TCDDM"), a product, in the reaction product solution after the reaction were analyzed by gas chromatography. As a result, the yield of TCDDM was found to be 97.9%.

[0257] Reference Experimental Example 3 Distillative Purification of Dicyclopentadiene (DCPD) 1,912 g of DCPD was charged into a simple glass distillation column and distilled under conditions of a pressure of 0.1 kPa, a column bottom temperature of 65°C, and a column top temperature of 60°C to obtain 1,832 g of a distillate, which was used as a DCPD-containing composition. The content of DCPD in the DCPD-containing composition was 99.7 GC area %.

[0258] The peroxide concentration in the DCPD-containing composition was measured using iodometric titration according to the following procedure. Under a nitrogen atmosphere, 5 mL of DCPD was added to a 50 mL pear-shaped flask, followed by 7.5 mL of a chloroform and acetic acid mixture (acetic acid:chloroform = 3:2, volume ratio), followed by 0.2 mL of saturated potassium iodide aqueous solution and stirring until the solution in the flask turned yellow or brown. The solution was diluted with 12.5 mL of distilled water and stirred for 1 minute to prepare a measurement sample. While stirring the measurement sample, a sodium thiosulfate aqueous solution (0.01 mol / L) was added dropwise as a standard solution until the measurement sample became colorless and transparent, and iodometric titration was performed. The peroxide concentration (unit: mmol / L) in the DCPD-containing composition was calculated based on the consumption of the added sodium thiosulfate aqueous solution, resulting in a peroxide concentration of 0.031 mmol / L.

[0259] Reference Experimental Example 4 Hydroformylation Reaction (First Run) In a 100 mL stainless steel autoclave reactor, 112.9 g of the DCPD-containing composition obtained in Reference Experimental Example 3 as a raw material compound for the hydroformylation catalyst and Rh(acac)(CO) ２After charging the reactor with 13.4 mg (0.0519 mmol), 1052.8 mg (1.623 mmol) of DBPO, and 85.4 g of methylcyclohexane as an organic solvent, the temperature of the reaction solution in the reactor was raised to 70°C while stirring at 1500 rpm. Next, a mixed gas of hydrogen and carbon monoxide (hydrogen:carbon monoxide = 1:1 (molar ratio)) was quickly injected through the gas inlet valve so that the pressure in the reactor was 3 MPaG, and while maintaining this pressure, the temperature of the reaction solution was raised to 100°C, and the reaction was allowed to proceed until hydrogen and carbon monoxide were no longer consumed by the reaction. The time from the introduction of the mixed gas of hydrogen and carbon monoxide into the reactor until hydrogen and carbon monoxide were no longer consumed by the reaction was defined as the reaction time of the hydroformylation reaction (also referred to simply as "reaction time" in this specification), and was used as an index of reaction efficiency. During the reaction, the amount of mixed gas consumed in the reaction was automatically introduced into the autoclave via an automatic pressure regulating valve, and the reaction was carried out while constantly maintaining the pressure in the reactor at 3 MPaG. After completion of the reaction, the reaction solution in the reactor was cooled to room temperature, and the remaining gas in the reactor was released to obtain 244.6 g of a hydroformylation reaction product liquid.

[0260] Evaluation of the First Hydroformylation Reaction Using a gas chromatograph (GC) and a gas chromatography total area method under the following GC measurement conditions, the DCPD content (99.7 GC area%) of the DCPD-containing composition obtained in Reference Experimental Example 3 and the hydroformylation reaction liquid product obtained in Reference Experimental Example 4 were used to determine the DCPD content (99.7 GC area%) of the DCPD-containing composition obtained in Reference Experimental Example 3 and the content (GC area%) of tricyclodecane dicarbaldehyde (TCDD) in the hydroformylation reaction liquid product. The DCPD conversion (unit: %) and TCDDD yield (unit: %) were calculated to be 99.4% and 96.5%, respectively. The reaction time of the hydroformylation reaction was 5.21 hours.

[0261] <GC measurement conditions> GC apparatus: GC-2025 (high-performance general-purpose gas chromatograph, manufactured by Shimadzu Corporation) Detector: hydrogen flame ionization detector (FID) Carrier gas: helium (column flow rate 1.23 ml / min) Column: capillary column DB-1 (manufactured by Agilent Technologies, size: length 30 m x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 120°C (no retention time) → heating at 10°C / min → 300°C (retention time 12 min) Injection port temperature: 200°C Detector temperature: 300°C Sample volume: 0.3 μL (split ratio: 1 / 30)

[0262] (Extraction Procedure) 74.04 g of methanol and 47.7 g of water were added to 224.6 g of the hydroformylation reaction product liquid obtained in Reference Experimental Example 4, and the mixture was stirred for 30 minutes under a nitrogen atmosphere. The mixture was then allowed to stand for 30 minutes to separate into two phases, and a lower layer (a1) and an upper layer (b1) were separated and recovered. 9.6 g of methylcyclohexane was added to the obtained lower phase (a1), and the mixture was stirred for 40 minutes. The mixture was then allowed to stand for 30 minutes to separate into two phases, and 287.4 g of a lower phase (a2) and 84.01 g of a mixture of the upper layers (b1) and (b2) were separated and recovered. The composition of the obtained lower phase (a2) was analyzed by gas chromatography, and it was found to be 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. Furthermore, the recovery rate of rhodium (Rh) metal and the recovery rate of tris(2,4-di-tert-butylphenyl)phosphite in the resulting mixture of the upper layer (b1) and the upper layer (b2) were analyzed by X-ray fluorescence spectrometry and inductively coupled plasma atomic emission spectrometry, and were found to be 99.0% and 99.0%, respectively.

[0263] [Experimental Example 9] <Hydroformylation Reactions (Second to Fourth Runs)> The hydroformylation reaction and extraction operation were carried out in the same manner as in Reference Experimental Example 4, except that the mixed solution of upper phases (b1) and (b2) obtained by the extraction operation in Reference Experimental Example 4 was used instead of the catalyst and solvent for the hydroformylation reaction described above, and further, rhodium (Rh) metal and DBPO were added to the mixed solution in the amounts lost in the extraction operation in Reference Experimental Example 4 so that the contents of Rh metal and DBPO were equivalent to those of the first hydroformylation reaction in Reference Experimental Example 4. This operation is referred to as the "second" hydroformylation reaction. The above operation was repeated two more times to obtain reaction solutions for the second to fourth hydroformylation reactions. The reaction solutions from the second to fourth hydroformylation reactions were analyzed using the gas chromatograph (GC) measurement device and the gas chromatography total area method, and it was found that the difference in reaction time between the second and fourth hydroformylation reactions (hereinafter also referred to as the "reaction time difference") was 1 minute. Furthermore, the rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions, as measured by Measurement Method 2 below, was 0.5%.

[0264] <Measurement Method 2> (Decrease in Reaction Rate Constant Per Hydroformylation Reaction) Procedure 1) Measurement of the Reaction Rate Constant of the Hydroformylation Reaction: Assuming that the reaction rate of the hydroformylation reaction can be approximated by a linear function relative to the concentration of the substrate DCPD, a graph is drawn on an XY graph with the hydroformylation reaction time on the X axis and the natural logarithm of "1-conversion / 100" on the Y axis. The slope of the approximate equation of the linear function in the conversion range of 60% to 80% is calculated, and this is used as the reaction rate constant of the hydroformylation reaction. Note that the "conversion" is measured in the same manner as described in the explanation of the evaluation of the hydroformylation reaction (first run). Step 2) On an XY graph, the X axis represents the number of hydroformylation reactions and the Y axis represents the reaction rate constant of the hydroformylation reaction calculated in Step 1. The reaction rate constants for the second to fourth hydroformylation reactions are plotted, and the resulting value is approximated by a linear function. The slope is calculated, divided by the reaction rate constant for the second reaction, and multiplied by 100 to obtain the "rate of decrease in the reaction rate constant per hydroformylation reaction for the second to fourth hydroformylation reactions."

[0265] Experimental Example 10: The DCPD-containing composition obtained in Reference Experimental Example 3 was placed in a 1-L glass bottle. To prevent the oxidation of dicyclopentadiene to produce dicyclopentadiene-derived peroxides, 2,6-di-tert-butyl-4-hydroxytoluene (BHT) was added to the bottle to a concentration of 150 ppm by mass. The bottle was then capped and stored for one month. The peroxide concentration in the DCPD-containing composition after one month of storage was measured using the same method as in Experimental Example 9 and found to be 0.323 mmol / L. Furthermore, the hydroformylation reaction and extraction procedure were repeated three times using the same method as in Experimental Example 9. The reaction time difference between the second and fourth hydroformylation reactions was 3 minutes. The rate of decrease in the reaction rate constant per hydroformylation reaction during the second to fourth hydroformylation reactions was 1.2%.

[0266] Comparative Experimental Example 1 The DCPD-containing composition obtained in Reference Experimental Example 3 was placed in a 1-L glass bottle, and the bottle was then closed and stored at room temperature (25°C) for one month. The peroxide concentration in the DCPD-containing composition after one month of storage was measured using the same method as in Experimental Example 9 and found to be 2.933 mmol / L. Furthermore, the hydroformylation reaction and extraction procedure were repeated three times using the same method as in Experimental Example 9. The reaction time difference between the second and fourth hydroformylation reactions was 23 minutes. The rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions was 7.4%.

[0267] The results of Experimental Examples 9 and 10 and Comparative Experimental Example 1 are summarized in Table 3 below.

[0268]

[0269] In Experimental Examples 9 and 10, the time difference between the second and fourth hydroformylation reactions was small. Furthermore, the rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions was also small. On the other hand, in Comparative Experimental Example 1, the peroxide concentration in the cyclic diene-containing composition was high compared to Experimental Examples 9 and 10, resulting in a large time difference between the second and fourth hydroformylation reactions and a large rate of decrease in the reaction rate constant per hydroformylation reaction in the second to fourth hydroformylation reactions. This indicates that when the peroxide concentration in the cyclic diene-containing composition is high, repeated hydroformylation reactions impair the activity of the rhodium-organic ligand complex catalyst contained in the reaction product liquid after the hydroformylation reactions.

[0270] The above results demonstrate that by controlling the peroxide concentration in the cyclic diene-containing composition, even when the rhodium-organic ligand complex catalyst contained in the reaction product liquid after the hydroformylation reaction is repeatedly recovered and reused, the activity of the catalyst can be prevented from decreasing, and good hydroformylation reaction efficiency can be maintained.

[0271] [Experimental Example 11] <Production of alcohol> 106.1 g of the lower phase (a2) obtained in Reference Experimental Example 3 and 2 g of nickel-chromium-supported diatomaceous earth catalyst were charged into a 0.2 L autoclave reactor, and the temperature of the reaction solution in the reactor was raised to 160 ° C. while stirring at 120 rpm. Next, hydrogen gas was injected into the reactor through the gas inlet valve so that the pressure in the reactor was 3 MPaG, and the reaction was carried out for 2.5 hours while maintaining this pressure and the temperature of the reaction solution. During the reaction, the amount of hydrogen gas consumed in the reaction was continuously introduced into the reactor while maintaining the pressure in the reactor at 3 MPaG. After completion of the reaction, the reaction solution in the reactor was cooled to room temperature, the remaining gas in the reactor was released, and the nickel-chromium-supported diatomaceous earth catalyst was separated by filtration using a 5 μm filter, yielding 98.3 g of a reaction product liquid. The content of the raw material compound tricyclodecane dicarbaldehyde contained in the reaction solution before the reaction and the product tricyclo[5.2.1.0] in the reaction product solution after the reaction were compared. ２，６ ] The content of decanedimethanol (hereinafter referred to as "TCDDM") was analyzed by gas chromatography, and the yield of TCDDM was found to be 98%.

[0272] Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications are possible within the scope of the effects of the invention. This application is based on Japanese Patent Application No. 2024-015094 filed on February 2, 2024, and Japanese Patent Application No. 2024-018008 filed on February 8, 2024, and is incorporated by reference in its entirety.

[0273] 1 Dimerization tank 2 Distillation column 3 Light boiling component removal column 4 Heavy boiling component removal column

Claims

1. A method for producing an aldehyde by hydroformylating a cyclic diene in a cyclic diene-containing composition, the method comprising reducing the content of oxygen-containing compounds in the cyclic diene-containing composition to a predetermined threshold value or less.

2. The method for producing an aldehyde according to claim 1, wherein the oxygen-containing compound is a cyclic diene oxide (provided that the cyclic diene does not include the cyclic diene oxide).

3. The method for producing an aldehyde according to claim 2, wherein the content of the cyclic diene oxide contained in the cyclic diene-containing composition is 1.2 GC area % or less.

4. The method for producing an aldehyde according to claim 2, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60 GC area % or more.

5. A method for producing an aldehyde according to claim 3, 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.

6. The method for producing an aldehyde according to claim 2, wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analysis is performed under the following GC measurement conditions, and the total content of the peaks with elution times of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC apparatus: gas chromatogram measuring apparatus (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 min) → heating at 10°C / min → 300°C (holding time: none) Injection port temperature: 200°C Detector temperature: 300°C Sample amount: 0.3 μL (split ratio: 1 / 30) 7. The method for producing an aldehyde according to claim 2, wherein the cyclic diene is a polycyclic diene.

8. The method for producing an aldehyde according to claim 7, wherein the cyclic diene is dicyclopentadiene.

9. The method for producing an aldehyde according to claim 2, 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.

10. The method for producing an aldehyde according to claim 2, 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.

11. The method for producing an aldehyde according to claim 8, wherein the cyclic diene is dicyclopentadiene, and the cyclic diene oxide comprises at least one compound 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): [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.] 12. The method for producing an aldehyde according to claim 11, wherein the cyclic diene is dicyclopentadiene and the aldehyde is tricyclodecane dicarbaldehyde.

13. A method for producing an aldehyde according to claim 2, wherein 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, and the method comprises carrying out the distillation and 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.

14. A method for producing an aldehyde according to claim 2, comprising controlling the 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.

15. The method for producing an aldehyde according to claim 14, wherein the control of the storage conditions includes controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

16. The method for producing an aldehyde according to claim 14, wherein the controlling of the storage conditions includes adding an antioxidant to the cyclic diene-containing composition.

17. A method for producing an alcohol, comprising producing an aldehyde by the production method according to any one of claims 1 to 16, and producing an alcohol from the aldehyde.

18. 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 claim 17, wherein the alcohol is decanedimethanol.

19. The method for producing an aldehyde according to claim 1, wherein the oxygen-containing compound is a peroxide.

20. The method for producing an aldehyde according to claim 19, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.8 mmol / L or less.

21. A method for producing an aldehyde according to claim 20, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

22. The method for producing an aldehyde according to claim 19, wherein the peroxide comprises a peroxide of an alkene compound.

23. The method for producing an aldehyde according to claim 19, wherein the concentration of the peroxide is measured by the following Measurement Method 1. <Measurement Method 1> Under a nitrogen atmosphere, a mixed solution of chloroform and acetic acid is added to a cyclic diene-containing composition, and then a saturated aqueous potassium iodide solution is added and stirred, and the mixture is further diluted with distilled water to prepare a measurement sample. The obtained measurement sample is subjected to iodine reduction titration using a 0.01 mol / L aqueous sodium thiosulfate solution as a standard solution, and the concentration of peroxide (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

24. The method for producing an aldehyde according to claim 19, wherein the cyclic diene is a polycyclic diene.

25. The method for producing an aldehyde according to claim 24, wherein the polycyclic diene is dicyclopentadiene.

26. A method for producing an aldehyde according to claim 19, wherein the cyclic diene-containing composition is a composition obtained by distillatively purifying a hydrocarbon decomposition product obtained by thermally decomposing a hydrocarbon-containing composition, and the method comprises carrying out the distillative purification so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

27. The method for producing an aldehyde according to claim 26, wherein the hydrocarbon decomposition product contains an antioxidant.

28. A method for producing an aldehyde according to claim 26, comprising adding an antioxidant to the hydrocarbon decomposition product so that the concentration of peroxides in the cyclic diene-containing composition is below a predetermined threshold.

29. A method for producing an aldehyde according to claim 26, comprising controlling storage conditions for the cyclic diene-containing composition so that the concentration of peroxide contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

30. The method for producing an aldehyde according to claim 29, wherein the controlling of the storage conditions includes controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

31. The method for producing an aldehyde according to claim 29, wherein the controlling of storage conditions includes adding an antioxidant to the cyclic diene-containing composition.

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

33. A method for producing an alcohol, comprising obtaining an aldehyde by the production method according to any one of claims 19 to 32, and producing a corresponding alcohol from the obtained aldehyde.

34. 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 claim 33, wherein the alcohol is decanedimethanol.

35. 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, the method comprising reducing the content of oxygen-containing compounds in the cyclic diene-containing composition to a predetermined threshold value or less.

36. The method for producing a cyclic diene-containing composition according to claim 35, wherein the oxygen-containing compound is a cyclic diene oxide. (However, the cyclic diene does not include the cyclic diene oxide.) 37. The method for producing a cyclic diene-containing composition according to claim 36, wherein the content of the cyclic diene oxide contained in the cyclic diene-containing composition is 1.2 GC area % or less.

38. A method for producing a cyclic diene-containing composition according to claim 36, 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.

39. A method for producing a cyclic diene-containing composition according to claim 36, 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.

40. The method for producing a cyclic diene-containing composition according to claim 39, wherein the controlling of the storage conditions includes controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

41. The method for producing a cyclic diene-containing composition according to claim 39, wherein said controlling storage conditions comprises adding an antioxidant to said cyclic diene-containing composition.

42. The method for producing a cyclic diene-containing composition according to claim 36, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60 GC area % or more.

43. A method for producing a cyclic diene-containing composition according to claim 41, 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.

44. The method for producing a cyclic diene-containing composition according to claim 36, wherein the content of the cyclic diene oxide is measured by the following measurement method 1. <Measurement method 1> Analysis is performed under the following GC measurement conditions, and the total content of peaks with elution times of 17.7 minutes to 18.8 minutes is measured. (GC measurement conditions) GC apparatus: gas chromatogram measuring apparatus (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 min) → heating at 10°C / min → 300°C (holding time: none) Injection port temperature: 200°C Detector temperature: 300°C Sample amount: 0.3 μL (split ratio: 1 / 30) 45. The method for producing a cyclic diene-containing composition according to claim 36, wherein the cyclic diene is a polycyclic diene.

46. The method for producing a cyclic diene-containing composition according to claim 45, wherein the cyclic diene is dicyclopentadiene.

47. A method for producing a cyclic diene-containing composition according to claim 36, 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.

48. The method for producing a cyclic diene-containing composition according to claim 36, wherein the cyclic diene oxide comprises 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.

49. The method for producing a cyclic diene-containing composition according to claim 46, wherein the cyclic diene is dicyclopentadiene, and the cyclic diene oxide comprises at least one compound 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): [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.] 50. The method for producing a cyclic diene-containing composition according to claim 36, wherein the hydrocarbon-containing composition is naphtha.

51. The method for producing a cyclic diene-containing composition according to claim 35, wherein the oxygen-containing compound is a peroxide.

52. The method for producing a cyclic diene-containing composition according to claim 51, comprising carrying out the distillation purification so that the concentration of peroxides contained in the cyclic diene-containing composition is equal to or less than a predetermined threshold value.

53. The method for producing a cyclic diene-containing composition according to claim 51, wherein the hydrocarbon decomposition products contain an antioxidant.

54. A method for producing a cyclic diene-containing composition according to claim 51, comprising adding an antioxidant to said hydrocarbon decomposition product so that the concentration of peroxides in said cyclic diene-containing composition is below a predetermined threshold.

55. A method for producing a cyclic diene-containing composition according to claim 51, comprising controlling storage conditions of the cyclic diene-containing composition so that the concentration of peroxide contained in the cyclic diene-containing composition is below a predetermined threshold.

56. The method for producing a cyclic diene-containing composition according to claim 55, wherein the controlling of the storage conditions includes controlling the dissolved oxygen concentration in the cyclic diene-containing composition.

57. The method for producing a cyclic diene-containing composition according to claim 55, wherein said controlling storage conditions comprises adding an antioxidant to said cyclic diene-containing composition.

58. A method for producing a cyclic diene-containing composition according to claim 51, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.8 mmol / L or less.

59. A method for producing a cyclic diene-containing composition according to claim 51, wherein the content of the cyclic diene contained in the cyclic diene-containing composition is 60.0 GC area % or more.

60. A method for producing a cyclic diene-containing composition according to claim 58, wherein the concentration of the peroxide contained in the cyclic diene-containing composition is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and particularly preferably 0.3 mmol / L or less.

61. The method for producing a cyclic diene-containing composition according to claim 51, wherein the concentration of the peroxide is measured by the following Measurement Method 1. <Measurement Method 1> Under a nitrogen atmosphere, a mixed solution of chloroform and acetic acid is added to the cyclic diene-containing composition, and then a saturated aqueous potassium iodide solution is added and stirred, and the mixture is further diluted with distilled water to prepare a measurement sample. The obtained measurement sample is subjected to iodine reduction titration using a 0.01 mol / L aqueous sodium thiosulfate solution as a standard solution, and the concentration of peroxide (mmol / L) in the cyclic diene-containing composition is determined based on the amount of the standard solution consumed.

62. The method for producing a cyclic diene-containing composition according to claim 51, wherein the cyclic diene is a polycyclic diene.

63. The method for producing a cyclic diene-containing composition according to claim 62, wherein the polycyclic diene is dicyclopentadiene.

64. The method for producing a cyclic diene-containing composition according to claim 51, wherein the hydrocarbon-containing composition is naphtha.

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

66. The cyclic diene-containing composition according to claim 65, wherein the cyclic diene content is 60 GC area % or more.

67. A cyclic diene-containing composition according to claim 65, 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.

68. The cyclic diene-containing composition according to claim 65, 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 of peaks with elution times of 17.7 minutes to 18.8 minutes. (GC measurement conditions) GC apparatus: gas chromatogram measuring apparatus (product name: GC-2025, manufactured by Shimadzu Corporation) Detector: hydrogen 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 x inner diameter 0.25 mm, film thickness 1.00 μm) Column temperature: 50°C (holding time 5 min) → heating at 10°C / min → 300°C (holding time: none) Injection port temperature: 200°C Detector temperature: 300°C Sample amount: 0.3 μL (split ratio: 1 / 30) 69. The cyclic diene-containing composition of claim 65, wherein the cyclic diene is a polycyclic diene.

70. The cyclic diene-containing composition of claim 69, wherein the cyclic diene is dicyclopentadiene.

71. The cyclic diene-containing composition according to claim 65, 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.

72. The cyclic diene-containing composition according to claim 65, wherein the cyclic diene oxide comprises at least one member 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.

73. The cyclic diene-containing composition according to claim 70, wherein the cyclic diene is dicyclopentadiene, and the cyclic diene oxide comprises at least one compound selected from the group consisting of compounds one enantiomer of which is represented by the following general formula (I), compounds one enantiomer of which is represented by the following general formula (II), and compounds one enantiomer of which is represented by the following general formula (III): [In formula (I), the hydroxyl group (—OH) is bonded to any position within the dicyclopentadiene ring structure shown.] 74. The cyclic diene-containing composition of claim 65, wherein the concentration of peroxide in the cyclic diene composition is 2.8 mmol / L or less.

75. The cyclic diene-containing composition of claim 74, wherein the concentration of the peroxide is 2.0 mmol / L or less, preferably 1.0 mmol / L or less, more preferably 0.6 mmol / L or less, and especially preferably 0.3 mmol / L or less.

76. The cyclic diene-containing composition of claim 74, wherein the peroxide comprises a peroxide of an alkene compound.

77. A method for producing an aldehyde, comprising subjecting the cyclic diene-containing composition according to any one of claims 65 to 76 to a hydroformylation reaction to produce an aldehyde.

78. A method for producing alcohol, comprising producing an aldehyde by the method according to claim 77 and producing an alcohol from the aldehyde.

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